JP3181165B2 - Light receiving member - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light receiving member which is susceptible to electromagnetic waves of light (here, light in a broad sense, such as ultraviolet light, visible light, infrared light, .GAMMA.-ray and .gamma.-ray).

[0002]

2. Description of the Related Art As a photoconductive material for forming an image forming member for electrophotography in a solid-state imaging device or an image forming field or a light receiving member in a document reading device, it has high sensitivity.
N ratio (photocurrent (Ip) / dark current (Id) is high, it has absorption spectrum characteristics matching the spectrum characteristics of the irradiating electromagnetic wave, photoresponse is fast, it has desired dark resistance value, On the other hand, various characteristics such as non-pollution are required.

As a photoconductive material which satisfies such severe conditions, has a high Vickers hardness and is excellent in durability, there is amorphous silicon (hereinafter abbreviated as "a-Si"). , The second
855718 discloses an application to an electrophotographic image forming member, and German Patent No. 2933411 describes an application to a photoelectric conversion reading device.

Further, for example, the light receiving member is disclosed in Japanese Patent Application Laid-Open Nos. 54-121743 and 57-4.
As disclosed in Japanese Patent Application Laid-open No. 053 and No. 57-4172, the light receiving layer is formed of two or more layers in which layers having different conductivity are laminated, and a depletion layer is formed inside the light receiving layer. Or JP-A-57-52178 and JP-A-52179.
No. 52180, No. 58159, No. 58160
No. 5,581,161, a multilayer structure in which a barrier layer is provided between the support and the light receiving layer and / or on the upper surface of the light receiving layer. Techniques have been proposed for improving the tolerance of design and improving the high light sensitivity even if the dark resistance is low to some extent.

[0005] Advances in these technologies have ensured a certain degree of characteristics, and have made it practical for use as a light receiving member for image formation for electrophotography. However, in order to satisfy the demands of the current electrophotographic apparatus, the light receiving member made of the conventional a-Si requires electrical, optical and photoconductive properties such as dark resistance, photosensitivity and photoresponsiveness. In fact, it is necessary to improve the overall characteristics in terms of characteristics and use environment characteristics such as moisture resistance, and further, in terms of stability over time.

For example, at present, with the increase in copy volume of an electrophotographic apparatus, the need for higher speed and higher durability, as well as the demand for higher image quality and higher definition from the market are increasing year by year. Furthermore, the size of the electrophotographic device itself has been reduced,
Power saving is required. Under such circumstances, if a conventional light receiving member is used as it is, particularly in a high-speed electrophotographic apparatus, the photosensitivity is insufficient particularly in an image forming process in which charging, exposure, development, transfer, and fixing are performed in one cycle. As a result, when used repeatedly for a long time, there is a problem that a high quality image cannot be obtained. For example, in an electrophotographic apparatus, parameters such as surface potential and surface temperature are detected by a built-in sensor and controlled by built-in control means so that the same image quality is obtained every time. On the other hand, if the light sensitivity is insufficient, it is necessary to increase the amount of light or the light intensity to compensate for the insufficient light sensitivity. Then, as the amount of light increases, the number of photocarriers generated in the deposited film also increases. This apparently increases the sensitivity, but also causes the following problem.

That is, as described above, when the light amount or the light intensity is increased to forcibly generate carriers to compensate for the photosensitivity, the number of generated carriers is large. Move in a direction parallel to the surface of the deposited film. As a result, electric charges also flow to a portion where light is not incident, causing image deletion and a reduction in resolution.

Therefore, it is difficult to maintain the same state every cycle, that is, a constant and uniform surface potential.
In the case of the light receiving member that cannot return to the initial state after one cycle, the value of the parameter detected by the sensor differs in each cycle.
It is adjusted by the control means for each cycle.
If such a state continues for a long period of time, it becomes difficult to maintain the same image quality, and the load on the control means also increases, which may affect the life of the main body of the machine.
Specifically, in some cases, unevenness in chargeability, unevenness in sensitivity, or deterioration in fine line reproducibility due to a decrease in resolution, white background fog, image unevenness, and the like during use are observed. Especially a
Since the photoreceptor member for forming an image of -Si electrophotography is mainly used in a high-speed copying machine having a large copy volume as described above, it is often used repeatedly for a long time. This problem is even more pronounced.

Further, in order to make full use of a light receiving member having insufficient light sensitivity with respect to such a process speed, the process speed must be limited and compensated by increasing the specifications of the electrophotographic apparatus main body. No.
Specifically, it is inevitable that the output of the exposure apparatus or the charger will be increased and the size thereof will be increased accordingly. As a result, not only is the cost increased, but also the degree of freedom in the design of the main body of the electrophotographic apparatus is reduced due to the enlargement of the auxiliary devices around the light receiving member, and the miniaturization and power saving of the main body are limited. Becomes

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the above-mentioned problems in the conventional light receiving member,
It is an object of the present invention to satisfy various requirements for a light receiving member having a light receiving layer mainly composed of a non-single crystal.

That is, the electrical, optical, and photoconductive properties are substantially always stable almost without depending on the use environment, are excellent in light fatigue resistance, and do not cause deterioration phenomenon even when used repeatedly. An object of the present invention is to provide a light receiving member having a light receiving layer made of a non-single crystal, which is excellent in durability and moisture resistance and has excellent light sensitivity which can sufficiently follow the process speed of a high-speed copying machine.

[0012] Another object of the present invention is to provide a non-single unit which is excellent in adhesion between a photoconductive layer provided on a support and a surface layer, strict and stable in structural arrangement, and has high layer quality. An object of the present invention is to provide a light receiving member having a light receiving layer composed of a crystal.

[0013]

Means for Solving the Problems The present inventors have made intensive studies to overcome the above-mentioned problems in the conventional light receiving member and achieve the above-mentioned object of the present invention. Obtained.

A non-single-crystal material containing at least silicon atoms, hydrogen atoms and / or halogen atoms as constituent atoms, ie, so-called hydrogenated a-Si, halogenated a
-Si, or halogen-containing hydrogenated a-Si, and polycrystalline silicon (hereinafter referred to as "nc-Si: (H,
X))), the light receiving member has a multilayer structure as described above, and each layer has a hydrogen atom or a fluorine atom to improve its electrical and photoconductive properties. Atom atoms and halogen atoms such as chlorine atoms, and boron atoms and phosphorus atoms for controlling electric conductivity, or other atoms for improving other properties are contained as constituent atoms, respectively. Depending on the content of atoms, a problem may occur in the electrical and photoconductive properties of the formed layer.

In particular, in the vicinity of the surface or at the interface between adjacent layers, the problem of charge behavior and structural stability, which vary variously depending on the contained atom, content, distribution state, and the like, or the problem of adhesion of each layer becomes particularly important. In order for the light receiving member to perform its intended function, there are many cases where control of this portion is the key to success or failure.

In a conventional light-receiving member for image formation for nc-Si electrophotography, an examination was conducted by focusing on the interface of each layer in order to further improve the image repetition characteristics and durability. As a result, as a result of examining the optical sensitivity and the repetition characteristics, etc. in the direction of solving the structural distortion near the surface or at the layer interface, the above problem was solved by designing the layer near the interface with a different concept from the bulk part. I got the knowledge that the point can be solved.

The present inventors have completed the present invention based on the above-mentioned findings, and the gist of the present invention is that a non-single-crystal photoreceptor having at least a silicon atom composed of a support, a photoconductive layer and a surface layer as a host is used. The member is characterized in that the hydrogen content in the vicinity of the interface between the photoconductive layer and the surface layer is higher than the hydrogen content in any of the photoconductive layer and the surface layer.

The light-receiving member of the present invention having the above-described layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical and photoconductive properties.
Shows usage environment characteristics and high characteristic stability.

In particular, when applied as an image forming member for electrophotography, in the image forming process, the light sensitivity can sufficiently follow the increase in the process speed, and can withstand repeated use for a long period of time. Characteristics are stable, high sensitivity, high SN ratio, excellent in light fatigue, repetitive use characteristics, especially repetitive use characteristics under high humidity atmosphere, high concentration, high resolution and high resolution A fine, high-quality visible image can be obtained.

Hereinafter, experimental examples performed by the present inventors will be described.

In each of the experimental examples and examples, a light receiving member was manufactured by a microwave discharge method unless otherwise specified. The outline and manufacturing procedure are described below.

FIGS. 3 and 4 show an apparatus for manufacturing a light receiving member for an image forming member for electrophotography used in the present invention. Here, FIG. 3 is a schematic vertical sectional view of a manufacturing apparatus by a microwave discharge method,
FIG. 4 is a schematic cross-sectional view taken along line XX of FIG.

In FIG. 1, reference numeral 301 denotes a reaction vessel having a vacuum tight structure. Reference numeral 302 denotes a microwave introduction dielectric window formed of a material (for example, quartz glass, alumina ceramics or the like) capable of efficiently transmitting microwave power into the reaction vessel 301 and maintaining vacuum tightness. . Numeral 303 denotes a waveguide for transmitting microwave power, which comprises a rectangular portion from the microwave power source to the vicinity of the reaction vessel, and a cylindrical portion inserted into the reaction vessel. The waveguide 303 is connected to a microwave power supply (not shown) together with a stub tuner (not shown) and an isolator (not shown). The dielectric window 302 is hermetically sealed to the inner wall of the cylindrical portion of the waveguide 303 to maintain the atmosphere in the reaction vessel. An exhaust pipe 304 has one end open to the reaction vessel 301 and the other end communicating with an exhaust device (not shown). Reference numeral 306 denotes a discharge space surrounded by the support 305. Power supply 311 is bias electrode 3
12 is a DC power supply (bias power supply) for applying a DC voltage to the electrode 12, and is electrically connected to the electrode 312.

The production of a light receiving member for electrophotography using such a production apparatus is performed as follows. First, the reaction vessel 3 is evacuated by a vacuum pump (not shown) through the exhaust pipe 304.
And the pressure in the reaction vessel 301 is reduced to 1 × 10 ⁻⁷ T
Adjust to orr or less. Then, by the heater 307,
The temperature of the support 305 is maintained at a predetermined temperature. still,
At this time, in order to improve the heat conduction between the heater and the support and uniformly heat the support in a short time, a gas that is stable against heat and does not react with the support (for example, an inert gas or hydrogen) is introduced. You may. When the temperature of the support reaches the predetermined temperature,
Once the inside of the reaction vessel is evacuated, it is introduced through a source gas introduction means (not shown) in the first layer region. That is, nc-S
i: A source gas such as a silane gas as a source gas of (H, X), a diborane gas as a doping gas, and a helium gas as a diluting gas is introduced into the reaction vessel 301. Simultaneously therewith, a microwave having a frequency of 500 MHz or more, preferably 2.45 GHz, is generated by a microwave power supply (not shown), and the dielectric window 30 is passed through the waveguide 303.
2 into the reaction vessel 301. Further, the DC power supply 311 electrically connected to the bias electrode 312 in the discharge space 306 allows the support 30 to be connected to the bias electrode 312.
5 is applied with a DC voltage. Thus the support 305
In the discharge space 306 surrounded by, the source gas is excited by microwave energy and dissociated, generating neutral radical particles, ion particles, electrons, etc., which react with each other and deposit on the surface of the support 305. A film is formed. At this time, the rotating shaft 309 on which the support 305 is installed is rotated by the motor 310, and the support 305 is rotated about the central axis in the direction of the base line of the base.
05 A deposited film is formed uniformly over the entire circumference.

In order to form a surface layer on the photoconductive layer formed as described above, the photoconductive layer is formed by changing the composition of the raw material gas, introducing the gas into the reaction vessel 301, and changing the composition of the surface layer. , Formed by restarting the discharge.

The amount of hydrogen atoms contained in the layer interface region between the photoconductive layer and the surface layer can be controlled, for example, by arbitrarily changing the flow rate of hydrogen gas introduced into the discharge space as desired. Further, control can also be performed by appropriately changing the microwave power introduced into the discharge space and the bias voltage applied. It is also possible to control by selecting the type of gas to be introduced so as to change the flow rate ratio of the silane gas and the disilane gas introduced into the discharge space, for example. (Experimental Example 1) In order to control the hydrogen content in the vicinity of the layer interface, a charge injection blocking layer was formed on an aluminum cylinder mirror-finished according to the manufacturing conditions shown in Table 1 using the manufacturing apparatus shown in FIGS. A photoreceptive member for a blocking type electrophotography having a three-layer structure of a photoconductive layer and a surface layer was formed. At this time,
The hydrogen flow rate and the applied bias voltage to be introduced during the preparation of the interface between the photoconductive layer and the surface layer were adjusted within the ranges shown in Table 1 for the source gas to be introduced and the bias voltage to be applied, and various light receiving members were obtained. A plurality of portions of the light receiving member corresponding to the upper and lower portions of the image area were cut out (hereinafter, referred to as “samples”), quantitative analysis of hydrogen atoms contained in the deposited film was performed by SIMS, and hydrogen content at the layer interface was measured. And the hydrogen content in the bulk layer were compared. Table 2 shows the results. The region with a large amount of hydrogen at the layer interface is 50 to 8000 °, and the hydrogen content at the layer interface is 1.0 to 2.2, which is the larger of the bulk hydrogen content.
It was possible to change by a factor of two. Then, as shown in Table 2, sample names of hydrogen atom content and layer thickness of each layer interface prepared under various conditions were given.

Next, the light sensitivity of the prepared sample (however, not used for SIMS analysis) was measured by the method shown in FIG.

First, FIG. 5 will be described. Reference numeral 400 denotes a sample, and a light receiving layer 402 is mounted on a support 401. 403 is a transparent conductive film ITO (In ₂
O ₃ + SnO ₂ ) is deposited on the glass, and is electrically connected to the DC power supply 404. 405 is a light source. Reference numeral 406 denotes a measuring device.

The measurement is performed as follows. First, the sample 400 is brought into close contact with the glass 403 on which the transparent conductive film is deposited by using a substance having a high relative dielectric constant such as glycerin so as to have no gap as shown in the drawing. Next, DC power supply 4
From 04, a predetermined voltage is applied between the support and the light receiving layer,
A predetermined surface potential is applied. Next, the sample 400 is irradiated with various amounts of light from the light source 405 through the glass 403. At this time, a photocurrent flows in the sample 400, and the current value and time at that time are measured by the measuring device 406. Then, a photocurrent value after a certain time from the moment when the sample is irradiated with light is obtained. The light amount required to obtain a predetermined photocurrent by adjusting the light source 405 was obtained, and this value was used as the light sensitivity. In this experiment, the initially set surface potential was 300 V, and 20 msec after light irradiation. The amount of light necessary to obtain a photocurrent having a photocurrent value of 15 μA later was determined. Table 3 shows the results. Here, ◎ indicates that the light sensitivity was very good, ○ indicates that the light sensitivity was good, Δ indicates that the light sensitivity was practically no problem, and x indicates that the light sensitivity was not practical. As is clear from Table 3, the region having a large hydrogen content near the layer interface between the photoconductive layer and the surface layer is 100 to 5000 ° C.
It was confirmed that the photosensitivity was excellent when the hydrogen content near the layer interface was 1.1 to 2.0 times the hydrogen content in the bulk layer.

The light receiving member of the present invention formed so that the hydrogen content near the layer interface between the photoconductive layer and the surface layer is larger than the bulk hydrogen content can be used as an electrophotographic image forming member. The reason why the photosensitivity is good when used as is considered as follows.

The characteristics of the light receiving member having a multilayer structure often depend on the bonding state of the constituent atoms at the layer interface. That is, since the structure of the layer is different at the interface of the layer, structural distortion occurs at the interface of the layer. Then, the layer interface becomes an electric barrier or becomes structurally unstable. Specifically, dangling bonds or various levels called interface states are formed in the band gap, and when light is irradiated, transmission of light near the interface is hindered. Not only does the efficiency decrease, but also the properties of the film near the interface are reduced, resulting in low carrier generation efficiency, that is, low quantum yield. In addition, when the above-mentioned interface states are present in a large amount, the energy band at the interface portion is rounded, so-called band bending, and the resistance in the in-plane direction parallel to the surface near the layer interface is reduced, resulting in a lateral flow of charges. . Further, the adhesion at the layer interface is reduced, and the mechanical strength is also reduced. On the other hand, by introducing hydrogen atoms in the vicinity of the interface, it is thought that the structural strain is partially relaxed, dangling bonds that can serve as traps are compensated, and characteristics and adhesion are improved. .

Further, the reason why there is an optimum range of the hydrogen-containing region and the content in the vicinity of the layer interface, which is one of the most significant features of the present invention, is considered as follows.

That is, if the region where the hydrogen content is increased is wide or the hydrogen content is too large, the film quality is structurally unstable because of the excessive hydrogen content. . That is, if hydrogen is present more than necessary to alleviate the structural strain, it is considered that the network of silicon atoms is hindered, or the bond is easily broken, and the structure becomes unstable. Conversely, if the region is too narrow or the hydrogen content is too small, it is difficult to alleviate the above-mentioned structural distortion, and it is considered that the effects of the present invention cannot be obtained.

Therefore, it is particularly important in the present invention to control the hydrogen content and its area near the layer interface. (Experimental Example 2) Using the manufacturing apparatus of the present experiment shown in FIGS. 3 and 4, mirror finishing was performed in the same manner as in Experimental Example 1 except that the thicknesses of the photoconductive layer and the surface layer were changed. A blocking type electrophotographic light-receiving member having a three-layer structure was formed on the thus-formed aluminum cylinder. A plurality of portions corresponding to the upper and lower portions of the image area were cut out from the light receiving member, and the relationship between the photosensitivity and the hydrogen content was evaluated in the same manner as in Experimental Example 1. As a result, when one or both of the photoconductive layer and the surface layer are extremely thin (1-2 μm).
m)), it was confirmed that the effect of the present invention is exhibited in a region having a large hydrogen content near the layer interface, preferably within 30% of the thinner of the photoconductive layer and the surface layer. (Experimental Example 3) Using the manufacturing apparatus of this experiment shown in FIGS. 3 and 4, samples in which the hydrogen content in the photoconductive layer and the surface layer were variously changed were prepared. When the relationship between the photosensitivity and the photosensitivity was examined, the hydrogen content in the bulk layer of the photoconductive layer and the surface layer was in the range of 0.05 to 40 atomic%, and the hydrogen content in the vicinity of the layer interface was in the range of 0.1 to 45 atomic%. As in Experimental Examples 1 to 3, the range with a large hydrogen content is 100 to 5
It was confirmed that the photosensitivity was excellent when the hydrogen content in the vicinity of the layer interface was 1.1 to 2.0 times the hydrogen content in the bulk layer.

However, at this time, the analysis of the hydrogen content was carried out by appropriately combining analysis methods such as SIMS, infrared absorption method and thermal desorption method according to the content.

From the above experimental examples, it was found that there was a range suitable for the hydrogen content near the layer interface and the thickness of the content region.

Hereinafter, the light receiving member of the present invention will be described in more detail with reference to the drawings.

FIG. 1 schematically shows a layer structure for explaining the structure of the light receiving member of the present invention. In the figure, an nc-Si layer (hereinafter, referred to as a “photoconductive layer”) 102 mainly containing hydrogen atoms and / or halogen atoms of a photoconductive silicon atom base material 102 and a surface layer 103 are formed on a support 101. The light receiving layer 100 is formed.
The hydrogen atoms contained in the photoconductive layer 102 and the surface layer 103 have a uniform concentration distribution in a direction parallel to the support surface, and the thickness direction of the layer is shown in FIG. As a result, the concentration is formed near the interface between the surface layer 103 and the photoconductive layer 102 so as to be higher than the bulk concentration.

As described above, the content of the hydrogen atoms contained in the surface layer 103 and the photoconductive layer 102 may be smaller than the content near the layer interface, and the content is not necessarily required to be constant in the entire layer. May have a gradual distribution.

Next, FIGS. 2A to 2H schematically show a typical distribution of the hydrogen content contained in the layer. However, the amount of hydrogen contained in each layer may be equal to or different from each other. Further, the hydrogen content contained in the layer may be constant or gradually change in the layer thickness direction. However, as already shown in the experimental examples, it is very important in the present invention to satisfy the following conditions for the hydrogen content.

That is, the hydrogen content rapidly increases only in the vicinity of the layer interface, in a specific limited range of the layer thickness, and further increases in the hydrogen content in a specific range. .

Therefore, in the present invention, it is particularly important to optimally control the hydrogen content near the layer interface and its region. In other words, in order to effectively exhibit the effect in the present invention, the hydrogen content near the layer interface is preferably 1.1 to 2.0 times the bulk hydrogen content, and optimally 1.2 times.
It is about 1.8 times. Further, the region having a large hydrogen content near the layer interface is preferably 100 to 5000 ° in the thickness direction of the layer centered on the layer interface, and most preferably 500 to 3000 °.
When the thickness of the photoconductive layer or the surface layer is small, the concentration of hydrogen at the interface between the layers also has an adverse effect on each bulk layer.
Desirably, it is within 0%.

In the present invention, while controlling the hydrogen content in the vicinity of the interface between the photoconductive layer and the surface layer, a charge injection blocking layer is further provided between the photoconductive layer and the support, and the charge injection blocking layer and the photoconductive layer are provided. It is also effective to simultaneously control the hydrogen content near the layer interface with the layer.

In the present invention, in order to optimally adjust the hydrogen content near the layer interface and to design a high-quality light receiving member, it is essential to analyze the hydrogen content at the layer interface. As the analysis method, in addition to the above-described SIMS, infrared absorption method, and thermal desorption method, a nuclear reaction method, a nuclear magnetic resonance method, an ESCA, an RBS, a gas analysis method, and the like are appropriately combined and analyzed. It is desirable to increase the accuracy of the measuring instrument.

As the halogen atom (X) contained in the light receiving member of the present invention, specifically, fluorine, chlorine, bromine, and iodine can be mentioned, and particularly, fluorine and chlorine can be preferably mentioned. . The amount of halogen atoms (X) contained in the photoconductive layer or the sum (H + X) of the amounts of hydrogen atoms and halogen atoms is usually 1 to 40 atm.
omic%, preferably 5 to 30 atomic%.

Further, the layer thickness of the light receiving member of the present invention is one of the important factors for efficiently achieving the object of the present invention. , It is necessary to take great care when designing the light receiving member,
Usually 1 to 100 μm, preferably 1 to 80 μm
m, more preferably 2 to 50 μm.

In the light receiving member of the present invention, the substance for controlling the conductivity can be contained in the entire layer region or a part of the layer region in a uniform or non-uniform distribution state. Examples of the substance that controls conductivity include so-called impurities in the semiconductor field, and an atom belonging to Group III of the periodic table that provides p-type conductivity (hereinafter, simply referred to as (Group III atom)), or An atom belonging to Group V of the periodic table that provides n-type conductivity [hereinafter simply referred to as (Group V atom)] is used. Specifically, the group III atoms include B (boron), Al (aluminum), Ga (gallium), In
(Isodium), Tl (thallium) and the like can be mentioned, and particularly preferable are B and Ga. P (phosphorus), As (arsenic), Sb
(Antimony), Bi (bismuth) and the like can be mentioned, and particularly preferred are P and Sb.

When the light receiving member of the present invention contains a group III atom or a group V atom which is a substance for controlling conductivity, whether it is contained in the whole layer region or in some layer regions. Varies depending on the intended purpose and the expected effect as described below, and accordingly, the amount to be contained also varies.

That is, when the main purpose is to control the conductivity type and / or the conductivity of the light receiving layer, it is contained in the entire region of the light receiving layer. The content of group atoms may be relatively small, usually
× 10 ^-3 to 1 × 10 ³ atomic ppm, preferably 5 ×
10 ^{−2 to} 5 × 10 ² atomic ppm, optimally 1 × 10 ⁻¹ to
It is 2 × 10 ² atomic ppm.

In order to function as a charge injection blocking layer, group III atoms or group V atoms are contained in a relatively high concentration and in a uniform distribution state in a part of the layer region in contact with the support, or This is performed by including the group III atoms or the group V atoms in the layer thickness direction such that the distribution concentration of the group III atoms or the group V atoms becomes high on the side in contact with the support. Part of the layer region containing the group III atom or the group V atom or the region containing the group III atom or the group V atom at a high concentration functions as a charge injection blocking layer. That is, when a group III atom is contained, the movement of electrons injected from the support side into the light receiving layer is more efficiently performed when the free surface of the light receiving layer is subjected to a positive polarity charging treatment. And the Vth
When a group atom is contained, the movement of holes injected from the support side into the light receiving layer is more efficiently prevented when the free surface of the light receiving layer is subjected to a unipolar charging treatment. be able to. And the content in this case is relatively large.
Specifically, the concentration is generally 30 to 5 × 10 ⁴ atomic ppm, preferably 50 to 1 × 10 ⁴ atomic ppm, and most preferably 1 × 10 ^{2 to} 5 × 10 ³ atomic ppm.

Further, in the light receiving member of the present invention,
For example, using an infrared laser, when used as a laser beam printer, for the purpose of suppressing the interference phenomenon that occurs when using coherent monochromatic light further on the support side of the photoconductive layer, to provide an infrared light absorbing layer It is also possible.
As such an absorption layer, for example, nc-Si: (H,
X) nc-S in which germanium atoms (Ge) are added to the layer
iGe: (H, X).

Next, a method for forming the light receiving member of the present invention will be described. Any of the amorphous materials of the present invention can be obtained by a sputtering method or a method of decomposing a source gas by heat (thermal CVD).
Method), a method of decomposing a source gas by light (photo CVD)
Method), a method of decomposing a raw material gas by direct current, high frequency, microwave glow discharge, or the like, and decomposing the raw material gas by plasma generated thereby (plasma CVD method). These manufacturing methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the load on capital investment, the manufacturing scale, and the characteristics desired for the light receiving member to be manufactured. The plasma CVD method is preferable because it is relatively easy to control the conditions for producing the silicon nitride, and the carbon atoms and the hydrogen atoms can be easily introduced together with the silicon atoms. For example, in order to form a layer composed of nc-Si: (H, X) by a plasma CVD method, basically, a silicon atom (S
A source gas for introducing hydrogen atoms and / or a source gas for introducing halogen atoms is introduced into a deposition chamber in which the inside pressure can be reduced together with a source gas for supplying Si that can supply i), and a glow discharge is generated in the deposition chamber. Then, a layer composed of nc-Si: (H, X) is formed on the surface of a predetermined support previously set at a predetermined position.

The source gas for supplying Si is Si
H_Four, Si_TwoH₆, Si_ThreeH₈, Si_FourH _Ten, Etc.
Or gasified silicon hydrides (silanes)
In particular, ease of layer formation work, good Si supply efficiency, etc.
In terms of SiH_Four, Si_TwoH₆Is preferred.

The source gas for introducing a halogen atom includes many halogen compounds. For example, a halogen gas, a halide, an interhalogen compound, a halogen-substituted silane derivative, or the like can be gasified or gasified. Halogen compounds are preferred. Specifically, fluorine,
Chlorine, bromine, halogen gas of iodine, BrF, ClF,
Interhalogen compounds such as ClF ₃ , BrF ₅ , BrF ₃ , IF ₇ , ICl, IBr, and SiF ₄ , Si ₂ F ₆ , SiC
and silicon halides such as l ₄ and SiBr ₄ . In the case of using the above-described gas state of silicon halide or a substance that can be gasified, a layer composed of nc-Si containing a halogen atom is formed without separately using a source gas for supplying Si. It is particularly effective because it can be done.

Examples of the source gas for supplying hydrogen atoms include hydrogen gas, halides such as HF, HCl, HBr, and HI, and SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ . Silicon hydride, or SiH ₂ F ₂ , SiH ₂ I ₂ , S
Halogen-substituted hydrogenated silicon hydride such as i ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , and SiHBr ₃ can be used, or a gas that can be gasified can be used. Alternatively, it is effective because the content of hydrogen atoms (H), which is extremely effective in controlling photoconductive properties, can be easily controlled. Here, in particular, as a method of controlling the amount of hydrogen near the layer interface between the photoconductive layer and the surface layer, the partial pressure of hydrogen in the atmosphere gas is changed by arbitrarily changing the flow rate of the hydrogen gas introduced into the discharge space as desired. Adjusting method, adjusting by changing discharge power, adjusting by changing applied bias voltage, adjusting by changing temperature of support, changing pressure in discharge space And a method of adjusting by changing the type of gas introduced into the discharge space and the flow ratio thereof. Among them, for example, in the case of producing a light receiving member by a microwave discharge method, a method of changing the amount of hydrogen introduced into a discharge space as desired, a method of changing a bias voltage to be applied, and a temperature of a support are changed. The method is particularly effective.

When the hydrogen halide or the halogen-substituted hydrogenated silicon is used, a hydrogen atom (H) is introduced simultaneously with the introduction of the halogen atom.
Especially effective.

The control of the amount of the hydrogen atom (H) and / or the halogen atom (X) contained in the nc-Si layer is performed by, for example, the temperature of the support, the hydrogen atom (H) and / or the halogen atom (X). This is performed by controlling the amount of the starting material to be introduced into the deposition chamber and the discharge power.

In the present invention, it is also effective that the photoconductive layer further contains at least one of oxygen, carbon and nitrogen. At this time, it is important that the content is at most 30 atomic% or less with respect to silicon atoms, since the photoconductivity is impaired if a large amount is contained. Also, it is effective to carry out layer design that oxygen, carbon, and nitrogen are contained in the photoconductive layer in a distributed manner, and it is important that the oxygen, carbon, and nitrogen be increased toward the lower part of the photoconductive layer. At this time, it is important that the average in the layer is 30 atomic% or less in order to maintain excellent photoconductivity.

Further, the surface layer in the present invention preferably contains silicon atoms and contains at least one of oxygen, carbon and nitrogen. As the surface layer, photoconductivity is not required, and excellent hardness and light transmittance are required. Therefore, the content of the above atoms is 50 atomic relative to silicon.
% Is important.

In the present invention, when a plasma CVD method is used to form a layer or a layer region containing an oxygen atom, a material selected as desired from the above-described starting materials for forming a light receiving layer is used. Starting materials for introducing oxygen atoms are added. As such a starting material for introducing an oxygen atom, almost any gaseous substance containing at least an oxygen atom or a substance that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing oxygen atoms (O) as constituent atoms, and hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms as necessary. Mixed with the raw material gas to be mixed at a desired mixing ratio, or silicon atom (Si)
Is mixed with a source gas having oxygen atoms (O) and hydrogen atoms (H) at a desired mixing ratio, or a silicon atom (S
The raw material gas containing i) and the raw material gas containing oxygen atoms (O) and hydrogen atoms (H) are also mixed at a desired mixing ratio, or silicon atoms (S
i) a constituent gas and a silicon atom (S
i), an oxygen atom (O), and a source gas having three hydrogen atoms (H) as constituent atoms can be used in combination.
In addition, oxygen atoms (O) may be added to the source gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms.
May be used as a mixture.

Specifically, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ),
Nitrous oxide (N ₂ O), Nitrous oxide (N ₂ O ₃ ), Nitrous oxide (N ₂ O ₄ ), Nitrous oxide (N ₂ O ₅ ), Nitric oxide (NO ₃ ) , Silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H) as constituent atoms, such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ). Lower siloxane and the like can be mentioned.

In the present invention, when a plasma CVD method is used to form a layer or a layer region containing a nitrogen atom, the starting material for forming the photoreceptive layer may be selected as desired from the above. A starting material for introducing a nitrogen atom is added. As such a starting material for introducing a nitrogen atom, almost any gaseous or gasizable substance containing at least a nitrogen atom as a constituent atom can be used. For example, a source gas having silicon atoms (Si) as constituent atoms, a source gas having nitrogen atoms (N) as constituent atoms,
If necessary, a raw material gas containing hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms may be mixed at a desired mixing ratio and used, or a raw material gas containing silicon atoms (Si) as constituent atoms A gas and a source gas containing nitrogen atoms (N) and hydrogen atoms (H) as constituent atoms can also be used in a mixture at a desired mixing ratio. Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing nitrogen atoms (N) as constituent atoms.

Forming a Layer or Layer Region Containing Nitrogen Atoms
Gas for introducing nitrogen atoms (N)
The starting material used effectively is either N as a constituent atom or
Or N and H as constituent atoms, for example, nitrogen (N_Two), A
Monmonia (NH_Three), Hydrazine (H_TwoNNH_Two),Horse mackerel
Hydrogen (HN_Three), Ammonium azide (NH_FourN_Three)etc
Or gasifiable nitrogen, nitrides and azides of nitrogen
And the like. In addition, nitrogen
Introduction of halogen atom (X) in addition to introduction of atom (N)
Nitrogen trifluoride (F_ThreeN), four
Dinitrogen nitride (F_FourN _Two) Etc.
Can be

In the present invention, for example, in order to form an nc-Si: (H, X) layer containing a carbon atom by a plasma CVD method, a raw material gas containing silicon atoms (Si) as a constituent atom, Whether the raw material gas having the atom (C) as a constituent atom and the raw material gas having a hydrogen atom (H) and / or a halogen atom (X) as a constituent atom are mixed at a desired mixing ratio, if necessary. Or silicon atom (S
The raw material gas containing i) and the raw material gas containing carbon atoms (C) and hydrogen atoms (H) are also mixed at a desired mixing ratio, or silicon atoms (S
i) a constituent gas and a silicon atom (S
i) mixing a source gas having carbon atoms (C) and hydrogen atoms (H) as constituent atoms, or further mixing a source gas having silicon atoms (Si) and hydrogen atoms (H) as constituent atoms; A raw material gas having (C) as a constituent atom is mixed and used.

Examples of the source gas containing Si, C and H as constituent atoms include alkyl silicides such as Si (CH ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ . Of course, H ₂ can also be used as a source gas for introducing H in addition to these source gases.

When the photoreceptor layer according to the present invention is formed by a plasma CVD method, a sputtering method, or an ion plating method, oxygen atoms, carbon atoms and nitrogen atoms to be introduced into nc-Si: (H, X) Control of the content of the group III atom or the group V atom is performed by controlling the gas flow rate and the gas flow ratio of the starting material introduced into the deposition chamber.

Conditions such as the temperature of the support at the time of forming the light receiving layer, the gas pressure in the deposition chamber, and the discharge power are important factors for obtaining a light receiving member having desired characteristics. Are appropriately selected in consideration of the functions of the above. Furthermore, since these layer forming conditions may vary depending on the type and amount of each of the above atoms contained in the light receiving layer, the conditions are determined in consideration of the type of the atoms to be contained or the amount thereof. There is a need.

Specifically, the temperature of the support is usually 50 to 4
The temperature is set to 00 ° C., particularly preferably 100 to 350 ° C. The discharge power condition is generally 10 W to 5000 W, particularly preferably 20 W to 20 W per support.
Approximately 00W. The gas pressure in the deposition chamber is usually 0.01 to 1 Torr by the RF discharge method, particularly preferably 0.1 to 0.5 Torr, and 0.2 mTorr to 100 mTorr by the microwave discharge method, and particularly preferably 1 mTorr. About 50 mTorr.

However, specific conditions such as the temperature of the support, the discharge power, and the gas pressure in the deposition chamber for forming these layers are usually difficult to determine independently of each other. Therefore, in order to form an nc-Si material layer having desired characteristics, it is desirable to determine the optimum conditions for forming the layer based on mutual and organic relationships.

In order to make the distribution of oxygen atoms, carbon atoms, nitrogen atoms, Group III or Group V atoms, hydrogen atoms and / or halogen atoms uniform in the photoreceptor layer of the present invention. It is necessary to keep the above conditions constant when forming the light receiving layer.

In the present invention, when forming the photoreceptive layer, the distribution concentration of oxygen, carbon, nitrogen, or group III or group V atoms contained in the layer is adjusted in the thickness direction of the layer. In order to form a light receiving layer having a distribution state in a desired layer thickness direction by changing to the above, if a plasma CVD method is used, an oxygen atom, a carbon atom, a nitrogen atom, or a group III atom or a V atom The gas is formed while appropriately changing the gas flow rate at the time of introducing the gas of the starting material for introducing group atoms into the deposition chamber in accordance with a desired rate of change, and keeping other conditions constant. In order to change the gas flow rate, specifically, the opening of a predetermined needle valve provided in the middle of the gas flow path system is gradually changed, for example, manually or by a method usually used such as an external drive motor. What is necessary is just to perform the operation which makes it. At this time, the change rate of the flow rate does not need to be a curve type. For example, a desired content curve can be obtained by controlling the flow rate according to a change rate curve designed in advance using a microcomputer or the like.

In the light receiving member for electrophotography of the present invention, for example, Si _{3 is used} for the purpose of further improving the adhesion of the deposited film between the support 101 and the charge injection blocking layer 102.
An adhesion layer formed of an nc-Si material or the like containing at least one of N ₄ , SiO ₂ , SiO, a hydrogen atom and a halogen atom, at least one of a nitrogen atom and an oxygen atom, and a silicon atom may be provided. .

The support 101 used in the present invention may be conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, Mo, Au, Nb, Ta, V, and T.
Metals such as i, Pt, and Pb or alloys thereof are exemplified.

Among them, aluminum is suitable for the present invention because it has a suitable strength, is excellent in workability, and is easy to manufacture and handle. When aluminum is used as the support material, it is preferable to contain 1 to 10% by weight of magnesium in order to improve the machinability. Further, the purity of aluminum before magnesium is 98% by weight or more, preferably 99% by weight or more is effective in the present invention.

Examples of the electrically insulating support include films or sheets of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, etc., glass, ceramics and paper. No. Preferably, one of the surfaces of these electrically insulating supports is subjected to a conductive treatment, and a light-receiving layer is provided on the conductive-treated surface side.

That is, for example, in the case of glass, Ni, Cr, Al, Au, Cr, Mo, Ir, N
d, Ta, V, Ti, Pt, In ₂ O ₃ , SnO ₂ , IT
Conductivity is imparted by providing a thin film made of O (In ₂ O ₃ + SnO ₂ ) or the like, or if it is a synthetic resin film such as a polyester film, NiCr, Al, A
g, Pb, Zn, Ni, Au, Cr, Mo, Ir, N
b, Ta, V, Tl, Pt, a thin film of a metal such as vacuum evaporation, electron beam evaporation, provided on the surface by sputtering, or the like, or the surface is laminated with the metal,
The surface is given conductivity.

The shape of the support may be any shape such as a cylindrical shape, a belt shape, and a plate shape, but the shape can be appropriately determined depending on the application and the desired. For example, FIG.
If the light receiving member 100 is used as an image forming member for electrophotography, it is desirable to use an endless belt or cylindrical shape for continuous high-speed copying. The thickness of the support is
It is appropriately determined so that a desired light receiving member can be formed, but when light repellency is required as the light receiving member, the thickness should be as thin as possible within a range where the function as a support can be sufficiently exhibited. Can be. However, the thickness is usually 10 μm or more from the viewpoints of production and handling of the support, mechanical strength and the like.

Hereinafter, the present invention will be described specifically with reference to Examples 1 to 7 and Comparative Examples 1 to 4, but the present invention is not limited thereto.

[0079]

【Example】

Example 1 A mirror-finished aluminum cylinder was set in the deposition film forming apparatus shown in FIGS. 3 and 4 and the same manufacturing conditions as in Sample e-3 of Experimental Example 1 (layers of the photoconductive layer and the surface layer) were used. A region having a large hydrogen content at the interface: 3000 °; a hydrogen content: 1.3 times of the bulk layer / however, no charge injection blocking layer is formed. A photographic light receiving member was formed.

The light receiving member thus prepared was placed in a copying machine manufactured by Canon Inc., NP7550 modified for experiments, and an image was formed on transfer paper at 1.2 times the speed of a normal copying process. This operation was repeated to endure 500,000 sheets, and the following evaluation was performed on the potential characteristics and the initial image and the image after the endurance to evaluate the electrophotographic characteristics of the amorphous silicon photosensitive drum. However, at this time, 6k
A voltage of V was applied to perform charging. Uneven charging performance: A copying machine is equipped with an aluminum cylinder on which a deposited film is formed, and the surface potential of the drum under a constant charge is measured at the developing device position while rotating the drum. The surface potential was measured every 3 cm from the top to the bottom of the drum, and the average was taken as the charging ability. Then, a value farthest from the average value in one drum was determined, and the obtained value was regarded as uneven charging ability. The same evaluation was performed for the six drums obtained in one deposition film formation, and the following determination was made for the drum having the largest uneven charging ability.

A: Very excellent uniformity.

.Largecircle .: Excellent uniformity.

△: There is no practical problem.

X: insufficient when used in a very high-speed copying apparatus. Uneven sensitivity: Charged in the same manner as described above, surface potential was measured every 3 cm from the top to the bottom of one drum under a constant exposure amount, and the average value was taken as the sensitivity. Similarly, of the values, the value farthest from the average value was regarded as sensitivity unevenness. And 6 obtained by one deposition film production
The same evaluation was performed on the drums of the book, and the drum having the largest sensitivity unevenness was judged as follows.

A: Very excellent uniformity.

.Largecircle .: Excellent uniformity.

△: There is no problem in practical use.

X: There is a danger that the quality will be reduced under severe conditions such as high temperature and high humidity and low temperature and low humidity. Fine line reproducibility: An image sample obtained when a normal original consisting of characters on the entire surface was placed on a platen and copied on a white background was observed, and it was evaluated whether the fine lines on the image were connected without interruption. However, at this time, when there was unevenness in the image, the evaluation was performed in the entire image area, and the result of the worst part was shown. The same evaluation was performed for six drums obtained by one deposition film production, and the following judgment was made for the worst one among them.

A: Good.

○: There is a partial interruption.

{Circle around (2)} Although there are many interruptions, they can be recognized as characters.

X: Some characters cannot be recognized as characters. White background fog: A normal image sample consisting of whole characters was placed on a platen on a white background, an image sample obtained when copying was observed, and the fog on the white background was evaluated. The same evaluation was performed for six drums obtained by one deposition film production, and the following judgment was made for the worst one among them.

◎: good.

○: There is a slight fog in part.

{Circle around (4)} The entire surface is covered, but there is no problem in character recognition.

X: There is a fog so that the character is hard to read. Image unevenness: An image sample obtained when an original half-tone document was placed on a platen and copied was observed, and the shading was evaluated. The same evaluation was performed for six drums obtained by one deposition film production, and the following judgment was made for the worst one among them.

◎: good.

○: There is a slight difference in shading.

△: There is a difference in shading over the entire surface, but there is no problem in character recognition.

X: There are irregularities so that the characters are difficult to read.

Table 4 shows the results.

Example 2 A mirror-finished aluminum cylinder was placed in the deposition film forming apparatus shown in FIGS. 3 and 4, and the photoconductive layer and the surface layer were produced under the same conditions as in Example 1. A charge injection blocking layer under the same conditions as in Experimental Example 1 was added to form a blocking type electrophotographic light-receiving member having a three-layer structure of a charge injection blocking layer, a photoconductive layer, and a surface layer.

The light-receiving member thus prepared was placed in a copying machine manufactured by Canon Inc., NP7550 modified for experiments, and an image was formed on transfer paper at a speed 1.2 times that of a normal copying process. However, at this time, charging was performed by applying a voltage of 6 kV to the charger. Based on the obtained image, the electrophotographic characteristics of the amorphous silicon photosensitive drum were evaluated in the same manner as in Example 1. The results are shown in Table 4 together with the results of Example 1.

Example 3 An aluminum cylinder subjected to mirror finishing was set in the deposition film forming apparatus shown in FIGS. 3 and 4, and under the conditions shown in Table 5, an IR absorption layer, a charge injection blocking layer, a photoconductive layer, A blocking type electrophotographic light-receiving member having a four-layer structure of a surface layer was formed. However, the hydrogen content at the layer interface between the photoconductive layer and the surface layer was adjusted to be the same as in Example 1.

The light receiving member thus prepared was placed in a copying machine manufactured by Canon Inc., NP7550 modified for experiments, and an image was formed on transfer paper at 1.2 times the speed of a normal copying process. However, at this time, charging was performed by applying a voltage of 6 kV to the charger. Based on the obtained image, the electrophotographic characteristics of the amorphous silicon photosensitive drum were evaluated in the same manner as in Example 1. The results are shown in Table 4 together with the results of Examples 1 and 2.

Example 4 A mirror-finished aluminum cylinder was set in the deposition film forming apparatus shown in FIGS. 3 and 4, and the charge injection blocking layer, charge transport layer, charge generation layer, A blocking type electrophotographic light-receiving member having a four-layer structure of a surface layer was formed. However, the hydrogen content at the layer interface between the photoconductive layer and the surface layer was adjusted to be the same as in Example 1.

The light-receiving member thus prepared was placed in a copying machine manufactured by Canon Inc., which was obtained by modifying NP7550 for experiments, and an image was formed on transfer paper at a speed 1.2 times faster than in a normal copying process. However, at this time, charging was performed by applying a voltage of 6 kV to the charger. Based on the obtained image, the electrophotographic characteristics of the amorphous silicon photosensitive drum were evaluated in the same manner as in Example 1. The results are shown in Table 4 together with the results of Examples 1, 2 and 3.

Comparative Example 1 A mirror-finished aluminum cylinder was set in the deposition film forming apparatus shown in FIGS. 3 and 4, and the hydrogen content near the interface between the photoconductive layer and the surface layer was not particularly manipulated. The other conditions were the same as in Example 1 to form an electrophotographic light-receiving member having a two-layer structure of a photoconductive layer and a surface layer.

The light receiving member thus prepared was placed in a copying machine manufactured by Canon Inc., NP7550 modified for experiments, and an image was formed on transfer paper at 1.2 times the speed of a normal copying process. However, at this time, charging was performed by applying a voltage of 6 kV to the charger. Based on the obtained image, the electrophotographic characteristics of the amorphous silicon photosensitive drum were evaluated in the same manner as in Example 1. The results are shown in Table 4 together with the results of Examples 1, 2, 3 and 4.

Comparative Example 2 A mirror-finished aluminum cylinder was installed in the deposition film forming apparatus shown in FIGS. 3 and 4, and the hydrogen content near the interface between the photoconductive layer and the surface layer was not particularly manipulated. Otherwise, a blocking type electrophotographic light receiving member having a three-layer structure of a charge injection blocking layer, a photoconductive layer, and a surface layer was formed under the same conditions as in Example 2.

The light-receiving member thus produced was placed in a copying machine manufactured by Canon Inc., NP7550 modified for experiments, and an image was formed on transfer paper at 1.2 times the speed of a normal copying process. However, at this time, charging was performed by applying a voltage of 6 kV to the charger. Based on the obtained image, the electrophotographic characteristics of the amorphous silicon photosensitive drum were evaluated in the same manner as in Example 1. The results are shown in Table 4 together with the results of Examples 1, 2, 3, 4 and Comparative Example 1.

Comparative Example 3 A mirror-finished aluminum cylinder was installed in the deposition film forming apparatus shown in FIGS. 3 and 4, and the hydrogen content near the interface between the photoconductive layer and the surface layer was not particularly manipulated. Otherwise, a blocking type electrophotographic light receiving member having a four-layer structure of an IR absorption layer, a charge injection blocking layer, a photoconductive layer, and a surface layer was formed under the same conditions as in Example 3.

The light-receiving member thus prepared was placed in a copying machine manufactured by Canon Inc., NP7550 modified for experiments, and an image was formed on transfer paper at 1.2 times the speed of a normal copying process. However, at this time, charging was performed by applying a voltage of 6 kV to the charger. Based on the obtained image, the electrophotographic characteristics of the amorphous silicon photosensitive drum were evaluated in the same manner as in Example 1. The results are shown in Table 4 together with the results of Examples 1, 2, 3, and 4 and Comparative Examples 1 and 2.

As is clear from Table 4, it was confirmed that the present invention was superior to the conventional art in various items caused by photoresponsiveness.

Comparative Example 4 A mirror-finished aluminum cylinder was installed in the deposition film forming apparatus shown in FIGS. 3 and 4, and the hydrogen content near the interface between the photoconductive layer and the surface layer was not particularly manipulated. The other conditions were the same as in Example 4 to form a blocking type electrophotographic light-receiving member having a four-layer structure of a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer.

The light receiving member thus prepared was placed in a copying machine manufactured by Canon Inc., NP7550, which was modified for experiments, and an image was formed on transfer paper at a speed 1.2 times that of a normal copying process. However, at this time, charging was performed by applying a voltage of 6 kV to the charger. Based on the obtained image, the electrophotographic characteristics of the amorphous silicon photosensitive drum were evaluated in the same manner as in Example 1. The results are shown in Table 4 together with the results of Examples 1, 2, 3, and 4 and Comparative Examples 1, 2, and 3.

As is clear from Table 4, it was confirmed that the present invention is superior to the prior art in various items caused by photoresponsiveness.

Example 5 A mirror-finished aluminum cylinder was set in the deposition film forming apparatus shown in FIGS. 3 and 4, and the same manufacturing conditions (charges) as those of samples a-1 to g-7 of Experimental Example 1 were used. A region having a large hydrogen content at the layer interface between the injection blocking layer and the photoconductive layer: 50 to 8000 °; a hydrogen content: 1.0 to 2.2 times in the bulk layer / excluding e-3)
When a light receiving member was prepared and evaluated in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3, a region having a large hydrogen content at the layer interface between the charge injection blocking layer and the photoconductive layer: 100 to 500
0 °; hydrogen content: within the range of 1.1 to 2.0 times the bulk layer, the effects of the present invention were confirmed as in Examples 1 to 3 and Comparative Examples 1 to 3.

(Example 6) The light receiving layer was formed by RF plasma CV.
Formed using Method D. FIG. 6 shows an apparatus for manufacturing a light receiving member by the RF plasma CVD method used in the present invention.

In the figure, 502, 503, 504, 505,
In the gas cylinder 506, a source gas for forming each layer of the present invention is sealed. For example, 502 is a SiH ₄ gas (purity: 99.999%) cylinder, and 503 is H ₂ . Diluted B ₂ H ₆ gas (purity 99.
999%, hereinafter abbreviated as B ₂ H ₆ / H ₂ ) cylinder, 504 is a CH ₄ gas (purity 99.999%) cylinder, 505 is S
iF ₄ gas (99.999% purity) cylinder, 506 is H ₂
It is a gas (purity 99.999%) cylinder.

To allow these gases to flow into the reaction chamber 501, the valves 522 to 52 of the gas cylinders 502 to 506 are used.
6. Confirm that the leak valve 535 is closed, and check the inflow valves 512 to 516 and the outflow valve 517.
After confirming that the auxiliary valves 532 and 533 are open, the main valve 534 is first opened to exhaust the reaction chamber 501 and the gas piping. Next, when the reading of the vacuum gauge 536 becomes about 5 × 10 ⁻⁶ Torr, the auxiliary valves 532 and 533 and the outflow valves 517 to 521 are closed.

An example in which a light receiving layer is formed on the substrate cylinder 537 will be described. SiH from gas cylinder 502
₄ gas, B ₂ H ₆ / H ₂ gas from gas cylinder 503 and CH ₄ gas from gas cylinder 504
23, 524 and 526 are opened and outlet pressure gauges 527 and 5
Adjust the pressure of 28, 529, 531 to 1 kg / cm ² ,
By gradually opening the inflow valves 512, 513, 514, and 516, the mass flow controllers 507, 508, 50
9, 511. Subsequently, the outflow valve 51
7, 518, 519, 521, auxiliary valves 532, 53
3 is gradually opened to allow the gas to flow into the reaction chamber 501. At this time, the outflow valves 517, 518, 519, and 521 are set so that the ratio of the SiH ₄ gas flow rate, the B ₂ H ₆ / H ₂ gas flow rate, the CH ₄ gas flow rate, and the H ₂ gas flow rate becomes a desired value.
And adjust the main valve 5 while watching the reading of the vacuum gauge 536 so that the pressure in the reaction chamber 501 becomes a desired value.
Adjust the opening of 34. After confirming that the temperature of the base cylinder 537 is set to a temperature in the range of 50 to 400 ° C. by the heater 538, the power supply 540
Is set to a desired power to generate a glow discharge in the reaction chamber 501, and a microcomputer (not shown) is used in accordance with a previously designed rate-of-change line.
H ₄ gas flow rate, B ₂ H ₆ / H ₂ gas flow rate, CH ₄ gas flow rate,
And the H ₂ gas flow rate while controlling the base cylinder 53
First, nc-S containing carbon and boron atoms
A layer composed of i (H, X) is formed.

After a lapse of a predetermined time, the valves 518, 513 and 526 for introducing the B ₂ H ₆ / H ₂ gas into the reaction chamber 501 are closed, and only the SiH ₄ gas, CH ₄ gas and H ₂ gas are supplied. By being introduced into the reaction chamber 501, the carbon- and boron-containing n-Si (H, X) -containing layer is formed on the layer made of nc-Si (H, X) containing no carbon and boron atoms.
A layer composed of c-Si (H, X) can be formed.

Needless to say, all the outflow valves other than the outflow valves required for forming each layer are closed, and when forming each layer, the gas used for forming the preceding layer is used in the reaction chamber 501. In order to avoid remaining in the gas pipe extending from the outflow valves 517 to 521 to the inside of the reaction chamber 501, the outflow valves 517 to 521 are closed, the auxiliary valves 532 and 533 are opened, and the main valve 534 is fully opened. Is once evacuated to a high vacuum as required.

Using this apparatus, as in Examples 1 to 5,
Producing a three-layer structure of a charge injection blocking layer, a photoconductive layer, and a surface layer, and a light-receiving member for blocking electrophotography having a four-layer structure of a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer; When evaluated in the same manner as in Example 1, good results were obtained as in Examples 1 to 5.

(Example 7) In Examples 2 to 6, the hydrogen content near the layer interface between the photoconductive layer and the surface layer was different from the hydrogen content near the layer interface between the charge injection blocking layer and the photoconductive layer. In the same manner as in Examples 2 to 6, a mirror-finished aluminum cylinder was installed in the deposited film forming apparatus shown in FIGS. As a result of evaluation, good results were obtained as in Examples 1 to 5.

[0127]

[Table 1]

[0128]

[Table 2]

[0129]

[Table 3]

[0130]

[Table 4]

[0131]

[Table 5]

[0132]

[Table 6]

[0133]

According to the present invention, the hydrogen content in the vicinity of the interface between the surface layer and the photoconductive layer can be reduced by using the photoconductive layer or the surface.
1.1 times more than the hydrogen content of any of the layers
Water in the vicinity of the interface
The region having a high elemental content is 1 in the layer thickness direction around the interface.
Not less than 00 ° and not more than 5000 °, and the photoconductive layer
By controlling the thickness within 30% of the thin layer area of the surface layer , the light responsiveness of the light receiving member is improved, and the charging ability unevenness is improved.
Alternatively, it is possible to obtain a high-quality nc-Si light receiving member by controlling the deterioration of fine line reproducibility, white background fog, image unevenness, and the like due to uneven sensitivity.

Further, according to the present invention, it is possible to produce a deposited film which maintains excellent electrophotographic characteristics even under poor charging conditions such as high temperature and high humidity or poor developing conditions such as low temperature and low humidity. became.

Further, the present invention becomes more effective in terms of durability by having a surface layer. in addition,
In the present invention, by providing the charge injection blocking layer,
The movement of electrons and holes can be effectively controlled.

[Brief description of the drawings]

FIG. 1 is a schematic view illustrating a layer configuration of a light receiving member of the present invention.

FIG. 2 is a schematic diagram showing the hydrogen content near the interface between the surface layer and the photoconductive layer in the light receiving member of the present invention.

FIG. 3 shows photoreception by a microwave discharge method in the present invention .
It is an outline side sectional view of a member manufacturing device.

FIG. 4 is a sectional view taken along the line XX of FIG . 3;

FIG. 5 is a schematic diagram of an experimental device for measuring photoresponsiveness according to the present invention.

FIG. 6 is a schematic side sectional view of a light receiving member manufacturing apparatus using an RF discharge method according to the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 100 light receiving layer 101 support 102 charge injection blocking layer 103 photoconductive layer 301 reaction vessel 302 microwave introduction window 303 waveguide 304 exhaust pipe 305 support 306 discharge space 307 heater 309 rotation axis 310 motor 311 DC power supply 312 bias electrode 400 sample 401 support 402 light receiving layer 403 conductive glass 404 DC power supply 405 light source 406 measuring means 501 reaction chamber 502 to 506 gas cylinder 507 to 511 mass flow controller 512 to 516 inflow cylinder 517 to 521 outflow cylinder 522 to 526 valve 527 to 531 Pressure regulator 532, 533 Auxiliary valve 534 Main valve 535 Leak valve 536 Vacuum gauge 537 Base cylinder 538 Heater 539 Motor 540 High frequency power source

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-182750 (JP, A) JP-A-59-113447 (JP, A) JP-A-59-119360 (JP, A) (58) Investigation Field (Int.Cl. ⁷ , DB name) G03G 5/08

Claims (5)

(57) [Claims] 1. A non-single-crystal photoreceptor comprising at least a support, a photoconductive layer and a surface layer and comprising silicon atoms as a host , wherein the hydrogen content in the vicinity of the interface between the photoconductive layer and the surface layer is determined by the photoconductive layer. Or any of the surface layers containing hydrogen
1.1 to 2.0 times more than the content of the layer with a large amount
And a region with a high hydrogen content near the interface
Is 100 ° or more and 5000 in the layer thickness direction around the interface.
Å, and the thinner layer of the photoconductive layer and the surface layer
A light receiving member which is within 30% of the area . 2. The method according to claim 1, wherein the surface layer contains silicon atoms.
Contains at least one atom of oxygen, carbon and nitrogen
The light receiving member according to claim 1, wherein: 3. At least one of oxygen, carbon and nitrogen
Content of silicon atom is 50 atom
c% or more.
Light receiving member. 4. The light receiving member further includes a support and a light receiving member.
It has a charge injection blocking layer between it and the photoconductive layer.
The light receiving part according to any one of claims 1 to 3,
Wood. 5. The non-single-crystal light receiving member is amorphous.
2. The photosensitive drum according to claim 1, wherein the photosensitive drum is a silicon photosensitive drum.
The light receiving member according to any one of claims 4 to 4.