JP3234697B2 - 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 photoreceptor which is sensitive to electromagnetic waves such as light (in this case, light in a broad sense meaning ultraviolet rays, visible rays, infrared rays, X-rays, .gamma.-rays, etc.). Regarding members, more specifically, photoreceptors and photosensors used in information processing apparatuses such as copiers, laser beam printers, and facsimile machines utilizing electrophotography, and photoreceptors sensitive to electromagnetic waves such as solar cells. Regarding members.

[0002]

2. Description of the Related Art A photoconductive material for forming an image forming member for electrophotography in a solid-state image pickup device or an image forming field or a light receiving member in a document reading device has a high sensitivity and an SN ratio [photocurrent (Ip) / Dark current (Id)] is high,
It is required to have characteristics such as having absorption spectrum characteristics suitable for the spectral characteristics of the irradiating electromagnetic wave, fast light response, having a desired dark resistance value, and being harmless to the human body during use. .

As a photoconductive material which satisfies such severe conditions, has high Vickers hardness and is excellent in durability, there is amorphous silicon (hereinafter referred to as "a-Si"). No. 86341, German Offenlegungsschrift No. 2,746,967 and No. 28557.
Japanese Patent Application Laid-Open No. 18-183 and the like describe an application to an image forming member for electrophotography, and Japanese Patent No. 2933411 describes an application to a photoelectric conversion reading device.

Further, for example, the light receiving member is disclosed in JP-A-54-121743 and JP-A-57-405.
No. 3, JP-A-57-4172, the light-receiving layer has a layer structure of two or more layers in which layers having different conductivity are stacked, and a depletion layer is formed inside the light-receiving layer, or JP-A-57-52178, JP-A-57-52179
JP-A-57-52180, JP-A-57-58159, JP-A-57-58160 and JP-A-57-58161, between a support and a light-receiving layer and / or a light-receiving layer. A multilayer structure in which a barrier layer is provided on the upper surface of the light-receiving member, to increase the design tolerance of the light-receiving member, and to enable the high light sensitivity to be used effectively even if the dark resistance is low to some extent. Various improvement techniques have been proposed.

[0005] With the advance of these techniques, for example, an image forming light receiving member for electrophotography has been put to practical use and commercialized. 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. Characteristics of use environment such as mechanical properties and moisture resistance,
Further, there is a problem that it is necessary to further improve overall characteristics in terms of stability over time.

That is, a-Si is now widely used as a light receiving member for forming an image for electrophotography because of its excellent characteristics due to the advance of these technologies. Therefore, higher performance, higher image quality, and higher durability are required.

Further, there is a demand for a compact copier body and energy saving. Under such circumstances, it is desired that the light receiving member has higher charging ability and higher sensitivity than ever.

[0008] For example, at present, the speed, speed and durability of an electrophotographic apparatus are further rapidly reduced. Also, to reduce service costs,
It is necessary to improve the reliability of each component and reduce the number of maintenance operations.

In particular, an increase in the copy volume requires a further increase in speed. In addition, in recent years, the demand for higher image quality and higher definition from the market is increasing year by year due to an increase in the number of copies of photographic originals.

Under these circumstances, especially in a high-speed electrophotographic apparatus, if a conventional light receiving member is used as it is, an image forming process in which charging, exposure, development, and transfer are performed in one cycle, particularly a photo-response member. In some cases, there is a problem that the quality or the running property of the optical carrier becomes insufficient, and as a result, when used repeatedly for a long time, a high quality image cannot be obtained.

Further, when a conventional electrophotographic apparatus using a light receiving member is used to make a copy of an image document based on halftone, such as a photographic image, image unevenness that cannot be recognized with a character document is also recognized. In some cases. In particular,
When an entire image is a halftone original of a single color and uniform density (for example, a photograph of a blue sky or a building wall, or a monochromatic colored paper, etc.), the uniformity of the density and resolution of the copied image is reduced, and unevenness is caused. It is easy to be recognized as. This phenomenon tends to become more pronounced in higher-speed electrophotographic apparatuses.

Further, the same problem may occur when the diameter of the conventional light receiving member is reduced as it is in order to reduce the size of the electrophotographic apparatus.

The electrophotographic apparatus detects parameters such as surface potential and surface temperature by a potential sensor and a temperature sensor built in the apparatus so as to obtain the same image quality every time, and controls them by built-in control means. Generally, if the light response to the process speed is insufficient, the state of the light receiving member after one cycle is not completely returned to the initial state. As a result, the values of the parameters detected by the sensors fluctuate,
Therefore, it must be adjusted by the control means every 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 apparatus main body. Specifically, in some cases, unevenness in charging performance during use, or deterioration in fine line reproducibility due to uneven sensitivity, white background fog, image unevenness, and the like may be observed. Especially a
Since the photoreceptor member for forming an image of -Si electrophotography is mainly used for a high-speed electrophotographic apparatus having a large copy volume as described above, it is often used repeatedly for a long time. This makes this problem even more pronounced.

When the conventional electrophotographic light-receiving member is directly mounted on a higher-speed electrophotographic apparatus, the photocarriers cannot sufficiently follow the process speed, and the running properties of the photocarriers become insufficient. . As a result, the light sensitivity may be insufficient with respect to the process speed.
Further, when performing image formation continuously, a so-called ghost in which a previous image remains in a halftone may be noticeable. Further, when the light receiving member continuously forms an image, it is general to irradiate a blank exposure in order to eliminate the surface charge so that the toner does not adhere to the portion corresponding to the space between the sheets. There may be a problem that a blank exposure memory in which the previous history of a portion exposed to blank exposure appears as uneven image density becomes noticeable (hereinafter, the ghost and the blank exposure memory are collectively referred to as an optical memory). ).

As described above, with the increase in the process speed, there is a case where the photoresponsiveness or the traveling property of the photocarrier becomes insufficient, and a problem that the charging ability is reduced may occur.
Further, due to the phenomenon that the optical memory becomes remarkable, a high-quality image may not be obtained as a result.

In particular, the mobility of photocarriers at two or more photoconductive layers having different optical band gap widths or at an interface between two function-separated photoconductive layers of a charge generation layer and a charge transport layer becomes insufficient. Ghosts, optical memories such as blank exposure memories, and the like, often become noticeable.

On the other hand, in order to reduce the size of the electrophotographic apparatus, it is necessary to reduce the diameter of the electrophotographic light receiving member. In this case, the same problem occurs. That is, when the diameter of the light receiving member is reduced, it is necessary to rotate at a higher speed in order to copy the same number of copies as a light receiving member having a normal diameter. That is, even if the number of copies is the same, the process speed is increased from the viewpoint of the light receiving member.

With respect to such a process speed, if the current electrophotographic characteristics are maintained, it is necessary to increase the capacity of the charger and to devise a way to charge efficiently in a short time. Further, it is necessary to increase the output of the exposure apparatus, and the size of the charger and the exposure apparatus is increased, so that the cost of the main body of the electrophotographic apparatus and the power consumption are increased. Also, it is difficult to make the electrophotographic device compact,
Rather, there is a problem that the size is increased.

[0019]

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 almost always stable without being substantially dependent on the use environment, are excellent in light fatigue resistance, and do not cause a deterioration phenomenon even when used repeatedly. Another 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, moisture resistance, and excellent in light responsiveness which can sufficiently follow the process speed of a high-speed copying machine.

It is another object of the present invention to provide a light-receiving member having a light-receiving layer having excellent adhesion between non-short crystal layers constituting the light-receiving layer, strict and stable structural arrangement, and high layer quality. is there.

In addition, another object of the present invention is to provide a light receiving member capable of reducing the size and cost of an information processing apparatus such as a copying machine.

[0023]

[0024]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above-mentioned object of the present invention, and as a result, completed the present invention. That is, the object of the present invention is a support,
A light-receiving member comprising a support and a light-receiving layer in which at least two non-single-crystal layers having at least silicon atoms and hydrogen atoms or halogen atoms are stacked in contact with each other on the support; It is achieved by the light-receiving member having an atomic and / or more regions in the vicinity of the interface between the layers of the content contact with each halogen atom.

[0025]

The present inventors have conducted intensive studies to overcome the above-mentioned problems in the conventional light receiving member and to achieve the above-mentioned object of the present invention. It is completed. Hereinafter, the light receiving member of the present invention will be described in detail.

Non-single-crystal materials containing at least silicon atoms, hydrogen atoms and / or halogen atoms as constituent atoms, ie, so-called hydrogenated a-Si and halogenated a-S
i, or halogen-containing hydrogenated a-Si, polycrystalline silicon, etc. (hereinafter collectively referred to as nc-Si: (H,
X)), the light receiving member is formed as a multilayer structure as described above, and each layer further includes a hydrogen atom or a fluorine atom in order to improve its electrical and photoconductive properties. Each atom contains a halogen atom such as an atom or a chlorine atom, a boron atom or a phosphorus atom for controlling electric conductivity, or another atom for improving other properties. 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, there are problems in the behavior of electric charge which varies variously depending on the kind of the contained atoms, their contents, distribution state, etc., structural stability, and adhesion of each layer. Is particularly important, and the success or failure of these controls is often the key to making the light receiving member exhibit its intended function.

For example, when an image-forming light receiving member for nc-Si electrophotography is produced by a generally known method, there are many cases where problems occur in repetition characteristics and durability of image quality. Although the mechanism is not yet clear, regarding the insufficient light response and repetition characteristics,
It is presumed that the cause was structural distortion near the surface or at the layer interface.

Known techniques for controlling the interface include, for example, (1) gradually changing the composition of the layer interface as a means of relaxing the strain at the layer interface having a different composition. (For example, US Pat. No. 4,254,429) (2) The photoconductive amorphous layer is configured to have a concentration distribution such that the hydrogen atom concentration decreases toward both ends in the layer thickness direction. (For example, JP-A-59-113647) (3) The photoconductive amorphous layer has a halogen atom concentration gradient such that it rises from the support side toward the surface side (for example, (4) The hydrogen atom concentration of the photoconductive amorphous layer decreases toward both ends in the layer thickness direction, and the halogen atom concentration increases. (For example, JP-A-59-119360) and the like have been disclosed and put to practical use.

However, regarding the technique (1),
When the composition of the interface between two different compositions is gradually changed, the gradually changing portion itself has a certain thickness, which may have an adverse effect. In other words, the portion where the composition changes, that is, the intermediate layer or the intermediate region shows not both of the characteristics of the layers on both sides but the intermediate characteristics of both layers. In order to affect the traveling performance of the carrier,
It cannot be neglected and may therefore affect the overall properties.

In the technique (2), the concentration distribution is set such that unnecessary hydrogen that adversely affects the stability of the structure is reduced toward both ends in the layer thickness direction. The volume is configured to be less than the bulk. Such a configuration improves structural stability,
Although some practical properties can be obtained, dangling bonds near the layer interface
Exists, and there is room for further improvement because of the influence on the injectability at the photocarrier interface.

In the case of (3), in the vicinity of the surface of the amorphous layer where the structural change is most likely to occur, the concentration of the halogen atom which is hard to be broken with silicon even at a relatively high temperature is increased, and the structure is also stabilized. It is effective and can obtain practically acceptable characteristics. However, depending on the content of halogen atoms in the vicinity of the layer interface, there may be a case where the electrical characteristics are adversely affected. In the case of (4),
It is an application of the technology of (3) in addition to the technology of (2).
The structural stability is further improved as compared with the case of (2), and a characteristic that can endure practical use can be obtained to some extent. But again,
There are the same problems as in (2), and further, depending on the content of halogen atoms in the vicinity of the layer interface, there may be a case where electric properties are adversely affected.

The present inventors focused on controlling the hydrogen and / or halogen content near the interface to form two different layers in order to achieve a structurally stable bond without deteriorating their properties. As a result of an experiment, it was found that the layer design near the interface was designed from a different viewpoint from the layer portion (bulk portion) excluding the interface vicinity, that is, the knowledge that the above-described problem could be solved by the above-described configuration. I got

The light receiving layer in the light receiving member of the present invention includes, for example, 1) a charge injection blocking layer and a photoconductive layer, and hydrogen and / or halogen near the interface between the charge injection blocking layer and the photoconductive layer. When the content is greater than the hydrogen and / or halogen content of any of the charge injection blocking layer and the photoconductive layer, 2) having a photoconductive layer and a surface layer, If the hydrogen and / or halogen content in the vicinity of the interface is greater than the hydrogen and / or halogen content of any of the photoconductive layer and the surface layer, or 3) the charge transport layer and the charge generation layer At least two layers as represented by the case where the hydrogen content in the vicinity of the interface between the charge transport layer and the charge generation layer is greater than the hydrogen content of any of the charge transport layer and the charge generation layer. Having. Further, a desired layer can be appropriately formed in the light receiving layer in addition to the above-mentioned layer constitution according to the purpose.

Here, the “interface” in the present invention refers to
A non-single-crystal layer having a different composition means a bonding portion or a bonding region.
When manufactured by the method and composed of the charge injection blocking layer and the photoconductive layer, a junction or a bonding region between the charge injection blocking layer and the photoconductive layer becomes an interface. That is, when the charge injection blocking layer is formed, the discharge is stopped once, the raw material gas is replaced, the discharge is started again, and the photoconductive layer is formed on the charge injection blocking layer. Is the interface. Also,
When the charge injection blocking layer and the photoconductive layer are continuously formed, the composition of the film between the charge injection blocking layer and the photoconductive layer is continuously changed microscopically. If the thickness of the change region is small and the composition changes significantly and the charge injection blocking layer and the photoconductive layer can be macroscopically considered to be in contact with each other, the junction region (change region) becomes the interface. Therefore, it can be said that all the layers have an interface except when the composition in the film changes over all the layers and cannot be discriminated as a plurality of layers.

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 electric characteristics, optical characteristics, photoconductive characteristics, Shows usage environment characteristics and high stability.

In particular, when applied as an image forming member for electrophotography, the optical response can sufficiently follow the increase in the process speed in the image forming process, and can withstand repeated use for a long time. The light receiving member has stable electrical characteristics, high sensitivity, and high SN ratio. In addition, it is excellent in light fatigue resistance, repeated use characteristics, especially in repeated use under high humidity atmosphere, high concentration,
It is possible to obtain a high-resolution, high-definition, high-quality visible image with a clear halftone and high resolution.

Further, when applied as an optical sensor, the light receiving member has a small light deterioration, a high SN ratio, and stable electric characteristics.

Further, when applied as a photovoltaic element such as a solar cell, the conversion efficiency is high and the light deterioration is small.
The light receiving member has stable electric characteristics.

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

FIGS. 1 to 3 are diagrams schematically showing a layer structure for explaining the structure of a light receiving member applied as an electrophotographic image forming member of the present invention.

The light receiving member of the present invention has a support and a light receiving layer having at least two layers of nc-Si having at least silicon, hydrogen and / or halogen atoms as constituent atoms. As an example of a possible embodiment of the invention, the configuration shown in FIGS. 1 to 3 can be taken, but of course the invention is not limited to this.

In FIG. 1, the light receiving layer 100 is a support 1
An nc-Si layer (hereinafter, referred to as a photoconductive layer) 102 having photoconductivity and a surface layer 103 are provided on the photoconductive layer 01. 2, the photoconductive layer 102 in FIG. 1 has a charge transport layer 104 and a charge generation layer 105. In FIG. 3, the surface layer 103 is not provided, and instead, the charge injection blocking layer 10 is provided between the support 101 and the photoconductive layer 102.
6 are provided. Hydrogen contained in at least the photoconductive layer 102 and the surface layer 103 in FIG. 1, in the charge transport layer 104 and the charge generation layer 105 in FIG. 2, and in the charge injection blocking layer 106 and the photoconductive layer 102 in FIG. The atoms and / or halogen atoms have a uniform concentration distribution state in the direction parallel to the support surface, and the concentration in the thickness direction of the layer is larger than the bulk concentration near the interface between both layers. It is formed so that it becomes. Taking hydrogen atoms as an example, for example, as shown in FIG. 4, the hydrogen content is increased near the interface.

In the light receiving member of the present invention, as described above, the content of hydrogen atoms and / or halogen atoms is large near the interface of each layer, in other words, the content of hydrogen atoms and / or halogen atoms contained in the bulk is large. The concentration of hydrogen atoms and / or halogen atoms in the entire region does not necessarily need to be constant, and the hydrogen concentration is determined in such a manner that there is only one peak at an arbitrary position in the region. The present invention is effective even when a high part exists.
What kind of density distribution is provided is a property appropriately selected depending on a balance between a function required for the image forming member and a manufacturing facility for the light receiving member. FIGS. 5 to 11 show typical content patterns of hydrogen atoms as an example. Of course, such a content pattern can also be applied to a halogen atom.

The amounts of hydrogen and / or halogen contained in each bulk layer may be equal or different. Further, the concentration of hydrogen and / or halogen contained in the bulk may be constant or change in the layer thickness direction, and the change may be continuous or change stepwise substantially. There is no difference.

For example, the content may not be constant and may have a gentle concentration gradient. When hydrogen atoms and halogen atoms are contained in the region near the layer interface, the bulk layer of each layer does not necessarily need to contain halogen atoms, and the concentration is substantially 0 (or below the detection limit). It may be. The distribution of the content of these atoms is appropriately selected in consideration of the function required for the image forming member and the equipment for manufacturing the light receiving member.

It is very important in the present invention that the hydrogen and / or halogen content satisfy the following conditions.

That is, according to the present invention, hydrogen and / or
Or, it is particularly important that a region having a high halogen content is present. However, the light receiving member of the present invention has a region where the hydrogen content and / or the halogen content increases near the layer interface. If the region where the halogen content is increased is wide, or if the hydrogen and / or halogen content is too large, the film quality is structurally unstable due to the excessive hydrogen and / or halogen content. It may be. That is, if there is more hydrogen than necessary to alleviate the structural distortion, it is considered that the network between silicon atoms is hindered, or the bond is easily broken, and the structure becomes unstable. Conversely, if the above-mentioned region is too narrow or the content of hydrogen and / or halogen is too small, a sufficient effect of the present invention cannot be obtained.

In order to effectively exhibit the effect in the present invention, the hydrogen and / or halogen in the vicinity of the layer interface must be minimized.
The large concentration is preferably 1.1 to 2 times the average concentration of hydrogen and / or halogen in the bulk (region excluding the layer interface of the layer forming the interface), and most preferably 1.2 to 1. Preferably, it is eight times. Further, the thickness of the region containing a large amount of hydrogen and / or halogen in the vicinity of the layer interface is preferably 100 to 10,000 in the layer thickness direction around the layer interface.
Å, more preferably 100-5000Å, optimally 50
Desirably, it is 0-3000 °. However, when the thickness of at least one of the bulk layers is small, the concentration of hydrogen and / or halogen at the layer interface adversely affects the bulk layer. The thickness is desirably within 30% of the layer thickness.

The hydrogen content in both layers forming the interface is preferably 0.1 to 45 atomic%, more preferably, in the portion where the concentration is maximum relative to all the constituent atoms, that is, in the region near the layer interface. 1 to 40 atom%, more preferably 0.5 to
In the bulk part, the average of the bulk part is preferably 0.05 to 40 atomic%, more preferably 0.3 to 30 atomic%, and further preferably 0.5 to 30 atomic%.
It is desirable to set it as atomic%.

In the light-receiving member of the present invention, the light-receiving layer 100 may further include, if necessary, a substance for controlling conductivity and at least one element selected from the group consisting of oxygen, carbon, and nitrogen. It can be contained.

In the light receiving layer of the present invention, a halogen atom (X)
When containing, as the halogen atom (X),
Specifically, fluorine, chlorine, bromine, iodine,
In particular, fluorine and chlorine are preferred. The amount of the halogen atoms (X) contained in the bulk of the light receiving layer 100 is preferably 0.05 to 40 atomic%, more preferably 0.3 to 30 atomic%, and most preferably 0.1 to 30 atomic%.
The content (H + X) of a hydrogen atom and a halogen atom when a halogen atom is contained is preferably 0.05 to 50 atom%, more preferably 0.3 to 50 atom%.
Desirably, the content is 45 atomic%, optimally 0.5 to 30 atomic%.

When the content of halogen atoms is increased at the layer interface, the proportion of all the constituent atoms near the layer interface is preferably 0.5 atomic ppm to 30 atomic%, more preferably 1 atomic%.
It is desirable to set the atomic ppm to 20 atomic%. Furthermore, when the halogen atom content near the interface is also contained in the bulk layer of the non-single-crystal layer adjacent to the interface, the halogen atom content is 1.1 times or more that of the bulk layer having a larger halogen atom content,
It has been confirmed from various experiments that it is desirable that the ratio is preferably 1.15 times or more, more preferably 1.2 times or more. Further, the thickness in the vicinity of the halogen atom-rich layer interface is preferably 100 ° to 1 μm, more preferably 5 μm.
It shall be 00-5000 °. However, for example, when the contacting photoconductive layer or surface layer is thin, the thickness of the halogen atom-rich region is set to prevent the halogen atoms contained in the vicinity of the interface from adversely affecting the bulk layer. Preferably, it is within 30% of the thickness of the thinner layer.

When both a hydrogen atom and a halogen atom are contained in the region near the interface, the total content thereof is preferably 0.5 to 55 atomic%, more preferably 1 to 50 atomic%. %, More preferably 1 atom p
pm to 35 at%. However,
When both the hydrogen atom and the halogen atom are contained in the region near the interface, the effect can be recognized even if only the hydrogen atom or only the halogen atom is within the above range.

Further, an interface between the light receiving layer 100 and the support,
A desired effect can be obtained by setting the concentration distribution of hydrogen and / or halogen atoms in the vicinity of the free surface of the surface layer 103 to be the same as that at the interface. That is, in FIG. 1, it is desirable that the same distribution is obtained even when the “layer interface” is replaced with the “interface between the light receiving layer and the support” or the “free surface of the light receiving layer”. In this case, there is no particular upper limit to the hydrogen and / or halogen atom content in the vicinity of the free surface of the light-receiving layer, but hydrogen and / or halogen
Alternatively, the point that the halogen atom-rich region must not be too thick is the same as in the case of the light receiving layer interface. When there is a layer that does not exhibit photoconductivity in the constituent layers of the light receiving layer, the content and the content of hydrogen and / or halogen atoms in the layer are arbitrary.

However, regarding the hydrogen and / or halogen atom content, as described above, the rapid increase in the hydrogen and / or halogen atom content is limited to a region near the layer interface and within a specific distance from the interface. It is desirable to satisfy the condition that the rate of increase in the content of hydrogen and / or halogen atoms is also within a specific range.

It is considered that there is no upper limit in the content of hydrogen and / or halogen atoms in the vicinity of the surface of the light receiving layer opposite to the support. This is because, since the surface is a free surface, there is no problem of adhesion to an adjacent layer or a support. However, even in the vicinity of the free surface, a region having a high hydrogen and / or halogen atom content is
As in the case of the layer interface, the thickness is desirably 100 ° to 1 μm. This is to prevent a bad influence on the intrinsic electrical characteristics of the semiconductor of the bulk layer as described above.

Further, it is not necessary to control the above-mentioned hydrogen and / or halogen atom content for all the vicinity of the interface.
It is only necessary to control the vicinity of the interface between layers having different compositions. If there are a plurality of interfaces, it is also possible to control the vicinity of any one of the interfaces.

In the present invention, analysis of the hydrogen and / or halogen content at the layer interface is essential to optimally adjust the hydrogen and / or halogen content near the layer interface and to design a high quality light receiving member. It is. As this analysis method, S
In addition to IMS, infrared absorption, thermal desorption, nuclear reaction, nuclear magnetic resonance, ESCA, RBS, Auger electron spectroscopy, radiochemical analysis, mass spectrometry, absorption spectroscopy, gas analysis It is desirable to perform the analysis singly or in combination as appropriate.

In the light receiving member of the present invention, the thickness of the photoconductive layer 102 is one of the important factors for achieving the effects of the present invention efficiently, and the desired characteristics of the light receiving member are required. Care must be taken in its design to give Therefore, it is usually 1 to 100 μm, preferably 1 to 80 μm, more preferably 2 to 5 μm.
Desirably, it is 0 μm.

In the present invention, in order to achieve the object effectively, the photoconductive layer 10 formed on the support 101 is
No. 2 is composed of nc-Si: (H, X) having the following semiconductor characteristics and exhibiting photoconductivity with respect to irradiated light. p-type nc-Si: (H, X)... containing only an acceptor or containing both a donor and an acceptor and having a high relative concentration of the acceptor. In the p ^- type nc-Si: (H, X)... type, the acceptor concentration (Na) is low or the acceptor relative concentration is low. n-type nc-Si: (H, X)... containing only a donor or containing both a donor and an acceptor and having a high relative donor concentration. n-type nc-Si: (H, X)... type in which the donor concentration (Nd) is low or the acceptor relative concentration is low. i-type nc-Si: (H, X)... where Na and Nd are almost 0, or where Na and Nd are almost equal.

In the light receiving member of the present invention, a substance for controlling the conductivity of the light receiving layer 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 for controlling the conductivity include so-called impurities in the field of semiconductors, and an element belonging to Group IIIB of the Periodic Table that gives p-type conduction characteristics (hereinafter abbreviated as “Group IIIB element”). ) Or an element belonging to Group VB of the Periodic Table that provides n-type conduction characteristics (hereinafter referred to as “V
Abbreviated as “Group B element”).

As the Group IIIB element, specifically,
There are B, Al, Ga, In, Tl, etc., and B and Ga are particularly preferable. As the VB group elements, specifically, P, A
There are s, Sb, Bi and the like, and P and Sb are particularly preferable.

When a group IIIB element or a group VB element, which is a substance for controlling the conductivity of the photoreceptive layer of the present invention, is contained, it is contained in the entire layer region or in a part of the layer region. Varies depending on the intended purpose and expected effects, 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 conductivity of the photoconductive layer, the photoconductive layer is contained in the entire region of the light receiving layer. The content of group element may be relatively small, usually 1 × 10 ⁻³ to 1 × 10 ³ atomic ppm, preferably 5 × 1
0 ^-2 ~5 × 10 ² atomic ppm, more preferably 1 × 10 ^{- 1}
Desirably, it is set to 〜2 × 10 ² atomic ppm.

In order for the photoconductive layer to function as a charge injection blocking layer, a charge injection blocking layer may be provided in a part of the layer region in contact with the support or separately from the photoconductive layer. In the case of providing between them, a group IIIB element or a group VB element is contained in a relatively high concentration and uniform distribution state,
Alternatively, a group IIIB element or a VB
It is carried out by including the group element at a high concentration on the side in contact with the support. Such a
Part of the layer region containing the group IIIB element or the group VB element or the region containing a high concentration thereof functions as a charge injection blocking layer. That is, when the group IIIB element is contained, the movement of the 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 the positive polarity charging treatment. Can be blocked.

When a group VB element is contained,
When the free surface of the light-receiving layer is subjected to a negative polarity charging treatment,
The movement of holes injected from the support side into the light receiving layer can be more efficiently prevented. And the content in this case is relatively large. Specifically, usually 30 to 5 × 1
Although the 0 ⁴ atom ppm, preferably 1:50 to × 10 ⁴ atomic ppm, more preferably, is preferably a 1 × 10 ² ~5 × 10 ³ atomic ppm.

In order to exhibit the effect efficiently, when a substance for controlling conductivity is contained in a partial region in the photoconductive layer, the partial layer region is denoted by t, and the other light Assuming that the thickness of the receiving layer is t0, it is desirable that a relationship of t / t + t0 ≦ 0.4 is satisfied, more preferably, the value of the relationship is 0.35 or less, more preferably 0.3 or less. It is desirable to make. The layer thickness of the layer region or the charge injection blocking layer is usually 3 × 10 ^{−3 to} 10 μm, preferably 4 × 10 ^{−3 to} 8 μm, more preferably 5 × 10 ^{−3 to} 8 μm.
× 10 ^{−3 to 5} μm.

Although the respective effects of the group IIIB element or the group VB element have been individually described above, to obtain a light-receiving member capable of achieving a desired object, the group IIIB element or the group VB element must be obtained. Alternatively, it goes without saying that the distribution state of the group VB element and the amount of the group IIIB element or the group VB element contained in the light receiving layer are appropriately combined as needed.

For example, when a charge injection blocking layer is provided at the end of the light receiving layer on the side of the support, a substance for controlling conductivity contained in the charge injection blocking layer in the light receiving layer other than the charge injection blocking layer. A material that controls the conductivity of a different polarity from the polarity of the photoconductive layer may be contained, or the material that controls the conductivity of the same polarity in the photoconductive layer may be more than the amount contained in the charge injection blocking layer. It may be contained in a small amount.

Further, regarding the distribution of the conduction type control substance, it is not always necessary to provide an independent concentration gradient for each layer, but it is also possible to provide a concentration gradient over a desired region or all layers of the light receiving layer. is there. For example, it is possible to maximize the content of the light-receiving layer on the support side, and to decrease the content as the distance from the support increases, or to give the opposite distribution. Further, it is also possible to distribute so that the maximum value or the minimum value is obtained in any arbitrary region of the photoconductive layer.

Further, in the light receiving member of the present invention,
A so-called barrier layer made of an electrically insulating material can be provided as a layer structure provided at the end on the support side, and both the barrier layer and the charge injection blocking layer can be used as constituent layers. A material constituting such a barrier layer is Al
Examples include inorganic electric insulating materials such as ₂ O ₃ , SiO ₂ and Si ₃ N ₄ and organic electric insulating materials such as polycarbonate.

Further, in the light receiving member of the present invention, the so-called red light having a narrow optical band gap is provided on the support side for the purpose of suppressing the interference phenomenon that occurs when coherent monochromatic light such as laser light is used. An outer (IR) absorption layer may be provided, and both the absorption layer and the charge injection blocking layer may be included as constituent layers. As such an absorption layer, for example, nc-SiG obtained by adding germanium atoms (Ge) or tin atoms (Sn) to an nc-Si: (H, X) layer.
e: (H, X) and nc-SiSn: (H, X).

As the surface layer, nc-SiC: (H,
X), nc-SiC: (H, X), nc-SiO:
A layer made of (H, X) or the like can be provided. This layer may further contain a group III element and a group V element uniformly or non-uniformly in the layer thickness direction. That is, by including C, N, O, Group III element and Group V element in the surface layer at an appropriate concentration and distribution, the electrical and photoconductive properties of the surface layer can be adjusted. For example, the distribution may be such that the concentration is increased on the free surface side, or may be distributed such that the concentration is increased on the photoconductive layer side. In addition, as a material of the surface layer, an inorganic electric insulating material such as Al ₂ O ₃ or SiO ₂ or a resin can be used.

Next, an example of a method for forming the light receiving member of the present invention will be described.

Any of the amorphous materials constituting the light receiving layer of the present invention may be a sputtering method, a method of decomposing a source gas by heat (thermal CVD method), or a method of decomposing a source gas by light (photo CVD method). The source gas is decomposed by direct current, high frequency or microwave glow discharge or the like, and the source gas is decomposed by plasma generated by the decomposition (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. For example, the plasma CVD method or the sputtering method is preferable because the conditions for manufacturing can be relatively easily controlled. Then, the plasma CVD method and the sputtering method may be formed in combination in the same apparatus system.

For example, by plasma CVD, nc
In order to form a layer composed of -Si: (H, X), a hydrogen gas (H) capable of supplying hydrogen atoms (H) is basically provided together with a source gas for supplying Si atoms capable of supplying silicon atoms (Si). A source gas for supply and / or a source gas for introducing halogen atoms (X) are introduced in a desired gas state into a deposition chamber in which the inside can be reduced in pressure, and a glow discharge is generated in the deposition chamber, and a predetermined position is previously determined. N on the surface of a predetermined support
What is necessary is just to form the layer which consists of c-Si: (H, X).

Examples of the substance that can be a source gas for supplying Si include gaseous silicon hydrides (silanes) such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H _10. Are effectively used. Particularly, in terms of easiness of a layer forming operation, good Si supply efficiency, etc.
H ₄ and Si ₂ H ₆ are preferred.

The source gas for introducing a halogen atom includes many halogen compounds.
Gaseous or gasifiable halogen compounds such as halogen gases, halides, interhalogen compounds, and silane derivatives substituted with halogen are preferred. Specifically, halogen gas such as fluorine, chlorine, bromine and iodine, BrF, C
_{lF, ClF 3, BrF 3,} BrF 5, IF 3, IF 7, I
Interhalogen compounds such as Cl and IBr, and SiF ₄ and S
Silicon halide such as i ₂ F ₆ , SiCl ₄ , SiBr _{4 and the} like can be mentioned. In the case of using the above-mentioned silicon halide gas state or a gas 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 raw material 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 Cl ₂ , S
Materials such as iH ₂ I ₂ , SiHCl ₃ , SiH ₂ Br ₂ , and SiHBr ₃ which can be used in the gaseous state or in a gasified state of halogen-substituted silicon hydride can be used. Alternatively, in terms of controlling the photoconductive properties, the content of hydrogen atoms (H) can be controlled very effectively, which is effective.

Here, as a method of controlling the amount of hydrogen and / or halogen in the vicinity of the layer interface of the layers adjacent to each other, the flow rate of hydrogen gas and / or halogen gas introduced into the discharge space is arbitrarily changed as desired. Adjustment method by changing the discharge power,
A method of adjusting by changing the applied bias voltage, a method of adjusting by changing the temperature of the support, a method of adjusting by changing the pressure in the discharge space, and the type of gas introduced into the discharge space And a method of adjusting the flow rate by changing the flow rate ratio. Above all, for example, when the light receiving member is manufactured by the microwave discharge method, a method of changing the amount of hydrogen introduced into the discharge space as desired and a method of changing the applied bias voltage are particularly effective. It is desirable that the gas flow rate be precisely controlled by a piezo valve or the like.

When the hydrogen halide or the halogen-substituted silicon hydride is used, the hydrogen atom (H) is introduced simultaneously with the introduction of the halogen atom, which is particularly effective.

The amount of hydrogen atoms (H) and / or halogen atoms (X) contained in the nc-Si layer can be controlled by, for example, the temperature of the support, the hydrogen atoms (H) and / or the halogen atoms (X). It can also be performed by controlling the amount of the starting material used for introducing the gas into the deposition chamber and the discharge power. Of course, the above methods may be appropriately combined.

In order to form a layer composed of nc-Si: (H, X) by a reactive sputtering method or an ion plating method, for example, in the case of a sputtering method, the halogen compound is introduced to introduce a halogen atom. Alternatively, a gas of a silicon compound containing a halogen atom may be introduced into the deposition chamber to form a plasma atmosphere of the gas.

For example, in the case of the reactive sputtering method, a Si target is used, and a gas for introducing a halogen atom and / or a hydrogen gas including an inert gas such as He or Ar are introduced into the deposition chamber as necessary. Then, a plasma atmosphere is formed, and a layer made of nc-Si: (H, X) is formed on the support by sputtering the Si target. In this case, as a method of controlling the hydrogen and / or halogen content at the layer interface, it is effective to increase the amount of hydrogen and / or halogen introduced during the formation near the layer interface. At this time, it is effective to keep the temperature of the support constant and change the partial pressure of the hydrogen-containing gas and / or the halogen-containing gas.

Nc-Si using a plasma CVD method, a sputtering method, or an ion plating method:
To form a layer composed of an amorphous material further containing (H, X) a Group IIIB element or a Group VB element, an oxygen atom, a carbon atom or a nitrogen atom, nc-Si:
In forming the (H, X) layer, a starting material for introducing a Group IIIB element or a Group VB element, a starting material for introducing an oxygen atom, a starting material for introducing a carbon atom, or a starting material for introducing a nitrogen atom. The starting materials can be used together with the starting materials for the formation of nc-Si: (H, X) described above to control their amount in the layer to be formed.

As a raw material for introducing a Group IIIB element, specifically, for example, for introducing a boron atom,
_{2 H 6, B 4 H 10} , B 5 H 9, B 5 H 11, B 6 H 10, B 6 H 12,
B ₆ H _{1 4} like _{borohydride, BF 3, BCl 3, BBr} 3
And the like. Other III
As a raw material for introducing a group B element, AlCl ₃ , Ga
Examples include Cl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , and TlCl ₃ .

As a raw material for introducing a group VB element, those effectively used in the present invention include, for example, phosphorus hydride such as PH ₃ and P ₂ H ₄ and PH ₄ for introducing a phosphorus atom.
_{I, PF 3, PF 5,} PCl 3, PCl 5, PBr 3, PB
and phosphorus halides such as r ₅ and PI ₃ . As a raw material for introducing a group VB element, AsH ₃ , As
F ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , Sb
F ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , Bi
Cl ₃ , BiBr _{3 and the} like can be mentioned.

When a plasma CVD method is used to form a layer or a layer region containing an oxygen atom, the oxygen atom is introduced into a material selected as desired from the above-described starting materials for forming a light receiving layer. Add starting material for
As such a starting material for introducing an oxygen atom, almost any gaseous substance having at least an oxygen atom as a constituent atom or a substance that can be gasified can be used.

For example, a source gas containing silicon atoms (Si) as a constituent atom, a source gas containing oxygen atoms (O) as a constituent atom, and a hydrogen atom (H) and / or a halogen atom (X) if necessary. Or a raw material gas containing silicon atoms (Si) as a constituent atom and oxygen gas (O) and hydrogen atoms (H) as constituent atoms. Or a source gas having silicon atoms (Si) as constituent atoms and a source gas having oxygen atoms (O) and halogen atoms (X) as constituent atoms. The raw material gas may be mixed at a desired mixing ratio or may further include a raw material gas containing silicon atoms (Si) as constituent atoms, and a raw material gas containing silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H). Mixing at a desired mixing ratio. It can be.

In addition, a raw material gas containing oxygen atoms (O) may be mixed with a raw material gas containing silicon atoms (Si) and hydrogen atoms (H). . Starting materials that can be effectively used as a gas for introducing oxygen atoms (O) in the present invention include, for example, oxygen (O ₂ ), ozone (O ₃ ), and nitric oxide (N
O), nitrogen dioxide (NO ₂ ), nitrous oxide (N ₂ O),
Dinitrogen trioxide (N ₂ O ₃ ), dinitrogen tetroxide (N ₂ O ₄ ), dinitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atom (Si), oxygen atom (O) and three hydrogen atoms (H) as constituent atoms, for example, disiloxane (H ₃ S
iOSiH ₃ ), trisiloxane (H ₃ SiOSiH ₂ O)
Lower siloxanes such as SiH ₃ ).

In order to form a layer or a layer region containing oxygen atoms by a sputtering method, a single crystal or polycrystal Si wafer or SiO ₂ wafer, or a wafer containing a mixture of Si and SiO ₂ is used as a target. These may be performed by sputtering in various gas atmospheres.

More specifically, for example, when a Si wafer is used as a target, a source gas for introducing oxygen atoms and, if necessary, hydrogen atoms and / or halogen atoms is diluted with a diluting gas as necessary. Then, the Si wafer is introduced into a sputtering deposition chamber, and these gas plasmas are formed to sputter the Si wafer.

Alternatively, by using Si and SiO ₂ as separate targets, or by using a single target in which Si and SiO ₂ are mixed, in a diluent gas atmosphere as a sputtering gas, Alternatively, it can be formed by sputtering in a gas atmosphere containing at least a hydrogen atom (H) and / or a halogen atom (X) as a constituent atom.

As the gas for introducing oxygen atoms, the source gas for introducing oxygen atoms among the source gases shown in the example of the plasma CVD method described above can be used as an effective gas also in the case of sputtering.

When a plasma CVD method is used to form a layer or a layer region containing nitrogen atoms, nitrogen atoms are introduced into a material selected as desired from the above-mentioned starting materials for forming a light receiving layer. Add starting material for
As such a starting material for introducing a nitrogen atom, almost any gaseous substance containing at least a nitrogen atom as a constituent atom or a substance that can be gasified can be used.

For example, a source gas containing silicon atoms (Si) as constituent atoms, a source gas containing nitrogen atoms (N) as constituent atoms, and hydrogen atoms (H) and / or halogen atoms (X) as necessary. Or a raw material gas containing silicon atoms (Si) as a constituent atom, and a raw material gas containing silicon atoms (Si) as a constituent atom and a nitrogen atom (N) and a hydrogen atom (H) as a constituent atom. And a method of mixing the raw material gas with a desired mixing ratio.

In addition to these, silicon atoms (Si) and hydrogen
Nitrogen (H) as a constituent atom
Even if a mixture of source gases containing (N) as a constituent atom is used.
good. When forming a layer or layer region containing nitrogen atoms
Effective as a source gas for introducing nitrogen atoms (N)
The starting material used for is N as a constituent atom, or
For example, nitrogen gas (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 to these,
In addition to the introduction of nitrogen atoms, the introduction of halogen atoms (X)
From the point that nitrogen trifluoride (F_ThreeN), four feet
Nitride (F_FourN_Two)) And the like.
be able to.

[0100] Nitrogen atoms are contained by sputtering.
Single or polycrystalline to form a layer or layer region
Si wafer or Si_ThreeN_FourWith wafer or Si
Si _ThreeN_FourTarget wafers containing
These are used as sputters in various gas atmospheres.
You can do this by doing

More specifically, for example, when a Si wafer is used as a target, a source gas for introducing nitrogen atoms and, if necessary, hydrogen atoms and / or halogen atoms is diluted with a diluting gas as necessary. Then, the Si wafer is introduced into a sputtering deposition chamber, and these gas plasmas are formed to sputter the Si wafer.

Also, separately, Si and Si_ThreeN_FourAnd another
As a target or Si and Si _ThreeN_FourOne piece mixed with
By using a target of
In an atmosphere of diluent gas as gas, or at least
Constructs a hydrogen atom (H) and / or a halogen atom (X)
Sputtering in gas atmosphere containing atoms
Can be formed.

As the gas for introducing nitrogen atoms, the source gas for introducing nitrogen atoms among the source gases shown in the example of the plasma CVD method described above can be used as an effective gas also in the case of sputtering.

When a layer or layer region containing carbon atoms is formed by the plasma CVD method, carbon atoms are introduced into a material selected as desired from the above-mentioned starting materials for forming a light receiving layer. Add starting material for
As such a starting material for introducing a carbon atom, almost any gaseous substance or a gasizable substance containing at least a carbon atom as a constituent atom can be used. As the source gas for introducing silicon atoms, the above-described source gas can be used.

For example, a raw material gas having silicon atoms (Si) as constituent atoms, a raw material gas having carbon atoms (C) as constituent atoms, and a hydrogen atom (H) and / or a halogen atom (X) if necessary. Or a source gas having silicon atoms (Si) as a constituent atom and a carbon atom (C) and a hydrogen atom (H) as constituent atoms. And a source gas containing silicon atoms (Si) as constituent atoms, and silicon atoms (Si), carbon atoms (C) and hydrogen atoms (H) as constituent atoms. Mix the source gas with a desired mixing ratio, use a mixture of a source gas having silicon atoms (Si) and hydrogen atoms (H) as constituent atoms and a source gas having carbon atoms (C) as constituent atoms, and the like. Can be used.

A starting material effectively used as a source gas for introducing carbon atoms (C) used in forming a layer or a layer region containing carbon atoms has C and H as constituent atoms. 1-5 saturated hydrocarbons, 2-5 carbon atoms
And acetylene-based hydrocarbons having 2 to 4 carbon atoms.

Specifically, as the saturated hydrocarbon, methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C
₃ H _8), n- butane _{(n-C 4 H 10)} , pentane (C ₅ H
₁₂ ) As the ethylene hydrocarbon, ethylene (C
₂ H ₄ ), propylene (C ₃ H ₆ ), butene-1 (CH ₂ =
CHC ₂ H _5), butene _{-2 (CH 3 CH = CHCH 3} ),
Isobutene ((CH ₃ ) ₂ C = CH ₂ ), pentene (C ₅ H
₁₀ ) As acetylene-based hydrocarbons, acetylene (C
₂ H ₂ ), methylacetylene (CH ₃ CCH), butyne (C ₂ H ₅ CCH) and the like.

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, in addition to these source gases, the aforementioned source gases for introducing S, H, X, and C may be added.

In order to form a layer or layer region containing carbon atoms by sputtering, a single crystal or polycrystalline Si wafer or C (graphite) wafer, or a wafer containing a mixture of Si and C is used as a target. These may be performed by sputtering in various gas atmospheres.

Specifically, for example, when a Si wafer is used as a target, a raw material gas for introducing carbon atoms and hydrogen atoms and / or halogen atoms as necessary is diluted with a diluting gas as necessary. Then, the Si wafer is introduced into a sputtering deposition chamber, and these gas plasmas are formed to sputter the Si wafer.

Alternatively, by using Si and C as separate targets or using a single target in which Si and C are mixed, it is possible to obtain a target in a diluent gas atmosphere as a sputtering gas. Alternatively, it can be formed by sputtering in a gas atmosphere containing at least a hydrogen atom (H) and / or a halogen atom (X) as a constituent atom.

As the gas for introducing carbon atoms, the source gas for introducing carbon atoms among the source gases shown in the example of the plasma CVD method described above can be used as an effective gas also in the case of sputtering. Further, as the source gas for introducing each element, the aforementioned source gas can be used as needed.

When the light receiving member of the present invention is formed by a plasma CVD method, a sputtering method, or an ion plating method, an oxygen atom, a carbon atom, and a nitrogen atom to be introduced into nc-Si: (H, X) or IIIB The content of the group V element or group VB element is controlled 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. It is appropriately selected in consideration of the function. 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, it is necessary to determine in consideration of the type or amount of the contained atoms and the like. .

Specifically, the temperature of the support is usually 50 to 4
The temperature is set to 00 ° C, more preferably 100 to 350 ° C. The discharge power condition is usually 1 per support.
0 to 5000 W, more preferably about 20 to 2000 W. In addition, the gas pressure in the deposition chamber is usually 0.01 to 1 Torr by the RF discharge method, preferably 0.1 to 0.5 Torr, and is usually 0.2 mTorr to 100 mTorr by the microwave discharge method. Preferably, it is about 1 to 50 mTorr.

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

In the present invention, an oxygen atom, a carbon atom, a nitrogen atom, a group IIIB element or a group V
In order to make the distribution state of the group B element or the hydrogen atom and / or the halogen atom uniform, it is necessary to keep the above-mentioned conditions constant when forming the light receiving layer.

In the present invention, when forming the photoreceptive layer, the distribution concentration of oxygen, carbon, nitrogen, group IIIB or group VB elements contained in the light receiving layer is adjusted in the layer thickness direction. In order to form a light receiving layer having a distribution state in a desired layer thickness direction by changing, if a plasma CVD method is used, an oxygen atom, a carbon atom, a nitrogen atom,
The gas may be formed while appropriately changing the gas flow rate when introducing a gas of a starting material for introducing a Group IB element or a Group VB element into the deposition chamber in accordance with a desired change rate, and keeping other conditions constant. In order to change the gas flow rate, specifically, a predetermined needle valve or a mass flow controller (MFC) provided in the middle of the gas flow path system is manually or manually operated by any method such as an external drive motor. An operation for gradually changing the opening may be performed. At this time, the rate of change 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 previously designed change rate curve using a microcomputer or the like.

When the light receiving layer is formed by a sputtering method, the distribution concentration of oxygen atoms, carbon atoms, nitrogen atoms, or a group IIIB element or a group VB element in the layer thickness direction is changed in the layer thickness direction. In order to form a desired distribution state in the layer thickness direction, a starting point for introducing an oxygen atom, a carbon atom, a nitrogen atom, or a group IIIB element or a group VB element is obtained in the same manner as in the case of using the plasma CVD method. The substance may be used in a gas state, and the gas flow rate when the gas is introduced into the deposition chamber may be changed according to a desired change rate.

In the light receiving member for electrophotography of the present invention, for example, Si ₃ N ₄ , S is used for the purpose of further improving the adhesion of the deposited film between the support 101 and the light receiving layer 102.
An adhesion layer formed of an nc-Si material or the like containing iO ₂ , SiO, or at least one of 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 may be electrically insulating. As the conductive support, for example, Ni, Cr, A
1, Cr, Mo, Au, Nb, Ta, V, Ti, Pt,
Examples include metals such as Pb and alloys of the above metals such as stainless steel.

Among them, aluminum is preferable in the present invention because it has an appropriate strength, is excellent in workability, and is easy to manufacture and handle. When aluminum is used as the support material, it is desirable to contain 1 to 10% by weight of magnesium in order to improve 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 resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyamide; glass, ceramics, paper and the like. Is mentioned. These electrically insulating supports are preferably
It is desirable that one of the surfaces 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, its surface
NiCr, Al, Au, Cr, Mo, Ir, Nd, T
a, V, Ti, Pt, In_TwoO_Three, SnO_Two, ITO (I
n_TwoO _Three+ SnO_Two) Etc.
Conductivity, or polyester film, etc.
Is a synthetic resin film of NiCr, Al, Ag,
Pb, Zn, Ni, Au, Cr, Mo, Ir, Nd, T
a, V, Tl, Pt and other metal thin films by vacuum evaporation
On the surface by vapor deposition, sputtering, etc.
Or by laminating with the metal film.
To impart conductivity to the surface.

The shape of the support can 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 or the need. For example, if the light receiving member 100 of FIG. 1 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 appropriately determined so that a desired light receiving member can be formed. However, when the light receiving member is required to have flexibility, a range in which the function as the support is sufficiently exhibited. Can be made as thin as possible. However, in terms of production and handling of the support, mechanical strength, etc.
μm or more.

In view of the fact that a stronger adhesion of the deposited film can be obtained, it is preferable to set the thickness to 2.5 mm or more especially in the case of a cylindrical support.

With respect to the light receiving member of the present invention, the surface shape may be processed after the conductive substrate is cut with a predetermined accuracy. For example, when image recording is performed using coherent light such as laser light, irregularities may be provided on the surface of the conductive substrate in order to eliminate image defects due to interference fringe patterns appearing in a visible image. Such irregularities are described in JP-A-60-168156 and JP-A-60-178.
No. 457, 60-225854, etc. can be provided by a known method.

Further, as another method for eliminating image defects due to interference fringe patterns when coherent light such as laser light is used, the surface of the conductive substrate may be provided with a plurality of concaves and convexes by spherical trace depressions. That is, the surface of the conductive substrate is provided with irregularities due to a plurality of spherical trace depressions, which are smaller than the resolution required for the electrophotographic photosensitive member. Such irregularities are disclosed in
It can be produced by a known method described in JP-A-231561.

Hereinafter, the present invention will be described in more detail.
In the following description, unless otherwise specified, a light receiving member was manufactured by a microwave discharge method.

FIG. 12 shows an apparatus for manufacturing a light receiving member for an electrophotographic image forming member used in the present invention. Here, (A)
1 is a schematic longitudinal sectional view of a manufacturing apparatus by a microwave discharge method, and FIG. 2B is a schematic transverse sectional view taken along line XX of FIG.

In these figures, reference numeral 301 denotes a reaction vessel, which has 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. Reference numeral 303 denotes a waveguide for transmitting microwave power, which has 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) via a stub tuner (not shown) and an isolator (not shown). Fusion window 3
Numeral 02 is hermetically sealed on the inner wall of the cylindrical portion of the waveguide 303 to maintain the atmosphere in the reaction vessel 301.
An exhaust pipe 304 has one end opened into the reaction vessel 301 and the other end communicating with an exhaust device (not shown). It is to be noted that the exhaust pipe and the exhaust device are used independently for the case of exhausting the air in the reaction vessel and the case of exhausting the film forming gas (reacted or unreacted). It is preferable in order to prevent the reaction due to the residual gas in the process. Reference numeral 306 denotes a discharge space formed by being surrounded by a plurality of cylindrical supports 305. Reference numeral 308 denotes an electrode for applying an external electric bias voltage for controlling the plasma potential, and a DC voltage is applied by a DC power supply 309. Each support 305 is set on a rotating shaft 311 and heated by a heater 307, and each holder can be appropriately rotated by a driving means (rotary motor) 310.

FIG. 15 shows another example of the apparatus shown in FIG. In the figure, the same reference numerals as those in FIG. 12 indicate the same members. The difference between FIGS. 12 and 15 is that the shape of the reaction vessel 301 is circular in FIG. 12, whereas the reaction vessel 301 in FIG. 15 is rectangular.

The production of a light receiving member for electrophotography using the apparatus can be carried out as follows.

First, the cylindrical support 3 is placed in the reaction vessel 301.
05, the support 305 is rotated by the support rotating motor 310, and the inside of the reaction vessel 301 is evacuated by the exhaust device (vacuum pump) (not shown) through the exhaust pipe 304 to reduce the pressure in the reaction vessel 301. Adjust to 1 × 10 ⁻⁷ Torr or less. At this time, it is desirable that the first exhaust is performed slowly (slow exhaust) so as not to blow up dust and the like in the vacuum container. Subsequently, the heater for heating the support 3
In step 07, the temperature of the support 305 is heated and maintained at a predetermined temperature. 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, hydrogen Etc.) may be introduced. When an oxide film is formed on the surface of the support, heating in an atmosphere containing oxygen is also effective.

When the temperature of the support reaches a predetermined temperature, the inside of the reaction vessel is once evacuated, and a raw material gas for forming the first layer is introduced through gas introduction means (not shown). That is,
nc-Si: silane gas as a source gas of (H, X);
A source gas such as diborane gas as a doping gas and helium gas as a diluting gas is introduced into the reaction vessel 301. At the same time, a microwave power supply (not shown) operates at a frequency of 500 MHz or more, preferably 2.45G.
A microwave of Hz is generated, and the microwave is introduced into the reaction vessel 301 through the waveguide 303 and the dielectric window 302.

Further, the bias electrode 3 in the discharge space 306
At 08, a DC voltage is applied to the support 305. Thus, in the discharge space 306 surrounded by the support 305, the raw material gas is excited by microwave energy and dissociated, and neutral radical particles, ionic particles, electrons, etc. are purified, and they react with each other to form a support. A deposited film is formed on the surface of 305. At this time, the rotating shaft 311 on which the support 305 is installed is rotated by the motor 310, and the support 305 is rotated around the central axis in the direction of the base line of the base, whereby a deposited film is uniformly formed over the entire circumference of the support 305. You.

In order to form the second layer on the first layer formed as described above, the composition or composition ratio of the raw material gas may be changed as required when forming the first layer. The deposited film may be formed by introducing into the reaction vessel 301 and starting discharge in the same manner as in the formation of the first layer.

At this time, it is not always necessary to increase the degree of vacuum in the reaction vessel 301, and gas flow control means (not shown)
It is also possible to gradually switch from the gas composition for forming the first layer to the gas composition for forming the second layer while maintaining discharge by manual or computer control.

The amounts of hydrogen atoms and halogen atoms contained in the interface between the first layer and the second layer can be determined by, for example, changing the flow rates of hydrogen gas and / or halogen gas introduced into the discharge space. Can be controlled by In particular, it is preferable to precisely control the flow rates of the gas for introducing hydrogen atoms and halogen atoms introduced by a piezo valve or the like. Furthermore, by appropriately changing the microwave power introduced into the discharge space, the applied bias voltage, and the temperature of the support, control can be performed more effectively. Control can also be performed by selecting the gas to be introduced.

For example, to control the introduction flow rate of silane gas and disilane gas into the discharge space to control the amount of introduced hydrogen atoms, and to control the content of halogen atoms, to control the content of halogen atoms, SiF ₄ gas and SiH ₂ F ₂ Control can also be performed by arbitrarily changing the flow ratio of gas introduced into the discharge space.

Next, the content of hydrogen atoms and halogen atoms in the vicinity of the layer interface, and the relationship between the content area and the carrier traveling property are examined. As a method, first, the content and the area of the hydrogen atom are fixed to change the content and the area of the halogen atom, and then the content and the area are fixed for the halogen atom and changed for the hydrogen atom, The carrier running property is measured and evaluated in each case.

The carrier traveling property is measured using a sample obtained by cutting the produced light receiving member in the layer thickness direction and using an apparatus schematically shown in FIG. In FIG.
400 is a sample, and the light receiving layer 4 is provided on the support 401.
02 is formed. Reference numeral 403 denotes a glass on which a transparent conductive film ITO (In ₂ O ₃ + SnO ₂ ) is vapor-deposited, and is connected to a DC power supply 404. 405 is a light source. Reference numeral 406 denotes a measuring device.

The measurement is performed as follows. First,
As shown in the figure, the sample 400 is closely attached to the glass 403 on which the transparent conductive film is deposited using a substance having a high relative dielectric constant such as glycerin without any gap. 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 short-pulse lights 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, from the relationship between the photocurrent flowing through the sample and the time, the time required for the photocarriers generated by the short pulse light to move through the deposited film is determined, and this time is defined as the transit time ( _tr ). This _tr value, the film thickness (d) of the sample and the applied voltage (E)
, The carrier traveling property (μ) is obtained by the following equation.

[0146]

Μ = d / (E · t _r )

The light receiving member formed such that the content of hydrogen atoms and / or halogen atoms in the vicinity of the interface between the non-single crystal layers having different compositions is larger than the content of hydrogen atoms and / or halogen atoms in the bulk layer. The reason why good carrier running properties are exhibited when used as an image forming member for electrophotography is considered as follows.

The characteristics of a light receiving member having a multilayer structure are often determined by the bonding state of atoms constituting the layer interface. That is, since the layers have different structures at the boundary of the layer, the interface becomes a so-called heterojunction interface, and structural distortion occurs at the interface. As a result, the layer interface becomes an electric barrier or becomes structurally unstable. Specifically, various levels called interface states are formed in dangling bonds or band gaps,
At the time of light irradiation, transmission of light near the interface is hindered, and not only the efficiency of light utilization is reduced, but also the properties of the film near the interface are reduced, and the efficiency of carrier generation, that is, the quantum yield is reduced. .

Further, if there are many interface states described above, bending of the energy band at the interface portion, that is, band bending occurs, and the resistance in the in-plane direction parallel to the surface near the layer interface decreases, and as a result, the charge Cross-flow occurs.
This is considered to be the cause of image deletion during strong exposure.

At the same time, the adhesion at the layer interface is reduced, and the mechanical strength is also reduced. In contrast, by introducing a hydrogen atom and / or a halogen atom in the vicinity of the interface, structural strain is partially relaxed, dangling bonds that can serve as traps are compensated, and characteristics and adhesion are improved. It is thought that it is. In particular, since the halogen atoms do not affect the optical band gap of the non-single-crystal layer, the bonding at the interface is considered to be smooth. Furthermore, it is considered that by simultaneously containing hydrogen atoms at a higher concentration in the vicinity of the interface than in the bulk layer, dangling bonds that could not be compensated for by the halogen atoms alone can be compensated. This is presumably because the hydrogen atom has a smaller atomic radius than the halogen atom. Therefore, it is considered that the carrier movement in the layer thickness direction becomes smooth by the introduction of hydrogen atoms and halogen atoms, and the carrier movement in the direction parallel to the free surface is suppressed.

The reason why there is an appropriate range in the thickness and the content of the hydrogen atom and halogen atom-rich region near the layer interface, which is one of the features of the present invention, is considered as follows.

The content of hydrogen atoms and halogen atoms in the vicinity of the interface between two non-single-crystal layers having different compositions and / or the vicinity of the interface between the non-single-crystal layer and the support is too large, or the content of hydrogen atoms and halogen atoms is too large. If the region with a large amount is too wide, the content of hydrogen atoms and halogen atoms is excessive, so that the layer interface or the vicinity of the layer interface becomes structurally unstable, and the film quality deteriorates. That is, if there are more hydrogen atoms and halogen atoms than necessary to alleviate the structural strain, the layers that are in contact with each other and the adhesion between the layers and the support are reduced, and the mechanical strength is reduced. In addition, it is considered that the inhibition of the network between silicon atoms adversely affects the intrinsic electrical characteristics of the semiconductor. In particular, when the halogen atom content in the bulk layer portion becomes unnecessarily large, this tendency becomes large. Conversely, if the region rich in hydrogen atoms and halogen atoms is too narrow or the contents of hydrogen atoms and halogen atoms are too small, it is difficult to alleviate the above-mentioned structural distortion, and improvement in properties cannot be expected.

As described above, in the light receiving member of the present invention, it is particularly important to control the contents of hydrogen atoms and halogen atoms in the vicinity of the layer interface and their regions.

FIG. 14 shows an apparatus for forming the light receiving layer of the light receiving member of the present invention by the RF plasma CVD method. Hereinafter, formation of a light receiving layer using the RF plasma CVD apparatus will be briefly described.

In the figures, gas cylinders 502, 503, 504, 505 and 506 contain raw material gases for forming each layer. For example, 502 is SiH ₄ (purity 9
9.999%) cylinder, 503 is B ₂ H diluted with H _2
6 gas (purity: 99.999%; hereinafter abbreviated as B ₂ H ₆ / H ₂ ); 504, a CH ₄ gas (purity: 99.999%) cylinder; 505: a SiF ₄ gas (purity: 99.999%) cylinder; Is an H ₂ gas (purity 99.999%) cylinder.

To allow these gases to flow into the reaction chamber 501, first, the valves 522 to 522 of the gas cylinders 502 to 506 are used.
526, the leak valve 535 is confirmed to be closed, and the inflow valves 512 to 516 and the outflow valve 51 are checked.
7 to 521, and confirm that the auxiliary valves 532 and 533 are open. Next, the main valve 534 is opened, and the inside of the reaction chamber 501 and the gas pipe are evacuated by a vacuum pump (not shown). Next, the reading of the vacuum gauge 536 is about 5 × 10 ^−6.
When Torr is reached, auxiliary valves 532, 533,
Close outflow valves 517-521.

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 the gas cylinder 503, CH ₄ gas from the gas cylinder 504 and H ₂ gas from the gas cylinder 506 are supplied to valves 522, 523, 524, respectively.
Opening 526, outlet pressure gauges 527, 528, 529,
The pressure of 531 was adjusted to 1 kg / cm ² and the inflow valve 51 was adjusted.
2, 513, 514, and 516 are gradually opened to flow into the mass flow controllers 507, 508, 509, and 511.

Subsequently, the outflow valves 517, 518, 5
19, 521 and the auxiliary valves 532, 533 are gradually opened to allow the gas to flow into the reaction chamber 501. SiH ₄ at this time
The outflow valve 5 is controlled so that the 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 become the desired values.
17, 518, 519, and 521 are adjusted, and the opening of the main valve 534 is adjusted while reading the vacuum gauge 536 so that the pressure in the reaction chamber 501 becomes a desired value.

Then, after confirming that the temperature of the base cylinder 537 is set to an appropriate temperature within the range of 50 to 400 ° C. by the heater 538, an appropriate voltage is applied from the power supply 540 to the inside of the reaction chamber 501. A glow discharge is generated at a time, and a microcomputer (not shown) is used in accordance with a previously designed rate-of-change curve.
While controlling the iH 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,
For example, first, a layer made of nc-Si (H, X) containing carbon atoms and boron atoms is formed on 37.

Next, for example, after a predetermined time has passed, B_TwoH₆/ H
_TwoGases 518, 513, and 5 are introduced into the reaction chamber 501.
23, close each valve_FourGas, CH_FourGas and
And H _TwoBy introducing only gas into the reaction chamber 501,
On the non-crystalline layer, carbon atoms containing no boron atoms
Forming a layer made of nc-Si (H, X) containing atoms
can do.

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 previous layer is used in the reaction chamber. Inside 501, outflow valve 517 ~
In order to avoid remaining in the gas pipe from 521 to the reaction chamber 501, the outflow valves 517 to 521 are closed, the auxiliary valves 532 and 533 are opened, and the main valve 5
The operation of fully opening 34 and once evacuating the system to high vacuum,
Perform as needed. Alternatively, by gradually adjusting the gas flow rate, it is possible to form all layers continuously without interrupting the film formation.

[0162]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto.

Example 1 In order to control the hydrogen content in the vicinity of the layer interface, a charge injection preventing layer was placed on a mirror-finished aluminum cylinder in accordance with the manufacturing conditions shown in Table 1 using a manufacturing apparatus shown in FIG. A blocking type electrophotographic light-receiving member having a three-layer structure of a photoconductive layer and a surface layer was formed. At this time, the flow rate of the introduced hydrogen and the applied bias voltage at the time of forming the layer interface between the charge injection blocking layer and the photoconductive 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 formed. Produced. A plurality of portions corresponding to the upper and lower portions of the image area of these light receiving members were cut out (hereinafter referred to as samples), and 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 contained in the bulk were compared. The thickness of the region with a high hydrogen content at the layer interface was 50 to 8000 °, and the hydrogen content at the layer interface could be changed to 1.0 to 2.2 times that of the bulk hydrogen content. The results are summarized in Table 2.
In Table 2, the sample numbers from a-A1 to g-A7 depend on the thickness of the region where the hydrogen content is large near the layer interface (lower) and the ratio of the hydrogen content to the bulk layer (upper). Gave.

[0164]

[Table 1]

[0165]

[Table 2] Note: Top: ratio of layer interface / hydrogen content of bulk layer, bottom: thickness of region with high hydrogen content near layer interface (Å)

The same sample prepared above (however, SI
Those not used for MS analysis) were measured for photoresponsiveness by the method described above.

First, the sample 400 is brought into close contact with the glass 403 on which the transparent conductive film is deposited as shown in FIG. At this time, the adhesion may be enhanced by incorporating a substance having a high relative dielectric constant such as glycerin between the glass and the sample. Next, a predetermined voltage is applied from the DC power supply 404 between the support and the light receiving layer. After a lapse of a predetermined time, the sample 400 is irradiated with a predetermined amount of light from the light source 405 via the glass 403. With such an operation, a photocurrent flows in the sample 400. The current value and time at that time are measured by the measuring means 406. From the measured results, the time required to reach a predetermined current value from the moment of light irradiation was calculated, the rate of change of the current value per unit time was calculated, and this value was defined as the light responsiveness. In this measurement,
The applied voltage is set to 150 V in order to make the carrier traveling property remarkable.
Low voltage, irradiation light quantity 5μW, reaching current value 10μA
And Table 3 shows the results. In Table 3, ◎ indicates that the light response was extremely good, ○ indicates that the light response was very good, Δ indicates that the light response was good, and x indicates that there was no practical problem.

[0168]

[Table 3]

As is apparent from Table 3, the photoresponsiveness is particularly excellent when the hydrogen content near the interface between the charge injection blocking layer and the photoconductive layer is 1.1 to 2 times the hydrogen content in the bulk layer. It was confirmed that. Thus, the light receiving member of the present invention formed so that the concentration of contained hydrogen atoms in the vicinity of the interface between the charge injection blocking layer and the photoconductive layer is higher than the concentration of contained hydrogen atoms in the bulk can be used as an image for electrophotography. The reason why the optical response is good when used as a forming member 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 from the boundary of the layer, structural distortion occurs at the layer interface. Then, the layer interface becomes an electric barrier or becomes structurally unstable. Specifically, so-called dangling bonds or various levels are formed in the band gap, and photocarriers generated in the photoconductive layer during light irradiation are trapped while traveling in the layer. Not only does the carrier become difficult to move, or the trap becomes a recombination center, but the carrier disappears, causing not only an obstacle to the carrier but also a decrease in adhesion at the interface between the layers. On the other hand, by introducing a higher concentration of hydrogen atoms at the layer interface than in the bulk layer as in the present invention, structural strain is reduced, dangling bonds that can serve as traps are compensated, and characteristics and adhesion are improved. It is thought to be.

Example 2 Using the manufacturing apparatus shown in FIG. 12, aluminum was mirror-finished according to the manufacturing conditions shown in Table 1 in the same manner as in Example 1 except that the thicknesses of the charge injection blocking layer and the photoconductive layer were changed. A blocking type electrophotographic light-receiving member having a three-layer structure was formed on a cylinder. A plurality of portions corresponding to the upper and lower portions of the image area of the light receiving member were cut out, and the relationship between photoresponsiveness and hydrogen content was evaluated in the same manner as in Example 1.
As a result, when one or both of the charge injection blocking layer and the photoconductive layer are thin (about 1 to 2 μm), the region having a large hydrogen content near the layer interface is the charge injection blocking layer and the photoconductive layer. It was confirmed that the effect of the present invention was effectively exhibited when the thickness of the thinner conductive layer was preferably within 30%.

Example 3 Using the manufacturing apparatus shown in FIG. 12, samples in which the hydrogen content in the charge injection blocking layer and the photoconductive layer were variously changed were prepared. When the relationship of the response was examined, the hydrogen content in the charge injection blocking layer and the bulk layer of the photoconductive layer was 0.05 to 40 atomic%, and the hydrogen content in the vicinity of the layer interface was 0.1 to 45 atomic%. In the range, the range where the hydrogen content is high near the interface is 100 to 500 as in the first embodiment.
It was confirmed that photoresponsiveness was excellent when the angle was 0 ° and the hydrogen content near the layer interface was 1.1 to 2 times the hydrogen content in the bulk layer. However, the analysis of the hydrogen content at this time was performed by appropriately combining analysis methods such as SIMS, infrared absorption method, and thermal desorption method according to the content.

Example 4 Using the manufacturing apparatus shown in FIG. 12, according to the manufacturing conditions shown in Table 4, an electrophotographic light-receiving member having two layers having different compositions was formed on a mirror-finished aluminum cylinder. At this time, the flow rate of the introduced hydrogen and the applied bias voltage were adjusted within the range shown in Table 4 for the source gas to be introduced and the bias voltage to be applied, at the time of forming the layer interface between the photoconductive layer and the surface layer.
Various light receiving members were produced. In the same manner as in Example 1, a plurality of portions corresponding to the upper and lower portions of the image area of the light receiving member were cut out, and quantitative analysis of hydrogen atoms contained in the deposited film was performed by SIMS. Was measured, and the same ratio as in Table 2 was obtained.

[0174]

[Table 4]

Next, the traveling of the carrier is performed by the above-described method.
The properties were measured. The light source is N _TwoPumped by laser
Initial setting table using a dye laser (wavelength 460 nm)
Line with a surface potential of 100 to 500 V and a pulse interval of 20 nsec
Was.

The results of the evaluation were evaluated as follows: キ ャ リ ア: Very good carrier runnability, ：: Very good carrier runnability, Δ: Good carrier runnability, ×: No practical problem The same results as in Table 3 were obtained. From this result, the region having a large hydrogen content in the vicinity of the layer interface between the photoconductive layer and the surface layer is 100 to 5000 °, and the hydrogen content in the vicinity of the layer interface is 1.1 to 2. It was confirmed that the carrier running property was particularly excellent at 0 times.

Example 5 A mirror-finished aluminum cylinder was set in the deposition film forming apparatus shown in FIG. 12, and under the conditions shown in Table 5, a photoreceptor for electrophotography consisting of a charge transport layer and a charge generation layer was formed. A member was formed.

[0178]

[Table 5]

When the obtained light receiving member was evaluated in the same manner as in Example 4, the same results as in Example 4 were obtained.

Example 6 An aluminum cylinder mirror-finished according to the manufacturing conditions shown in Tables 4 and 5 in the same manner as in Examples 4 and 5 except that the thickness of the bulk layer was changed using the manufacturing apparatus shown in FIG. An electrophotographic light-receiving member having a two-layer structure was formed thereon. A plurality of portions corresponding to the upper and lower portions of the image area of the light receiving member were cut out, and the relationship between the traveling property of the carrier and the hydrogen content was evaluated in the same manner as in Example 4.
As a result, when the thickness of one or both of the bulk layers is small (about 1 to 2 μm), the region having a large hydrogen content near the interface between the layers is preferably 30 μm in the thinner bulk layer.
%, It was confirmed that the effects of the present invention were effectively exhibited.

Example 7 Using the manufacturing apparatus shown in FIG. 12, samples in which the hydrogen content in the bulk layer was variously changed were prepared.
The hydrogen content in the bulk layer of the photoconductive layer and the surface layer was 0.05 to 40 atomic%, and the hydrogen content in the vicinity of the layer interface was 0.1 to 45.
In the range of atomic%, the range where the hydrogen content near the interface is large is 100 to 5000 ° similarly to Example 4, and the hydrogen content near the layer interface is 1.1 to 1.0% of the hydrogen content in the bulk layer. It was confirmed that the carrier was excellent in running property when it was doubled. However, the analysis of the hydrogen content at this time was performed by appropriately combining analysis methods such as SIMS, infrared absorption method, and thermal desorption method according to the content.

Example 8 Using a manufacturing apparatus shown in FIG. 12, four layers of a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer were formed on a mirror-finished aluminum cylinder in accordance with the manufacturing conditions shown in Table 6. A light receiving member for electrophotography was formed. At this time,
The flow rate of the hydrogen introduced and the bias voltage applied during the preparation of the layer interface between the charge transport layer and the charge generation layer were adjusted within the ranges shown in Table 6 for the source gas to be introduced and the bias voltage to be applied, and various light receiving members were produced. As in Example 1, a plurality of portions corresponding to the upper and lower portions of the image area of the light receiving member are cut out,
Quantitative analysis of hydrogen atoms contained in the deposited film was performed by SIMS, and the thickness ratio of the region having a large amount of hydrogen at the layer interface and the amount ratio of the hydrogen content of the region to the bulk layer were measured. Was obtained.

[0183]

[Table 6]

Next, when the prepared sample was evaluated in the same manner as in Example 4, similar results were obtained. From these results, it is found that the region having a large hydrogen content near the layer interface between the charge transport layer and the charge generation layer is 100 to 5000 °, and the hydrogen content near the layer interface is 1.1 to 2 times the hydrogen content in the bulk layer. It was confirmed that the mobility of the carrier was excellent when the ratio was 0.0.

Example 9 An aluminum cylinder mirror-finished in the same manner as in Example 8 except that the thicknesses of the charge transport layer and the charge generation layer were changed using the manufacturing apparatus shown in FIG. A blocking type electrophotographic light receiving member having a four-layer structure was formed thereon. A plurality of portions corresponding to the upper and lower portions of the image area of the light receiving member were cut out, and the relationship between the traveling property of the carrier and the hydrogen content was evaluated in the same manner as in Example 4. As a result, when one or both of the charge transport layer and the charge generation layer are thin (1-2 μm).
m), and it is confirmed that the effect of the present invention is effectively exhibited when the region having a large hydrogen content in the vicinity of the layer interface is preferably within 30% of the thinner of the charge transport layer and the charge generation layer. Was.

Example 10 Mirror finishing was performed in the same manner as in Example 8 except that the hydrogen content in the charge transport layer and the charge generation layer was variously changed using the manufacturing apparatus shown in FIG. A blocking type electrophotographic light receiving member having a four-layer structure was formed on the applied aluminum cylinder, and the relationship between the hydrogen content and the traveling properties of the carrier was examined in the same manner as in Example 4. The hydrogen content in the bulk layer of the layer is 0.05-4
0 atomic%, the hydrogen content in the vicinity of the layer interface is in the range of 0.1 to 45 atomic%, the range in which the hydrogen content in the vicinity of the interface is large is 100 to 5000 ° as in Example 8, and The hydrogen content is between 1.1 and 2 of the hydrogen content in the bulk layer
It was confirmed that the carrier was excellent in runnability at twice. However, the analysis of the hydrogen content at this time was performed by appropriately combining analysis methods such as SIMS, infrared absorption method, and thermal desorption method according to the content.

Example 11 The same manufacturing conditions as in sample e-A3 of Example 1 (thickness of the region having a large hydrogen content near the layer interface between the charge injection blocking layer and the photoconductive layer: 3000 °, hydrogen content of the region) : 1.3 times that of the bulk layer, but the surface layer was not prepared), a blocking type electrophotographic light comprising a charge injection blocking layer and a photoconductive layer on a mirror-finished aluminum cylinder. A receiving member was produced.

Example 12 A charge injection blocking layer and a photoconductive layer were formed on an aluminum cylinder mirror-finished under the same conditions as in Example 11,
Further, the surface layer of Example 1 was formed to produce a blocking type electrophotographic light-receiving member having a three-layer structure.

Example 13 A mirror-finished aluminum cylinder was set in the deposition film forming apparatus shown in FIG. 12, and a four-layer structure including an IR absorption layer, a charge injection blocking layer, a photoconductive layer, and a surface layer was obtained under the conditions shown in Table 7. An electrophotographic light-receiving member for blocking electrophotography was formed. However, the hydrogen content near the layer interface between the charge injection blocking layer and the photoconductive layer was adjusted to be the same as in Example 11.

[0190]

[Table 7]

Example 14 A mirror-finished aluminum cylinder was set in the deposition film forming apparatus shown in FIG. 12, and a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer were formed according to the conditions shown in Table 8. An electrophotographic light-receiving member for blocking electrophotography was formed. However,
The hydrogen content near the layer interface between the charge injection blocking layer and the charge transport layer was adjusted to be the same as in Example 11.

[0192]

[Table 8]

Comparative Example 1 A three-layer structure of a charge injection blocking layer, a photoconductive layer, and a surface layer under the same conditions as in Example 12 except that the hydrogen content near the layer interface between the charge injection blocking layer and the photoconductive layer was not manipulated. An electrophotographic light-receiving member for prevention of electrophotography was produced.

Comparative Example 2 An IR absorption layer, a charge injection blocking layer, a photoconductive layer, and a surface layer were prepared under the same conditions as in Example 13 except that the hydrogen content near the interface between the charge injection blocking layer and the photoconductive layer was not changed. A light receiving member for blocking electrophotography having a four-layer structure was prepared.

Comparative Example 3 The charge injection blocking layer, the charge transport layer, the charge generation layer, and the surface layer were prepared under the same conditions as in Example 14 except that the hydrogen content near the interface between the charge injection blocking layer and the charge transport layer was not changed. A light receiving member for blocking electrophotography having a four-layer structure was prepared.

Examples 11 to 14 and Comparative Examples 1 to 3
The light receiving member manufactured by the above method was used with a Canon copier, NP75
An image was formed on a transfer paper at a speed 1.2 times faster than a copying process in a normal durability test by setting the 50 in an electrophotographic apparatus modified for experiments. This operation was repeated, and the durability of 500,000 sheets was performed. The following evaluation was performed on the potential characteristics and the initial image and the image after the durability, and the electrophotographic characteristics of the light receiving member were evaluated. However, at this time, the charging operation was performed by applying a voltage of 6 kV to the charger.

Uneven Charging Ability: A photoreceptor for electrophotography was set in an experimental apparatus, a high voltage of +6 kV was applied to the charger, corona discharge was performed, and the surface potential of the dark part of the photoreceptor was measured by a surface voltmeter. 3c from top to bottom of the light receiving member
The surface potential was measured every m and the average was taken as the charging ability.
Then, a value farthest from the average value in one light receiving member was obtained, and the obtained value was regarded as uneven charging ability. The same evaluation was performed on the six light-receiving member samples obtained in one deposition film formation, and the sample having the largest uneven charging ability was judged according to the following criteria. A: Extremely excellent uniformity.・ ・ ・: Excellent uniformity. Δ: No problem in practical use. C: When used in a very high-speed copying apparatus, image quality may be reduced.

Uneven sensitivity: The light receiving member for electrophotography was charged to a constant dark area surface potential in the same manner as described above, and immediately irradiated with a light image. The xenon lamp light source was used for the light image, and light excluding light in the wavelength range of 550 nm or less was irradiated using a filter. At this time, the bright part surface potential of the light receiving member was measured by a surface voltmeter. The exposure amount is adjusted so that the bright portion surface potential becomes a predetermined value, and the exposure amount is used as the sensitivity. The same measurement was performed every 3 cm from the top to the bottom of the light receiving member, the average was taken as the average sensitivity, and the value farthest from the average was taken as the uneven sensitivity. And one
The same evaluation was performed for the six light-receiving member samples obtained in each deposition film formation, and the sample with the largest sensitivity unevenness was judged according to the following criteria. A: The uniformity is extremely excellent.・ ・ ・: Excellent uniformity. Δ: No problem in practical use. ×: The quality may deteriorate under severe conditions such as high temperature and high humidity and low temperature and low humidity.

Fine line reproducibility: An ordinary original consisting of characters on a white background was placed on a platen, and an image sample obtained at the time of copying was observed to evaluate whether or not the fine lines on the image were connected without interruption. In addition, when there was unevenness on the image, the evaluation was performed over the entire image area, and the result of the worst part was shown. The same evaluation was performed on the six light-receiving member samples obtained by one deposition film formation, and the worst of them was determined according to the following criteria. A: Very good.・ ・ ・: Good. Δ: There are some interruptions, but there is no practical problem. X: Characters can be read although there is a break.

White background fogging: A normal original consisting of characters on the entire white background was placed on a platen, and an image sample obtained at the time of copying was observed, and the fogging of the white background was evaluated. The same evaluation was performed on the six light-receiving member samples obtained by one deposition film formation, and the worst of the samples was judged according to the following criteria. A: Very good.・ ・ ・: Good. ○ ・ ・ ・ There is. Δ: There is a slight fog, but no problem in character recognition. ×: There is fogging over the entire surface, but there is no problem in character recognition.

Image Unevenness: A halftone original was placed on an original platen, and an image sample obtained at the time of copying was observed to evaluate shading. The same evaluation was performed on the six light-receiving member samples obtained by one deposition film formation, and the worst of the samples was judged according to the following criteria. A: Very good.・ ・ ・: Good.・ ・ ・: There is a slight difference in density. Δ: There is a slight difference in shading, but there is no problem in character recognition. ×: There is a difference in shading over the entire surface, but there is no problem in character recognition. Table 9 shows the results.

[0202]

[Table 9]

As is clear from Table 9, it was confirmed that the present invention was superior to the comparative examples in various items caused by photoresponsiveness.

Example 15 The same manufacturing conditions as in Sample e-A3 of Example 4 (thickness of the region having a large hydrogen content near the layer interface between the photoconductive layer and the surface layer: 3000 °, hydrogen content of the region: bulk) (1.3 times the layer thickness) to produce a light receiving member for electrophotography having a two-layer structure of a photoconductive layer and a surface layer on a mirror-finished aluminum cylinder.

Comparative Example 4 An electron having a two-layer structure of the charge injection blocking layer and the photoconductive layer under the same conditions as in Example 11 except that the hydrogen content near the layer interface between the charge injection blocking layer and the photoconductive layer was not changed. A light receiving member for photography was prepared.

Comparative Example 5 An electrophotographic photoreceptor comprising a two-layer structure of a photoconductive layer and a surface layer under the same conditions as in Example 15 except that the hydrogen content near the interface between the photoconductive layer and the surface layer was not manipulated. A member was manufactured.

Examples 11 to 15 and Comparative Examples 1 to 5
The light receiving member manufactured by the above method was used with a Canon copier, NP75
50 was installed in an electrophotographic apparatus modified for experiments, and an image was formed on transfer paper at a normal copying process speed (A) and at a speed (B) 1.2 times the copying process of a normal durability test. At this time, the same evaluation as described above was performed for charging ability and sensitivity, and the following evaluation was performed for electrophotographic characteristics such as residual potential.

Residual potential: The photoreceptor is charged to a constant dark area surface potential and immediately irradiated with a constant quantity of relatively strong light. The light image is irradiated with light excluding light in the wavelength range of 550 nm or less using a filter using a xenon lamp light source. At this time, the surface potential of the light receiving member is measured by a surface potential meter.

Halftone unevenness: A halftone chart made by Canon (part number: YF9-9042) is placed on a platen,
0.05m diameter on the copy image obtained when copying
The image density at 100 points was measured using a circular area of m as one unit, and the variation in the image density was evaluated. The same evaluation was performed for the six drums obtained by one deposition film formation, and the worst of the six drums was judged as follows. A: Very good.・ ・ ・: Very good. Δ: good. ×: No problem in practical use. Table 10 shows the results.

[0210]

[Table 10]

As is clear from Table 10, it was confirmed that the present invention was superior to the comparative example in various items caused by the traveling properties of the carrier.

Example 16 The same manufacturing conditions as those of the sample e-A3 of Example 8 (thickness of the region having a large hydrogen content near the layer interface between the charge transport layer and the charge generation layer: 3000 °), hydrogen content of the region: 1.3 times that of the bulk layer (however, no charge injection blocking layer was prepared), a three-layer structure consisting of a charge transport layer, a charge generation layer, and a surface layer on an aluminum cylinder mirror-finished under the same conditions as described above. A function-separated light receiving member for electrophotography was produced.

Example 17 The same manufacturing conditions as those of the sample e-A3 of Example 8 (thickness of the region containing a large amount of hydrogen near the layer interface between the charge transport layer and the charge generation layer: 3000 °), hydrogen content of the region: A function-separation-prevention electrophotograph comprising a charge injection prevention layer, a charge transport layer, a charge generation layer, and a surface layer on an aluminum cylinder mirror-finished under the same conditions as (1.3 times the bulk layer). A light receiving member was prepared.

Example 18 A mirror-finished aluminum cylinder was set in the deposited film forming apparatus shown in FIG.
A blocking type electrophotographic light receiving member having a five-layer structure including an absorption layer, a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer was formed. However, the hydrogen content near the layer interface between the charge transport layer and the charge generation layer was adjusted to be the same as in Example 16.

[0215]

[Table 11]

Comparative Example 6 The charge transport layer was prepared under the same conditions as in Example 16 except that the hydrogen content near the interface between the charge transport layer and the charge generation layer was not changed.
An electrophotographic light-receiving member having a three-layer structure including a charge generation layer and a surface layer was prepared.

Comparative Example 7 The charge injection preventing layer, the charge transport layer, the charge generation layer, and the surface layer were prepared under the same conditions as in Example 17 except that the hydrogen content near the interface between the charge transport layer and the charge generation layer was not changed. A blocking type electrophotographic light-receiving member having a four-layer structure was produced.

Comparative Example 8 An IR absorbing layer was prepared under the same conditions as in Example 18 except that the hydrogen content near the layer interface between the charge transport layer and the charge generation layer was not changed.
5 of charge injection blocking layer, charge transport layer, charge generation layer and surface layer
A blocking type electrophotographic light-receiving member having a layer structure was produced.

The above Examples 16 to 18 and Comparative Examples 6 to 8
The light receiving member manufactured by the above method was used with a Canon copier, NP75
50 was installed in an electrophotographic apparatus modified for experiments, and images were formed on transfer paper at a normal copying process speed (A) and at a speed (B) 1.2 times the normal copying process. The following evaluation was performed on the obtained image to evaluate the electrophotographic characteristics of the light receiving member. However, at this time, the charging operation was performed by applying a voltage of 6 kV to the charger.
The charging ability, sensitivity and residual potential were evaluated by the above-mentioned methods, and the optical memory was evaluated by the following methods.

Light memory: The light receiving member is charged to a constant dark area surface potential with blank exposure turned off.
At this time, the surface potential of the dark part in the circumferential direction of the light receiving member is measured by a surface voltmeter and stored in a computer.
Next, the surface potential of the dark portion in the circumferential direction is measured and stored in the same manner with the blank exposure ON. The above two data were superimposed, the surface potential difference of the portion exposed to the blank exposure was calculated, and this value was used as the optical memory by the blank exposure. However, when the two data were superimposed, the timing was adjusted at the time of measurement so that the same measurement portion was formed on the light receiving member.

The following judgment was made on the optical memory obtained by the above measurement. A: Very good.・ ・ ・: Very good. Δ: good ×: no problem in practical use Table 12 shows the results.

[0222]

[Table 12]

As is clear from Table 12, it was confirmed that the present invention was superior to the prior art in the chargeability characteristics and the optical memory characteristics.

Example 19 In each of Examples 10 to 18 described above, the thickness of the region having a large hydrogen content near the layer interface was set to 100 to 5000 °,
The effects of the present invention were confirmed in the same manner as in Examples 10 to 18 when the hydrogen content in the region was 1.1 to 2.0 times the bulk layer.

Embodiment 20 Using the apparatus shown in FIG. 14, similar to the above embodiment,
Electrophotographic light-receiving members having various layer constitutions were produced and evaluated in the same manner as in the evaluation of each example. As a result, good results were obtained as in each example.

Example 21 Using the apparatus shown in FIG. 12, an electrophotograph comprising two semiconductor layers (blocking layer-photoconductive layer) having different compositions on a mirror-finished aluminum cylinder according to the manufacturing conditions shown in Table 13. A light-receiving layer was formed.

[0227]

[Table 13]

At this time, the source gas to be introduced and the bias voltage to be applied when forming the layer interface between the blocking layer and the photoconductive layer are shown in Table 1.
Adjustment was performed in the range shown in No. 3 to obtain various light receiving members. This light receiving member was cut in the layer thickness direction to obtain a plurality of samples. For this sample, the halogen atoms contained in the deposited film were quantified by SIMS, and the halogen atom content was compared between the vicinity of the layer interface and the bulk layer. Table 14 shows the results. The thickness of the halogen-rich region at the layer interface varies from 50 ° to 2 μm, and the ratio of halogen atoms at the layer interface to all constituent atoms varies from 0.1 atomic ppm to 35 atomic%. Each sample was given a name as shown in Table 14 based on the halogen atom content and the layer thickness at the layer interface prepared under various conditions.

[0229]

[Table 14]

Next, the carrier running μ of these samples was measured by the method shown in FIG. In this measurement, a dye laser (wavelength: 460 nm) excited by an N ₂ laser was used as a light source, and an initially set surface potential of 100 to 100 nm was used.
500 V, pulse interval 20 nsec. And

Table 15 shows the measurement results. Where ◎
Indicates that the carrier has very good runnability, ○ indicates that the carrier has very good runnability, Δ indicates that the carrier has good runnability, and X indicates that there is no practical problem.

[0232]

[Table 15]

As is clear from Table 15, the thickness of the halogen atom-rich region near the interface between the blocking layer and the photoconductive layer was 10%.
It was confirmed that the carrier mobility was excellent when the range of 0 ° to 1 μm and the ratio of halogen atoms to all the constituent atoms in the region was 0.5 atomic ppm to 30 atomic%.

Example 22 Using the apparatus shown in FIG. 12, two semiconductor layers (photoconductive layer-surface layer or optical layer) having different compositions were formed on a mirror-finished aluminum cylinder under the manufacturing conditions shown in Tables 16 and 17. An electrophotographic light-receiving layer comprising a conductive layer and a photoconductive layer) was formed. At this time, the flow rate of the halogen-containing raw material gas to be introduced and the bias voltage to be applied were adjusted in the ranges shown in Tables 16 and 17 at the time of preparing each layer interface, and various light-receiving members were obtained. A sample was taken from this light receiving member in the same manner as in Example 21.
Similarly, the relationship between the carrier running property and the halogen atom content was evaluated. As a result, a result similar to that of Example 21 was obtained.

[0235]

[Table 16] * 1 Halogen-rich region * 2 Hydrogen-rich region

[0236]

[Table 17] * 1 Halogen-rich region * 2 Hydrogen-rich region

Example 23 Example 2 was repeated except that the thicknesses of the photoconductive layer and the surface layer were changed.
In the same manner as in Example 1, according to the manufacturing conditions in Tables 13, 16 and 17, two semiconductor layers having different compositions (blocking layer-photoconductive layer,
Various photoreceptive members were obtained by forming a photoreceptive layer for electrophotography comprising a photoconductive layer-surface layer or a photoconductive layer-photoconductive layer). A sample was taken from this light receiving member in the same manner as in Example 21, and the relationship between the carrier running property and the halogen atom content was similarly evaluated. As a result, when the thickness of one or both of the two adjacent semiconductor layers is extremely small (about 1 to 2 μm), the thickness of the halogen-rich region near the layer interface is preferably smaller than the thickness of the thinner layer. It was found that good results were obtained when the content was within 30%. However, such a relationship did not hold for a layer that did not substantially exhibit photoconductivity. This is considered to be because the photoconductive properties of a layer having substantially no photoconductivity, for example, an insulating layer, are not changed by the halogen atom content.

Example 24 A mirror-finished aluminum cylinder was set in the deposited film forming apparatus shown in FIG.
Two layers, a charge injection blocking layer and a photoconductive layer, were formed to obtain a photoreceptor for electrophotography. At this time, the halogen atom content at the layer interface was adjusted to be the same as that of e-B8 in Example 21 (thickness of halogen atom-rich region near layer interface: 500).
0 °, ratio of halogen atoms to all constituent atoms: 1 atomic%).

[0239]

[Table 18]

The light receiving member thus produced was set in an apparatus in which a copying machine NP7550 manufactured by Canon Inc. was disassembled for experiments, and an image was formed on a transfer paper at a speed of 1.2 times the normal copying process speed and a normal durability test. Produced.

At that time, the electrophotographic characteristics such as charging ability, sensitivity, residual potential, and halftone were evaluated by the above-described operations and criteria.

[0242]

[Table 19]

Example 25 In the same manner as in Example 24, according to the production conditions shown in Table 20, two layers of a photoconductive layer and a surface layer were formed to obtain a light receiving member for electrophotography. Next, a sample was prepared and evaluated in the same manner as in Example 24. The results are shown in Table 19.

[0244]

[Table 20]

Example 26 In the same manner as in Example 24, three layers of a charge injection blocking layer, a photoconductive layer, and a surface layer were formed according to the manufacturing conditions shown in Table 21 to obtain a blocking type electrophotographic light receiving member. Obtained. Next, a sample was prepared and evaluated in the same manner as in Example 24. The results are shown in Table 19.

[0246]

[Table 21]

Example 27 In the same manner as in Example 24, according to the manufacturing conditions shown in Table 22, four layers of an IR absorption layer, a charge injection blocking layer, a photoconductive layer, and a surface layer were formed. A light receiving member was obtained.
Next, a sample was prepared and evaluated in the same manner as in Example 24. The results are shown in Table 19.

[0248]

[Table 22]

Example 28 In the same manner as in Example 24, four layers of a charge injection blocking layer, a charge transporting layer, a charge generating layer, and a surface layer were formed according to the manufacturing conditions shown in Table 23, and A light receiving member for photography was obtained. Next, a sample was prepared and evaluated in the same manner as in Example 24. The results are shown in Table 19.

[0250]

[Table 23]

Comparative Examples 9 to 13 Various light-receiving layers were formed on an aluminum cylinder in the same manner as in Example 24 except that the content of halogen atoms in the vicinity of the layer interface was not particularly changed. Obtained. That is, (1) two layers of the charge injection blocking layer and the photoconductive layer under the manufacturing conditions of Table 18, (2) two layers of the photoconductive layer and the surface layer under the manufacturing conditions of Table 20, and (3) the manufacturing conditions of Table 21. (4) IR absorption layer, charge injection blocking layer, photoconductive layer, and surface layer, and (5) Table 23. Forming four layers of a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer under the following conditions:
A sample was prepared from the obtained light receiving member and evaluated in the same manner as in Example 24. The results are shown in Table 19 as Comparative Examples 9 to 13 in the order of (1) to (5) above.

As is clear from Table 19, it was found that the light receiving member of the present invention was superior to those of the comparative examples in the characteristics related to the running of the carrier.

Example 29 The mirror-finished aluminum cylinder was set in the deposited film forming apparatus shown in FIG.
A light receiving member having the same layer configuration as that of Example 1 and having a larger halogen atom content in the vicinity of the interface between the support and the semiconductor layer than the bulk layer of the semiconductor layer was formed. When a sample was prepared and evaluated for the obtained light receiving member in the same manner as in Example 24, excellent characteristics similar to those in the above Example were recognized.

Example 30 In the same manner as in Example 29 except that the halogen atom content in the vicinity of the free surface of the semiconductor layer on the side opposite to the support was desired to be larger than that of the bulk layer of the semiconductor layer, Examples 24 to 28 were performed. A light receiving member having the same layer configuration was obtained, and the sample was evaluated. As a result, excellent characteristics similar to those of the above-described example were recognized.

Example 31 The mirror-finished aluminum cylinder was set in the deposited film forming apparatus shown in FIG.
Sample a-B1 of Example 21 having the same layer configuration as
G-B16 (Table 14, but excluding e-B8) (thickness of halogen-rich region near layer interface: 50 °)
2 μm, halogen atom content with respect to all constituent atoms:
(0.1 atomic ppm to 35 atomic%). About the obtained light receiving member,
When a sample was prepared and evaluated in the same manner as in Example 24, the thickness of the halogen-rich region near the layer interface was 10%.
In the composition range of 0 ° to 1 μm and the content of halogen atoms with respect to all the constituent atoms of 0.5 atomic ppm to 30 atomic%, particularly excellent characteristics were recognized as in the above-described examples.
At this time, no upper limit was found for the content of halogen atoms on the free surface opposite to the support within this test range.

Example 32 A light-receiving member was produced in the same manner as in Examples 26 to 30 except that the hydrogen content was adjusted only in the vicinity of an arbitrary layer interface, and a sample was produced and evaluated in the same manner. As a result, excellent characteristics similar to those of the above-described example were recognized.

Example 33 Using the RF plasma CVD apparatus shown in FIG. 14, three layers of a charge injection blocking layer, a photoconductive layer, and a surface layer were appropriately formed in accordance with each of Examples 26 and 28 to 32. And a functional separation preventing type electrophotographic light receiving member by forming a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer. When the obtained light receiving member was evaluated in the same manner as in Example 24, excellent characteristics similar to those in the above Example were recognized.

Example 34 Using the apparatus shown in FIG. 12, two non-single-crystal layers (blocking layer-photoconductive layer) having different compositions were formed on a mirror-finished aluminum cylinder in accordance with the manufacturing conditions shown in Table 24. Thus, a light receiving member for electrophotography was formed.

[0259]

[Table 24] * 1 Halogen-rich region * 2 Hydrogen-rich region

At this time, the source gas to be introduced and the bias voltage to be applied when forming the layer interface between the blocking layer and the photoconductive layer are shown in Table 2.
Adjustment was made in the range shown in FIG. 4 to obtain various light receiving members. This light receiving member was cut in the layer thickness direction to obtain a plurality of samples. With respect to this sample, hydrogen atoms and halogen atoms contained in the deposited film were quantified by SIMS, and the hydrogen atom and halogen atom contents were compared between the vicinity of the layer interface and the bulk layer. As a result, the thickness of the hydrogen-rich region at the layer interface is in the range of 50 to 8000 °, and the hydrogen content in that region depends on the hydrogen content of the bulk layer of the layer having a large hydrogen atom content among the two layers forming the interface. The range was 1.0 to 2.2 times the atomic content.

The thickness of the halogen atom-rich region is in the range of 50 ° to 2 μm, and the ratio of halogen atoms to all constituent atoms is 0.1 atomic ppm to 35 atomic%.
Was in the range. However, the halogen in this case is fluorine.

Next, the carrier traveling μ of these samples was measured by the method shown in FIG. In this measurement, a dye laser (wavelength: 460 nm) excited by an N ₂ laser was used as a light source, and an initially set surface potential of 100 to 100 nm was used.
500 V, pulse interval 20 nsec. And

Table 25 and Table 26 show the measurement results.
Here, ◎ indicates that the mobility of the carrier was very good, ○ indicates that the mobility of the carrier was very good, Δ indicates that the mobility of the carrier was good, and x indicates that there was no practical problem.

[0264]

[Table 25]

[0265]

[Table 26]

As is clear from Tables 25 and 26,
(1) The thickness of the hydrogen atom-rich region near the layer interface between the blocking layer and the photoconductive layer is 100 to 5000 °, and the hydrogen content in that region is larger than that of the two layers forming the interface. 1.1 relative to the hydrogen atom content of the bulk layer of the layer
(2) the thickness of the halogen atom-rich region near the interface between the blocking layer and the photoconductive layer is 100
It was confirmed that carrier mobility was particularly excellent when the thickness was in the range of 、 to 1 μm and the ratio of halogen atoms to all constituent atoms in the region was 0.5 atomic ppm to 30 atomic%.

Further, when halogen atoms are also contained in the bulk layer of the non-single-crystal layer adjacent to the non-single-crystal layer, the halogen atom content in the vicinity of the layer interface is changed to the bulk layer having the larger halogen atom content. It was confirmed that when the halogen atom content was 1.1 times or more, the traveling properties of the carrier were good.

Example 36 Using the apparatus shown in FIG. 12, two semiconductor layers having different compositions (blocking layer, photoconductive layer, and surface) were formed on a mirror-finished aluminum cylinder under the manufacturing conditions shown in Tables 27 and 28. Layer or blocking layer-photoconductive layer-photoconductive layer) to obtain a light receiving member for electrophotography.

[0269]

[Table 27] * 1 Halogen-rich region * 2 Hydrogen-rich region

[0270]

[Table 28] * 1 Halogen-rich region * 2 Hydrogen-rich region

Here, the reason why the blocking layer is included in any of the layer constitutions is as follows. (1) To effectively measure the traveling properties of carriers This is because it is difficult to obtain accurate data if charges are injected from the support. However, if the entire light receiving member has a sufficient stopping power, there is no need to provide a separate layer called a blocking layer. Further, a barrier layer may be provided instead of the blocking layer. (2) A sample was taken from the obtained light-receiving member in the same manner as in Example 34 in order to facilitate the comparison, and the relationship between carrier traveling properties and the content of hydrogen atoms and halogen atoms was similarly evaluated. . As a result, a result similar to that of Example 34 was obtained.

Example 36 A mirror-finished aluminum cylinder was prepared in the same manner as in Example 34 except that the thickness of the non-single-crystal in contact with each other was variously changed, according to the manufacturing conditions in Tables 24, 27 and 28. Forming two non-single-crystal layers having different compositions (blocking layer-photoconductive layer, blocking layer-photoconductive layer-surface layer, and blocking layer-photoconductive layer-photoconductive layer) to form a photoreceptor for electrophotography. A member was obtained. A sample was taken from this light receiving member in the same manner as in Example 34, and the relationship between the carrier running property and the content of hydrogen atoms and halogen atoms was similarly evaluated. As a result, when the thickness of one or both of the two non-single-crystal layers in contact with each other is extremely small (about 1 to 2 μm), the thickness of the halogen-rich region near the layer interface becomes smaller than the thickness of the thinner layer. It has been found that good results are obtained when the content is preferably within 30%.

Example 37 In the same manner as in Example 34 except that the content of halogen atoms in the non-single-crystal bulk layer adjacent to each other was variously changed, Table 2 was used.
According to the fabrication conditions of 4, 27 and 28, two non-single-crystal layers having different compositions (blocking layer-photoconductive layer, blocking layer-photoconductive layer-surface layer, and blocking layer) were formed on a mirror-finished aluminum cylinder. -Photoconductive layer-photoconductive layer) to obtain a light receiving member for electrophotography. A sample was taken from this light receiving member in the same manner as in Example 34, and the relationship between the carrier running property and the content of hydrogen atoms and halogen atoms was similarly evaluated.
As a result, when the bulk layer also contains halogen atoms, the halogen atom content in the vicinity of the layer interface is within the range in which good characteristics are provided in Example 34, and is 1.1 times the content of the bulk layer. In the above cases, it was confirmed that a light receiving member having excellent characteristics was obtained.

Example 38 The same samples as in Examples 34 to 37 were formed and evaluated using chlorine, bromine and iodine as halogen, respectively, and the same results as those examples were obtained.

From the results of Examples 34 to 38 above, the region rich in hydrogen atoms and halogen atoms near the layer interface was
It has been found that an optimum range exists for the thickness and the content of those atoms.

Example 39 The mirror-finished aluminum cylinder was set in the deposition film forming apparatus shown in FIG. 12, and two layers, a charge injection blocking layer and a photoconductive layer, were formed thereon according to the manufacturing conditions shown in Table 29. Thus, a light receiving member for electrophotography was obtained. The halogen atom was fluorine.

[0277]

[Table 29]

At this time, the content of hydrogen atoms and halogen atoms at the layer interface was set to a value within the range evaluated as ◎ in Example 34 (thickness of hydrogen atom-rich region at layer interface: 3).
000 °, ratio of hydrogen content to bulk layer: 1.
5. Thickness of halogen atom-rich region near layer interface: 500
0 °, ratio of halogen atoms to all constituent atoms: 1 atomic%).

The prepared photoreceptor member was set in an apparatus obtained by modifying a copying machine NP7550 manufactured by Canon Inc. for an experiment, and an image was formed on transfer paper at a speed of 1.2 times the normal copying process speed and a normal durability test. did.

At this time, the charging ability, sensitivity and residual potential were evaluated as described above, and electrophotographic characteristics such as strong exposure image deletion were evaluated by the following operations and criteria.

Strong exposure flow: The light-receiving member for electrophotography was charged to a constant dark area surface potential in the same manner as in the case of the study of uneven charging ability and sensitivity. Next, after adjusting the charging current value so that the surface potential of the dark portion of the light receiving member at the developing machine position becomes 400 V, halogen light for forming a latent image is irradiated at an intensity of 21 lux seconds, and a large number of thin lines are formed. Copy the written manuscript, measure the length of blur at the boundary between the lighted and unlit areas of the resulting image, and make a relative comparison of the spread length of each image. did. The same evaluation was performed for the six light receiving members obtained by one deposition film formation, and the largest light-receiving member was judged according to the following criteria. A: Very good.・ ・ ・: Very good. Δ: good ×: no problem in practical use

White spot: A canon full black chart (part number FY9-9073) made by Canon is placed on a platen and a diameter of 0.2 m within the same area of a copied image obtained when copying is performed.
The number of white spots of m or less was counted. A: Very good.・ ・ ・: Very good. Δ: good ×: no problem in practical use

Image deletion: A Canon test chart (part number: FY9-9058) consisting of whole characters on a white background was placed on a document table, irradiated with a normal exposure, and a copy was taken. The obtained image was observed, and it was evaluated whether the thin lines on the image were connected without interruption by the following four steps. In addition, when there was unevenness in the image, the worst part in the whole image area was evaluated. A: Very good.・ ・ ・: Very good. Δ: good ×: no problem in practical use

Ghost: A ghost test chart (part number: FY9-9040, manufactured by Canon Inc.) having a reflection density of 1.
1. A black circle having a diameter of 5 mm of a ghost chart recognized on a halftone copy in a copy image obtained by placing a black circle having a diameter of 5 mm on a platen and overlaying a halftone chart made by Canon on the platen. And the reflection density of the halftone portion were measured and evaluated. A: Very good.・ ・ ・: Very good. Δ: good ×: no problem in practical use Table 30 shows the above results.

[0285]

[Table 30]

Example 40 In the same manner as in Example 39, two layers of a photoconductive layer and a surface layer were formed according to the production conditions shown in Table 31, to obtain a light receiving member for electrophotography. At this time, the content of hydrogen atoms and halogen atoms at the layer interface was adjusted in the same manner as in Example 39. next,
Sample preparation and evaluation were performed in the same manner as in Example 39, and the results are shown in Table 30.

[0287]

[Table 31]

Example 41 In the same manner as in Example 39, three layers of a charge injection blocking layer, a photoconductive layer, and a surface layer were formed in accordance with the manufacturing conditions shown in Table 32, to obtain a blocking type electrophotographic light receiving member. Obtained. At this time, the content of hydrogen atoms and halogen atoms at the layer interface was adjusted in the same manner as in Example 39. Next, a sample was prepared and evaluated in the same manner as in Example 39. The results are shown in Table 30.

[0289]

[Table 32]

Example 42 In the same manner as in Example 39, according to the production conditions shown in Table 33, four layers of an IR absorption layer, a charge injection prevention layer, a photoconductive layer, and a surface layer were formed. A light receiving member was obtained.
At this time, the content of hydrogen atoms and halogen atoms at the layer interface was adjusted in the same manner as in Example 39. Next, a sample was prepared and evaluated in the same manner as in Example 39. The results are shown in Table 30.

[0291]

[Table 33]

Example 43 In the same manner as in Example 39, four layers of a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer were formed according to the production conditions shown in Table 34, and A light receiving member for photography was obtained. At this time, the content of hydrogen atoms and halogen atoms at the layer interface was adjusted in the same manner as in Example 39. Next, a sample was prepared and evaluated in the same manner as in Example 39. The results are shown in Table 30.

[0293]

[Table 34]

Example 44 In the same manner as in Example 39, two layers of a photoconductive layer and a surface layer were formed according to the production conditions shown in Table 35 to obtain a light receiving member for electrophotography. At this time, the content of hydrogen atoms and halogen atoms at the layer interface was adjusted in the same manner as in Example 39. next,
Sample preparation and evaluation were performed in the same manner as in Example 39, and the results are shown in Table 30.

[0295]

[Table 35]

Comparative Examples 14 to 19 Various light-receiving layers were formed on an aluminum cylinder in the same manner as in Example 39 except that the content of hydrogen atoms and halogen atoms near the layer interface was not particularly manipulated. A receiving member was obtained. That is, (1) two layers of the charge injection blocking layer and the photoconductive layer under the manufacturing conditions of Table 29, (2) two layers of the photoconductive layer and the surface layer under the manufacturing conditions of Table 31, and (3) the manufacturing conditions of Table 32. (3) a charge injection blocking layer, a photoconductive layer, and a surface layer.
Four conditions of the IR absorption layer, the charge injection blocking layer, the photoconductive layer, and the surface layer under the preparation conditions of Table 33, and (5) the charge injection blocking layer, the charge transport layer, the charge generation layer, and the surface layer under the preparation conditions of Table 34 Four layers, and (6) two layers of a photoconductive layer and a surface layer under the production conditions shown in Table 35;
Was formed, and a sample was prepared from the obtained light receiving member and evaluated in the same manner as in Example 39. The results are shown in Table 30 as Comparative Examples 14 to 18 in the order of (1) to (5) above.

As is clear from Table 30, it was confirmed that the light receiving member of the present invention was superior to those of the comparative examples in the properties related to the traveling properties of the carrier.

Example 45 In the same manner as in Example 39, Examples 39 to 43 were used, respectively.
The light receiving member has the same layer structure as that of the above, and has a larger content of hydrogen atoms and halogen atoms in the vicinity of the interface between the support and the non-single-crystal layer than in the bulk layer of the non-single-crystal layer. did. When a sample was prepared and evaluated for the obtained light receiving member in the same manner as in Example 39, excellent characteristics similar to those in the above Example were recognized.

Example 46 In the same manner as in Example 39, the content of hydrogen atoms and halogen atoms in the vicinity of the layer interface was determined using Tables 25 and 26 of Example 34.
(However, the conditions of Example 39 were excluded), and a light receiving member having the same layer configuration as in Examples 39 to 43 was obtained, and the sample was evaluated. As a result, the hydrogen content of the hydrogen atom-rich region at the layer interface is 1.1 to 2.0 times that of the bulk layer, and the thickness of the region is 100 to 100%.
When the content of halogen atoms with respect to all constituent atoms in the halogen-rich region near the layer interface is 0.5 atomic ppm to 30 atomic% and the thickness of the region is 100 ° to 1 μm, As in the example,
Particularly excellent properties were observed.

Example 47 In the same manner as in Example 39, only the content of hydrogen atoms in the vicinity of an arbitrary layer interface was controlled, and light receiving members similar to Examples 41 to 44 were produced. When a sample was prepared and evaluated for the obtained light receiving member in the same manner as in Example 39, excellent characteristics substantially similar to those in the above Example were recognized.

Example 48 In place of halogen, fluorine, chlorine, bromine and iodine were used.
When samples were prepared and evaluated in the same manner as in Examples 39 to 47, excellent characteristics similar to those in the above Examples were recognized.

Embodiment 49 Using the RF plasma CVD apparatus shown in FIG. 14, according to each of Embodiments 39 to 48 except for Embodiment 42,
Where appropriate, two layers of a photoconductive layer-a surface layer, three layers of a charge injection blocking layer-a photoconductive layer-a surface layer, and four layers of a charge injection blocking layer-a charge transport layer-a charge generation layer-a surface layer are formed. Thus, a light receiving layer for electrophotography was obtained. About the obtained light receiving member, Example 3
Evaluation was performed in the same manner as in Example 9, and as a result, excellent characteristics similar to those in the above-mentioned Example were recognized.

[0303]

According to the method of the present invention, the hydrogen and / or halogen content in the vicinity of the interface between the non-single-crystal layers having different compositions (composition ratios) of at least two layers of the light-receiving layer is determined by the above-mentioned method. By controlling so that the content of hydrogen and / or halogen in the bulk of any of the layers becomes higher, the light responsiveness of the light receiving member is improved, and the fine line reproduction caused by uneven charging ability or uneven sensitivity is achieved. Deterioration of properties, white background fog, image unevenness, etc. can be suppressed.
It has become possible to obtain a high-quality nc-Si light-receiving member that does not adversely affect electrophotographic characteristics such as sensitivity and residual potential and does not adversely affect image characteristics.

Further, according to the present invention, it is possible to provide a light-receiving member 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. It has become possible.

When both hydrogen and halogen are contained, high-quality nc-, which causes less image deletion especially under strong exposure and does not adversely affect many image characteristics, is obtained.
A Si light receiving member was obtained. This was more pronounced than when the hydrogen content was increased near the interface.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram for explaining a layer configuration of a preferred example of an electrophotographic light-receiving member according to the present invention.

FIG. 2 is a schematic configuration diagram for explaining another preferred layer configuration of the electrophotographic light-receiving member according to the present invention.

FIG. 3 is a schematic configuration diagram for explaining a layer configuration of another preferred example of the electrophotographic light-receiving member according to the present invention.

FIG. 4 is a graph showing a change pattern of a hydrogen content in the vicinity of a layer interface in the present invention.

FIG. 5 is a graph showing a change pattern of a hydrogen content in the vicinity of a layer interface in the present invention.

FIG. 6 is a graph showing a change pattern of a hydrogen content in the vicinity of a layer interface in the present invention.

FIG. 7 is a graph showing a change pattern of a hydrogen content in the vicinity of a layer interface in the present invention.

FIG. 8 is a graph showing a change pattern of a hydrogen content in the vicinity of a layer interface in the present invention.

FIG. 9 is a graph showing a change pattern of a hydrogen content in the vicinity of a layer interface in the present invention.

FIG. 10 is a graph showing a change pattern of the hydrogen content in the vicinity of the layer interface in the present invention.

FIG. 11 is a graph showing a change pattern of a hydrogen content in the vicinity of a layer interface in the present invention.

FIG. 12 shows an example of an apparatus for forming a light receiving layer of a light receiving member for electrophotography according to the present invention,
(A) is a schematic longitudinal sectional view of an apparatus for manufacturing a photoreceptor member for electrophotography by a microwave discharge method, and (B) is an X-ray image of (A).
It is a schematic cross section in -X '.

FIG. 13 is a schematic view of an experimental apparatus for measuring photoresponsiveness and carrier traveling properties in an example of the present invention.

FIG. 14 is a schematic sectional side view of a light-receiving member manufacturing apparatus using an RF discharge method according to the present invention.

15 shows another example of the apparatus shown in FIG. 12, (A) is a schematic longitudinal sectional view of an apparatus for producing a photoreceptor for electrophotography by a microwave discharge method, and (B) is It is a schematic cross section in XX 'of (A).

[Explanation of symbols]

 REFERENCE SIGNS LIST 100 light receiving layer 101 support 102 photoconductive layer 103 surface layer 104 charge transport layer 105 charge generation layer 106 charge injection blocking layer 301 reaction vessel 302 microwave introduction dielectric window 303 waveguide 304 exhaust pipe 305 support 306 discharge Space 307 Heater 308 Bias electrode 309 DC power supply 310 Driving means 311 Rotation axis 400 Sample 401 Support 402 Light receiving layer 403 Conductive glass 404 DC power supply 405 Light source 406 Measurement means 501 Reaction chamber 502-506 Raw material gas cylinder 507-511 Mass flow controller 512 -516 Gas inflow valve 517-521 Gas outflow valve 522-526 Raw material gas cylinder valve 527-531 Pressure regulator 532,533 Auxiliary valve 534 Main valve 535 Leak valve 5 36 Vacuum gauge 537 Support cylinder 538 Heater 539 Motor 540 High frequency power supply

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 5-290561 (32) Priority date November 19, 1993 (November 19, 1993) (33) Priority claim country Japan (JP) (72) Inventor Ryuji Okamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Hiroyuki Katagiri 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Invention Person Satoshi Furushima 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-1-159664 (JP, A) JP-A-63-294569 (JP, A) JP-A-63 JP-A-273874 (JP, A) JP-A-63-273872 (JP, A) JP-A-6-11875 (JP, A) JP-A-5-181296 (JP, A) JP-A-3-223870 (JP, A) JP-A-5-134439 (JP, A) JP-A-4-352167 (JP , A) (58) Fields surveyed (Int. Cl. ⁷ , DB name) G03G 5/08

Claims (29)

(57) [Claims] 1. A light-receiving member comprising: a support; and a light-receiving layer in which at least two non-single-crystal layers each having at least a silicon atom and a hydrogen atom or a halogen atom are in contact with each other and laminated on the support. the light-receiving member having a number areas near the interface between the layers of the content contact with each of the hydrogen atoms and / or halogen atoms in the layer thickness direction of the layer. 2. A than the content of hydrogen atoms and / or halogen atoms of a portion of the layer excluding the area of any layer of the hydrogen atoms and / or halogen atom content of the phase contact two layers of the area The light-receiving member according to claim 1, wherein the number is greater. 3. The light receiving member according to claim 1, wherein the region has a thickness of 30% or less of a layer thickness. 4. The maximum concentration of hydrogen atoms and / or halogen atoms in the region where the content of hydrogen atoms and / or halogen atoms is increased in the vicinity of the interface between the layers is equal to the maximum concentration of hydrogen atoms and / or halogen atoms in the layer excluding the region. The light receiving member according to claim 2, wherein the light receiving member has an average concentration of 1.1 to 2.0 times the average concentration of halogen atoms. 5. The concentration of 1.1 to 2.0 times the concentration of the layer excluding the region where the average content of hydrogen atoms and / or halogen atoms is higher in the portion of the layer excluding the region of the adjacent layer. The light receiving member according to claim 4, wherein the value is a value with respect to an average density of a portion of the layer. 6. A thickness of the region in the case of only the hydrogen atoms are 100～5000A, claims 1 to 5 noise when containing a halogen atom is 100~10000Å
Light-receiving member according to Re preceding paragraph. 7. The light receiving member according to claim 1, wherein the region is provided on an interface side formed by layers that are in contact with each other . 8. The method according to claim 1, wherein the region is on an interface side formed by adjacent layers, and is included in both layers .
Light-receiving member according to any one. 9. At least one of the layers has a free surface, the area to claim 1 further comprising on the free surface side
7. The light-receiving member according to any one of 6 . 10. At least one of the layers is provided in contact with the support, the light of any one of claims 1 to 6 wherein the region has a side that further contact with the support of the layer Receiving member. 11. The light-receiving member according to any one of claims 1 to 10 the content of hydrogen atoms and / or halogen atoms is non-uniform in the layer thickness direction in the said region. 12. The light receiving member according to claim 1, wherein the laminated layers include a charge injection blocking layer and a photoconductive layer. 13. The light-receiving member according to claim 1, wherein the laminated layers include a charge transport layer and a charge generation layer. 14. The light-receiving member according to claim 1, wherein the laminated layers include a photoconductive layer and a surface layer. 15. The method according to claim 12, further comprising a surface layer.
4. The light receiving member according to 3. 16. A method according to claim 1, further comprising a charge injection blocking layer
5. The light receiving member according to 4 . 17. The hydrogen atom content of the region is 0.1
17. The method according to claim 1, wherein the content is at least 45 atomic% .
Item 2. The light receiving member according to item 1 . 18. The method of claim 1 to 16 Neu content of halogen atoms in the region is 0.5 atomic% to 30 atomic%
Zureka light-receiving member according to item 1. 19. is a content of 0.05 atomic% to 40 atomic% of hydrogen atoms of the layer excluding the region claims 1 to 1
7. The light-receiving member according to any one of 6 . 20. is a halogen atom content of 0.05 atomic% to 40 atomic% of the layer excluding the region claim 1 乃
17. The light receiving member according to any one of to 16 . 21. The layer contains hydrogen atoms and halogen atoms, and the sum of the content of halogen atoms and hydrogen atoms in the layer excluding the region is 0.05 atomic% to 50 atomic%. 17. The light receiving member according to any one of 1 to 16 . 22. The light-receiving member according to claim 1, wherein at least one of the non-single-crystal layers further contains an element belonging to Group III or V of the periodic table. 23. The light receiving member according to claim 1, wherein at least one of the non-single-crystal layers further contains at least one selected from the group consisting of carbon, nitrogen and oxygen. 24. The two non-single-crystal abutting layers are in contact with each other.
The light-receiving member according to claim 1, wherein the light-receiving member has a different composition . 25. The light receiving member according to claim 1, wherein the composition ratios of the elements constituting the two non-single-crystal adjacent layers are different. 26. The charge injection blocking layer according to claim 3, wherein
12 or 1 containing an element belonging to Group V or Group V.
7. The light receiving member according to 6 . 27. The light receiving member according to claim 14 , wherein the surface layer contains at least one element selected from the group consisting of carbon, nitrogen, and oxygen. 28. The content of a hydrogen atom and / or a halogen atom in the region has a maximum value at the interface.
3. The light receiving member according to 1. 29. The semiconductor device according to claim 1, wherein the region has silicon atoms, hydrogen atoms, and halogen atoms, and a portion of the layer excluding the region has substantially only silicon atoms and hydrogen atoms.
3. The light receiving member according to 1.