JPS61264346A - Photoreceptive member - Google Patents

Abstract

PURPOSE:To provide excellent moisture resistance, continuous repetitive use characteristic, voltage withstanding property and durability to using environment characteristic to a titled member and to improve the photosensitivity and dark resistance thereof by specifying the layer constitution of a photosensitive layer constituted of halogen-contg. hydrogenated amorphous silicon germanium. CONSTITUTION:This photoreceptive member consists of a base 101 and the photoreceptive layer laminated with the 1st layer 102 which is constituted of an amorphous material consisting basically of silicon atoms on the base 101 and has photoconductivity and the 2nd layer 103 which is constituted of an amorphous material consisting basically of silicon atoms and contg carbon atoms and material controlling conductivity. The photoreceptive layer contains the germanium atoms in the uniformly distributed state in the entire region of the 1st layer 102, contains the material controlling conductivity in the nonuniformly distributed state in the entire region or part of the region of the 1st layer 102 and contains the nitrogen atoms in either of at least the entire region of the 1st layer 102 and part of said region and the 2nd layer 103.

Description

[Detailed Description of the Invention] [Technical Field to which the Invention Pertains] The present invention relates to the use of light such as light (here, light in a broad sense, meaning ultraviolet rays, visible light, infrared rays, X-rays, γ-rays, etc.). The present invention relates to a light-receiving member sensitive to electromagnetic waves.

[Description of prior art]

As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it has high sensitivity and a high signal-to-noise ratio [photocurrent (Ip)].
/Dark current (Id)) is high, has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has the desired dark resistance value, and does not cause any pollution to the human body during use. In addition, solid-state imaging devices are required to have characteristics such as being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is important.

Based on these points, amorphous silicon (hereinafter referred to as a-8i) is a light-receiving member that has recently attracted attention. The use as an image forming member for electrophotography and the application to a photoelectric conversion/reading device are described in DE 2933411 A1.

However, the conventional photoreceptive member having a photoreceptive layer composed of a-3i has poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and usage environment characteristics. , and in terms of stability and durability over time, respectively.
Although efforts have been made to improve individual characteristics, the reality is that there is room for further improvement in terms of improving overall characteristics.

For example, when applied to electrophotographic image forming members, when trying to achieve high photosensitivity and high dark resistance at the same time, conventional methods often leave a residual potential during use. If you continue to use it repeatedly for a long time,
There are many disadvantages such as the accumulation of fatigue due to repeated use and the so-called ghost phenomenon, which causes afterimages.

In addition, when the photoreceptive layer is composed of a Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and control of electrical conductivity are added. For this reason, boron atoms, phosphorus atoms, etc., or other atoms for improving properties, are contained in the photoreceptive layer as constituent atoms. In this case, problems may arise in the electrical or photoconductive properties or electrical withstand voltage of the next layer formed.

That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoreceptive layer is not sufficient, the injection of charges on the support side in dark areas is not sufficiently prevented, or transfer There are image defects commonly called "white spots" on images transferred to paper, which are thought to be caused by local discharge breakdown phenomena, and "white streaks", which are thought to be caused by rubbing when a blade is used for cleaning. Image defects that are said to have occurred. Furthermore, if the product is used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image often occurs.

Furthermore, when the layer thickness exceeds 10-odd microns, the layer may lift or peel off from the support surface, or cracks may occur as the time elapses after it is left in the air after being removed from the vacuum deposition chamber for layer formation. It is possible to win by causing phenomena such as the occurrence of problems. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the electrophotographic field, and there are several problems that need to be solved in terms of stability over time. be.

Furthermore, a light-receiving member having a light-receiving layer composed of a-8i has high sensitivity over all wavelengths, and in particular, the light sensitivity in the long wavelength range is higher than that of selenium-based photoreceptors. It has excellent characteristics. However, in recent years, attempts have been made to put a laser printer using a semiconductor laser (770 to 800 μm) as a light source into practical use for electrophotography, and this type of printer is required to be faster. It has become necessary to further sensitize a photoreceptive member having a photoreceptive layer composed of , a-3i in the long wavelength range.

Therefore, while efforts are being made to improve the properties of the a-3i material itself, it is necessary to devise ways to solve all of the above-mentioned problems and to satisfy the above-mentioned requirements when designing light-receiving members. There is.

[Purpose of the invention]

It is an object of the present invention to solve the above-mentioned problems and to satisfy the above-mentioned requirements regarding a light-receiving member having a light-receiving layer made of a-8i.

That is, the main object of the present invention is to have electrical, optical, and photoconductive properties that are virtually always stable without depending on the usage environment, have excellent resistance to light fatigue, and do not deteriorate even after repeated use. It is an object of the present invention to provide a light-receiving member made of a-8i and having a fluorescent light-receiving layer, which does not cause any phenomenon, has excellent durability and moisture resistance, and has no or almost no residual potential observed.

Another object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-8i, which has high photosensitivity in the entire visible light range, has excellent matching properties with semiconductor lasers, and has a fast photoresponse. It is about providing.

Still another object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-8t, which has high photosensitivity, high signal-to-noise ratio characteristics, and high electrical voltage resistance.

Another object of the present invention is to have excellent adhesion between a layer provided on a support and the support and between each layer of laminated layers,
A-
An object of the present invention is to provide a light-receiving member having a light-receiving layer made of 3i.

Still another object of the present invention is to obtain high-quality images with high density, clear halftones, and high resolution without any image defects or image blurring even after long-term use. A light-receiving member for electrophotography having a light-receiving layer composed of a-3i? It is about providing.

Another object of the present invention is that when applied as an electrophotographic image forming member, it has sufficient charge retention ability during charging processing for electrostatic image formation.

The object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-8i and having excellent electrophotographic properties to which ordinary electrophotography can be applied very effectively.

[Structure of the invention]

The present invention achieves the above-mentioned object, and has the product feasibility and applicability of a-8i as a light-receiving member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive and intensive research including matters such as applicability, silicon atoms (St) and germanium atoms (Go) were discovered.
e An amorphous material as a matrix, especially an amorphous material that has silicon atoms and germanium atoms as a matrix and contains at least one of hydrogen atoms (H) or halogen atoms (force);
So-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter referred to as "a-8iGe (H,X) J".

] A light-receiving member created by specifying the layer structure of the light-receiving member having a layer region configured as described below,
It is not a fool's errand and exhibits extremely good photoreceptive properties in practical use, but it is superior in all respects to conventional light-receiving materials, and has particularly excellent properties as a light-receiving material for electrophotography. This was completed based on the discovery that this material has excellent absorption spectrum characteristics on the long wavelength side.

That is, the light-receiving member of the present invention includes a support and silicon atoms on the support. The first layer is composed of an amorphous material as a matrix and has photoconductivity, and the first layer is composed of an amorphous material as a matrix and has carbon atoms and conductivity as a matrix. A substance to control? and a second layer made of an amorphous material containing germanium atoms. The first layer contains a substance that is uniformly distributed in the entire layer area, and a substance that controls conductivity is distributed unevenly in the entire layer area or a part of the layer area of the first layer. and further, if necessary, the photoreceptive layer further contains oxygen atoms,
It is characterized in that it is contained in at least one of the entire layer region of the first layer, a part of the layer region, and the second layer.

As the amorphous material having a silicon atom as a host constituting the first layer, in particular, an amorphous material having a silicon atom (St)e host and containing at least one of a hydrogen atom (H) or a halogen atom (X). material, i.e. a
-8t(H,X)? : Use. A substance that uses silicon atoms as a parent body and controls carbon atoms (C) and conductivity, which constitutes the second layer? The containing amorphous material is particularly a silicon atom (St) as a matrix, and contains a carbon atom (C), a substance that controls conductivity, and at least one of a hydrogen atom (H) or a halogen atom (X). Amorphous material [hereinafter referred to as ra-8iCM(H,X)J (however,
M represents a substance that controls conductivity. ). )
Use.

The substances that control conductivity include so-called impurities in the semiconductor field, and atoms belonging to Group 1 of the periodic table (hereinafter simply referred to as "Group 1 atoms") that provide P-type conductivity. ), or an atom belonging to Group V of the periodic table (hereinafter simply referred to as "Group V atom") that provides n-type conductivity. Specifically, as the Group 1 atoms, B
(Boron)%At (Aluminum), Ga (Gallium)
, In (indium), Tt (thallium), etc., but 8% Ga is particularly preferably used. Also,
Group V atoms include P (phosphorus), As (arsenic), sb
Among them, P and AS are particularly preferably used. The conductivity-controlling substance contained in the first layer and the conductivity-controlling substance contained in the second layer may be the same or different.

By the way, the purpose of containing germanium atoms in the first layer of the light-receiving layer of the light-receiving member of the present invention is mainly to improve the absorption spectrum characteristics of the light-receiving member on the long wavelength side.

That is, by containing germanium atoms in a uniform distribution state in the first layer, the light-receiving member of the present invention has high photosensitivity over the entire visible light range and has good matching properties with a semiconductor laser. It has excellent properties and fast photoresponsiveness.

Further, in the light-receiving member of the present invention, the first layer, which is a substance that controls conductivity, is added to the entire layer region or a part of the layer region of the first layer.
It contains group atoms or group V atoms in a non-uniform distribution state, but the conductivity type and/or conductivity of the first layer can be changed by containing a substance that controls conductivity in the first layer. control, formation of a charge blocking layer, improvement of charge transfer between the first layer and the second layer, or increase in apparent dark resistance during charging treatment. It is. As will be described in detail later, whether the layer area of the first layer that contains the substance that controls conductivity is the entire layer area or a part of the layer area, or whether the conductivity that is contained in the first layer is The above-mentioned effects will differ depending on whether the conductivity type of the substance controlling conductivity is the same as or different from the conductivity type of the substance controlling conductivity contained in the second layer. It is necessary to appropriately select the layer region containing the substance that controls conductivity and the conductivity type of the substance that controls conductivity, depending on the expected effect.

Further, in the light-receiving member of the present invention, nitrogen atoms are uniformly or nonuniformly distributed in at least one of the entire layer region or a part of the first layer region and the entire layer region of the second layer. By containing nitrogen atoms in the first layer, high photosensitivity and high dark resistance of the light-receiving member, and between the support and the first layer or between the first layer and the second layer. This has effects such as improving adhesion between layers. Regarding these effects, whether nitrogen atoms are contained in the entire layer region of the first layer, in a part of the layer region of the first layer, or in the second layer. , or whether they are contained in a uniformly distributed state or in a non-uniformly distributed state.The layers or layer regions and distributions in which nitrogen atoms are contained are determined depending on the purpose and expected effect. It is necessary to select the state appropriately.

The second layer of the present invention is provided on the first layer in order to improve the moisture resistance, continuous repeated use characteristics, electrical pressure resistance, usage environment characteristics, and durability of the light receiving member, This can be achieved by including carbon atoms in the second layer. Furthermore, when such a second layer is provided on the first layer, problems such as the generation of residual potential and the generation of electrostatic charge marks during charging processing often occur. Is this problem caused by the inclusion of Group A atoms or Group II atoms, which are substances that control the conductivity of the metal? It can be prevented.

The first layer and second layer of the present invention contain hydrogen atoms (H) and/or halogen atoms (X) as needed. Specific examples of the halogen atom (X) include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. The amount of hydrogen atoms CH) or the amount of halogen atoms <X> contained in the first layer and the second layer of the present invention, or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is generally is I x 1
0 to 4 x 10 atomic %, preferably 5 x 10 to 3 x 10 atomic %, optimally I x 10 to 25 atomic %.

Hereinafter, the specific layer structure of the light-receiving member of the present invention will be explained in detail with reference to the drawings.

1 to 4 are detailed schematic diagrams illustrating the layer structure of the light-receiving member of the present invention, and in each figure, 100 is a light-receiving member;
101 is a support, 102 is a first layer, 103 is a second layer, 104 is a free surface, and 105 to 109 are layer regions.

Support The support 101 used in the present invention may be electrically conductive or electrically insulating. As the conductive support, for example, NiCr,
At, Cr%Mo%Au%Nb5Ta, V, Ti, P
Examples include metals such as t and Pb, and alloys such as [jt. As the electrically insulating support, polyester, polyethylene,
Films or sheets of synthetic resins such as polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, etc.
Examples include glass, ceramic, paper, etc. It is preferable that at least one surface of these electrically insulating supports is conductively treated, and a light-receiving layer is provided on the conductively treated surface side.

For example, if it is made of glass, there is NiCr on its surface.

htlCr, Mo, Au, Ir, Nb, Ta, V%Ti
1Pt 1Pd% In2O5, Snow, ITO
(rn, o, +5nOz), etc., or if it is a synthetic resin film such as a polyester film, NiCr%A1
%Ag, Pb, Zn, Ni%Au, Cr, M2
A thin film of metal such as S ■r, Nb%'l'a%V%'l'i, pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the above metal. and imparts conductivity to its surface. The support may have any shape such as a cylinder, a belt, or a plate. Its shape can be determined as appropriate depending on the purpose and desire, but for example, if it is used as an image forming member for electrophotography and for continuous high-speed copying, it may have an endless belt shape or a cylindrical shape. is desirable.

The thickness of the support is appropriately determined so as to form a light-receiving member of a desired thickness. However, if flexibility is required as a light-receiving member, the thickness of the support may be determined depending on its function as a support. It can be made as thin as possible within the range that allows for sufficient performance.

However, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 10μ or more.

The first layer 102 is provided on the support 101 and contains germanium atoms, group 1 atoms or group V atoms which are substances that control conductivity, and optionally nitrogen. It is composed of a-8i (H,X) containing atoms.

The germanium atoms are uniformly distributed over the entire layer region of the layer 102, and the group II atoms or group V atoms are distributed non-uniformly over the entire layer region or a part of the layer region. Furthermore, the nitrogen atoms are distributed in the layer 10.
It is distributed uniformly or non-uniformly in the entire layer area or a part of the layer area of 2. Here, the uniform distribution state means that the distribution concentration of the contained atoms is uniform both in the plane direction parallel to the support surface of the first layer and in the layer thickness direction of the first layer. A uniform distribution state means that the distribution concentration of the contained atoms is uniform in the plane parallel to the support surface of the first layer, but is non-uniform in the layer thickness direction of the first layer. thing? say.

Since the light-receiving member of the present invention contains germanium atoms in a uniform distribution in the entire layer region of the first layer 102,
Those with outstanding characteristics such as improved absorption spectrum characteristics on the long wavelength side, high photosensitivity in the entire visible light range from relatively short wavelengths to relatively long wavelengths, and fast photoresponsiveness. becomes. And those in the long wavelength range such as semiconductor lasers? When used as a light source,
Since the first layer 102 can substantially completely absorb light in the long wavelength range, it is possible to prevent the phenomenon of interference due to reflection from the support surface. Therefore, it is particularly important to include germanium atoms in the first layer. Is the amount of germanium atoms contained in the first layer the purpose of the present invention? It is determined as appropriate according to the desired characteristics that can be achieved, and is usually 1 to 6.
105105ato ppm, preferably 10
~3 x 10' atomic ppm, optimally I x 102-2 x 105105ato p
It is desirable to set it to pm.

Is the first layer of the present invention a group 1 atom or a group Ⅰ atom that is a substance that controls conductivity? As will be described later, the action and effect achieved by containing the atoms in the first layer depend on the distribution state of the atoms, or the conductivity type of the Group 1 atoms or Group V atoms contained in the first layer is different from that in the second layer. It differs depending on whether the conductivity type is the same as or different from the conductivity type of the Group 1 atom or Group V atom contained in the atom.

Therefore, in order to obtain a light-receiving member having desired characteristics according to the purpose, the layer region containing Group 1 atoms or Group V atoms in a non-uniform distribution should be the entire layer region. or some layer regions, and whether the conductivity type of the group 1 atoms or group V atoms is the same as that of the second layer or different? It is necessary to select appropriately. moreover,
The amount of group (III) atoms or group (III) atoms contained in the first layer also varies depending on the purpose and expected effect, so in order to obtain a light-receiving member with desired characteristics depending on the purpose, It is also necessary to appropriately select the amount of group (I) atoms or group V atoms to be contained in the first layer.

That is, when the entire layer region of the first layer contains Group 1 atoms or Group Ⅰ atoms, there is an effect of controlling the conductivity and/or conductivity of the first layer. In this case, the Group 1 atoms or V atoms contained in the first layer region
The amount of group atoms may be relatively small, typically I
-3 to 1x io atomic ppm,
Preferably 5 x 10"-" to 5 x 10"ato
mic ppm, optimally I x 10-”~2x
It is desirable to set it to 10 atomic ppm. Also, in this case, the conductivity contained in the first layer? The conductivity type of the substance to be controlled may be the same as or different from the conductivity type of the substance contained in the second layer, which will be described later.

Further, in the first layer, the content of Group 1 atoms or Group Ⅰ atoms is relatively large on the side in contact with the support.
When the content of Group A atoms or Group V atoms is made to be relatively small or substantially close to zero on the side in contact with the second layer, the content of Group A atoms or Group V atoms is A charge blocking layer is formed by the layer region containing a relatively large amount. In this case, the amount of Group 1 atoms or Group V atoms contained in the first layer is relatively large, usually 3 x 10 to 5 x 10 atoms.
mic ppm, preferably 5 x 10 to I
10' atomic ppm, optimally 1x10
2 to 5 x 103103ato ppm.

Next, the amount of Group 1 atoms or Group V atoms contained in the first layer is relatively large on the support side and decreases from the support side toward the interface with the second layer. What are some typical examples where Group 1 atoms or Group V atoms are distributed so that they are relatively small or virtually non-existent near the interface with the second layer? , and will be explained with reference to FIGS. 5 to 13, but the present invention is not limited to these examples.

In each figure, the horizontal axis shows the distribution concentration C of Group 1 atoms or Group V atoms, the vertical axis shows the layer thickness of the first layer 102, and t is the thickness between the support 101 side and the first layer. The interface position 21 tsubo indicates the interface position between the second layer 103 and the first layer.

FIG. 5 shows a first typical example of the distribution state of Group 1 atoms or Group Ⅰ atoms contained in the first layer in the layer thickness direction. In this example, up to the interface position t, where the first layer containing Group 1 atoms or Group V atoms and the support surface are in contact, and the position t1, the distribution concentration C of Group Ⅰ atoms or Group Ⅰ atoms is Assuming that CI is a constant value, the interface position t? where the first layer contacts the second layer is determined by the position. Until then, the distribution concentration C of group II atoms or group V atoms decreases continuously from the concentration C7, and the interface position t? In this case, the distribution concentration C of Group 1 atoms or Group V atoms is C5.

FIG. 6 shows one other typical example.

In this example, the Group I atoms or the Group V atoms contained in the first layer are
The distribution concentration C of the group atoms decreases continuously from the concentration C4 from the position tm to the position t7, and the distribution concentration C of the group atoms decreases continuously from the concentration C4 to the position t? The density becomes C3.

In the example shown in FIG. 7, from position t1 to position t2t, the first
The distribution concentration C of group atoms or group V atoms maintains a constant value of concentration C6, and the distribution concentration C of group 1 atoms or group V atoms gradually increases from the concentration C7 from position The distribution concentration C of Group V atoms or Group V atoms decreases continuously and becomes substantially zero at position 1T.However, here, substantially zero refers to the case where the amount is below the detection limit. .

In the example shown in FIG. 8, the distribution concentration C of Group 1 atoms or Group V atoms is at position t, and at position t! until the concentration C6
The distribution concentration C of Group 1 atoms or Group V atoms becomes substantially zero at position t〒.

In the example shown in FIG. 9, the distribution concentration C of Group 1 atoms or Group V atoms is between position t and position t.
, and from position t to position t, the density decreases in a negative order number from C0 to C,O.

In the example shown in FIG. 10, the distribution concentration C of the group V atoms or the group V atoms is until the concentration C is compared to the position - the position t.
From the position t4 to the position t↑, the concentration decreases in a linear manner from the concentration C,2 to the concentration CI3 at a constant value of 1l.

In the example shown in FIG. 11, the distribution concentration C of Group 1 atoms or Group Ⅰ atoms is from position t to position t! The concentration decreases in a linear manner from C14 until it becomes substantially zero.

In the example shown in FIG. 12, the distribution concentration C of group II atoms or group V atoms is the concentration C8 from position t to position -.
, decreases in a linear function until the concentration C0, and the position t
The density C, 6 is maintained at a constant value from , to position C.

Finally, in the example shown in FIG. 13, the distribution concentration C of group 1 atoms or group V atoms is the concentration CI □ at position tB, and from position t to position t6, the concentration C is slow at first from the concentration CI7. decreases rapidly near position t0,
At position -, the concentration is C111. Next, from position t6 to position brightness, the concentration decreases rapidly at first, then slowly decreases gradually, and at position 4, the concentration becomes CtO.

Further, between t7 and position -, it gradually decreases very slowly and reaches a density of 020 at position t. Well, on the next page, the position is from 8 to position t? The concentration gradually decreases from 02G until it reaches substantially zero.

As in the examples shown in FIGS. 5 to 13, the distribution concentration C of Group 1 atoms or Group V atoms is on the side of the first layer closer to the support.
In the case where the distribution concentration C has a part with a very low concentration or a part with a concentration substantially close to zero on the interface side of the first layer with the second layer, In this method, a localized region where the distribution concentration of group 1 atoms or group V atoms is relatively high is provided in a portion close to the support side, preferably from the interface position where the localized region At contacts with the support surface. By providing within 5μ, Group 1 atoms or V
The above-mentioned effect that the region having a high distribution concentration of group atoms forms a charge injection blocking layer can be achieved even more efficiently.

Also, contrary to the above case, a relatively large amount of Group 1 atoms or Group Ⅰ atoms, which are substances that control conductivity, are contained on the side of the first layer in contact with the second layer. In this case, if the conductivity types of the substances controlling conductivity contained in the first layer and the second layer are the same, the energy level consistency between the first layer and the second layer is improved, The effect of increasing charge transfer between both layers is achieved, and this effect is particularly noticeable when the second layer is thick and has a high dark resistance.

Furthermore, in the case where the first layer contains Group 1 atoms or Group V atoms, which are substances that control conductivity, in a relatively large amount on the side of the first layer in contact with the second layer, the first layer If the conductivity types of the substance controlling conductivity contained in the second layer and the second layer are different, the region of the next layer containing a large amount will actively act as a junction between the first layer and the second layer. The effect of increasing the apparent dark resistance during the charging process is achieved.

In either case, if a relatively large amount of Group (III) atoms or Group (V) atoms are contained in the side of the first layer that is in contact with the second layer, Some typical examples of the distribution state in the first layer of t are the typical examples shown in FIGS. Let the interface position between the layer 103 and the first layer 102 be t? The same explanation can be given by assuming that the position is the interface position between the support and the first layer. Then, on the side in contact with the second layer, Group 1 atoms or V
When a relatively large amount of group atoms is contained, the amount may be relatively small, usually 1 x 10-3 to I
103ato103ato, preferably 5X
10"-2~5 x 102102ato ppm
, optimally I x 10-” to 2 x 102ato
It is desirable to set it to 102ato.

As mentioned above, regarding the distribution state of Group Ⅰ atoms or Group V atoms,
Although the effects of each have been described individually, in order to obtain a light-receiving member having characteristics that can achieve the desired purpose, the distribution state of these Group 1 atoms or Group V atoms and the content in the first layer are important. i of the group 1 atoms or group V atoms that cause the i to be used in appropriate combinations as necessary,
Needless to say.

In the light-receiving member of the present invention, the photosensitivity and dark resistance of the first layer are increased by containing nitrogen atoms in the first layer, and further, the support and the first layer or the first layer are This improves the adhesion of the second layer.

The layer region of the first layer containing nitrogen atoms may be the entire layer region of the first layer, or may be a part of the layer region. Furthermore, the distribution state of nitrogen atoms in the layer region may be uniform or non-uniform. As described later, it depends on whether the layer region containing nitrogen atoms is the entire layer region or a part of the layer region, or whether the distribution state of nitrogen atoms in the region is uniform or non-uniform. Depending on the method, the effects produced will differ. Therefore, is there a photoreceptor member that can efficiently achieve the desired purpose and expected effects? In order to obtain this, it is necessary to appropriately select the layer region and distribution state in which nitrogen atoms are contained. Furthermore, the amount of nitrogen atoms contained in the first layer also differs depending on the desired effect, so in order to obtain a light-receiving member that achieves the desired purpose and effect, It is also necessary to appropriately select the amount of nitrogen atoms contained in the layer.

That is, as schematically shown in FIG. 1, when nitrogen atoms are contained in the entire layer region of the first layer, the effect of increasing the photosensitivity and dark resistance of the first layer is achieved.

In this case, the amount of nitrogen atoms contained in the first layer is relatively small in order to maintain high photosensitivity.

Further, as schematically shown in FIG. 2, nitrogen atoms may be contained in a uniform distribution in a part of the layer region 105 in contact with the support of the first layer, or nitrogen atoms may be contained in a uniform distribution in a part of the layer region 105 that is in contact with the support of the first layer. When nitrogen atoms are contained so that the distribution concentration of nitrogen atoms is relatively high on the side, the effect of improving the adhesion between the support 101 and the first layer is achieved.

Furthermore, as schematically shown in FIG. When nitrogen atoms are contained so that the distribution concentration of nitrogen atoms is relatively high on the side in contact with the layer, the effect is that the adhesion between the first layer and the second layer is improved. .

Furthermore, the effect of improving the adhesion between the first layer and the second layer can also be achieved by containing nitrogen atoms in a uniform distribution in the second layer, which will be described later. be.

Regarding the non-uniform distribution of nitrogen atoms in a relatively large amount on the support side of the first layer or the side of the first layer in contact with the second layer, as described above, the nitrogen atoms of Group 1 or V It is the same as when group atoms are distributed non-uniformly,
Typical examples thereof are shown in FIGS. 5 to 13, but the present invention is not limited to these examples.

When nitrogen atoms are included to improve the adhesion between the support and the first layer, or between the first layer and the second layer, the amount of nitrogen atoms contained in the first layer is determined by the amount of nitrogen atoms contained in the first layer. It is preferable to use a relatively large amount to ensure good performance.

Furthermore, as mentioned above, in the present invention, it is possible to improve the adhesion between the support and the first layer by containing nitrogen atoms at a relatively high concentration on the side of the first layer that is in contact with the support. However, in this case, by providing localized regions containing nitrogen atoms at a high concentration, the adhesion can be further improved. If such localized regions are described using the symbols shown in FIGS. 5 to 13,
Interface position 1. It is desirable to provide the nitrogen atoms within 5 μm, and such localized regions are located in some layer regions 1 containing nitrogen atoms.
It may be all of 05, or it may be a part of some layer regions.

The effects of each of the distribution states of nitrogen atoms have been described above, but in order to achieve two or more of these effects simultaneously in the light-receiving member of the present invention, a layer containing nitrogen atoms is required. It goes without saying that the regions and nitrogen atom distribution states may be appropriately combined.

For example, in order to improve the adhesion between the support and the first layer and to improve the photosensitivity and dark resistance of the first layer, it is necessary to Nitrogen atoms may be distributed so that the concentration is relatively high on the body side, and nitrogen atoms are distributed so that the concentration is relatively low in other layer regions.

In the present invention, the amount of nitrogen atoms contained in the first layer is determined based on the properties required for the first layer itself, or when nitrogen atoms are contained in a part of the layer region in contact with the support or the second layer, the amount of nitrogen atoms in the adjacent layer is It is determined by considering the mutual and organic relationship, such as the relationship with the characteristics of the layer or support, and usually I
The range is 10'-3 to 50 atomic%, preferably 2x10-3 to 40 atomic%, most preferably 3x10-3 to 30 atomic%. Well, if nitrogen atoms are contained in the entire layer region of the first layer, or if the proportion of a part of the layer region containing nitrogen atoms in the first layer is sufficiently large, the amount of nitrogen atoms can be increased. It is desirable that the upper limit of is sufficiently smaller than the above value. For example, when the layer thickness of a part of the layer region containing nitrogen atoms is two-fifths or more of the layer thickness of the first layer, the amount of nitrogen atoms to be contained in the part of the layer region The upper limit of is usually 30 at
omic%, preferably 20 atoms
ic, the optimum value is 10 atomic% or less.

Furthermore, when forming a localized region containing a high concentration of nitrogen atoms, the maximum value CmX of the distribution concentration of nitrogen atoms is usually 5 x 10210 as the distribution state of nitrogen atoms in the layer thickness direction.
2ato ppm or more, xp preferably 8 x 102
102ato ppm or more, optimally 1x103103
It is desirable to form a distribution state in which the amount is at least ppm.

In the present invention, the above-mentioned effects are obtained by containing nitrogen atoms in the first layer.
In order to further enhance these effects, the first layer may further contain oxygen atoms in addition to the nitrogen atoms mentioned above. (9) As mentioned above, the nitrogen atoms of the present invention may be contained in the second layer, but in this case as well, oxygen atoms may be further contained for the same purpose. When containing oxygen atoms, their distribution state and content are the same as those for nitrogen atoms, that is,
When the main purpose is to increase the photosensitivity and the dark resistance, it is contained in the entire layer area of the first layer, and the amount thereof is relatively small. Improved adhesion between layer and second layer? When the main purpose is to reduce the amount of water, as shown in Figures 2 and 3 above, a relatively large amount may be distributed uniformly or non-uniformly in some layer areas of the first layer. Make it contain. The layer area, content, or distribution of nitrogen atoms and oxygen atoms may be the same or different.

As explained above, the first layer of the present invention contains a germanium atom, a Group 1 atom or a Group V atom, a nitrogen atom, or an oxygen atom, and each of these atoms contains In order to efficiently obtain the desired properties aimed at in the present invention, the content of each atom and the distribution state of each atom are appropriately selected and used, and the layer regions containing each atom are different from each other. You can also
Furthermore, they may partially overlap each other. Below, Part 1 is shown in Figure 4.
An example is shown, but the present invention is not limited by the layer. In the example shown in FIG. 4, the first layer consists of layer regions 107, 108, and 109 from the support side, and the layer region 107 contains Group 1 atoms or Group V atoms. atom? The layer region 108 is assumed to contain a high concentration of germanium atoms and oxygen atoms.
It contains a group atom or a group V atom at a low concentration, and further contains a germanium atom and an oxygen atom.

It is assumed that the layer region 109 does not contain group (I) atoms, group (II) atoms, or oxygen atoms, but only germanium atoms.

The layer thickness of the first layer 102 is one of the important factors for efficiently achieving the objective of the present invention, and is determined as appropriate depending on the desired objective.

Further, germanium atoms contained in the first layer,
Depending on the required properties, such as the amount of group atoms or group Ⅰ atoms, nitrogen atoms, oxygen atoms, hydrogen atoms and/or halogen atoms, or the relationship between the mutual layer thickness of the first layer and the second layer, etc. It is also necessary to make decisions based on mutual and organic relationships. Furthermore, it is necessary to take into account productivity and mass production, and to give sufficient consideration to economic efficiency.

For this reason, the thickness of the first layer is usually 1 to I
102μ, preferably 1 to 80μ, optimally 2
It is desirable to set it to ~50μ.

The second layer 103 of the light-receiving member of the present invention is a-8iC (
H,
It is provided on the first layer for the purpose of improving moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability, etc.

This objective can be achieved by structurally introducing carbon atoms into the amorphous material constituting the second layer. When carbon atoms are structurally introduced into the second layer, the above-mentioned properties improve as the amount of carbon atoms increases;
Too high an amount of carbon atoms reduces the layer quality and also reduces the electrical and mechanical properties. For this reason, the carbon atom content is usually 1 x 10-3 to 90 atOmiC, preferably 1 to 90 atomic%, most preferably 10 to 80 atomic%.

Further, in order to improve the characteristics of continuous repeated use and durability, it is preferable to increase the thickness of the second layer, but a thick layer causes residual potential to occur. The generation of such a residual potential can be prevented or suppressed to the extent that there is no substantial effect by including a substance that controls conductivity in the second layer, that is, a group 1 atom or a group Ⅰ atom. can do. In addition, although this type of second layer normally has excellent mechanical durability, if the surface of the layer is rubbed or pressed with something with a sharp tip, the surface may be damaged. Even if they do not remain as so-called scratches, they often appear as electrostatic traces during the charging process, resulting in a deterioration in the image quality of the toner-transferred image. In such cases, is there a substance that controls the aforementioned conductivity in the second layer? By including it, such problems can be prevented from occurring. Therefore, by including group (III) atoms or group (III) atoms, which are substances that control conductivity, in the second layer, it is possible to create a second layer having the desired properties that can achieve the object of the present invention. It is important to form. The amount of Group 1 atoms or Group V atoms contained in the second layer is usually 1.0 to 10' atomic pp
m, preferably 10 to 5 x 103103a
to ppm, optimally 102″'5X 10310
3ato ppm and Runoka Nozomi.

The second layer 103 of the light-receiving member of the present invention includes the first layer 1
In order to improve the adhesion between 02 and the second layer 103,
Nitrogen atoms or oxygen atoms may be contained in the entire layer region of the layer 103 in a uniform distribution state, especially when the first layer 102 contains at least nitrogen atoms and also no oxygen atoms. , the second layer 103 contains at least nitrogen atoms and, if necessary, oxygen atoms. The amount of nitrogen atoms or oxygen atoms contained in the second layer 103 is usually I x 10''-3 to 50
atomic%, preferably 2×10'
−3 to 40 atomic%, optimally 3×10−3 to
It is set to 30 atomic%.

The second layer 103 must be carefully formed to obtain the desired properties. That is, a silicon atom, a carbon atom, a hydrogen atom and/or a hydrogen atom, and a first
Substances whose constituent atoms are group atoms or group V atoms vary in form from crystalline to amorphous depending on the content of each constituent atom and other preparation conditions, and their electrical properties range from conductivity to conductivity. From semiconductivity to insulating properties, and photoelectric properties from photoconductive to non-photoconductive properties? , respectively, it is important to select the content of each constituent atom, production conditions, etc. so that the second layer 103 containing desired characteristics according to the purpose can be formed.

For example, when the second layer 103 is provided with the main purpose of improving electrical withstand voltage, the amorphous material constituting the second layer 1031 is a material that exhibits remarkable electrical insulating behavior under the usage conditions. form as. In addition, when the second layer 103 is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the second layer 103''f and the constituting amorphous material have the above-mentioned electrically insulating properties. Although the degree is moderated to some extent, it is formed to have a certain degree of sensitivity to the irradiated light.

Also, in the present invention, is the layer thickness of the second layer also an object of the present invention? This is one of the important factors for efficiently achieving this, and is determined as appropriate depending on the intended purpose, but the Group 1 atoms, Group V atoms, and carbon atoms contained in the layer It is necessary to mutually and organically determine the amount of hydrogen atoms, nitrogen atoms, and hydrogen atoms, or the properties required for the second layer. Furthermore, it is also necessary to consider economic efficiency, which also takes into account productivity and mass production. For this reason, the layer thickness of the second layer is usually 3 x 10-3 to 30μ.
However, more preferably 4 x 10-3 to 20μ,
Particularly preferably, it is 5 x 10'' to 10μ.

By having the above-mentioned layer structure, the light-receiving member of the present invention can solve all of the problems of conventional light-receiving members having a light-receiving layer made of amorphous silicon, and has extremely excellent secondary electrical properties. , optical, photoconductive properties, electrical voltage resistance and usage environment characteristics? It also has high photosensitivity in the entire visible light range, and has excellent matching with semiconductor lasers.
In addition, it has outstanding characteristics such as fast photoresponsiveness. When the light-receiving member of the present invention is applied as an image forming member for electrophotography, there is no influence of residual potential on image formation, its electrical characteristics are stable, high sensitivity, and a high signal-to-noise ratio. It has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

Further, in the light-receiving member of the present invention, the light-receiving layer formed on the support has a strong layer structure, and also has good adhesion to the support and adhesion between the layers provided on the support. Because of its excellent properties, it can be used repeatedly at high speed for long periods of time.

Next, a method for forming the photoreceptive layer of the present invention will be explained.

The amorphous material constituting the photoreceptive layer of the present invention is deposited by a vacuum deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blasting method. These manufacturing methods depend on the manufacturing conditions and the amount of equipment capital investment.

They are selected and adopted as appropriate depending on factors such as the production scale and the desired characteristics of the light-receiving member to be produced, but the conditions for producing the light-receiving member with the desired characteristics are relatively easy to control. The glow discharge method or the sputtering method is preferable because carbon atoms and hydrogen atoms can be easily introduced together with reeds and silicon atoms.

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

For example, a-8iQe(H,X
), basically, a raw material gas for Si supply that can supply silicon atoms (Si)e, a raw material gas for Ge supply that can supply germanium atoms (Ge)e, and a raw material gas for Ge supply that can supply germanium atoms (Ge)e. Accordingly, a raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure,
A glow discharge is generated in the deposition chamber, and a-8iGe (H
, X). In addition, when forming by sputtering method, for example, in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases,
When sputtering using two targets, one composed of i and one composed of Ge, or a mixed target of Si and Ge, hydrogen atoms (H) or/and A gas for introducing halogen atoms (X) may be introduced into a deposition chamber for sputtering.

Compounds that can be used as raw material gas for supplying Si used in the present invention include SiH4% S 1tHa, S
Examples include gaseous or gasifiable silicon hydride (7ranes) such as tsI (as S 14Hto),
In particular, SiH4 and S12)Ls are preferred from the viewpoint of ease of handling during layer forming work, good Si supply rate, etc.

As a compound that can be used as a raw material gas for supplying Ge, Ge
H4, G%&, Ge5Hss Ge4Hton Ge5
Grts GeaHn, Ge, H, 6, Ge, H,...
GeH4, Ge
2Ha, Ge5Hs are preferred.

There are many halogen compounds that are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas.

Gaseous or gasifiable halogen compounds such as halides, interhalogen compounds, halogen-substituted silane derivatives are preferred.

Furthermore, a silicon hydride compound containing a silicon atom, a halogen atom, and a gaseous or gasifiable halogen atom as a total constituent may also be mentioned as an effective compound.

Specifically, halogen compounds that can be preferably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, and CtF.

C6Fss B"Fss BrF,, ENGF',,IF
Examples include interhalogen compounds such as 711CLs IBr.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
I F4 s S 12Fa, 5jC4, 5tBr+
Preferred examples include silicon halides such as .

When employing such a silicon compound containing a halogen atom and using a glow discharge method to form the light-receiving member of the present invention, hydrogenation as a raw material gas that can be supplied as a Si along with a raw material gas for supplying Ge. A layer of a-5ice containing nitrogen atoms on a desired support without the use of silicon gas? can be formed.

Silicon halide as a gas, germanium hydride as a raw material gas for supplying Ge, and a gas such as Ar%He are mixed at a predetermined mixing ratio and gas flow rate to form a first layer region (deposition layer). Although a layer can be formed on a desired support by introducing these gases into a chamber and generating a glow discharge to form a plasma atmosphere of these gases, it is easier to control the ratio of hydrogen atoms introduced. In order to obtain the desired result, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer.

Moreover, each gas may be used not only singly but also in a mixture of multiple types at a predetermined mixing ratio.

In order to form a layer made of a-8I Ge (H, Alternatively, a target rattler consisting of Si and Ge is used and sputtered in a desired gas plasma atmosphere, and in the case of an ion blasting method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are sputtered. are housed in the evaporation ports as evaporation sources, and the evaporation sources are heated and evaporated by a resistance heating method or an electron beam method (EB method), and the flying evaporates are passed through a desired gas plasma atmosphere.

At this time, whether halogen atoms are present in the layer formed in either the sputtering method or the ion blating method. In order to introduce the gas, a gas of the halogen compound or a silicon compound containing the halogen atom may be introduced into the deposition chamber to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, gases such as silanes or the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of gases.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, % HF, HCl.

Hydrogen halides such as HBr, HI, SiH2F2%
SiH2F2.5IH2C4% 5IHCt3.81
Halogen-substituted silicon hydrides such as H2Brz s 5tHBr3, and GeHF, , GeH2F, , GeH,
F.

GeHC4, GeH2CAts GeH3C2% G
eHB r3% GeH2B r2, GeH, Br%
Hydrogen atoms such as GeHI, GeH21, GeHaI, etc. Halides containing hydrogen atoms as one of their constituents such as germanium, GeF, GeC1
,,GeBr,,GeI4%GeF2%GeC
Gaseous or gasifiable substances such as kermanium halides such as 4% Ge13r, % GeI2, etc. may also be mentioned as useful starting materials for the formation of a-8iGe(H,X).

Among these substances, halides containing hydrogen atoms are
When forming a-8iGe (u, It can be used as a raw material.

In order to structurally introduce a hydrogen atom into a-8iGe (H,
Silicon hydride such as 2H1l, 5isL, 5i4H1o, etc. with germanium or germanium compound for supplying Ge, or GeH4, Ge2H1l, Ge5Hs
, Cxe4H10s Ge5Hr□, Ge2H1l,
Ge? Germanium hydride such as H□, , Ge, H, , Ge2H1l and silicon or silicon compound for supplying Stt coexist in the deposition chamber and discharge? This is also possible by causing it to occur.

In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in a-8iGe (H, The sum of the amounts of atoms (H+X) is usually 0.0
1-40 atomie%, preferably 0.05-3
0 atomic%, optimally 0.1-25 atom
It is desirable to set it as ic%.

a-3iGe (H,X) using glow discharge method, sputtering method or ion blating method
A layer composed of an amorphous material containing group atoms or group II atoms, nitrogen atoms, oxygen atoms, or carbon atoms? In order to form a layer composed of a-8iGe (H, a
-8iGe (H,

For example, in order to form a layer or a layer region composed of a-S x Ge (Ht
e (H,
By mixing diluent gas such as Ar gas at a predetermined mixing ratio,
The support 101 is introduced into a vacuum deposition chamber where the support 101 is installed, and the introduced gas is turned into gas plasma by generating a glow discharge to form Group (I) or Group V atoms on the support (101). What is necessary is just to deposit a-8iGe(H,X) contained therein.

As a starting material for such introduction of Group 1 atoms or Group V atoms, are gaseous substances or substances that can be gasified containing Group 1 atoms or Group Ⅰ atoms as constituent atoms? Any gasified material may be used.

In the present invention, starting materials that can be effectively used for introducing boron atoms include BtHa, B4H101B6HO1BsHn,
sBaHx. , B, H, , , boron hydride such as P6H14, BF, , boron halide such as BC4% BBr3, etc. In addition, %AtC15%G
&C15s InC4, TtCl, etc. may also be mentioned.

In the present invention, the starting materials that are effectively used for introducing Group V atoms are, specifically, those for introducing phosphorus atoms:
Hydrogen ratios such as PH3, P2H4, PH, I, P F, s
P Fa s PO21PC4, PBr3, PB
Examples include halogen ratios such as r, , and PIs. Others s AsH3, A8Fs s A8Ct5, ASBra
%ASFs, 5bHs, SbF3% SbF5
．． 5bCt, , 5bCts, BiH3, BiCz,
, B1Br5, etc. can also be mentioned.

For example, to form a nitrogen atom-containing amount or layer region, the starting material for nitrogen atom introduction may be added to the a-8i
It is used in conjunction with a layer-forming starting material consisting of Ge(H,

That is, in order to form a layer or a layer region containing nitrogen atoms using the glow discharge method, the above-mentioned a-8iQe(H,X)
A material selected as desired from among the starting materials used when forming a layer composed of by glow discharge method,
Starting material for the introduction of nitrogen atoms is added. For example, a raw material gas containing silicon atoms (St)' as constituent atoms, a raw material gas containing germanium atoms (Ge)e constituent atoms, a raw material gas containing nitrogen atoms (N), and hydrogen atoms as necessary. (H) or a raw material gas containing halogen atoms (X) are mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si)e and germanium atoms ( A raw material gas containing GO)' as constituent atoms and a raw material gas containing nitrogen atoms (N) and hydrogen atoms (H) can also be used by mixing them at a desired mixing ratio. can.

Separately, germanium atoms (Ge) are added to a raw material gas whose constituent atoms are silicon atoms (Si) and hydrogen atoms (H).
Raw material gas and nitrogen atom (N)' as constituent atoms of i
It is also possible to use a mixture of raw material gases as constituent atoms.

The starting material for introducing nitrogen atoms may be any gaseous substance having at least nitrogen atoms as a constituent atom, or any substance that can be gasified.

Specifically, starting materials for introducing nitrogen atoms include nitrogen (N2) and ammonia (NH3), which have a nitrogen atom as a constituent atom or a nitrogen atom and a hydrogen atom as constituent atoms.
, hydrazine (H, NNL), hydrogen azide (HN, )
, nitrogen such as ammonium azide (NH4N3), and nitrogen compounds such as nitrides and azides.

In addition, nitrogen trifluoride (F3N), nitrogen tetrafluoride (F4N)
Examples include halogenated nitrogen compounds such as
When using these halogenated nitrogen compounds, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced.

In the present invention, as mentioned above, in order to further enhance the effect obtained by containing nitrogen atoms, oxygen atoms can be further contained in addition to nitrogen atoms. As the raw material gas for introducing the ninth oxygen atom, for example, oxygen (02), ozone (O
3), -nitrogen oxide (No), nitrogen dioxide (NO2),
-Nitrogen dioxide (N20), nitrogen sesquioxide (N20s
) -trinitric oxide (Nt 04 ), nitrogen sesquioxide (
N20!1), nitrogen trioxide (NO3), silicon atoms (
Si), oxygen atom (0), and hydrogen atom (H) as constituent atoms, for example, disiloxane (H,5iO8iH,)
, trisiloxane (Has iOS 1H20S IH
Examples include lower siloxanes such as 3).

To form a layer region containing nitrogen atoms by a sputtering method, a monocrystalline or polycrystalline Si wafer, a Si, N, wafer, or a wafer containing a mixture of Si, Si, and N4 is used as a target. ,
These steps may be performed by sputtering in various gas atmospheres.

For example, when used as a Si wafer target, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluting gas as necessary, and a deposition chamber for sputtering is prepared. The Si wafer 2 is then introduced into the Si wafer 2 to form a gas plasma of these gases.
All you have to do is ring Supatutatei.

Alternatively, by using Si and Si3N as separate targets, or by using a single target containing a mixture of 3i, Si, and N4, it is possible to use a diluted gas atmosphere as a sputtering gas or at least hydrogen. Atom (H)
Or/and by sputtering in a gas atmosphere containing halogen atoms (X)'i- as constituent atoms. As the raw material gas for nitrogen atom introduction, the raw material gas for nitrogen atom introduction among the nine raw material gases shown in the glow discharge example described above can also be used as an effective gas in the case of sputtering.

To form a layer containing oxygen atoms by a sputtering method, a single crystal or polycrystalline Si wafer or an S
Sputtering may be performed using an iO□ wafer or a wafer containing a mixture of Si and SiO□ as a target in various gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gas for introducing oxygen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as necessary, and the material gas is diluted with a diluent gas as necessary to create a deposition chamber for sputtering. The Si wafer may be sputtered by introducing the Si wafer into the Si wafer and forming a gas plasma of these gases.

Alternatively, Si and SiO□ can be used as separate targets, or by using one mixed target of Si and 5iO2, in an atmosphere of diluent gas as a sputtering gas, or at least hydrogen atoms (H) can be used. or/and by sputtering in a gas atmosphere containing halogen atoms as constituent atoms.

As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

For example, the second layer is a-8iC(H,X)C or less, a-stcM(H,X
) (However, M represents a Group 1 atom or a Group V atom.)
It is written as. ], but in order to form the second layer by the glow discharge method, a-8iCM (H
, A-8iCM (H
, X) f: Just deposit it.

As the raw material gas for a-8iCM(H,X) formation, 5
i1 Any gaseous or gasifiable substance whose constituent atoms are at least one of C, H and/or halogen atoms, and Group 1 atoms or Group V atoms. It may be something.

Si% When using a raw material gas containing St as one of the Group 1 atoms or Group Ⅰ atoms of C, H and/or halogen atoms, for example, the raw material gas containing Si mirror atoms and , a raw material gas containing Ct constituent atoms, a raw material gas containing H and/or halogen atoms, and a raw material gas containing Group 1 atoms or Group V atoms in a desired mixing ratio. Or, the raw material gas and C and H and/or halogen atoms as the sir constituent atoms? Either the raw material gas containing constituent atoms and the raw material gas containing Group 1 atoms or Group V atoms are mixed at a desired mixing ratio, or the raw material gas containing gx k constituent atoms ,
A raw material gas containing three of Si, C, H and/or halogen atoms as constituent atoms and a raw material gas containing Group 1 atoms or Group V atoms can be mixed and used.

Alternatively, a raw material gas containing Si, H and/or halogen atoms as constituent atoms, a raw material gas containing C as constituent atoms, and a raw material gas containing Group 1 atoms or Y group atoms as constituent atoms are mixed. You may also use it as

5iH4s 5itHa s 51sHa , 5L whose constituent atoms are Si and H are effectively used as raw material gas for forming a layer composed of a-8iC(H,X).
Silicon hydride gas such as silane (5itane) such as 4H10, which has C and H as constituent atoms, for example, carbon number 1~
4 saturated hydrocarbons, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (CtHa), propane (CA), n-butane (n-C4Hto), pentay (C5Htt),
Ethylene hydrocarbons include ethylene (C+H4),
Propylene (C5Ha), Butene-X (C+H8),
Butene-2 (C4H8), imbutylene (CA), pentene (C@HIO), acetylene hydrocarbons include acetylene (CtH2'), methylacetylene (0
3H4), butyne (C4H6), and the like.

As a raw material gas containing Si, C, and H as constituent atoms, s
Alkyl silicides such as St (CH3)4 and St (C2H6)4 can be mentioned. In addition to these raw material gases, H7 can of course also be used as the raw material gas for H introduction.

Specifically, starting materials for the introduction of Group 1 atoms include B2H6, B4HIO, B5HQ, B2H6, B4HIO, B5HQ, and
sHo %Ba Hto s BISHst, BJ(1
Examples of sieves include boron hydrides such as No. 4, boron halides such as BF3, BO2, BBr, and the like.

In addition, AtC45GaC4%Ga (CH3)! ,
I nC4s TtCls and the like can also be mentioned.

As a starting material for introducing Group 1 atoms, specifically for introducing phosphorus atoms, hydrogen ratios such as PHs%PzH<, PH
4I% PF3s PFs, PCLs, P C4
Examples include sPBrs, PBr, , Pl, etc. with a halogen ratio. In addition, ASHs, ASFa, A3
Cl3 s AS Bra s ASFs, 5bHa,
5k) Fs, 5bFa, 5bcz, % 5bCt
5% BiH3% B1C43, BIBrs etc. are also the first
These can be mentioned as effective starting materials for the introduction of group atoms.

To form the second layer composed of a-3iCM (H, Sputtering is performed using a wafer as a target in a desired gas atmosphere.

For example, when using Si Milani as a target, the raw material gas for introducing carbon atoms, Group 1 atoms or Group V atoms, and hydrogen atoms and/or halogen atoms may be Ar, Ar, or It is sufficient to dilute it with a diluent gas such as He, introduce it into a deposition chamber for sputtering, form a gas plasma of this gas, and sputter Si Milaninol.

In addition, when Si and C are used as separate targets or when Si and C are used as a mixed target, Group 1 atoms or Group V atoms and hydrogen atoms are used as the sputtering gas. Or/and the raw material gas for introducing halogen atoms may be diluted with a diluting gas as necessary and introduced into a deposition chamber for sputtering to form gas plasma and perform sputtering.

As the raw material gas for introducing each atom used in the sputtering method, the raw material gas used in the glow discharge method described above can be used as is.

As described above, the first layer and the second layer of the light-receiving layer of the light-receiving member of the present invention are formed using a glow discharge method, a sputtering method, etc. Germanium atoms, Group 1 atoms or Group V atoms contained in the layer
group atoms, nitrogen atoms or even oxygen atoms, carbon atoms,
Alternatively, the content of hydrogen atoms and/or hydrogen atoms can be controlled by the gas flow rate of each atom-supplying starting material flowing into the deposition chamber or the gas flow rate between each atom-supplying starting material. This is done by controlling the ratio.

Furthermore, conditions such as the support temperature, gas pressure in the deposition chamber, and discharge power during the formation of the first layer and the second layer are important factors in order to obtain a light-receiving member with desired characteristics. , is selected appropriately taking into consideration the function of the layer to be formed. Furthermore, since these layer formation conditions may differ depending on the type and amount of each of the atoms mentioned above to be contained in the first layer and the second layer, consideration should be given to the type and amount of the atoms to be contained. You also need to make a decision.

Specifically, 7I21 contains a Group 1 atom or a Group V atom, and a carbon atom, a nitrogen atom, or an oxygen atom.
．． When forming a layer consisting of a-8t (H,

The gas pressure in the deposition chamber is usually between o, oi and I Torr, particularly preferably between 0.1 and Q, 5 Torr. Friend, the discharge power is usually 0.005 to 50 W/-, but preferably 0.01 to 30 W/-.
-1 Particularly preferably o, oi to 20 W/i.

When forming a layer consisting of a-8ice (H2X), or when forming a layer consisting of a-8iGe (H2X) containing Group 1 atoms or Group V atoms, nitrogen atoms, oxygen atoms, etc. , the support temperature is usually 50~
The temperature is 350°C, preferably 50 to 300°C, particularly preferably 100 to 300°C. The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, but
Preferably, it is 0.001 to 3'1'orr, particularly preferably 0.1 to ITOrr. Further, the discharge power is usually 0.005 to 50 W/cn, preferably 01 to 30 W/cd, and particularly preferably 0.01 to 20 W/cd.

However, the specific conditions for layer formation, such as support temperature, discharge power, and gas pressure in the deposition chamber, are usually difficult to determine individually. Therefore, in order to form an amorphous material layer with desired characteristics, it is desirable to determine optimal conditions for layer formation based on mutual and organic relationships.

By the way, in the present invention, germanium atoms, Group 1 atoms, or Group V atoms contained in the first layer and the second layer are
In order to make the distribution state of group atoms, nitrogen atoms, oxygen atoms, and carbon atoms uniform, it is necessary to keep the above conditions constant when forming the first layer and the second layer. be.

Further, in the present invention, when forming the first layer, the distribution concentration of Group 1 atoms, Group V atoms, nitrogen atoms, or oxygen atoms contained in the layers is changed in the layer thickness direction to form a desired layer. In order to form the first layer having a distribution state in the thickness direction, if the glow radiation method is used, a starting material for introducing Group 1 atoms or Group V atoms, a starting material for introducing nitrogen atoms, or The gas flow rate when introducing the gas of the starting material for introducing oxygen atoms into the deposition chamber is changed as appropriate according to the desired rate of change, and other conditions are kept constant.

In order to change the gas flow rate, the gas flow rate can be changed by using any commonly used method, such as manually or using an externally driven motor, by opening a predetermined needle pulp in the middle of the gas flow path system. What is necessary is to perform an operation to gradually change the value. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a ratio change rate curve designed in advance to obtain a desired content rate curve.

In addition, when forming the first layer using a sputtering method, the distribution concentration of Group 1 atoms, Group Ⅰ atoms, nitrogen atoms, or oxygen atoms in the layer thickness direction may be changed to obtain a desired layer thickness. In order to form a directional distribution state, as in the case of using the glow discharge method, a starting material for introducing a group 1 atom or a group V atom, a starting material for introducing a nitrogen atom, or a starting material for introducing an oxygen atom is used. The substance is used in a gaseous state and the gas flow rate at which the gas is introduced into the deposition chamber is varied as desired.

〔Example〕

Hereinafter, the present invention will be explained in more detail according to Examples 1 to 13, but the present invention is not limited thereto.

In each example, the first layer and the second layer were formed using a glow discharge method. FIG. 14 shows an apparatus for manufacturing a light-receiving member of the present invention using a glow discharge method.

In the gas cylinders 202, 203, 204, 205, and 206 in the figure, the next raw material gas that forms each layer of the present invention is sealed.
2 was diluted with He and ft SiL gas (purity 99.99
9%, hereinafter abbreviated as SiH4/He) cylinder, 203 is H
Diluted with e and 7'? BzHa gas (purity 99.999CH, hereinafter abbreviated as B, H, /He) cylinder, 204 is He
NI (3 gases (purity 99.999%,
Hereinafter abbreviated as NH3/He. ) cylinder, 205 is C, H
, gas (purity 99.999%) cylinder, 206 is H
This is a GeH4 gas (purity 99.999%, hereinafter abbreviated as GeH4/He) diluted with e.g.

When introducing halogen atoms into the layer to be formed, S
For example, the cylinder may be changed to use siF gas instead of iH gas.

To allow these gases to flow into the reaction chamber 201, make sure that the pulps 222 to 226 and leak pulp 235 of the gas cylinders 202 to 206 are closed. After confirming that ports 232 and 233 are open, first, the main pulp 234 is opened to exhaust the reaction chamber 201 and gas piping. Next, the reading on the vacuum gauge 236 is approximately 5 x 10
' When the torr is reached, the auxiliary pulp is 232.2
33. Close the outflow pulps 217-221.

An example of forming the first layer 102 on the base cylinder 237 is shown in e6. S iH4/ from gas cylinder 202
He gas, gas cylinder 203! J B2H6 Fe gas, from gas cylinder 204, NH3/He gas, GeH, /He gas from gas cylinder 206, respectively, by opening pulp 222.223.224.226 and checking the pressure on outlet pressure gauge 227.228.229.231. I Adjust to Kf/i, gradually open the inflow pulp 212, 213, 214, 216, mass flow control, 7207, 20
8.209.211. Subsequently, the outflow pulps 217, 218, 219, 221, and auxiliary pulps 232, 233 are gradually opened to allow gas to flow into the reaction chamber 201. At this time, Sin/He gas erosion, BzH
a/He gas flow rate, Nus/He gas flow rate and GeH
Adjust the outflow pulp 217, 218, 219, 221 so that the ratio of 4/He gas flow rate becomes the desired value, and adjust the vacuum gauge 236 so that the pressure inside the reaction chamber 201 becomes the desired value.
Adjust the opening of the main pulp 234 while checking the reading. Then, the temperature of the base cylinder 237 becomes higher than that of the heating heater 2.
After confirming that the temperature is set in the range of 50 to 400° C. by 38, the power source 240 is set to the desired power to generate glow discharge in the reaction chamber 201, and the microcomputer ( B2H, l/H according to a pre-designed change rate line using
e gas flow rate, NH3/He gas flow rate, 3 iH,/He
First, a layer region containing germanium atoms, boron atoms, and nitrogen atoms is formed on the base cylinder 237 while controlling the ratio of gas flow rates.

Next, after a predetermined period of time, BtH6/He gas and NHa/
By blocking the introduction of He gas into the reaction chamber 201 by closing the pulp of each corresponding gas introduction tube and continuing glow discharge for a predetermined period of time, a layer containing germanium atoms but not boron atoms or nitrogen atoms is formed. to form.

When containing halogen atoms in the first layer, the above gas may be, for example, SiF41He gas? It is sufficient to add more and send it to the reaction chamber.

In order to form a second layer on the first layer formed on the base cylinder 237 by the above operation, for example, S
By diluting each of iH4 gas, C2H4 gas, and PH3 gas with a diluent gas such as He as necessary, and flowing them into the reaction chamber 201 at a desired flow rate ratio to generate a glow discharge according to desired conditions. will be accomplished.

Needless to say, all the outflow pulps other than the outflow pulp for the gas necessary when forming each layer are closed, and when forming each layer, the gas used to form the previous layer is inside the reaction chamber 201 and the outflow pulp is closed. From the pulps 217 to 221 to the reaction chamber 201
In order to avoid gas remaining in the gas piping leading to the system, close the outflow pulps 217 to 221 as necessary, open the auxiliary pulps 232 and 233, fully open the main pulp 234, and once evacuate the inside of the system to a high vacuum. Perform the operation.

Further, while forming the second layer, the base cylinder 237 is constantly rotated by a motor 239 at a desired speed in order to ensure uniform layer formation.

Example 1 Using the manufacturing apparatus shown in FIG. 14, two layers were formed on a drum-shaped aluminum substrate which had been washed in a conventional manner, according to the layer forming conditions shown in Table 1. At this time, B2H6/
Changes in the 5IH4 gas flow rate ratio were automatically adjusted by microcomputer control in accordance with a pre-designed flow rate ratio change line shown in FIG.

The drum-shaped light-receiving member for electrophotography thus obtained was
A copy test was conducted using a Canon high-speed copying machine that had been modified for experiments, using a Canon test chart as a manuscript, and selecting appropriate image forming process conditions (a tungsten lamp was used as the light source). We were able to obtain high-quality images.

Example 2 Same as Example 1 except that the 5B2H6/SiH4 gas flow rate ratio and the NHs/Si & gas flow rate ratio were controlled according to the flow rate ratio change lines shown in FIGS. 8 and C, respectively, under the layer formation conditions shown in Table 2. A drum-shaped light-receiving member for electrophotography was obtained, and the same copying test as in Example 1 was carried out, and a high-quality image with excellent resolution could be obtained.

Example 3 Example 1 except that the B2H6/SiH4 gas flow rate ratio, NHs/Sin, and gas flow rate ratio were controlled according to the flow rate ratio change lines shown in FIG. 8 and FIG. C, respectively, under the layer forming conditions shown in Table 3. A drum-shaped light-receiving member for electrophotography was obtained in the same manner as in Example 1, and when the same copying process as in Example 1 was carried out, it was possible to obtain a very high quality image with excellent resolution.

Example 4 Under the layer forming conditions shown in Table 4, the B2Ha/SiH4 gas flow rate ratio was controlled according to the flow rate ratio change line shown in the diagram, and the same procedure as in Example 1 was carried out except for the following to produce a drum-shaped photoreceptor for electrophotography. When we obtained the parts and conducted a copying test similar to that in Example 1, we found that high-quality images with excellent resolution were obtained. I was able to get it.

Example 5 Under the layer forming conditions shown in Table 5, the B2HJ/SiH4 gas flow rate ratio was controlled according to the flow rate ratio change line shown in FIG. When the member was obtained and subjected to the same copying test as in Example 1, a high quality image with excellent resolution could be obtained.

Example 6 Example 1 except that the NHs/SiH, gas flow rate ratio, and B2H6/SiH4 gas flow rate ratio were controlled according to the flow rate ratio change lines shown in Figures C and F, respectively, under the layer forming conditions shown in Table 6. A drum-shaped light-receiving member for electrophotography was obtained in the same manner as in Example 1, and the same copying test as in Example 1 was carried out.
Next you can get high quality images with excellent resolution.

Example 7 A drum-shaped light-receiving member for electrophotography was produced in the same manner as in Example 1, except that the B2H6/SiH4 gas flow rate ratio was controlled according to the flow rate ratio change line shown in Figure A under the layer forming conditions shown in Table 7. When we conducted a copying test similar to that in Example 1, we found that a high-quality image with excellent resolution was obtained. I was able to get it.

Example 8 A drum-shaped light-receiving member for electrophotography was produced in the same manner as in Example 1, except that the B2H6/SiH4 gas flow rate ratio was controlled according to the flow rate ratio change line shown in FIG. 8 under the layer forming conditions shown in Table 8. When a copying test similar to that in Example 1 was carried out, high-quality images with excellent resolution could be obtained.

Example 9 Example 1 except that when forming the second layer (n) in Table 1, the layer thickness was varied as shown in Table 9.
Each light-receiving member (sample &
901 to 907) i Created and evaluated each by applying the same image forming process as in Example 1.
The results shown in the table were obtained.

Example 10 The same procedure as in Example 1 was followed except that the gas flow rate ratio C2H4/SiH4 in Table 1 was changed to the value shown in Table 10 when forming the second layer (n). Each light-receiving member (Samples 41001 to 1007) was prepared under substantially the same conditions and evaluated in the same manner as in Example 1. As a result, the reproducibility of halftones was good in each, and high-quality images were obtained. Just in case you can.

Furthermore, in a durability test involving repeated and continuous use, it was possible to obtain images of a quality that was comparable to the initial image quality, and it was demonstrated that the image quality was excellent in durability.

Example 11 In Table 1, the gas flow rate ratio G during the formation of the first layer
eH4/S tL value? Each light-receiving member (Samples 41101 to 1105) was prepared using the same procedure and substantially the same conditions as in Example 1, except for the values shown in Table 11.
When similar evaluations were carried out, it was found that the reproducibility of halftones was good in each case, and high-quality images could be obtained.

Furthermore, in a durability test involving repeated and continuous use, it was possible to obtain images of a quality that was comparable to the initial image quality, and it was demonstrated that the image quality was excellent in durability.

Example 12 Under the layer forming conditions shown in Table 12, Bz Ha/S IH4
A drum-shaped light-receiving member for electrophotography was obtained in the same manner as in Example 1 except for the following, with the gas flow rate ratio being controlled according to the flow rate ratio change line shown in the figure, and the same copying test as in Example 1 was conducted. However, we were able to obtain high-quality images with excellent resolution.

Example 13 In Examples 1 to 12, the light source was an 810 nm GaAS semiconductor laser (10 mW) instead of a tungsten lamp.
) i was used to form an electrostatic image, and the same image forming process as in each example was applied, except for reversal development. When the image quality of the toner transfer image was evaluated, it was found that it had excellent resolution and We were able to obtain clear, high-quality images with good tonal reproducibility.

[Summary of effects of the invention]

The light-receiving member of the present invention has a light-receiving layer composed of a-31 (H, , a-8
All of the problems in conventional light-receiving members having a light-receiving layer composed of i can be solved. That is, the light-receiving member of the present invention has particularly excellent moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability, etc., and also has improved light sensitivity and dark resistance. It has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers, and has fast photoresponsiveness.When used in cases where there is no influence of residual potential, its electrical characteristics are It is stable and the images obtained using it are of excellent quality, with high density and clear halftones.

In addition, in the light-receiving member of the present invention, the light-receiving layer formed on the support has a strong layer structure, and also has good adhesion to the support and adhesion between each layer provided on the support. Due to its excellent durability, it can be used repeatedly and continuously for long periods of time at high speeds.

[Brief explanation of drawings]

Figures 1 to 4 are diagrams schematically showing the layer structure of the light receiving member of the present invention, and Figures 5 to 13 are diagrams showing group 1 atoms or atoms in the first layer of the light receiving member of the present invention. FIG. 14 is a concentration distribution diagram showing a typical example of the distribution state of group V atoms, nitrogen atoms, or oxygen atoms, and FIG. This is an example of a manufacturing device, and is a schematic explanatory diagram of a manufacturing device using a glow discharge method. Figures A to F show changes in the gas flow rate ratio during layer formation of the light receiving member of the present invention. It is a diagram. 100... Light receiving member, 101... Support, 102
...First layer, 103...Second layer, 104...
Free surface, 201... Reaction chamber, 202-206...
Gas cylinder, 207-211...Mass 70 controller, 7.212-216...Inflow valve, 217-22
1...Outflow valve, 222-226...Valve, 2
27-231...Pressure regulator, 2321.233...
・Auxiliary valve, 234... Main valve, 235...
・Leak valve, 236... Vacuum gauge, 236... Base cylinder, 238... Heater, 239...
・Motor, 240...High frequency power supply

Claims (2)

[Claims] (1) A support, a first layer on the support that is made of an amorphous material containing silicon atoms and has photoconductivity, carbon atoms containing silicon atoms as a matrix, and controlling conductivity. a second layer made of an amorphous material containing a substance; and a light-receiving layer formed by stacking
germanium atoms are uniformly distributed in the entire layer region of the first layer, and a substance for controlling conductivity is non-uniformly distributed in the entire layer region or a part of the layer region of the first layer. and further contains nitrogen atoms in at least one of the entire layer region of the first layer, a part of the layer region, and the second layer. A light-receiving member. (2) The photoreceptive layer further contains oxygen atoms in at least one of the entire layer region of the first layer, a partial layer region thereof, and the second layer. A light-receiving member according to claim (1), characterized in that: