JPS61236555A - Light receiving member - Google Patents

Abstract

PURPOSE:To enhance electric, optical and photoconductive characteristics and to obtain excellent use-circumstance change resistance characteristics by incorporating oxygen in a uniform distribution in at least one layer region of two amorphous silicon type light receiving layers consisting respectively of specified compsn. formed on a substrate. CONSTITUTION:The first layer 102 made of a-SiGe(H,X) and on this layer the second layer 103 made of a-Si contg. C and a conductivity governing substance are laminated on the substrate 101 to form the light receiving layer and a part or the total of the layer region of one of the layers 102, 103 contains oxygen in a uniform distribution and the addition of Ge in the layer 102 in a uniform distribution permits absorption spectrum characteristics in the longer wavelength region to be enhanced, photosensitivity to be especially enhanced in the whole visible wavelength region, matching with semiconductor laser beams to be improved and optical responsivity to be enhanced. Further, the addition of C to the structure of the layer 103 permits the light receiving member to be enhanced in each of humidity resistance, successive repeated use resistance, high voltage resistance, use circumstance change resistance characteristics and durability to be enhanced and the addition of conductivity governing substance permits residual potential to be prevented and consequently, images high in quality to be obtained stably for a long period.

Description

[Detailed Description of the Invention] [Technical Field to which the Invention Pertains] The present invention relates to light (here, light in a broad sense, meaning ultraviolet rays, visible light, infrared rays, X-rays, r11!, etc.). The present invention relates to a light-receiving member sensitive to electromagnetic waves.

[Description of prior art]

As a photoconductive material 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 is highly sensitive and has a photocurrent (Ip) of 8N ratio.
/Dark current (Id)) is high and has absorption spectral characteristics that match the spectral characteristics of the electromagnetic waves to be irradiated;
It has fast photoresponsiveness, has a desired dark resistance value, is non-polluting to the human body during use, and in solid-state imaging devices, afterimages can be easily processed within a predetermined time. characteristics are required. 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 an important point.

Based on these points, amorphous silicon (hereinafter referred to as 1a-8iJ) is a photoreceptive material that has recently attracted attention.

), for example, German Publication No. 2746967,
German Publication No. 2,855,718 describes its use as an electrophotographic image forming member, and German Publication No. 2,933,411 describes its application to a photoelectric conversion/reading device.

However, the conventional photoreceptive member having a photoreceptive layer composed of a-8i 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 an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, conventional methods often leave a residual potential during use. When a member is used repeatedly for a long period of time, fatigue due to repeated use occurs, resulting in a number of disadvantages such as a so-called ghost phenomenon in which an afterimage occurs.

In addition, when the photoreceptive layer is composed of A-81 material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type Boron atoms, phosphorus atoms, etc. are contained as constituent atoms in the light-receiving layer for control purposes, or other atoms for the purpose of improving other properties, but depending on how these constituent atoms are contained, This may cause problems in the electrical or photoconductive properties or electrical voltage resistance of the formed layer.

That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoreceptive layer is not sufficient, or the injection of charges from the side of the support in a dark area is not sufficiently prevented, or Images transferred to transfer paper may have image defects commonly called "white spots," which are thought to be caused by localized discharge breakdown, and when a blade is used for cleaning, there may be "white streaks," which may be caused by rubbing. This caused an image defect that is said to have occurred. Furthermore, when 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 surface of the support as time passes after it is left in the air after being removed from the vacuum deposition chamber for layer formation. This tends to cause phenomena such as cracks in the layer. 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 the entire wavelength range, and has particularly high photosensitivity in the long wavelength range. It has the characteristics of being superior compared to others. However, in recent years,
Attempts have been made to put a laser printer into practical use using electrophotography using a semiconductor laser (770 to 800 μm) as a light source. It has become necessary to further sensitize light-receiving members having a light-receiving layer composed of the following in the long wavelength range.

Therefore, while efforts are being made to improve the properties of the a-8i material itself, it is necessary to take measures to solve the above-mentioned problems and to satisfy the above-mentioned requirements when designing a light-receiving member.

:Object of the invention] The present invention aims to solve the above-mentioned problems and satisfy the above-mentioned requirements regarding a light-receiving member having a light-receiving layer composed of a-8i. be.

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 having a light-receiving layer composed of a-8i, 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-8i, which has high photosensitivity, high signal-to-noise ratio characteristics, and high electrical voltage resistance.

Another object of the present invention is to provide excellent adhesion between a layer provided on a support and the support and between each of the laminated layers, to provide a dense and stable structural arrangement, and to provide layer quality. An object of the present invention is to provide a light-receiving member made of a-8i with high hardness.

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, and ordinary electrophotographic methods can be applied extremely effectively. An object of the present invention is to provide a light-receiving member having a light-receiving layer composed of a-8i and having excellent electrophotographic properties.

Still another object of the present invention is to easily obtain high-quality images with no image defects or image blurring, high density, clear halftones, and high resolution during long-term use. An object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-8i for electrophotography.

[Structure of the invention]

The present invention is intended to achieve the above-mentioned objects, and to improve product feasibility, applicability, 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 such matters,
An amorphous material that has silicon atoms as its base and contains germanium atoms, especially an amorphous material that has silicon atoms as its base and contains at least one of germanium atoms (Ge) and hydrogen atoms (H) or halogen atoms, so-called Hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing water-X amorphous silicon germanium [hereinafter referred to as [a-8iGe (H,X) J]. The layer structure of a light-receiving member having a light-receiving layer composed of ] is designed and produced under a specific two-layer structure as described below. We have discovered the fact that not only this, but also superior in all respects to conventional light-receiving members, and that it has particularly excellent properties as a light-receiving member for electrophotography. It was completed based on.

That is, the light-receiving member of the present invention is composed of a support and an amorphous material having silicon atoms as a matrix and containing germanium atoms, and having photoconductivity that may contain a substance that controls conductivity. The first layer is laminated with a second layer made of an amorphous material that uses silicon atoms as a matrix, contains structurally introduced carbon atoms, and contains a substance that controls conductivity. At least one of the first layer or the second layer contains oxygen atoms uniformly distributed in the entire layer region or a part of the layer region. It is characterized by:

The amorphous material containing silicon atoms as a matrix and containing germanium atoms, which constitutes the first layer, is particularly suitable for the amorphous material containing silicon atoms as a matrix and germanium atoms (Ge) as a matrix.
and at least one of a hydrogen atom (H) or a hydrogen atom (X) [hereinafter referred to as "a-8iGe (Hlx)"]. ] using
In particular, the amorphous material containing silicon atoms as a matrix and containing carbon atoms and a substance that controls conductivity, which constitutes the second layer, has silicon atoms as a matrix and contains carbon atoms (C).
, a substance that controls conductivity (b), and at least one of a hydrogen atom) or a halogen atom (3) [hereinafter referred to as "a-stcM (H,
) J (However, M represents a substance that controls conductivity.

). ] is used.

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 decay 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, excellent matching with semiconductor lasers, and quick photoresponsiveness.

Examples of the substance that controls conductivity include so-called impurities in the semiconductor field, such as atoms belonging to group Ⅰ of the periodic table (hereinafter referred to as group Ⅰ atoms) that give P-type conductivity, or n Atoms belonging to Group V of the periodic table (hereinafter referred to as Group V atoms) that provide type conductivity are used. Specifically, group Ⅰ atoms include B (boron), AJ (aluminum), Ga (gallium), In (indium), and TI.
(thallium) etc., particularly preferably B, ()a. Group III atoms include P (phosphorus), As (arsenic), sb (antimony), Bi (bismuth), etc.
Particularly preferably, p and sb are used. Even if the conductivity controlling substance contained in the first layer and the conductivity controlling substance contained in the second layer are the same,
Or they may be different. These conductivity controlling substances are contained uniformly in the entire layer area or in a part of the layer area for the first layer, and are contained uniformly in the entire layer area for the second layer. It is contained in a distribution state.

Further, the purpose of structurally introducing carbon atoms into the amorphous material constituting the second layer of the present invention is to
The objective is to improve moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability, etc.

Furthermore, the purpose of containing oxygen atoms in the first layer and/or the second layer is to increase photosensitivity and increase dark resistance, and furthermore, to increase the density between the support and the first layer or between the first layer and the first layer. In order to improve the adhesion between the second layer, it may be contained in the first layer in a uniform distribution over the entire layer area of the first layer, or , it may be contained in a uniform distribution only in a part of the layer region of the first layer.

Hereinafter, the light receiving member of the present invention will be explained in detail according to the drawings.

1 to 4 are diagrams schematically shown to explain the layer structure of the light-receiving member of the present invention. In each figure, 100 is the light-receiving member, 101 is the support for the light-receiving member, and 102 is the support for the light-receiving member. first layer, 103 is second layer, 104 is free surface, 105~
109 represents a layer area.

Each layer constituting the light receiving member 100 of the present invention will be described in detail below.

Support The support 101 used in the present invention may be electrically conductive or electrically insulating. As the conductive support, for example, NiCr.

Stainless steel, Al, Cr, Mo, Au, Nb
, Ta, V, Ti.

Examples include metals such as PT and PB, and alloys thereof.

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, ceramic, and paper. 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 glass, NiCr is applied to its surface.

AI, Cr, Mo, Au, Ir, Nb,
Ta, V, Ti, Pt, Pd.

In2O3, Snug, ITO, (In2O5+5n
02), etc., or if it is a synthetic resin film such as a polyester film, NiCr, AI, Ag, Pb,
Zn, Ni, Au, Cr.

MO, Ir, Nb, Ta, v, 'ri, Pt
Conductivity is imparted to the surface by providing a thin film of metal such as by vacuum evaporation, electron beam evaporation, sintering, or Q-tuttering, or by laminating the surface with the metal.

The shape of the support can be any shape such as a cylinder, a belt, a plate, etc., but the shape can be determined as appropriate depending on the purpose and desire. For example, if the light-receiving member 100 of FIG. 1 is used as an electrophotographic image forming member, it is desirable to use an endless belt-like or cylindrical-like shape for continuous high-speed copying. The thickness of the support is determined as appropriate so as to form a light-receiving member of the desired thickness, but if flexibility is required as a light-receiving member, the support can sufficiently function as a support. It can be made as thin as possible within the range.

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

The first layer 102 formed on the first layer support 101 is a-8
It is composed of iGe (H,

The first layer 102 contains germanium atoms in a uniform distribution over the entire layer region, that is, in a continuous and uniform distribution in the layer thickness direction of the first layer and in the plane parallel to the support surface. I'm being forced to do it. Since the first layer contains germanium atoms, the absorption spectrum characteristics on the long wavelength side are improved, and as a result, the light receiving member of the present invention can be used in the entire range from relatively short wavelengths to relatively long wavelengths. It can have excellent sensitivity to light of different wavelengths. And when using a semiconductor laser,
This is particularly effective since the first layer can substantially completely absorb light on the longer wavelength side, thereby preventing interference due to reflection from the surface of the support. The amount of germanium atoms contained in the first layer is determined appropriately according to the desired properties that can achieve the object of the present invention, but is usually 1 to 1 x 10' atomic ppm, preferably I X 10"~9,5 X 105atom10
5ato, optimally 5 x 10" to 8 x 10'a
tomic ppm.

Further, oxygen atoms, group II atoms, or group V atoms are uniformly distributed in the entire layer region or a part of the first layer composed of a-8iGe (H,X). . In order to explain an example in which the content is contained in a part of the layer area, FIG. 1 shows an example in which the content is uniformly distributed in the entire layer area of the first layer, and FIG. In the third example, the content is uniformly distributed in a part of the layer region 105.
The figures schematically show examples in which the first layer is contained in a uniform distribution state in a part of the layer region 106 in contact with the second layer, but these are representative examples and are limited to these. It's not a thing.

Regarding the inclusion of oxygen atoms in the first layer, if the main purpose is to increase photosensitivity and increase dark resistance, oxygen atoms should be included in the entire layer area as shown in Figure 1, and oxygen atoms should be included in the support and the first layer. When the main purpose is to improve the adhesion between the layers, it is contained in a part of the layer region 105 shown in FIG. Furthermore, when the main purpose is to improve the adhesion between the first layer and the second layer, it is contained in a part of the layer region 106 shown in FIG.

The content of oxygen atoms may be relatively small when the purpose is to increase photosensitivity and dark resistance, and it is desirable that the content of oxygen atoms be relatively large when the purpose is to improve adhesion. In addition, the content of oxygen atoms must be determined by taking into consideration the relationship between the characteristics of the layer containing oxygen atoms and other layers adjacent to it, and the characteristics of the interface between the layer containing oxygen and other layers. There is also. Usually l x 10-3w 50 at
o+nfc q6, preferably 2 X 10-
3-40 atomic%, optimally 3 X 10-”
~30 atomic units. When the proportion of the layer region containing oxygen atoms in the first layer is high,
Alternatively, when oxygen atoms are contained in the entire layer region of the first layer, it is desirable that the upper limit of the content of oxygen atoms is sufficiently smaller than the above-mentioned value. That is, for example, when the layer thickness of the layer region containing oxygen atoms is 2A or more of the layer thickness of the first layer, the upper limit value is usually 30 atomic%.
and preferably 20 atomic%, optimal busyness is 10
atomic%.

Regarding the inclusion of a substance that controls conductivity in the first layer, that is, group II atoms or group V atoms, there are two cases in which the substance is contained uniformly in the entire layer area, and there are cases in which the substance is contained in a uniform distribution state in the entire layer area, and in other cases only in a part of the layer area. In some cases, it is contained in a uniformly distributed state.

When the main purpose is to control the conductivity type and/or conductivity of the first layer, it is contained in the entire layer region as shown in FIG. The content of group atoms may be relatively small, usually 1×10 to 1
x 103103ato ppm.

Preferably 5 x 10”””-5X lo”atoms
ic ppm, optimally 1 x 10-1-2 x
10" atomic ppm. Furthermore, in this case, even if the conductivity type of the substance controlling conductivity contained in the first layer is the same as that contained in the second layer,
Or it may be different.

In addition, as shown in FIG. 2, when a part of the layer region 105 in contact with the support contains Group II atoms or Group V atoms in a uniform distribution state, the layer region 105 is used as a charge injection blocking layer. It has the following effects. The content in this case is relatively large, usually 3Dw 5 x
10'atomic ppm, preferably 50-IX
10'atomic ppm, optimally 1x 102
~5 x 103103ato ppm. Furthermore, in order to efficiently exhibit this effect, the layer thickness of the layer region 105 is set to t, and the layer thickness of the first layer other than the layer region 105 is set to
In the case of Also, the layer thickness of the layer region 105 is usually 3
X 10-' to 10μ, preferably 4
10"-'s ~ 8μ, optimally 5 x 10-3 ~ 5μ
It is.

Furthermore, contrary to the above case, as shown in FIG. When containing in a distributed state, if the conductivity type of the substance controlling conductivity contained in the first layer and the second layer is the same, the main purpose is to control the energy between the first layer and the second layer. The objective is to improve level matching and enhance charge transfer between both layers. When the second layer is thick and has a high dark resistance, the effect produced by containing group (I) atoms or group V atoms becomes even more remarkable.

In addition, in the case where the layer region 106 as shown in FIG. 3 contains group (III) atoms or group V atoms, the conductivity type thereof is the same as the conductivity type of the group (III) atoms or group V atoms contained in the second layer. If they are different, the layer region 106 does not actively serve as a junction between the first layer and the second layer, and the main purpose is to increase the apparent dark resistance during the charging process. Become.

As shown in FIG. 3, a part of the layer region 106 in contact with the second layer
In the case where a group (I) atom or a group V atom is contained, the content may be relatively small.

Usually I x 10-3 to 1 x 10"atomic
ppm, preferably 5 x 10-2~5
x 102102ato ppm, optimally 0.1
w 2 x 10” atomic ppm.

The above description focuses on the case where oxygen atoms, group (I) atoms, or group V atoms are contained in the entire layer region or a part of the layer region of the first layer of the light-receiving member of the present invention, respectively. This is an example of implementation, but in addition,
It is of course possible to freely combine the content states of these atoms depending on the purpose so as to simultaneously achieve various purposes. Although FIG. 4 shows an example of such a case, the present invention is not limited to this, and many other combinations are possible.

FIG. 4 shows a-8iGe (H,X) on the support 101.
The first layer 102 and a-staM(H,x)
A second layer 103 composed of the following layers is provided in this order, and the first layer further includes a first layer region 107, a second layer region 108, and a third layer region 109 from the support side. This is an example of the configuration. The first layer region 107 contains both group (II) atoms or group V atoms and oxygen atoms, and the second layer region 108 contains oxygen atoms, but group (II) or group V atoms do not contain oxygen atoms. Contains no. and third layer area 10
9 does not contain any Group M atoms or Group V atoms and oxygen atoms. In the example shown in FIG. 4, the first layer region 107 and the second layer region 108 contain oxygen atoms to improve photosensitivity and dark resistance, and
Adhesion between the support and the first layer can be improved. Furthermore, by containing group (I) atoms or group V atoms in the first layer region 107, it is possible to prevent charge injection when performing charging treatment from the free surface 104 side of the second layer 103. can.

In addition, as an alternative to the example shown in FIG. 4, the second layer region 10
Of course, it is possible to make 8 a layer region that contains a group (I) atom or a group V atom but does not contain an oxygen atom.

Second Layer The second layer 103 is provided on the first layer 102 for the purpose of improving moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability, and the like. This objective can be achieved by structurally introducing carbon atoms into the amorphous material constituting the second layer. When carbon atoms are introduced structurally in the 20th layer, as the amount of carbon atoms increases, the above-mentioned properties improve, but if the amount of carbon atoms is too large, the layer quality deteriorates and the electrical and Mechanical properties are also reduced. For these reasons, the carbon atom content is usually 1X10-3 to 90 atomfc%, preferably 1 w 90 atomic, optimally 10 to 90 atomfc%.
It is 80 atomic.

Furthermore, in order to improve the characteristics of continuous repeated use and durability, it is preferable to increase the thickness of the second layer, but if the layer thickness becomes thick, it becomes a cause of generation of residual potential. The generation of such a residual potential can be prevented or suppressed to the extent that it has no substantial effect by containing a substance that controls conductivity in the second layer, that is, a group II atom or a group V atom. can do. Normally, this type of second layer has excellent mechanical durability, but if the surface of the layer is rubbed or pressed with something with a sharp point, it may leave so-called scratches on the surface. Even if it is not present, it often appears as an electrostatic trace value during the charging process, resulting in a deterioration in the image quality of the toner-transferred image.

Even in such a case, such a problem can be prevented from occurring by including the above-mentioned conductivity controlling substance in the second layer. Therefore, by including atoms belonging to group Ⅰ or group V, which are substances that control conductivity, in the second layer, it is possible to obtain a second layer having the desired properties that can achieve the object of the present invention. It is important to form layers. The amount of Group II atoms or Group V atoms contained in the second layer is usually 1.0 w 10'ato
mic ppm, preferably 10-5 x 1
0'atomic ppm, optimally 102w 5
It is desirable to set x 103ato to 103ato.

Furthermore, the second layer 103 has high light sensitivity and high dark resistance.
Furthermore, for the purpose of improving the adhesion between the first layer and the second layer, oxygen atoms can be contained, especially in the first layer 1.
When 02 does not contain oxygen atoms, the second layer is made to contain oxygen atoms.

The second layer 103 is made of
Must be carefully formed. That is, silicon atoms, carbon atoms, hydrogen atoms and/or halogen atoms, and
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 electrical properties vary from conductive to semiconductive. , up to insulating properties, and photoelectric properties range from photoconductive properties to non-photoconductive properties, so each configuration can be adjusted to form a second layer with desired properties depending on the purpose. It is important to select production conditions such as the content of atoms.

For example, when the second layer is provided with the main purpose of improving electrical voltage resistance, the amorphous material constituting the second layer is
Forms with remarkable electrically insulating behavior under the conditions of use. In addition, when the second layer is provided for the main purpose of continuous repeated use or improvement of usage environment characteristics, the amorphous material constituting the second layer may have the above-mentioned degree of electrical insulation reduced to some extent. However, it is formed so as to have a certain degree of sensitivity to the irradiating light.

The layer thicknesses of the first layer and the second layer are one of the important factors for efficiently achieving the purpose of the present invention, and are determined as appropriate depending on the desired purpose. Depending on the amount of oxygen atoms, Group Ⅰ atoms, Group V atoms, carbon atoms, nitrogen atoms, and hydrogen atoms contained in each layer, or the mutual layer thickness of each layer, the mutual It is also necessary to make decisions based on natural and organic relationships. Furthermore,
It is also necessary to consider economic efficiency, which also takes into account productivity and mass production. For this reason, the thickness of the first layer is usually 1-100μ, preferably 1N80μ, optimally 2-50μ, and the thickness of the second layer is usually axlo-
3-30μ, preferably 4×10−”μ, optimally 5
xio-”~10μ.

The light-receiving member of the present invention solves all of the problems of conventional light-receiving members having a light-receiving layer made of amorphous silicon by virtue of the above-mentioned layer structure. In addition to exhibiting excellent physical, optical, and photoconductive properties, electrical voltage resistance, and use environment characteristics, it has high photosensitivity in the entire visible light range, particularly excellent matching with semiconductor lasers, and fast photoresponsiveness. It is something that exhibits outstanding characteristics.

Furthermore, when applied to an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it has 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.

In addition, in the light-receiving member of the present invention, the light-receiving layer formed on the support is strong and has excellent adhesion to the support, so it can be used continuously at high speed for a long time. Can be used repeatedly.

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

The photoreceptive layer of the present invention is a non-containing material in which a-8i (H, Layers or partial layer regions made of crystalline materials are combined to form a specific layer structure as described above. or a vacuum deposition method using discharge development such as an ion blating method. These methods are selected and used as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and characteristics required of the light-receiving member to be manufactured. Since it is relatively easy to control the manufacturing conditions, and carbon atoms, hydrogen atoms, and/or halogen atoms can be easily introduced together with silicon atoms, the glow discharge method or the The e-tuttering method is preferred. Further, the glow discharge method and the Snow Q-Tuttering method can be used together in the same apparatus system.

For example, by glow discharge method, a −5i(H,X)
To form a layer composed of, basically, along with a raw material gas for supplying Si that can supply silicon atoms (Si)
or/and halogen atom (3) for introducing hydrogen atom (H)
A raw material gas for introduction is introduced into a deposition chamber whose interior can be reduced in pressure, a glow discharge is generated in the deposition chamber, and a -8i (H
, X).

Specific examples of the halogen atom (3) that may be included in the layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred.

As the raw material gas for supplying Si, 51 g of SiH4
Examples include silicon hydride (silanes) in a gaseous state or that can be gasified, such as H6, 5i3H9, 5i4HIQ, etc., and in particular, from the viewpoint of ease of layer formation work, good S1 supply efficiency, etc.
SiH, 5i2H, is preferred.

Further, as the raw material gas for introducing halogen atoms, there are many halogen compounds, such as halogen gas,
Gaseous or gasifiable halogen compounds are preferred, such as halides, interhalogen compounds, and halogen-substituted 7-rane derivatives. Specifically, fluorine, chlorine, bromine,
Iodine/% Rogen gas, BrF, CIF, C
IF5, BrF51BrF3, IFe, I
Interhalogen compounds such as CI, IBr, and 5iF
Examples include silicon halides such as a, 5i2Fa, 5i (J4, 5iBrt, etc.) When using silicon halides in a gaseous state or those that can be gasified as described above, a raw material gas for S1 supply is used separately. This is particularly effective because a layer composed of a-8i containing halogen atoms can be formed without any halogen atoms.

Further, as the raw material gas for supplying hydrogen atoms, hydrogen gas, halides such as HF, HCI, HBr, HI + 5iH415t2H6,si, HB, 5i4
H engineering. silicon hydride such as, or SiH2F2.5iH
2I2.8iH2C/2.5iH (J3゜5iH2Br
Gaseous or gasifiable materials such as halogen-substituted silicon hydrides such as 2.5iHBr5 can be used, and when these raw material gases are used, they are extremely effective in terms of controlling electrical or photoelectric properties. Hydrogen atoms which are effective (effective because the uniform content can be easily controlled; and when the above-mentioned hydrogen halide or the above-mentioned halogen-substituted silicon hydride is used) - introduction of halogen atoms; This is particularly effective since hydrogen atoms (H) are also introduced at the same time.

The amount of halogen atoms (3), the amount of hydrogen atoms, or the sum of the amounts of halogen atoms and hydrogen atoms (X0H) is usually 0.0
1-40 atomic%, preferably 0.05-3
0 atomic %, optimally 0, 1-25 ato
It is desirable to set it to mic%. K controls the amount of hydrogen atoms (H) and/or halogen atoms (K) contained in the layer, for example, the support temperature, hydrogen atoms (H) and/or hydrogen atoms (3) to be introduced. This is done by controlling the amount of starting material used for the deposition into the deposition chamber, the discharge power, etc.

K, which forms a layer of a-8i (H, Sputtering is performed in an atmosphere, and in the case of the ion blating method, polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is used by a resistance heating method, an electron beam method (HB method), etc. This can be carried out by heating and evaporating the flying evaporated material and passing it through a predetermined gas plasma atmosphere.

At that time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion blasting method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. Then, a plasma atmosphere of the gas may be formed.

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H2 or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. good.

For example, in the case of the reactive sputtering method, an S1 target is used, and a plasma atmosphere is created by introducing a gas for introducing halogen atoms and H2 gas, including inert gases such as He and Ar as necessary, into the deposition chamber. A layer consisting of a -5i(H,X) is formed on the support by forming and sputtering the Si target.

A non-containing material containing a germanium atom, a group II atom or a group V atom, an oxygen atom, or a carbon atom in a-si(a, To form a layer composed of a crystalline material, when forming a layer of a-8i (H, A substance, a starting material for introducing an oxygen atom, or a starting material for introducing a carbon atom can be used together with the starting material for forming a-8i (H, This is done by controlling the content.

For example, by glow discharge method, a-8iGe (H,X)
K forming the layer composed of a-8i (H
, As the starting material for introducing germanium atoms, almost any gaseous or gasifiable substance containing at least germanium atoms can be used.

Specifically, Gem, ()e2H6,Ge3H1 are used as materials that can be used as raw material gas for introducing germanium atoms.
3゜Ge4H1o, GeaHlz, f)e
6H14, Ge, H16, GeBHlB, 089
Examples include germanium hydride in a gaseous state such as H20°, which can be gasified, but ease of handling during layer creation work, G
eGeH4゜Ge2H in particular from the point of view of good supply efficiency, etc.
, Ge, and sHe are preferred.

When forming the first layer using the glow discharge method, basically silicon halide is used as a raw material gas for S1 supply, dermaium hydride is used as a raw material for Ge supply, Ar,
By heating gases such as H2 and He to a predetermined mixing ratio and gas flow rate and introducing them into the deposition chamber, a glow discharge is generated to form a plasma atmosphere of these gases, thereby forming a support. In order to make it easier to control the content of hydrogen atoms (H), which is extremely effective in controlling the electric or photoelectric properties of the force ζ that forms the first layer 102 on the layer 101, The above-mentioned raw material gas for supplying hydrogen atoms can also be mixed with these gases.

To form a layer made of a-8iGe (H, Using a target made of Ge, this is sputtered in a desired gas plasma atmosphere, and in the case of the ion blating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are used as evaporation sources, respectively. The evaporation source is housed in a evaporation boat, and the evaporation source is heated using resistance heating method or electron beam method (BB
This can be carried out by heating and evaporating the flying evaporated material using a method such as the above method, and passing the flying evaporated material through a desired gas plasma atmosphere.

When introducing halogen atoms into the layer formed by either the sputtering method or the ion blasting method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. to form a plasma atmosphere of the gas. Further, when introducing hydrogen atoms, the raw material gas for introducing hydrogen atoms may be introduced into a deposition chamber for sputtering.

To form the second layer composed of a-8iCM (H,X) by the glow discharge method, a-8iCM (H,
) Source gas for formation and Ar as necessary.

A diluent gas such as He is mixed at a predetermined mixing ratio and introduced into a deposition chamber for vacuum deposition where the support 101 is installed.
The introduced gas is turned into gas plasma by causing glow discharge. The raw material gas for forming a-8iCM(H,X) is si.

Any gasified substance or gasified substance containing at least one of C, H and/or halogen atoms, and Group I atoms or Group V atoms. It may be something.

When using a raw material gas containing Sl as one of the St, C, H and/or nitrogen atoms, Group II atoms, or Group V atoms, for example, a raw material gas containing Sl as a constituent atom. a gas, a raw material gas containing C as a constituent atom, a raw material gas containing H and/or nitrogen atoms as constituent atoms, and
A raw material gas containing group atoms or group V atoms as a constituent atom may be mixed at a desired mixing ratio, or a raw material gas containing Si as a constituent atom and C and H and/or A raw material gas whose constituent atoms are atomic atoms and a raw material gas whose constituent atoms are group Ⅰ atoms or group V atoms are mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are 81 atoms are mixed together at a desired mixing ratio. It is possible to use a mixture of a gas, a raw material gas whose constituent atoms are Si, C, H and/or halogen atoms, and a raw material gas whose constituent atoms are Group II atoms or Group V atoms. .

Alternatively, a raw material gas containing Sl, H and/or halogen atoms as constituent atoms, a raw material gas containing C as constituent atoms, and a raw material gas containing Group II atoms or Group V atoms as constituent atoms are mixed. You may also use it as

A material gas effectively used for forming a layer composed of a-SiC(H,
Silicon hydride gas such as silane (5ilane) such as HIO, whose constituent atoms are C and H, for example, carbon number 1 to 4
saturated hydrocarbons, ethylene hydrocarbons having 2 to 4 carbon atoms,
Examples include acetylene hydrocarbons having 2 to 3 carbon atoms.

Specifically, the saturated hydrocarbon is methane (OH,)
, ethane (C2H6), pro, en (C3H8), n-
Butane (n-C, Hlo), pentane (C5H12),
Examples of ethylene hydrocarbons include ethylene (CaH4),
Propylene (C3H6), Buti 7-1 (C4H8), Buti y-2 (c, a8), Inobuti L/7 (C4HEl)
, pentene (05H10), acetylene hydrocarbons include acetylene (C2H2), methylacety'' (C3
Ha).

Examples include butyne (C4H6).

As a raw material gas containing Si, C, and H as constituent atoms, 5
Examples include alkyl silicides such as i(Cas)4r5i(CaHa)4. In addition to these raw material gases, H
Of course, H2 can also be used as the raw material gas for introduction.

Specifically, starting materials for introducing a group Ⅰ atom include B2H6, B4HIO* B5Hp for introducing a boron atom.
.

B6H1l, B6H10, B6Hxz, B6H
Boron hydride such as 14, BF3, BCj3, BB
Examples include boron chloride such as rs. In addition, A
JCJ3. GaCJs, Ga(CHs)2゜InC
Js, TlCl3, etc. may also be mentioned.

As starting materials for introducing Group V atoms, specifically for introducing phosphorus atoms, hydrogen north neighbors such as PH3, P2H, PH4
I, PF3. PF3. PCl3. PCl6.
PBr3. An example is a halogen north neighbor such as PBr6°PIs. In addition, AsH3, AsF3. AsCJ3.
AaBr3. AsF5. SbH3, SbF3゜5
bFa, 5b(J'3.5b(J5. BiH3,B
iCl3. B1Br15 and the like can also be mentioned as effective starting materials for introducing Group V atoms.

In order to form a layer or layer region containing oxygen atoms, one starting material for introducing an oxygen atom is added to the starting materials selected as desired from among the starting materials for forming the photoreceptive layer, and the starting material is added to the layer to be formed. The content of oxygen atoms may be controlled while controlling the amount of oxygen atoms.

When a glow discharge method is used to form a layer or layer region containing oxygen atoms, a starting material for introducing oxygen atoms is added to a material selected as desired from among the starting materials for forming the photoreceptive layer described above. is added. As such a starting material for introducing oxygen atoms, almost any gaseous substance or substance that can be gasified can be used as long as it has at least an oxygen atom as a constituent atom.

For example, a raw material gas containing silicon atoms (Si), a raw material gas containing oxygen atoms (0), and a raw material containing hydrogen atoms (3) or halogen atoms (3) as necessary. or a raw material gas containing silicon atoms (Sl) as constituent atoms and a raw material gas containing oxygen atoms (0) and hydrogen atoms (H) as constituent atoms. are also mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Sl) and silicon atoms (Si) and oxygen atoms (0) are mixed at a desired mixing ratio.
and hydrogen atoms) can be mixed and used.

Alternatively, a raw material gas containing silicon atoms (si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing oxygen atoms (0) as constituent atoms.

Specifically, for example, oxygen (0,), ozone (03), -
Nitric oxide (No), nitrogen dioxide (NO2), -nitrogen dioxide (N20), nitrogen sesquioxide (Nap3), nitrogen tetroxide (N2O4), nitrogen sesquioxide (N,05),
Lower siloxanes such as nitrogen trioxide (No3), silicon atoms (Si), oxygen atoms (0), and hydrogen atoms (H), such as disiloxane (H3SiO8iHs) and trisiloxane (H38i0SiH20SiH3), etc. can be mentioned.

In order to form a layer or a layer region containing oxygen atoms by a sputtering method, a monocrystalline or polycrystalline S1 wafer or a 5in2 wafer, or a wafer containing a mixture of Si and 5i(h) is used as a target. These steps may be performed by sputtering in various gas atmospheres.

For example, if 81 Ueno-- is used as a target, the raw material gas for introducing oxygen atoms and optionally hydrogen atoms and/or halogen atoms can be diluted with a diluent gas as necessary to create a sputtering target. The Si wafer may be sputtered by introducing the gas into a deposition chamber and forming a gas plasma of these gases.

Alternatively, by using Sl and 5in2 as separate targets or by using a mixed target of Sl and 8102, at least hydrogen atoms (9 ) or/and by sputtering in a gas atmosphere containing halogen atoms (2) 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 anti-stumbling.

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. The content of each of germanium atoms, Group Ⅰ atoms, Group V atoms, oxygen atoms, carbon atoms, hydrogen atoms and/or halogen atoms to be contained in the deposition chamber can be controlled by controlling the content of each of the atoms flowing into the deposition chamber. This is carried out by controlling the gas flow rate of the starting materials or the gas flow rate ratio between the respective starting materials for supplying atoms.

In addition, conditions such as the support temperature, gas pressure in the deposition chamber, electric discharge, and e-warping 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. Ash,
It is selected as appropriate, 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 must be given to the type and amount of the atoms to be contained. It is also necessary to consider and make a decision.

Specifically, when forming a layer consisting of a-8i (H, X), or a-81 (H, When forming a layer consisting of
The temperature is preferably 50°C, particularly preferably 50 to 250°C. The gas pressure in the deposition chamber is usually 0.01 to I Torr, particularly preferably 0.1 to 0.5 Torr. In addition, the discharge QW is 0.005 to 50W/cWL
Normally, the value is 2, preferably 0.01~
30W/α2, especially busy preferably 0.01-20W/cI
Let it be rL2. Regarding the case of forming a layer consisting of a-8iGe (H, X), or the case of forming a layer consisting of a-8iGe (H, The support temperature is usually 50 to 350°C, preferably 50 to 300°C.
℃, particularly preferably 100 to 300℃. and,
The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.001 to 3 Torr, particularly preferably 0.1 to 1 Torr. In addition, the discharge
The power is usually 0.005 to 50 W/cIIL, preferably 0.01 to 30 W/α2, particularly preferably 0.01 to 20 W/cIIL2.

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 (I) 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, oxygen atoms, and carbon atoms uniform, it is necessary to keep the above-mentioned conditions constant when forming the first layer and the second layer.

〔Example〕

Hereinafter, the present invention will be explained in detail according to Examples 1 to 14, 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. 5 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, raw material gases for forming the respective layers of the present invention are sealed.
2 is SiH gas diluted with He (purity 99.999
%, hereinafter abbreviated as SiH4/He) cylinder, 203 is B2Ha gas diluted with He (purity 99.999%,
Hereinafter abbreviated as Bz Ha/He. ) cylinder, 204 is GeH gas diluted with He (purity 99.99%, hereinafter abbreviated as Oe H4/He) cylinder, 205 is Ca
H&gas (purity 99.999cm) cylinder, 206 is O2
．． It's a gas cylinder.

When introducing halogen atoms into the layer to be formed, S
Instead of iH, gas or S 12H6 gas, e.g.
Just change the cylinder to use iF gas.

To allow these gases to flow into the reaction chamber 201, make sure that the valves 222 to 226 of the gas cylinders 202 to 206 and the leak valve 235 are closed. Make sure that 232.233 is open,
First, the main valve 234 is opened to exhaust the reaction chamber 201 and gas piping. Next, the vacuum gauge 236 reads approximately 5 x
When the temperature reaches 10””’Torr, the auxiliary/signal lubricant 23
2.233. Close the outflow valves 217-221.

A method for forming the first layer 102 on the base cylinder 237 will be described. Gas cylinder 202) siH.

/He gas, BgHa/He gas from gas cylinder 203, GeH, /He gas from gas cylinder 204, 02 gas from gas cylinder 206. , the pressure of 231 is 1 kg/c
Adjust to rrL2, inflow valve 212, 213.214
．． Gradually open 216 and connect mass flow controller 207.
．． 208.209.211.

Subsequently the outflow valve 217.218.219.221
．． The auxiliary ζ-sives 232 and 233 are gradually opened to allow gas to flow into the reaction chamber 201. At this time, S iH4/
He gas flow rate, B2H6/ He gas flow rate, GeH4/
Adjust the outflow valves 217, 218, 219, 221 so that the ratio of He gas flow rate and 02 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. Main valve 234 while checking the reading.
Adjust the aperture. After confirming that the temperature of the base cylinder 237 is set to a temperature in the range of 50 to 400 degrees Celsius by the heating heater 238, the power source 240 is set to the desired power to cause a glow discharge in the reaction chamber 201. to form a first layer of a-8iGe (H+x) containing boron atoms and oxygen atoms on the base cylinder 237.

For example, when the first layer is made of a layer region containing boron atoms and oxygen atoms and a layer region not containing boron atoms and oxygen atoms, after a predetermined period of time has elapsed. The valve of the gas introduction pipe for introducing B2 H6/He gas into the reaction chamber and the valve of the gas introduction pipe for introducing 02 gas into the reaction chamber are closed to shut off, and glow discharge is subsequently performed.

When halogen atoms are contained in the first layer, SiF4/He, for example, is further added to the above gas and fed into the reaction chamber.

In order to form the second layer on the first layer formed on the base cylinder 237 by the above operation, for example, the S
In, gas, (4H4 gas, PH3 gas, respectively, are diluted with a diluent gas such as He as necessary, and flowed into the reaction chamber 201 at a desired flow rate ratio to generate a glow discharge according to desired conditions. It is accomplished by

Needless to say, all outflow valves other than those required for forming each layer are closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow into or out of the reaction chamber 201. From valves 217 to 221 to reaction chamber 201
In order to avoid remaining in the gas piping leading to the system, close the valves 217 to 221, open the auxiliary valves 232 and 233, and fully open the main valve 234 to make the system a high vacuum. Perform the operation to exhaust the air.

Further, during layer formation, the base cylinder 237 is constantly rotated by a motor 239 at a desired speed to ensure uniform layer formation.

Example Ta.

Photosensitive drum thus obtained (image forming member for electrophotography)
was installed in a copying machine, corona charging was performed for 0.2 seconds at e5 KV, and a light image was irradiated. The light source used was a Gesten lamp, and the light intensity was 1.01 ux-sec. The latent image was developed with a charged developer (containing toner and carrier) and transferred to ordinary paper, and the transferred image was extremely good. The toner remaining on the photosensitive drum without being transferred is cleaned by the fm blade, and the toner moves to the next copying process. Even when such steps were repeated over 150,000 times, the resulting images were excellent without any deterioration.

Examples 2 to 16 Using the manufacturing apparatus shown in FIG. 5, other materials were prepared on a cylindrical aluminum substrate under the conditions listed in Tables 2 to 16 with the symbols corresponding to the display numbers of Examples 2 to 16. Layer formation was carried out under the same conditions and operations as in Example 1.

The obtained photosensitive drum was the same as Example 1, except that the charging polarity and development polarity were set to e and ■ in Examples 5 to 14 and 16, and ■ and e in Examples 2 to 4 and 15. When the image forming process was applied and evaluated, good results were obtained as in the case of Example 1.

[Summary of effects of the invention]

In the present invention, the light receiving member having the light receiving layer composed of a-81 has the above-described layer structure.
A light-receiving member having a light-receiving layer composed of -81 and solving all of the problems of conventional light-receiving members can be obtained. That is, the light-receiving member of the present invention not only exhibits extremely excellent electrical, optical, photoconductive properties, electrical pressure resistance, and use environment characteristics, but also has high photosensitivity in the entire visible light range, and is particularly suitable for semiconductor lasers. It exhibits outstanding properties such as excellent matching properties with other materials and fast photoresponsiveness. Furthermore, when applied to an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, it is highly sensitive, and it has a high 81 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.

In addition, the light-receiving member of the present invention has a strong layer structure of the light-receiving layer formed on the support and extremely excellent adhesion to the support, so it can be used continuously at high speed and for a long time. Can be used repeatedly.

[Brief explanation of the drawing]

Figures 1 to 4 are diagrams schematically showing the layer structure of the light-receiving member of the present invention, and Figure 5 is an example of an apparatus for manufacturing the light-receiving member of the present invention, using a glow discharge decomposition method. 1 is a schematic explanatory diagram of a manufacturing apparatus according to

Claims (1)

[Claims] a support, a photoconductive first layer composed of an amorphous material containing silicon atoms and germanium atoms, and which may contain a conductivity controlling substance;
and a second layer made of an amorphous material containing silicon atoms as a matrix and carbon atoms and a substance that controls conductivity, and at least the first layer or A light-receiving member characterized in that either one of the second layers contains oxygen atoms in a uniformly distributed state in the entire layer region or a part of the layer region.