JPS60138556A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain stably an image having high quality by providing a photoreceptive layer formed successively with the 1st amorphous layer contg. Si and Ge and the 2nd amorphous layer contg. Si and C on a base and increasing continuously the concn. distribution of N from the base side toward the layer thickness direction in the 1st amorphous layer. CONSTITUTION:The 1st amorphous layer 102 which contains Si and Ge and in which the concn. distribution uniform or increasing in the layer thickness direction from the base 101 side is provided to the Ge and the concn. distribution increasing in the layer thickness direction is provided to the N is formed on the surface of a conductive base 101 such as an Al drum or the like. The 2nd amorphous layer 103 contg. Si and C is then formed and a photoconductive member 100 formed with a photoreceptive layer 104 consisting of the layers 102 and 103 is manufactured. Further, H or halogen or both are incorporated in the layer 102 and the III group element B, etc. and V group element P, etc. governing conductivity are contained therein. The photoconductive member which has high sensitivity over a wide visual light range, good resolution and stable under all environments is thus obtd.

Description

Detailed Description of the Invention The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (herein, light in a broad sense refers to ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, etc.). Regarding.

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)), have absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, have fast photoresponsiveness, have a desired dark resistance value, and be harmless to the human body during use. Furthermore, 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 an important point.

Based on this point, amorphous silicon (hereinafter referred to as a-3i) is a photoconductive material that has recently been promoted.
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

On the other hand, a photoconductive member having a conventional photoconductive layer composed of A-3I has a low dark resistance value and a low light sensitivity.

Electrical, optical, and photoconductive properties such as photoresponsiveness.

The reality is that there are still areas that need to be further improved in terms of use environment characteristics such as temperature resistance and stability over time, and it is necessary to improve overall characteristics.

For example, in the case of applying it to an electrophotographic image forming member, when trying to achieve high light sensitivity and high dark resistance at the same time, in the past, it has often been observed that residual particles remain during use. When a photoconductive member is used repeatedly for a long period of time, fatigue due to repeated use accumulates, resulting in so-called ghost development, which causes an afterimage. Or,
Repeated use at high speeds often causes disadvantages such as a gradual decrease in responsiveness.

Furthermore, compared to the short wavelength side of the visible light region, a-3t has a relatively smaller absorption coefficient in the long wavelength region than the long wavelength region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when using commonly used halogen lamps and fluorescent lamps as light sources, there remains room for improvement in that they do not effectively utilize light on the longer wavelength side. In addition, if the irradiated light is not sufficiently absorbed in the photoconductive upper layer and the amount of light reaching the support increases, the support itself will absorb the light that passes through the photoconductive layer. When the reflectance is high, interference due to multiple reflections occurs within the photoconductive layer, causing "blurring" of one image.

This effect becomes larger as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source.

Furthermore, when forming a photoconductive layer using a-3i 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 included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties, but depending on how these constituent atoms are contained, However, problems may arise in the electrical or photoconductive properties of the formed layer.

That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer may not be sufficient, or the injection of charge from the support side may not be sufficiently prevented in dark areas. There are many cases.

Furthermore, when the layer thickness exceeds 1000 yen, the layer may lift or peel off from the surface of the support, or cracks may develop as the time elapses after it is left in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs particularly when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that need to be solved in terms of stability over time.

Therefore, while efforts are being made to improve the properties of the a-3i material itself, it is necessary to take measures to solve all of the problems mentioned above when designing photoconductive members.

The present invention has been made in view of the above-mentioned points, and the present invention focuses on the applicability of a-3i as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive and intensive research studies from this viewpoint, we found that silicon atoms and germanium atoms are IJW, and amorphous 4. I material, so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter referred to as r
a-3iGe (H, The photoconductive member not only exhibits extremely superior properties in practical use, but also surpasses conventional photoconductive members in all respects, especially as a photoconductive member for electrophotography. The present invention is based on the discovery that it has characteristics and has excellent absorption spectrum characteristics on the long wavelength side.

The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member that is durable, does not cause deterioration even after repeated use, and has no or almost no residual potential observed.

Another object of the present invention is to have high photosensitivity in the entire visible light range;
In particular, it is an object of the present invention to provide a photoconductive member that is excellent in matching with a semiconductor laser and has a fast optical response.

Still another object of the present invention is to provide excellent adhesion between a layer provided on a support and a support, and between each laminated layer, and to provide a dense and stable structural arrangement. It is an object of the present invention to provide a high quality photoconductive member.

Still another object of the present invention is that when applied as an image forming member for electrophotography, the charging process for electrostatic image formation can be performed to such an extent that ordinary electrophotography can be applied very effectively. It is an object of the present invention to provide a photoconductive member which has sufficient charge retention ability and excellent electrophotographic properties with almost no deterioration of the properties observed even in a humid atmosphere.

Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution.

Still another object of the present invention is to provide a photoconductive member having high photosensitivity, high signal-to-noise ratio characteristics, and good electrical contact with a support.

The photoconductive member of the present invention includes a support for the photoconductive member, a photoconductive first layer made of an amorphous material containing silicon atoms and germanium atoms, and a photoconductive first layer made of an amorphous material containing silicon atoms and germanium atoms. and a second layer made of an amorphous material containing a photoreceptive layer, the first layer has a layer region (N) containing nitrogen atoms, and the layer The region (N) is a region (N) in which the distribution concentration C(N) of nitrogen atoms in the layer thickness direction increases continuously from the support side toward the light-receiving layer side.
Y).

The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems and has extremely excellent electrical and optical properties.

Shows photoconductive properties, electrical pressure resistance, and usage environment properties.

In particular, when the photoconductive member of the present invention is applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical properties are stable, and it has high sensitivity and high sensitivity. It has a high signal-to-noise ratio, 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 photoconductive member of the present invention, the photoreceptive layer formed with the top layer of the support is strong itself and has excellent adhesion to the support, so that it can be repeatedly used continuously at high speed for a long time. can be used.

Furthermore, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, and is particularly excellent in matching with semiconductor lasers.
One light response is fast l/).

Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings.

FIG. 1 is a schematic configuration diagram for explaining the layer configuration of a photoconductive member according to a first embodiment of the present invention.

The photoconductive member lOO shown in FIG. - a second layer (, II) 1O3 provided on the substrate. The first layer (I) 102 is made of a-3iGe (H,X), contains nitrogen atoms, and has photoconductivity. First layer (I
) 102 and the second layer (II) lO3 constitute a photoreceptive layer 104. Germanium atoms are present in the first layer (I
) 102 so that the first layer (I
) 102, or it may be contained evenly in the layer thickness direction, but the distribution concentration may be non-uniform. In any case, the first layer (I) 10
In order to make the properties uniform in the in-plane direction, it is necessary for germanium atoms to be uniformly distributed and evenly contained in the in-plane direction parallel to the surface of the support. It is.

In particular, it is contained evenly in the layer thickness direction of the first layer (I) 102, and on the side opposite to the side where the support 101 is provided (the free surface of the photoreceptive layer 108). 105 side), so that it is more distributed on the support 101 side (the interface side between the photoreceptive layer and the support 101), or the opposite distribution state is created. The first layer (I) 102 contains germanium atoms.

In the photoconductive member of the present invention, as described above, the distribution state of the germanium atoms contained in the first layer (I) 102 takes the above-mentioned 4j state in the layer thickness direction, and It is desirable that the particles be uniformly distributed in the in-plane direction parallel to the surface of the body 101.

Figures t52 to io show typical examples where the distribution state of germanium atoms contained in the first layer (1,) 102 in the layer thickness direction is non-uniform.

In FIGS. 2 to 10, the horizontal axis shows the germanium atom fraction 711 mlF=C, the vertical axis shows the layer thickness of the first 2(1)102 exhibiting photoconductivity, and t8 is the support 10.
ta indicates the position of the surface of the first layer (I) 102 on the side opposite to the support side. That is, the first layer (I) 102 containing germanium atoms is tv
The layer is formed from the , side toward the t□ side.

FIG. 2 shows a first typical example of the state of germanium atoms contained in the first layer (I) 102 in the layer thickness direction.

In the example shown in FIG. 2, the surface on which the first layer (I) 102 containing germanium atoms is formed and the support 10
From the interface position t, which is in contact with the surface of the first layer (I), to the position tl, the distribution concentration C of germanium atoms is contained in the first layer (I) while taking a constant value C, and from the position t1 to the interface position t. The distribution concentration gradually and continuously decreases from C2 up to C2. At the interface position t, the distribution concentration C of germanium atoms is O3.

In the example shown in FIG. 3, the first layer (I) 102
The distribution concentration C of germanium atoms contained in is at position 1B
A distribution state is formed in which the concentrations gradually and continuously decrease from C and L until reaching a further position, reaching the concentration C5 at position tA.

In the case of FIG. 4, the distribution concentration C of germanium atoms contained in the first layer (I) 102 is from position t to position t2.
The distribution density C is set to a constant value up to CG, gradually and continuously decreased between the positions t2 and t1, and at the position tr, the distribution density C is substantially zero (here, the distribution density C is substantially zero). Zero means less than the detection limit).

In the case of Fig. 5, the distribution concentration C of germanium atoms contained in the first layer (1) 1O2 is as follows:, -/j, tB
The concentration is gradually decreased continuously from C9 until reaching position tT, and becomes substantially zero at position tA.

In the example shown in FIG. 6, the distribution concentration C of germanium atoms contained in the first layer (I) 102 is a constant value of concentration C9 between the positions E and 3, and the concentration C9 is a constant value at the position t1. , the 0 position t where the concentration C5° is applied, and the position t1
, the distribution concentration C decreases in a descendant manner from position E3 to position WE.

In the example shown in FIG. 7, the first layer (I) 102
The distribution concentration C of germanium atoms contained in is at the position t,
The concentration C7, takes a constant value up to position t4, and at position t
The distribution state is such that the concentration c decreases from 4 to the position tT, and decreases linearly from 2 to the concentration Cn.

In the example shown in FIG. 8, the distribution concentration C of germanium atoms contained in the first layer (I) 102 decreases from 01 to substantially zero from position t to position ti-. It decreases linearly.

In FIG. 9, the distribution concentration C of germanium atoms contained in the first layer (I) 102 varies from position t8 to position t.
5, the density is decreased numerically from C1 to C1, and between position t5 and position d,
An example is shown in which the concentration C26 is set to a constant value. In the example shown in FIG. At first, the concentration CI7 is slowly decreased until it reaches the position , and then it decreases rapidly near the position t, and the concentration C1 is reached at the position t6.
It is said to be □.

Between position 1G and position t7, the concentration decreases rapidly at first, then gradually decreases to reach CI9 at position 7, and between position t7 and position t, the concentration CI decreases very slowly. and gradually decreased to position 1. In, °
The concentration reaches C2o. Position 1. and position tT, the concentration is reduced from C2° to substantially zero according to a curve shaped as shown in the figure.

As described above, according to Fig. 2 to fJSlO diagram, the first layer (I)
As described in some of the typical examples of the distribution state of the germanium atoms contained in 102 in the layer thickness direction, in the present invention, the support lot side has a portion with a high distribution concentration C of germanium atoms. , on the interface t□ side, the distribution state of germanium atoms has a portion where the distribution concentration C is considerably lower than that on the support 101 side.
I) 102 is one of the preferred examples.

The first layer (I) 1 containing the photoconductive member in the present invention
02 preferably has a localized region (A) containing germanium atoms at a relatively high concentration on the support 101 side or, conversely, on the free surface 105 side, as described above. is desirable.

For example, if the localized region (A) is explained using the symbols shown in FIGS. 2 to 1O, it is desirable that the localized region (A) be provided within 5IL in the layer thickness direction from the interface position tB.

The localized region (A) may be the entire layer region (LT) up to 5w thick from the interface position, or may be a part of the layer region (LT).

Whether the localized region (A) is a part or all of the layer region (LT) is determined as appropriate depending on the characteristics required of the first layer (I) 102 to be formed.

In the localized region (A), the distribution state of the germanium atoms contained therein in the layer thickness direction is preferably such that the maximum value Crxax of the distribution concentration of germanium atoms is too much with respect to the sum of the germanium atoms and the silicon atoms.

It is desirable that the layer be formed in such a manner that it can have a distribution state of atomic ppm or more, more preferably 5000 atomic ppm or more, and optimally txio atomic ppm or more.

That is, in the present invention, the first layer (I) 102 containing germanium atoms has a maximum distribution concentration within 5 pL in layer thickness from the support 101 side (layer region 5 μL thick from 1B). It is preferable that it is formed so that Cmax exists.

In the present invention, the content of germanium atoms contained in the first layer (I) 102 may be determined as desired so as to effectively achieve the object of the present invention.
Preferably 1 to 9.5X with respect to the sum with silicon atoms
More preferably 100-8X10 atomic ppm, optimally 5.00-7 XIO atomic ppm
It is desirable to set it as pm.

The 4j-like IE of germanium atoms in the first layer (I) 102 is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration C of germanium atoms in the layer thickness direction is from the support lot side. If a decreasing change is given toward the free surface 105 side of the light-receiving layer 104 or vice versa, the rate of change curve of the distribution concentration C is arbitrarily designed as desired. By doing so, it is possible to realize the first layer (I) 102 having the required characteristics as desired.

For example, the distribution concentration C of germanium atoms in the first layer (I) 102 is sufficiently increased on the support 101 side, and the distribution concentration C of germanium atoms in the first layer (I) 102 is sufficiently increased on the side of the free clothing Li'i' 1105 of the photoreceptive layer j04. By giving the distribution concentration curve of germanium atoms a change in the distribution concentration C that is as small as possible, it is possible to change the wavelength of light in the entire range from relatively short wavelengths to relatively long wavelengths, including the visible light region. In contrast, high photosensitivity can be achieved, and interference with coherent light such as laser light can be effectively prevented.

Furthermore, as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the end of the first layer (I) 102 on the side of the support lot, it is possible to , the light on the long wavelength side that cannot be fully absorbed on the laser irradiated surface side of the photoreceptive layer 104 is substantially completely absorbed in the end layer region of the photoreceptive layer 104 on the support 101 side. As a result, interference due to reflection from the support surface can be effectively prevented.

In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and increasing dark resistance, and further improving the adhesion between the support and the first layer (I') 102, First layer (I) 102
Nitrogen atoms are contained therein. First layer (I) 10
The nitrogen atoms contained in 2 are the second layer (II), 103
It is particularly abundant near the support 101 and, if necessary, near the support 101.

11 to 13 show typical examples of the distribution state of nitrogen atoms in the entire first layer (I) 1026.
Signals used throughout these descriptions have the same meanings as used in FIGS. 2 through 10. In the example shown in Figure il1, the distribution concentration C(N) of nitrogen atoms varies from 0 to 0 from position t to position d.
It monotonically increases continuously up to 21.

In the example shown in FIG. 12, the distribution concentration C(N
) has a distribution concentration C22 at the position t, and decreases monotonically and continuously from the distribution concentration C22 until reaching the position t, and reaches the distribution concentration C2 at the position t9. position t
9 to position t1, the distribution concentration of nitrogen atoms C
(N) increases continuously and monotonically from the position t, and becomes the distribution density CZa at the position t□.

The example in FIG. 13 is relatively similar to the example in FIG. 12, but the difference is that the position tea and the position t, 1
It does not contain any nitrogen atoms.

Between position 1B and position to, the distribution concentration decreases monotonically from position C4 at position to O at position t+a, and between position t11 and position LA, position t
The distribution concentration increases continuously and monotonically from the distribution concentration O at position 11 to the distribution concentration C2 at position 1B.

In the photoconductive member of the present invention, as typical examples are shown in FIGS. 11 to 13, more nitrogen atoms are added to the lower surface and/or upper surface side of the first layer (I) 102. By containing nitrogen atoms and containing fewer nitrogen atoms toward the inside of the first layer (I), 102, and by continuously changing the distribution concentration C (N) of nitrogen atoms in the layer thickness direction, For example, efforts are being made to increase the light sensitivity and dark resistance of the photoreceptive layer.

In addition, by continuously changing the distribution concentration C(N) of nitrogen atoms, the change in refractive index in the layer thickness direction due to the inclusion of nitrogen atoms is made gradual, and the interference caused by coherent light such as laser light is suppressed. effectively prevented.

In the present invention, the nitrogen atom content in the nitrogen atom-containing layer region (N) provided in the first layer (I) 102 depends on the characteristics required for the layer region (N) itself or the layer region (N). When the region (N) is provided in direct contact with the support 101, the region (N) may be appropriately selected depending on the organic relationship, such as the relationship with the characteristics at the contact interface with the support 101. I can do it.

In addition, when another layer region is provided in direct contact with the layer region (N), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region may also be determined. The nitrogen atom content is appropriately selected in consideration of the above.

The amount of nitrogen atoms contained in the layer region (N) can be adjusted as desired depending on the properties required of the photoconductive member to be formed.
A certificate is given, but preferably o, ooi to 50 atomic %, more preferably t L < ha 0, with respect to the sum of silicon atoms, germanium atoms, and nitrogen atoms (hereinafter referred to as rT (S i GeN) J). 002 to 40 at%, optimally.

The content is preferably 0.003 to 30 at%.

In the present invention, the layer region (N) is the first layer (I) 102
Or, even if it does not occupy the entire area of the first layer (I) 102, the ratio of the layer thickness To of the layer region (N) to the layer thickness T of the first layer (I) 102 is sufficient. If the amount of nitrogen atoms is large, it is desirable that the upper limit of the content of nitrogen atoms contained in the layer region (N) is sufficiently smaller than the above value.

In the present invention, when the layer thickness TO of the layer region (N) accounts for two-fifths or more of the layer thickness T of the first layer (I) 102, the layer region (N) The upper limit of the amount of nitrogen atoms contained in N) is preferably 30 atomic % or less, more preferably 20 atomic % or less, based on T (SiGeN).
It is desirable that the content be at most atomic %, most preferably at most 10 atomic %.

In the present invention, the layer region containing nitrogen (f-)
N) is a localized region (B) in which nitrogen atoms are contained at a relatively high C degree near the support lot side and/or the second layer (■■) 103 side as described in "-". In this case, it is possible to further improve the adhesion between the support lO1 and the first layer (I)'102 and to improve the acceptance potential.

The localized region (B) is preferably provided within 51L from the surface of the first layer (I) 102 on the support 101 side and the second layer (II) 103 side.

In the present invention, the localized region (B) is formed in the first layer (
I) 102 from the support 101 or from the second layer (II
) It may be the entire layer region (LT) up to a thickness of 5p from the surface on the 103 side, or it may be a part of the layer region (LT).

Whether the localized region CB) is to be a part or all of the layer region (LT) is determined as appropriate depending on the characteristics required of the light-receiving layer 104 to be formed.

In the localized region (B), the maximum value Cmax of the distribution concentration C(N,) of nitrogen atoms as the distribution state of the nitrogen atoms contained therein in the layer thickness direction is preferably 500 atomic ppm or more,
It is desirable that the layer be formed in such a manner that a distribution state can be achieved, more preferably t±8001 χ pp+m or more, most preferably 1000 atomic ppm or more.

That is, in the present invention, in the first layer (I) 102,
The layer region ('N) containing nitrogen atoms is the support 101
It is desirable to form the layer so that the maximum value Cmax of the distribution concentration exists within five layers in thickness from the surface of the side and second layer (II) 403. In the present invention, the halogen atoms contained in the first layer (I) 102 as necessary include:
Specific examples include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred.

In the photoconductive member of the present invention, the first layer (I) 102
By containing a substance (CD) that controls the conduction characteristics, the conduction characteristics of the first layer (I) 102 can be arbitrarily controlled as desired.

The substance (D) that governs such conduction characteristics can be the so-called impurities in the semiconductor field, and in the case of Kibatsu 11, the substance (D) that constitutes the first layer (I) 102 to be formed can be mentioned. For a-3iGE (H, Specifically, p-type impurities include atoms belonging to Group ■ of the periodic table (Group ■ atoms), such as boron (B), aluminum (text A), and gallium (
Among them, B and Ga are particularly preferably used. In addition, as n-type impurities, atoms belonging to Group V of the periodic table (
(Group V atoms), such as phosphorus (P), arsenic (As), antimony (sb), bismuth (Bi), etc., and particularly preferably used are P and As.

In the present invention, the content of the substance (D) that controls conduction properties contained in the first layer (I) 102Φ is determined by the content of the substance (D) that controls the conduction properties required for the second layer (I) 102 or the content of the substance (D) that controls the conduction properties. The layer (I) 102 can be appropriately selected depending on the organic relationship, such as the relationship with the characteristics at the contact interface with the support 101 provided in direct contact with it.

In addition, the substance (D) that controls the conduction characteristics described above is included in the first layer (
I) 102, the -th N(I) lo
When it is contained locally in the desired layer region of 2, especially when it is contained in the support side end layer region of the first 73 (I) 102, it is in direct contact with the layer region. The content of the substance (D) that controls the conduction properties is appropriately selected in consideration of the characteristics of the other layer regions provided and the relationship with the characteristics at the contact interface with the other layer regions.

In the present invention, the content of the substance (D) controlling the conductive properties contained in the first layer (I) 102 is preferably 0.01 to 5×to atomic ppm, more preferably is 0.5 to t x t o' atoms ppm, optimally 1
It is desirable that the amount is 5XlO atoms ppm.

In the present invention, the content of the substance (D') that controls conduction characteristics in the layer region containing the substance (D') is preferably 30 atomic ppm or more, more preferably 50 atomic ppm.
m or more, optimally 100 atomic ppia or more, the substance (D) that governs the conduction properties of the first layer (I
) It is desirable to locally contain it in some layer regions of layers 10 and 2, and it is particularly desirable to make it unevenly distributed in the support side end layer region (E) of the first layer (I) 102.

Among the above, the substance (D) that controls the conductive properties is contained in the support side end layer region (E) of the first layer (I) 102 in an amount of 1 or more than the above value. By,
For example, if the substance (D) is the above p-type impurity,
When the free surface 105 of the photoreceptive layer 104 is subjected to polar charging treatment, the movement of electrons injected into the photoreceptive layer 104 from the support 101 side is effectively prevented.

In addition, when the substance controlling the conduction characteristics is the n-type impurity, the free surface 10 of the photoreceptive layer 104
When 5 is charged to O polarity, the movement of holes injected from the support lot side into the photoreceptive layer 104 can be effectively prevented.

In this way, when the support-side end layer region (E) contains a substance (D) that controls conductivity and ν property of one polarity, the remaining part of the first layer (I) 102 layer area, i.e.
Layer region of the portion excluding the support side end layer region (E)
Z) may contain a substance that controls the conduction characteristics of the other polarity, or a substance that controls the conduction characteristics of the same polarity may be added to the material contained in the support side end layer region (E). It may be contained in an amount much smaller than the amount of .

In such a case, the content of the substance (D) that controls the conductive properties contained in the layer region (Z) depends on the polarity and the content of the substance contained in the support side end layer region (E). It is determined as desired depending on the content, but
Preferably 0.001-1000 atomic ppm+, more preferably 0.05-500 atomic ppm, optimally o
, t~200j, j ppm is desirable.

In the present invention, when the support side end layer region (E) and the layer region (Z) contain the same type of substance that controls conductivity, the content of the substance in the layer region (Z) The content is preferably 30 atomic ppm or less. In addition to the above-mentioned cases, in the present invention, the first layer (
I) In 102, a layer region containing a substance controlling conductivity having one polarity and a layer region containing a substance controlling conductivity having the other polarity are brought into direct contact. It is also possible to provide a so-called depletion layer in the contact layer region. For example, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in the first layer (I) 102 so as to be in direct contact with each other, so that the so-called p-n A junction can be formed to provide a depletion layer.

In the present invention, the first layer (I) 102 composed of a-3IGe (H, For example, by glow discharge method, a-3iGe ()i,X
) In order to form the first layer (I) 102, basically a raw material gas for supplying silicon atoms that can supply silicon atoms and a raw material gas for supplying germanium atoms that can supply germanium atoms. The gas and raw material gas for hydrogen atom introduction and/or raw material gas for halogen atom introduction are introduced into a deposition chamber in a desired gas pressure state in which the internal pressure can be reduced, and a glow discharge is generated in the deposition chamber. a-5i on a predetermined support surface, which has been previously placed in a predetermined position.
A layer consisting of Ge (H,X) may be formed. or,
First layer (I) with germanium atoms in a non-uniform distribution state
In order to contain it in l'02, the proportion of germanium atoms lI
a-3i while controlling the i concentration according to the desired rate of change curve.
It is sufficient to form a layer consisting of Ge (H, configured target, or
The target and a target composed of germanium atoms are used, or a mixed target of silicon atoms and germanium atoms is used, and if necessary, the target is diluted with a diluent gas such as He or Ar. The first layer (I) 102 is formed by introducing a raw material gas for supplying germanium atoms and a gas for introducing hydrogen atoms and/or halogen atoms into a deposition chamber for sputtering to form a plasma atmosphere of a desired gas. Form. In this sputtering method, if the distribution of germanium atoms is to be made non-uniform, the target may be sputtered while controlling the gas flow rate of the raw material gas for supplying germanium atoms according to a desired rate of change curve.

In the case of the ion blating method, for example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition port as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam. Except for heating and evaporating by method (EB method) etc. and passing the flying evaporated material through the desired gas plasma atmosphere,
The first layer (I) 102 can be formed in the same manner as in the case of sputtering.

Substances that can be used as a raw material gas for supplying silicon atoms used in the present invention include S t H+, Si, H
, , Si, H, , Si4H, gaseous or gasifiable silicon hydride (silanes) can be mentioned as one that can be effectively used, especially for ease of handling in the layer forming operation 11'F. In terms of silicon atom supply efficiency, Si
Preferred examples include H4 and Si2H6.

Substances that can be used as raw material gas for supplying germanium atoms include G e H4, G e, H,, G e3H,, G
e4H,,,G e,H,,,G e,H,4,G
e7H,,G e,H,.

Germanium hydride in a gaseous state or capable of being gasified, such as Ge, H2°, etc., can be mentioned as being effectively used.
In particular, GeH4, Ge2HG, G
e, H, are listed as preferred.

Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be turned into a scum, and which has a silicon atom and a halogen atom as constituent elements, can also be mentioned as an effective compound in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CJljF, CF6, BrF, and B
Examples include interhalogen compounds such as r H3, I H3, I H7, ICU, and IBr.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
Silicon halides such as i F S i,F, 5iC9,4゜24ゝ5iBr are preferred.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing halogen atoms, a raw material capable of supplying silicon atoms together with germanium and a raw material gas for supplying atoms is used. A first layer (I) made of a-3iGe containing halogen atoms can be formed on a desired support 101 without using silicon hydride gas as a gas.
102 can be formed.

According to the glow discharge method, the first layer containing halogen atoms (
I) When manufacturing 102, basically, for example, silicon halide is used as a raw material gas for supplying silicon atoms, germanium hydride is used as a raw material gas for germanium atoms supply, and gases such as Ar, H, He, etc. A desired support 1014 is introduced into a deposition chamber for forming a photoreceptive layer at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. However, in order to more easily control the introduction ratio of hydrogen atoms, hydrogen gas or a silicon compound containing hydrogen atoms may be added to these gases. A layer may also be formed by mixing a desired amount of these gases.

Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio.

In order to introduce halogen atoms into the first W (I) 102 formed in either the sputtering method or the ion blating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced. The gas may be introduced into the deposition chamber to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms into the first layer (I) 102, a raw material gas for introducing hydrogen atoms, for example, H2, or the above-mentioned silanes and/or gases such as germanium hydride, is sputtered. A plasma atmosphere of the gas may be formed by introducing the gas into a deposition chamber.

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, HC, HBr, HI! ￥Nohydrogenhalide, S i H2P2, S i H2I2, S i H
2Cl,, 5iHC secret S i H2B r2.5fHB
halogen-substituted silicon hydrides such as r, and G e HF,
,GeH2F2,GeH3P,GeHCfL,
, G e H2Cl, , G e JCl, G e HB
r,, G e H, B r2, G e H, B r,
Halides containing hydrogen atoms as one of their constituent elements, such as germanium hydrogenated halides such as G e HI, G e H, G e H, I, GeF4, GeC, G e
B r, , G e I, , GeF4, G'e CL.

Gaseous or gasifiable substances such as germanium halides such as GeBr2, GeI2, etc. can also be mentioned as useful starting materials for forming the first layer (I) 102.

Among these substances, halides containing hydrogen atoms are hydrogen atoms that are extremely effective in controlling electrical or photoelectric properties at the same time as introducing halogen atoms into the layer when forming the first layer (I) 102. Since halogen is also introduced, it is used as a suitable raw material for halogen introduction in the present invention.

In order to structurally introduce hydrogen atoms into the first layer (I) 102, in addition to the above, H2, S i H4, S i,
Silicon hydride such as H,, Si, H,, Si, H, 9 with germanium or germanium compound for supplying germanium atoms, or GeH4, Ge, H,,
G e,H,,G e4H,,,G e,H,,,G
e, H,,G e,H,,,G e,H,,G e,
H. The method can also be carried out by coexisting germanium hydride (e.g., silicon or a silicon compound for supplying silicon atoms) in a deposition chamber to generate an electric discharge.

In a preferred example of the present invention, the amount of hydrogen contained in the first layer (I) 102 of the photoconductive member to be formed, or the star of halogen atoms, or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 0.01 to 40 atomic %, more preferably 0.05 to 30 atomic %, optimally 0.1 to 2 atomic %.
It is desirable that the content be 5 at.%.

The amount of hydrogen atoms and/or halogen atoms contained in the first layer (I) 102 can be controlled, for example, by controlling the support temperature or/and the starting material used to contain the hydrogen atoms or halogen atoms. the amount of material introduced into the deposition system;
In order to provide the layer region (N) containing discharge atoms, the starting material for introducing nitrogen atoms is used for forming the first layer (I) 102 as described above during the formation of the first layer (I) 102. It may be used together with the starting materials and contained in the layer to be formed while controlling its amount.

When a glow discharge method is used to form the layer region (N), a starting material for introducing nitrogen atoms is added to a material selected as desired from among the starting materials for forming the first Jffl (I) 102 described above. Substances are added. As the starting material for introducing nitrogen atoms, most of the gaseous substances containing at least nitrogen atoms or gasified substances that can be gasified can be used.

A starting material that can be effectively used as a raw material gas for introducing nitrogen atoms used when forming the layer region (N) has nitrogen as a constituent atom, or has nitrogen and hydrogen as constituent atoms. For example, nitrogen (N2), ammonia (NH3)
), hydrazine (H2N NH,), hydrogen azide (HN), ammonium azide (NH4N, In addition to this, nitrogen trifluoride (F3N) and nitrogen tetrafluoride CF4N2 can be used in addition to nitrogen atoms because they can also introduce halogen atoms.
) and other halogenated nitrogen compounds.

In the present invention, the layer region (N) may further contain oxygen atoms in addition to nitrogen atoms in order to further enhance the effect obtained by nitrogen atoms.

Examples of raw material gases for introducing oxygen atoms into the layer region (N) include oxygen (O2) and ozone (O2).
i), -nitrogen oxide (NO), nitrogen dioxide (NO,), -
・Nitrogen dioxide (Nρ), nitrogen sesquioxide (N, Oρ, trinitrogen tetraoxide (N, 04), nitrogen pentoxide (NyuO8), nitrogen trioxide (No,) silicon atoms, oxygen atoms, hydrogen atoms and For example, disiloxane (H,5i
O3iH,).

Examples include lower siloxanes such as trisiloxane (H3SiO3iH20SiH,).

In order to form the layer region (N) by the sputtering method, when forming the first layer (I) 102, a single crystal or polycrystalline silicon wafer or a 5ilN wafer, or a mixture of silicon atoms and S t3N is used. This can be carried out by sputtering the wafers containing the wafers in various gas atmospheres, using them as targets.

For example, if a silicon wafer is used as a target, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as required.

The silicon wafer may be sputtered by introducing the gas into a deposition chamber for sputtering and forming a gas plasma of these gases.

Alternatively, silicon atoms and 313N4 can be used as separate targets, or by using a single target that is a mixture of silicon atoms and Si, N4, in a dilution gas atmosphere as a sputtering gas. Sputtering may be performed in a gas atmosphere containing at least hydrogen atoms and/or halogen atoms as constituent atoms.

As the raw material gas for introducing nitrogen atoms, the raw material gas for introducing nitrogen 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.

In the present invention, when a layer region (N) containing nitrogen atoms is provided when forming the first J'3(I) 102,
The distribution concentration C(N) of nitrogen atoms contained in the layer region (N)
) in the layer thickness direction to form a layer region (N) having a desired depth profile in the layer thickness direction, in the case of glow discharge, the distribution concentration C(N
) may be introduced into the deposition chamber while changing its gas flow rate appropriately according to a desired change rate curve.

For example, the opening of a predetermined needle valve provided in the gas flow path system 4 may be appropriately changed by any commonly used method, such as manually or by using an externally driven motor.

When forming the layer region (N) by sputtering, the distribution concentration C(N) of nitrogen atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution of nitrogen atoms in the layer thickness direction. To create the depth profile, firstly, as in the case of the glow discharge method, the starting material for the introduction of nitrogen atoms is used in a gaseous state, and the depth profile is This is accomplished by appropriately changing the gas flow rate as desired.

Second, if a target containing a mixture of silicon atoms and 3i3N, & is used as a sputtering target, for example, the mixing ratio of silicon atoms and SiN should be adjusted in the layer thickness direction of the target. This is done by changing it in advance.

In the first layer (I) 102, a substance that controls the conduction properties;
For example, in order to structurally introduce a group II atom or a group V atom, a starting material for introducing a group II atom or a starting material for introducing a group V atom is deposited in a gaseous state during layer formation. It may be introduced into the chamber together with other starting materials for forming the first layer (I) 102. As the starting material for such introduction of Group (I) atoms, it is desirable to employ materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for the introduction of group Ⅰ atoms include B2H,, B4H, , B, H,, B, H, , B,
H,,,B6H,,,B,H,- boron hydride, B F
Examples include boron halides such as , , B Cl, , BBr, and the like. In addition, AuC1yo, GeCmonyo, G e (
CHJ), I n CJLJ, T-cross Cl, etc. can also be mentioned.

In the present invention, effective starting materials for introducing Group V atoms include P H,
, P H4, etc., P H4I, P F,, P
F,,PCJl,,P Cl,,PBr,,PBr,.

Examples include phosphorus halides such as P I. In addition, As
Hl, AsF,, As Cl,, As B r,,
A s F,, S b H,, 5bFJ, SbF,, s
bc milk, sbc island, BiH, BiCL, B i B
r, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

In the present invention, the layer thickness of the layer region constituting the first layer (I) 102 and containing a substance that controls conduction properties and provided unevenly on the support lO1 side is as follows: It is appropriately determined as desired depending on the characteristics required for the other layer regions constituting the first layer (I) 102 formed on the layer region, but the lower limit is preferably 30λ or more, more preferably 40λ or more, optimally 50λ
It is desirable that it be λ or more. Further, the content of the substance controlling the conductive properties contained in the layer region is 30 atomic pp.
When the thickness is greater than m, the upper limit of the layer thickness of the layer region is preferably 10 g or less, preferably 8 μ or less, and most preferably 5 μm or less.

In the photoconductive member 100 shown in FIG. 1, the second layer (II) 103 formed on the first layer (I) 102 has a free surface and mainly has moisture resistance, continuous repeated use characteristics, This is provided in order to achieve the objectives of the present invention in terms of electrical pressure resistance, use environment characteristics, and durability.

Further, in the present invention, the first layer (I) 102 and the second M! fcII) Since each of the amorphous materials constituting 103 has a common constituent element of silicon atoms,
Chemical stability is sufficiently ensured at the laminated interface of both layers (I) 102 and (II) 103.

The second layer (II) 103 in the present invention is an amorphous material (hereinafter ra-(Six
C+-x) y(H,X)ryJ However, 0<x, y<1
).

a −(S ixc+ −x) y(H,X)+−rc
The second layer 103 (II) is formed by a glow discharge method, a sputtering method, an ion implantation method, an ion blating method, an electron beam method, or the like. These manufacturing methods are based on manufacturing conditions, WQ
## Manufacturing conditions for manufacturing a photoconductive member having the desired characteristics are selected and adopted as appropriate depending on factors such as the level of capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be created. The glow discharge method or the sputtering method has advantages such as relatively easy control of carbon atoms and halogen atoms as well as silicon atoms can be easily introduced into the second layer (II) 103 to be produced. Suitably adopted.

Furthermore, in Kibatsu'j1, a glow discharge method and a sputtering method are used together in the same system to form the second layer (II).
103 may be formed.

To form the second layer (II) 103 by the glow discharge method, a −(S 1xcrx)! (H,X) +
-y-forming raw material gas is mixed with a dilution gas at a predetermined mixing ratio as needed, and introduced into a deposition chamber for vacuum deposition where the support 101 is installed, and the introduced gas is By generating a glow discharge, it becomes a gas plasma,
The first layer (I) has already been formed on the support 101.
) on 102 a −(S ixc+ −x)! (H,
X)+-y may be deposited.

In the present invention, a-(Siic+-x)y (H,
X) The raw material gas for ry formation is a gaseous substance whose constituent atom is at least one of silicon atoms, carbon atoms, hydrogen atoms, and halogen atoms, or a gasified substance that Most of them can be used.

When using a raw material gas having a silicon atom as one of silicon atoms, carbon atoms, hydrogen atoms, and halogen atoms, for example, a raw material gas having a silicon atom as a constituent Ha atom and a carbon atom as a constituent atom. A raw material gas to be
If necessary, raw material gas containing hydrogen atoms or/
and a raw material gas whose constituent atoms are halogen atoms at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms and a raw material gas whose constituent atoms are carbon atoms and hydrogen atoms. and a raw material gas whose constituent atoms are halogen atoms, also mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms,
A raw material gas consisting of silicon atoms, carbon atoms and hydrogen atoms, or a raw material gas consisting of silicon atoms, carbon atoms and halogen atoms can be used in combination.

Alternatively, a raw material gas containing carbon atoms as constituent atoms may be mixed with a raw material gas containing silicon atoms and hydrogen atoms, or a raw material gas containing silicon atoms and halogen atoms as constituent atoms may be used. In the present invention, preferred halogen atoms contained in the second layer (41) 103 are fluorine, chlorine, bromine, and iodine, especially fluorine and chlorine. It is desirable.

In the present invention, raw material gases that can be effectively used to form the second layer (II) 103 include:
Examples include substances that are in a gaseous state at room temperature and pressure, or substances that can be easily gasified.

In the present invention, 5IH4, Si, H, S, which has #I constituent atoms of silicon atoms and hydrogen atoms, is effectively used as the raw material gas for forming the second layer (II) 103.
i,H,,,S i,H,. etc. 0) Si y 7 (Si
Silicon hydride gas such as 5Lane), saturated hydrocarbons having carbon atoms and hydrogen atoms, such as saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, carbon la2
-3 acetylenic hydrocarbons, simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon, silicon hydride, and the like.

Specifically, methane (CH4) is a saturated hydrocarbon.
, ethane (C,H6), propane (cJHt) n-butane (n -C,j(,,), pentane (CrHl,
), ethylene hydrocarbons include ethylene (C2H4
), propylene (C,H,), butene-1 (C4H,
), butene-2 (C4HF), inbutylene (C+H
t), pentene (CtH, ), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3H4), butyne (C4H6), and simple halogens include fluorine, chlorine, bromine, iodine, and elementary halogen gases. , hydrogen halides include FH, Hl, HC
u, HBr, interhalogen compounds include B rF, C
uF, CuF, ,Cu Fs, BrF, BrF, ,I
F7, IF5. ICJJ, IBr, silicon tahalides include S i F4, S i2F, .
S i Cl,, S i C1, B r, S i C
1, Br2.5iC9, Br3.5iCJ1,1. S
iBr4, as halogen-substituted silicon hydride, Si
H2F2, S i H, C look 2, 5iHC look 3, S i
H3C, S i H3B r, S i H,B
r2.5iHBr, as silicon hydride, S I
Silane (Si
lane), etc.

In addition to these, CF, CCUa, CBr4, CHF,...
CH, F2, CH3F, CH3Cl, CH, Br,
CH,I.

Halogen-substituted paraffinic hydrocarbons such as C2H and Cdan,
Fluorinated sulfur compounds such as SF, SF, etc., 5i (CHj
Alkyl silicide such as S i (C:, Hr)4 and S
i CM (CH,),, S ic see, (CH,
Silane derivatives such as halogen-containing alkyl silicides such as SiCl, CH, etc. can also be mentioned as effective.

These second layer (II) 103 forming substances contain silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms in a predetermined composition ratio in the second layer (II) 103 to be formed. is selected and used as desired when forming the second layer (II) 103 so that it contains.

For example, 5i can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and can form a layer with desired characteristics.
(CIIJ) 4 and 5iHC Kai, S i H, Cl as a substance containing a halogen atom.

5iC1° or S i H, CJlj, etc. at a predetermined mixing ratio and introduced in a gas state into the apparatus for forming the second layer (H) 103 to generate a glow discharge.
? ra −(SixC+−X) Y (C writer H)+−
A second layer (II)'103 consisting of y can be formed.

To form the second layer (II) 103 by sputtering, a single crystal or polycrystalline silicon wafer, a graphite wafer, or a wafer containing a mixture of silicon atoms and carbon atoms is used as a target.

These may be performed by sputtering in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements, if necessary. For example, if a silicon wafer is used as a target, the raw material gas for introducing carbon atoms, hydrogen atoms, and/or halogen atoms is diluted with #i dilution gas as necessary, and placed in a deposition chamber for sputtering. The silicon wafer may be sputtered by introducing these gases and forming a gas plasma of these gases. Alternatively, silicon atoms and carbon atoms may be used as separate targets, or a single target containing silicon atoms and carbon atoms may be used to contain hydrogen atoms and/or halogen atoms as necessary. Sputtering may be carried out in a waste atmosphere. The second W (I
I) The material for forming 103 can also be used as an effective material in the sputtering method.

In the present invention, the diluent gas used when forming the second layer (II) to 3 by a glow discharge method or a sputtering method is a so-called rare gas such as He, Ne, A
r, etc. can be mentioned as suitable ones.

The second layer (II) 103 in the present invention is carefully formed so that its required properties are imparted as desired. That is, substances whose constituent atoms are silicon atoms, carbon atoms, hydrogen atoms and/or halogen atoms as necessary,
Depending on the manufacturing conditions, the structure can range from crystalline to amorphous, and the electrical properties can vary from conductive to semiconductive to insulating, and from photoconductive to non-photoconductive. In the present invention, a −(S
In order to form ixC+-x) y(H, For example, in order to provide the second layer (II) 103 with the main purpose of improving electrical voltage resistance, a-(SixC+-X
)Y (H,

In addition, when the second r(II) 103 is provided with the main purpose of improving the characteristics of continuous repeated use or the characteristics of the usage environment, the degree of electrical insulation described above is relaxed to some extent, and the irradiated light is As an amorphous material with a certain degree of sensitivity, a - (S 1xc1- x ) y[H, X)
1-y is created.

On the surface of the first layer (I) 102, a−(Sixc+−
Second layer (11) 1 consisting of X)y (H,X)+-y
The temperature of the support lO1 during layer formation is an important factor that influences the structure and properties of the formed layer. It is desirable that the temperature of the support during layer formation be tightly controlled so that SixCI X)V (H,X)+-Te can be formed as desired. In the present invention, an optimal range is appropriately selected in accordance with the method of forming the second layer (H) 103 in order to effectively achieve the desired purpose, and the second layer (H) 103 is
1) Formation of 103 is carried out, and the support temperature during layer formation is preferably 20 to 400°C, more preferably 50°C.
It is desirable that the temperature be 100 to 300°C, most preferably 100 to 300°C.

To form the second layer (F) to 3, glow discharge is used to form the second layer (F) to 3. However, when forming the second layer (II) 103 using these layer forming methods, the discharge power during layer formation should be adjusted as well as the support temperature described above. is created a
-(S ixc+-x )yXl-y is one of the important factors that influences the characteristics of y.

a having the characteristics for achieving the object of the present invention;
-(S ixc+ -x)yX+-y is preferably produced at a high productivity and effectively at a discharge power condition of lO to 300W, more preferably 20 to 250W, and optimally 50 to 200W. is desirable.

The gas pressure in the deposition chamber is preferably between o, oi and 1'Torr.
, more preferably about 1 to 0.5 Torr.

In the present invention, the support temperature and discharge power for forming the second layer (II) 103 may be within the above-mentioned ranges, but these layer formation factors may be determined independently and separately. The desired characteristics a − (S 1xc1- x ) y (H,
) It is desirable that the optimum value of each layer forming factor be determined based on the mutual organic relationship so that the second layer (II) 103 consisting of 1-y is formed.

Second layer (II) 103 in the photoconductive member of the present invention
The amount of carbon atoms contained in the second layer (II) 103
This is an important factor for forming the second layer (II) 103 that provides the desired characteristics to achieve the object of the present invention. Second layer (II) 1 in the present invention
The amount of carbon atoms contained in 03 is the same as that of the second layer (II).
It can be determined as desired depending on the type of amorphous material constituting the material 103 and its characteristics.

That is, the general formula a-(SixC1-x) y(H,
The amorphous material represented by
It is written as a-S 1ac1-aJ.

and hydrogen atoms (hereinafter referred to as r a
It is written as -(SibC1-b)cH+-cl. however,
0<b, cal), and an amorphous material composed of silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms (hereinafter ra-(StdC+-d) e (H,
X)+−eJ. However, it is classified as 0<d, e<1).

In the present invention, the second layer (II) 103 is a-3ia
When composed of C4-a, the amount of carbon atoms contained in the second layer (II) 103 is preferably 1X1O to 90
atomic %, more preferably 1 to 80 atomic %, optimally lO~
A desirable content is 75 atomic %. That is, if we use the previous representation a-3iaC1-ac7)a(7), a
is preferably o, i~0.99999, more preferably 0
．． 2 to 0.99, optimally 0.25 to 0.9.

In the present invention, the second layer (II) 103 is a-(S
When composed of ibC1-b)c Ih-c, the amount of carbon atoms contained in the second layer (11) 103 is preferably lXl0 to 90 at%, more preferably 1
The content of hydrogen atoms is preferably 1 to 40 at%, more preferably 5 to 30 atoms for 2-b. %, and the photoconductive member formed when the hydrogen content is within these ranges is
It is excellent in practice and can be fully applied.

That is, first ty) a - (S 1bc1-b) Hl-
If expressed as c, b is preferably 0.1-0.9999
9, more preferably 0.1 to 0.99, optimally 0.15
-0.9, C is preferably 0.6-0.99, more preferably 0.65-0.98, optimally 0.7-0.95.

The second ty) layer (II) 103 is a −(S idC+
-d)e (H,X)ie, the content of carbon atoms contained in the second layer (II) 103 is preferably l The content of halogen atoms is preferably 1 to 90 atom %, optimally 10 to 80 atom %, and the content of halogen atoms is preferably 1 to 20 atom %, more preferably 1 to 18 atoms. %, optimally 2 to 15 atomic %,
A photoconductive member produced when the halogen atom content is within these ranges can be sufficiently applied in practice, and furthermore, the hydrogen atom content may be preferably contained as needed. is 19 atomic % or less, more preferably 1
It is desirable that the content be 3 atomic % or less.

That is, the previous a −(SidC+−d) e (H,X)
If expressed as d and e of +-e, d is preferably 0.1
~0.99999, more preferably 0.1-0.99, optimally 0.15-0.9°e, preferably 0.8-0.
99. More preferably 0.82 to 0.99, most preferably 0.
It is desirable that it is 85 to 0.98.

The number range of the layer thickness of the second layer (II) 103 in the present invention is one of the important factors for effectively achieving the purpose of preventing explosions, and effectively achieving the purpose of the present invention. It can be determined as desired depending on the intended purpose.

Moreover, the layer thickness of the second layer (II) 103 is the same as that of the layer (II) 1
The amount of carbon atoms contained in 03 and the first layer (I) 10
The relationship with the layer thickness in 2 also needs to be appropriately determined according to the desired characteristics based on the characteristics required for each layer area. It is also desirable to consider the economical aspects, including mass production.

The thickness of the second layer (II) 103 in the present invention is preferably 0.003 to 30 JL, more preferably 0.003 to 30 JL.
It is desirable that the angle is between 0.004 and 20Ji, most preferably between 0.005 and 10Ji.

The support 101 used in the present invention may be electrically conductive or electrically insulating.

Examples of the conductive support include NiCr, stainless steel, AU, Cr, Mo, Au, and Nb.

Examples include metals such as Ta, V, Ti, Pt, and Pd, and alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, paper, etc. are usually used. Ru.

Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, NiCr, ,A
n, Cr, Mo, Au, Ir.

Nb, Ta, V, Ti, PL, Pd, I n20. , S
Conductivity is imparted by providing a thin film consisting of n O,, I To (I n, O, + S no ρ, etc.)
Alternatively, if it is a synthetic resin film such as a polyester film, NiCr, -AJI, Ag, Pb, Zn, Ni,
Au, Cr, Mo, Ir, Nb.

Conductivity is imparted to the surface by providing a thin film of a metal such as Ta, V, Ti, or Pt on the surface by vacuum evaporation, electron beam evaporation, sputtering, or the like, or by laminating the surface with the metal.

The support 101 may have any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. 1 may be used as an electrophotographic image forming member. In the case of continuous high-speed copying, it is desirable to use an endless belt or a cylindrical shape.

The thickness of the support 101 is determined as appropriate so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the thickness of the support 101 may be determined so that it can sufficiently function as a support. It is made as thin as possible within the range. In such a case, the thickness of the support 101 is preferably lO# from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.
It is considered to be L or higher.

Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained.

FIG. 14 shows an example of a photoconductive member manufacturing apparatus.

In the figure, gas cylinders 1102 to 1106 are sealed with raw material gases for forming the photoconductive member of the present invention. 99.999%, hereinafter S
i Abbreviated as H4/He. ) cylinder, 1103 is He
GeH4 gas (purity 99.999%, hereinafter abbreviated as GeH4/He) cylinder, 1104 is H
S i F4 gas diluted with e (purity 99.99%,
Hereinafter abbreviated as S i F4/He, ) cylinder, 110
5 is NH3 gas (purity 99.999%) cylinder, 11
06 is a H gas (purity 99.999%) cylinder.

In order to flow these gases into the reaction chamber 1101, valves 1122 to 112B of gas pumps 1102 to 1106,
Make sure the leak valve 1135 is closed,
In addition, inflow valves 1112 to 1116 and outflow valve 111
After confirming that 7 to 1121 and auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, the reading valves 1132 and 1133 of the vacuum gauge 1136 and the outflow valves 1117 to 1121 are closed.

Next, to give an example of forming a photoreceptive layer on the cylindrical substrate 1137 as a support, Si H4/He gas from the gas cylinder 1102,
The G e H4/He gas from the gas pump 1103 and the NH gas from the gas pump 1105 are supplied to the valve 1122.
, 1123.1125 and outlet pressure gauge 1127.
1128°1130 (7) By adjusting the pressure to 1 kg/crn' and gradually opening the inlet valves 1112, 1113, and 1115, the mass flow controller 1107
．． 1. t o a and t t to respectively. Subsequently, the outflow valve 1117°111B, 1
120, gradually open the auxiliary valve 1132 to allow each gas to flow into the reaction chamber 1101; S i at this time
Adjust the outflow valves 1117, 1118, and 1120 so that the ratio of 84/ He gas flow rate and G e H4/ Adjust the opening of main valve 1134 while watching the reading on vacuum gauge 1136 so that the pressure is at the desired value. After confirming that the temperature of the substrate 1137 is set to a temperature in the range of 50 to 400°C by the overheating heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. At the same time, according to a pre-designed rate of change curve, the valve 11 is manually or externally driven by a motor, etc.
The flow rate of the NH3 gas is adjusted by appropriately changing the opening 20, thereby controlling the distribution concentration C(N) of nitrogen atoms contained in the layer formed. Thus, the first layer (I) 102 is formed on the base 1137.

First layer (I) 1 formed to a desired layer thickness as described above
To form the second layer (TI)' 103 on the 02, each of 1, for example, SiH4 gas, C2H, and gas, is required by the same valve operation as in the formation of the first layer (I) 102. Accordingly, the reaction chamber 1101 is diluted with a diluent gas such as He.
The glow discharge may be generated according to desired conditions.

In order to contain halogen atoms in the second layer (II) 103, for example, add S i F4 gas and C2H gas, or add S i H gas to this and form the second layer (II) in the same manner as above. ) 103 may be formed.

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 1101. In order to avoid gas remaining in the gas piping leading from the valves 1117 to 1121 to the reaction chamber 11O1, the outflow valves 1117 to 1121 are closed, the auxiliary valves 1132 and 1133 are opened, and the main valve 1134 is fully opened to temporarily drain the system. Perform operations to evacuate to high vacuum as necessary.

The amount of carbon atoms contained in the second layer (II') 103 can be determined by, for example, changing the flow rate ratio of S f H4 gas and C2 gas introduced into the reaction chamber 1101 in the case of glow discharge as desired. Alternatively, when forming a layer by sputtering, the desired shape can be formed by changing the sputtering area ratio of the silicon wafer and graphite wafer when forming the target, or by changing the mixing ratio of silicon powder and graphite powder and forming the target. It can be controlled accordingly. The amount of halogen atoms contained in the second layer (II) 103 can be determined by adjusting the flow rate when a raw material gas for introducing halogen atoms, for example, S r F4 gas, is introduced into the reaction chamber 1101. It will be done.

Further, during layer formation, it is desirable that the base 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation.

Examples will be described below.

Example 1 Using the manufacturing apparatus shown in FIG. 14, (sample Mail-1-13-3) as an electrophotographic image forming member was placed on a cylindrical An substrate as a support under the conditions shown in Table 1. (Table 2).

The content distribution concentration of germanium atoms in each sample is the first
The distribution concentration of nitrogen atoms is shown in FIG. 5, and in FIG. 16.

Each sample thus obtained was placed in a charging exposure experimental device (15), corona charged for 0.3 seconds (sec) using OKV, and immediately exposed to a light image.

The light image uses a tungsten lamp light source, 2fLux*s
A light amount of EC was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the sample (imaging member) by cascading the surface of the sample (imaging member) with a θ-chargeable developer (including toner and carrier). The toner image on the sample is +5
, transferred onto transfer paper with 0KV corona charging, l, S
Even for samples with misalignment, clear, high-density images with excellent resolution and good gradation reproducibility were obtained.

In the above, each sample was subjected to the same toner image forming conditions except that an 810 nm GaAs semiconductor laser (10 mW) was used instead of a tungsten lamp as a light source and 11 electrostatic images were formed. When the image quality m4' 1lIt+ of the toner-transferred image was tested, all samples showed clear, high-quality images with excellent resolution and good gradation reproducibility.

Example 2 Using the manufacturing apparatus shown in FIG. 14, samples (sample positive, 21-1 to 23 -5
) were created respectively (Table 4). In addition, in Table 3, the layer (
I)) The first layer was formed on the A pattern substrate, and the second layer was formed on the first layer.

The concentration distribution of germanium atoms in each sample is shown in Figure 15, and the distribution concentration of nitrogen atoms is shown in Figure 16.

When each of these samples was subjected to image evaluation tests similar to those in Example 1, it was found that the other samples also provided high quality toner transfer images.
When tested 200,000 times in an 80% RH environment, none of the samples showed even one drop in image quality.

Example 3 Sample No. of Example 1 except that the conditions for forming the layer (h) 103 were as shown in Table 5.

11-1. Similar to 12-1.13-1 - and hand Fj
Each of the electrophotographic imaging members (sample no.
, 1l-1-1~11-1-8.12-1-1~12-
1-8.24 samples from 13-1-1 to 13-1-8)
It was created.

Each of the electrophotographic image forming members obtained in this way was individually installed in a copying machine, and the electrophotographic image formation corresponding to each example was performed under the same conditions as described in Section 91. For each member, an overall image quality evaluation of the transferred image and an evaluation of durability after repeated continuous use were conducted.

Table 6 shows the results of the overall image quality evaluation of the transferred image of each sample and the evaluation of durability after repeated and continuous use.

Example 4 When forming the layer (IL) 103, one layer (It) 10 was formed by changing the target area ratio of silicon wafer and graphite.
Each of the image forming members was created in exactly the same manner as Sample No. 11-1 of Example 1, except that the content ratio of silicon atoms and carbon atoms in Sample No. 3 was changed. After repeating the image forming, developing, and cleaning steps approximately 50,000 times as described in Example 1 for each of the image forming members thus obtained, image evaluation was performed, and the results shown in Table 7 were obtained. Obtained.

Example 5 When forming the layer (1) 103, SiH4 gas, C, H,
Each of the image forming members was prepared in the same manner as Sample No. 12-1 of Example 1, except that the content ratio of silicon atoms and carbon atoms in the first layer (M) 103 was changed by changing the gas flow rate ratio. It was created.

After repeating the steps up to transfer approximately 50,000 times using the method described in Example 1 for each image forming member thus obtained,
When the image was evaluated, the results shown in Table 8 were obtained.

Example 6 When forming the layer (I) 103, Si H4 gas, Si
By changing the flow rate ratio of F+ gas, C and H4 gas, layer (and) 1
Each of the image forming members was created in exactly the same manner as Sample No. 13-1 of Example 1, except that the content ratio of silicon atoms and carbon atoms in Sample No. 03 was changed. After repeating the image forming, developing and cleaning steps as described in Example 1 approximately 50,000 times for each of the image forming members thus obtained, image evaluation was performed and the results shown in Table 9 were obtained.

Example 7 Each of the image forming members was created in exactly the same manner as Sample No. 11-1 of Example 1, except that the layer thickness of layer (n) 103 was changed. The image forming, developing and cleaning steps as described in Example 1 were repeated to obtain the results shown in Table 10.

\1, ゝ\ \ Table 2 Table 4 Table 10 The layer forming conditions in the embodiments of the present invention shown in Table 10 and above are shown below.

Substrate temperature: germanium atom (Ge) containing layer...approximately 2
00℃ Discharge frequency +13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[Brief explanation of the drawing]

Fig. 1 is a 42-style layer structure diagram for explaining the layer structure of the photoconductive member of Kiba IJJ, and Figs. 2 to 1O are, respectively.
Explanatory diagrams for explaining the distribution state of germanium atoms in the first layer (I), and FIGS. 11 to 13 respectively explain the distribution state F1 of nitrogen atoms in the first layer (I). FIG. 14 is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS. 15 and 16 respectively show the content distribution concentration state of each atom in the example of the present invention. It is a distribution state diagram. 100... Photoconductive member 101... Support 102... First R(I) 103... Second layer (II) 104... Photoreceptive layer Applicant: Canon Co., Ltd. Figure 1 +05 1o. Figure 4 1111-C C C C(N) C(N) (1-%) (1502) (+5031 Figure 16 (1601) (atomic %) (+602) (+603)

Claims (8)

[Claims] (1) a support for a photoconductive member; a first layer exhibiting photoconductivity and provided on the support; - a second layer formed of an amorphous material containing silicon atoms and carbon atoms, the first layer containing nitrogen atoms; The layer region (N) has a layer region (N) in which the distribution concentration C(N) of nitrogen atoms in the layer thickness direction continuously increases from the support side toward the light-receiving layer side. A photoconductive member characterized by having (Y). (2) The photoconductive member according to claim 1qr, wherein the first layer contains hydrogen atoms. (3) The photoconductive member according to claims 1 and 2, wherein the first layer contains halogen atoms. (4) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer is non-uniform in the layer thickness direction. (5) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer is uniform in the layer thickness direction. (6) The photoconductive member according to claim 1, wherein the first layer contains a substance that controls conductivity. (7) The photoconductive member according to claim 6, wherein the substance that governs conductivity is an atom belonging to Group Ⅰ of the periodic table. (8) The photoconductive member according to claim 6, wherein the substance that controls conductivity is an atom belonging to Group V of the periodic table.