JPS60138557A - Photoconductive member - Google Patents

Abstract

PURPOSE:To improve sensitivity, durability, etc. 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 forming the 1st amorphous layer in such a way that the concn. distribution of N in said layer is smooth in the layer thickness direction and that the max. concn. part exists in the layer. CONSTITUTION:The 1st amorphous layer 102 contg. Si and Ge is formed on a conductive base 101 such as an Al drum in such a way that Ge is distributed uniformly in the layer thickness direction, or has the max. concn. in the surface of the base 101 and decreases gradually in the layer thickness direction. At the same time N is incorporated into the layer 102 in such a way that the concn. distribution thereof decreases gradually and smoothly in the layer thickness direction and that the area distributed with the max. distribution exists near the surface of the layer on the side opposite from the base 101. A layer 103 contg. Si and C is laminated on such layer 102 to form a photoreceptive layer 104. The photoconductive member which has high photosensitivity, is not limited by the using environment, has excellent durability, etc. and yields the image having high quality 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 resistance (Id)), absorption spectrum characteristics that match the spectral characteristics of the electromagnetic waves to be irradiated, fast photoresponsiveness, desired dark resistance value, and resistance to the human body during use. Solid-state imaging devices are required to have characteristics such as being non-polluting and being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member that is incorporated into an electrophotographic apparatus used in an office as an S-motor, the above-mentioned non-polluting property during use is an important point.

Based on these points, amorphous silicon (hereinafter referred to as a-5i) is an optical G-type member that has recently attracted attention.
Publication No. 855738 describes an image forming member for electrophotography,
DE 2933411 describes an application to a photoelectric conversion reader.

According to Heigo et al., a photoconductive member having a photoconductive layer composed of conventional A-5I 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 points that can be further improved in terms of use environment characteristics such as moisture resistance and stability over time, and it is necessary to improve the 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, in the past, it has often been observed that residual potential remains during use, and this type of When a conductive member is repeatedly used for a long period of time, fatigue due to repeated use accumulates, resulting in so-called ghost development in which an afterimage occurs. Alternatively, when used repeatedly at high speeds, inconveniences such as a gradual decrease in responsiveness often occur.

Furthermore, a-3i has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it different from the semiconductors currently in practical use. In matching, when commonly used halogen lamps and fluorescent lamps are used as light sources, there is still room for improvement in that the long wavelength side light cannot be used effectively. . Additionally, if the irradiated light is not absorbed sufficiently in the photoconductive layer and more of the light reaches the support, the support itself will absorb more of the light that passes through the photoconductive layer. When the reflectance is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images.

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

Furthermore, when the photoconductive layer is composed of a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive 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 thickness of one layer exceeds a thickness of about 100 mm, the layer may lift or peel off from the surface of the support, or cracks may occur in the layer as time passes 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 above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the above points, and includes the applicability of a-Si as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., and its lε uses. As a result of comprehensive research and consideration from this perspective, we have developed an amorphous material containing 117 silicon atoms and germanium atoms and at least one of hydrogen atoms or halogen atoms, so-called hydrogenated amorphous silicon germanium, and halogenated amorphous material. Amorphous silicon germanium or halogen-containing hydrogenated amorphous silicon germanium [hereinafter referred to as r
a-5iGe(H, This photoconductive material not only shows extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in every respect, especially as a photoconductive material for electrophotography. The present invention is based on the discovery that it has the following properties 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 the support and between each layer of the a-layer, and to have a dense and stable structural arrangement; An object of the present invention is to provide a photoconductive member with high layer quality.

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

Yet another object of the invention is high concentration.

To provide a photoconductive member for electrophotography, which can easily produce high-quality images with 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 photo@type member of the present invention includes a support for a photoconductive member, a first layer exhibiting photoconductivity made of an amorphous material containing silicon atoms and germanium atoms, and silicon atoms and carbon atoms. and a second layer made of an amorphous material containing nitrogen atoms, the first layer containing nitrogen atoms and having a smooth concentration distribution in the layer thickness direction. It is characterized in that the maximum distribution concentration is within the first layer.

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 on the support is strong, has excellent adhesion to the low support, and can be used continuously at high speed for a long time. Can be used for reversing.

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 is fast light response.

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

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

The photoconductive member lOO shown in FIG. 1 includes a support 101 for photoconductive member, a first layer (I) 1'02 provided on the support 101, and a first layer (I) 102,,
A second layer (II) 103 provided in I-.

The first layer (I) 102 is a-3iGe (II,
X), contains nitrogen atoms, and has photoconductivity.

The first layer (I) 102 and the second layer (II) 103 constitute a photoreceptive layer 104.

The germanium atoms may be contained in the first layer (I) 102 so as to be evenly distributed in the first layer (I) 102, or may be contained evenly in the layer thickness direction. However, the distribution concentration may be non-uniform. In either case, in the first layer (I) 102, germanium atoms are uniformly distributed and contained evenly in the in-plane direction parallel to the surface of the support. This is necessary from the point of view of making the characteristics uniform in the inward direction.

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 105 of the photoreceptive layer 104). side)
+04 to the side of the support lO1 (the interface side with the support lot of the light receiving chamber 1), or so that the distribution is the opposite. First layer (I) 102
Germanium atoms are contained therein.

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

FIGS. 2 to 1O show typical examples in which the distribution state of germanium atoms contained in the first layer (I) 102 in the layer thickness direction is non-uniform.

In Figures 2 to 1θ, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the first W(I) indicating photoconductivity.
102, t is the position of the layer surface on the support 101 side, and tT is the first layer (I) on the opposite side from the support side.
The position of the surface of 102 is shown. That is, the first layer (I) 102 containing germanium atoms is formed from the position t toward the position t□.

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

In the example shown in FIG. 2, from the interface position ff1t8 where the surface of the first layer (I) 102 containing germanium atoms and the surface of the support 101 are in contact with each other, the germanium atoms have a distribution concentration C is contained in the first layer (I) while taking a constant value of C7, and from the position t to the interface position t
It is contained in (I) of the first layer so that the distribution concentration gradually and continuously decreases from 02 up to □. At one interface position, the distribution concentration C of germanium atoms is C3.

In the example shown in FIG. 3, the first layer (I) 102
The distribution concentration C of germanium atoms contained in is at the position t,
A distribution state is formed in which the concentration gradually and continuously decreases from C4 until reaching position tT, and reaches C6 at the position.

In the case of FIG. 4, the distribution concentration C of germanium atoms contained in the first 5(I) 102 is from position 1B to position t2.
The concentration C6 is a constant value from position t2 to position tT.
The distribution concentration C is gradually and continuously reduced as it approaches , and the distribution concentration C is substantially zero at position t (substantially zero here means less than the detection limit amount).

In the case of FIG. 5, the distribution concentration C of germanium atoms contained in the first layer (I) 102 is from position tB to position t,
The concentration is gradually decreased from Cg until reaching , and becomes substantially zero at the position Cg.

In the example shown in FIG. 6, the distribution concentration C of germanium atoms contained in the first layer (I) 102 has a constant concentration Cte between position tB and position 13, and In this case, the concentration officer will be criticized. Between the position t and the position 1T, the distribution density C is reduced in a wide-uniform manner from the position t3 to the position tT.

In the example shown in FIG. 7, the first layer (I) 102
The distribution concentration C of germanium atoms contained in is at position tB
The concentration C11 takes a constant value up to position t4, and
From position 4 to position 1, the distribution state is such that the concentration decreases linearly from C22 to C13.

In the example shown in FIG. 8, the distribution concentration C of germanium atoms contained in the first W (I) 102 is a linear function such that the concentration CI4 reaches substantially zero from position t8 to position t1. is decreasing.

In FIG. 9, the distribution concentration C of germanium atoms contained in the first layer (I) 102 varies from position 1B to position t.
5, the concentration CI decreases in a linear manner until the concentration C1G reaches position t, and position t.

An example is shown in which the concentration CI6 is set to a constant value between .

In the example shown in FIG. 10, the distribution concentration C of germanium atoms contained in the first layer (I) is 017'I1% at position t, and this concentration C1° up to position t. At first, the concentration is decreased slowly, and around the position t6, it is rapidly decreased to the concentration CIf at the position 1G. Between position 1G and position Ht7, the concentration decreases rapidly at first, and then gradually decreases to reach CI4 at position t7, and then between position t7 and position 1.
．． is gradually reduced very slowly to reach the concentration C2o at the lower position. Between position t8 and position MtT, the concentration is reduced from C2° to substantially zero according to a curve shaped as shown in the figure.

As described above, according to FIGS. 2 to 10, the first layer (I
), 102, as described above, in the present invention, on the support lO1 side, the portion where the distribution of germanium atoms is high at 0 degrees C. and on the interface 1T side,
A preferred example is a case where the first layer (I) 102 is provided with a distribution state of germanium atoms having a portion where the distribution concentration C is considerably lower than that on the support 101 side.
It is mentioned as one of the

First layer (I) 1 constituting 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 five ends in the layer thickness direction from the interface position t8.

The above localized region (A) may be the entire layer region (LT) from the interface position t to a thickness of 5IL, or may be a part of the layer region (L). .

Whether the localized region (A) is a part or all of the layer region (L,) is determined as appropriate according to the characteristics required of the first layer (I) 1 (12) to be formed. .

In the localized region (A), the distribution state of the germanium atoms contained therein in the layer thickness direction is such that the maximum value Cmax of the distribution concentration of germanium atoms is the sum of the distribution concentration of germanium atoms and silicon atoms.
Preferably 1000 atomic ppm or less, more preferably 5000 atomic ppm or more, optimally 1xlO atomic ppm
It is desirable that the layers be formed so that the distribution state described above can be achieved.

That is, in the present invention, the first layer (I) 102 containing germanium atoms has a maximum distribution concentration ( a II is formed so that C1aX exists
It's frightening.

In the present invention, the content of germanium atoms contained in the first layer (I) '102 is determined as desired so as to effectively achieve the object of the present invention. Preferably 1 to 9.
5X10 atomic ppm, more preferably ioo~8X
I O' atoms ppm, optimal Niha, 500~7X
10/[It is preferable to set it as a child ppm.

The distribution state 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 such that the distribution state of germanium atoms is such that the germanium atoms are distributed in the entire layer region. If a decreasing change is provided towards the free surface 105 side of the layer 104 or vice versa, the rate of change curve of the distributed concentration C can be arbitrarily designed as desired. By doing so, the first W(D 102) having the required characteristics can be realized as desired.

For example, the distribution concentration C of germanium atoms in the first layer (I) 102 should be sufficiently increased on the support lot side, and should be as low as possible on the free surface 105 side of the photoreceptive layer 104. By applying changes in the distribution concentration C to the distribution concentration curve of germanium atoms, high photosensitivity can be achieved for light in the entire range of wavelengths from relatively short wavelengths to relatively long wavelengths, including the visible light region. In addition, it is possible to effectively prevent interference with coherent light such as laser light.

Furthermore, as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the end of the first layer CI) 102 on the side of the support 1O1, when a semiconductor laser is used, Light on the long wavelength side that cannot be absorbed sufficiently on the laser irradiation surface side of the photoreceptive layer 104 can be substantially completely absorbed in the end layer region of the support lot side of the photoreceptive layer 104. , interference due to reflection from the support surface can be effectively prevented.

In the photoconductive member of the present invention, the first layer (I ) 102 is provided with a layer region (N) containing nitrogen atoms. Nitrogen atoms may be contained evenly in the entire layer region of the first layer (I) 102, or may be contained only in a part of the layer region of the first layer (t)toz so that they are omnipresent. You can let me.

In the present invention, the distribution state of nitrogen atoms in the layer region (N) is uniform in the in-plane direction parallel to the surface of the support 101, but The layer is non-uniform in the thickness direction.

In the example shown in FIG. 11, the distribution concentration C(N
) has a concentration C,1 in the layer region from surface position t8 to position tq of the first layer 102 on the side of the support, and at position t
, to position t1. ．． In the layer reading up to, position 1L
? from position t1. The distribution density rapidly increases to a peak value C7 at position t1°. from position Rt, , to position tI
In the layer region up to +, the distribution concentration of nitrogen atoms C(N)
decreases rapidly as it approaches position tll, and support 1
The concentration C at the surface position ta of the first layer 102 on the opposite side from 01
It will be 21.

In the example shown in FIG. 12, the distribution concentration C(N
) is the concentration C in the layer region from position t8 to position t12.
In the layer region from position t12 to position tIB, which is assumed to be ZI, it rapidly increases from position t12 to position t13, and then at position t1
1, the distribution concentration takes a peak value C2, and decreases to almost zero in the layer region from position tn to position tT as it approaches position tT.

In the example shown in FIG. 13, the distribution concentration C(N
) is C4 in the layer region from position tI to position t14.
It increases gradually from 02 ma to 02 ma, and reaches the peak value CxL of the distribution concentration at position t14, and in the layer region from position t14 to position t, it decreases rapidly as the position approaches 02, and at position 0, the concentration reaches C2. becomes.

In the example shown in FIG. 14, the distribution concentration C(N
) is from position tB to position tIs with one concentration C2°.
The concentration decreases as it approaches , and reaches the concentration CXt at position t13. In the layer region from position t13 to position t16, the distribution concentration C(N) of nitrogen atoms is constant at concentration C2. In the layer region from position 1G to position t1□, the nitrogen atom distribution concentration C(N) increases, and the position tnn distribution composition (
N) takes the peak value C2.

In the layer region from position t, 7 to position t□, the distribution concentration C(N) of nitrogen atoms decreases and reaches the concentration Czr at position t1.

In the present invention, when the main purpose of the layer region (N) containing nitrogen atoms provided in the first layer (I) 102 is to improve photosensitivity and dark resistance, the layer region (N) containing nitrogen atoms provided in the first layer (I) 102 is Layer (I)
In order to prevent charge injection from the free surface of the photoreceptive layer, it is provided so as to occupy the entire layer area of the support and the photoreceptive layer. When the main purpose is to strengthen the adhesion between the first W (I) 102 and the end layer region (
E).

In the case of the above first objective, the content of nitrogen atoms contained in the layer region (N) is relatively small in order to maintain high photosensitivity, and in the case of the above second objective, the content of nitrogen atoms contained in the layer region (N) is kept free of the photoreceptive layer. Relatively large eaves to prevent charge injection from the surface, No. 3 above.
In the case of (1), it is desirable to use a relatively large amount in order to ensure enhanced adhesion to the support.

In addition, in order to achieve the above-mentioned champions at the same time, the concentration should be distributed at a relatively high concentration on the support side, the concentration should be distributed at a relatively low concentration in the center, and the interfacial layer region on the free surface side should be distributed at a relatively high concentration. , the layer region (
N) It may be formed inside.

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 one-layer region (N) itself or the layer. 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) is determined as desired depending on the properties required of the photoconductive member to be formed, but it is Preferably, 0.001 to 50 at%, more preferably 0.002 to 40 at%, optimally 0.003
It is desirable that the content be 30 atomic %.

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 ratio of the layer thickness TO of the first layer region (N) to the layer thickness T of the first layer (I) 102 is two-fifths or more, the layer region (N) ) is preferably 30 atomic % or less, more preferably 30 atomic % or less, based on T (SiGeri),
It is desirable that the content be 20 atomic % or less, most preferably 1O atomic % or less.

In the present invention, the layer region (N) containing nitrogen atoms is formed on the support 101 side or/and the second layer (I) as described above.
I) It is preferable to provide a localized region (B) in which nitrogen atoms are contained at a relatively high concentration near the 103 side, and in this case, the support 101 and the first layer (I ) 102 and the acceptance potential can be further improved.

The localized region (B) is preferably provided within 5 IL from each of the surface of the support 101 of the first layer (I) 102 and the surface of the second scrap (II) 103.

In the present invention, the localized region (B) is formed in the first layer (
I) 102, the surface of the support 101 or the second layer (II
) In some cases, it may be the entire layer region (LT) from the surface of the 103 example to a thickness of 5 μl, or in other cases, it may be a part of the layer region (LT).

Whether the localized region (B) is 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 Ctstsx of the distribution concentration C(N) of nitrogen atoms as a state in the layer thickness direction of the nitrogen atoms contained therein is preferably 500 atomic ppm or more, more preferably is more than 800 atomic ppm, optimally 1
It is desirable that the layer be formed in such a manner that a distribution state of 0,000 atomic ppm or more can be achieved.

That is, in the present invention, in the first layer (I) 102,
The layer region (N) containing nitrogen atoms is formed such that the maximum value Cmax of the distribution concentration exists within 5 layers in layer thickness from the support 101 side and the surface of the second layer (II) 103. It is desirable to In the present invention, the first
The halogen atoms contained in the layer (I) 102 are as follows:
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 therein a substance (D) that controls the conductive properties, the conductive properties of the first layer (I) 102 can be arbitrarily controlled as desired.

As the substance (D) that controls such conductive characteristics, there can be mentioned so-called impurities in the semiconductor field, and in the present invention, the first (7) layer (I) 102 to be formed
For a-3iGe(H,X) constituting the a-3iGe (H, Specifically, p-type impurities include atoms belonging to Group 1 of the Periodic IP Table (Group ■ atoms), such as boron (B), aluminum (A), gallium (Ga), indium (In), Thallium (Tl)
etc., and 11. is particularly preferably used. It is Ga. In addition, n-type impurities include atoms belonging to group V of the periodic table (WSV group atoms), such as phosphorus (P), arsenic (A
Among them, P and As are particularly preferably used.

In the present invention, the content of the substance (D) that controls the conductive properties contained in the first layer (I) 102 is determined by the conductive properties required for the second layer (I) 102 or It can be selected as appropriate based on the organic relationship, such as the relationship with the characteristics of the contact interface with the support 101 in which the second waste (I) 102 is provided in direct contact.

In addition, the substance (D) that controls the conduction characteristics described above is included in the first layer (
I) 102, the second layer (I) 10
When it is contained locally in a desired layer region of 2, particularly when it is contained in a layer region at the end of the support side of the first layer (I) 102, it is in direct contact with the layer region. The properties of the other layer regions provided and the relationship with the properties at the contact interface with the other layer regions are also considered, and the substance (D
) content is selected appropriately.

In the present invention, the content of the substance (D) that controls conduction characteristics contained in the first ff1(I) 102 is as follows:
Preferably from 0.01 to 5×1 O atoms ppm, more preferably from 0.5 to 1×1 O atoms ppm, optimally from 1 to 1×1 O atoms ppm.
Preferably, it is 5×10 atomic 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.
As described above, optimally, in the case of 100 atomic ppm or more, the substance (D) controlling the conduction characteristics is contained in the first layer (I) 1
It is desirable to locally contain the layer (E) in some layer regions of the first layer (I) 102, especially in the support side end layer region (E) of the first layer (I) 102.
) is desirable.

Among the above, by containing the substance (D>) that controls the conductive characteristics in the support side end layer region (E) of the first layer (I) 102 in a content that is equal to or more than the above value, For example, if the substance (D) is the p-type impurity described above, when the free surface 105 of the photoreceptive layer 104 is subjected to polar charging treatment, it is injected from the support 101 side into the photoreceptor Ql 04. It can effectively block the movement of electrons, and
When the substance supporting the conduction characteristics is the n-type impurity, when the free surface 105 of the photoreceptive layer 104 is charged to θ polarity, the photoreceptor layer 104 is charged from the support toi side.
It is possible to effectively prevent the movement of holes injected therein.

In this way, when the support side end layer region (E) contains the substance (D) that controls the conductivity of one polarity, the remaining layer region of the first layer (I) 102, i.e. The layer region (Z) excluding the support side end layer region (E) may contain a substance that controls the conduction characteristics of the other polarity, or may contain a substance that controls the conduction characteristics of the same polarity. The substance that controls
It may be contained in an amount much smaller than the actual amount contained in the support side end layer region (E).

In such a case, the content of the substance (D) that controls the conductive properties contained in the layer region (Z) is determined by the amount of the material (D) contained in the layer region (Z) at the end layer region J! ! It is determined as desired depending on the polarity and content of the substance contained in (E), but preferably 0.001-1000 atomic ppm.
, more preferably 0.05 to 500 atomic ppm, most preferably 0.1 to 200 atomic ppm.

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) - is preferably 30 atoms ppn+ or less. In addition to the above-mentioned case, in the present invention, the first scrap (I) 102 includes a layer region containing a substance that controls conductivity when it has one polarity, and a layer region that contains a substance that controls conductivity when it has one polarity. It is also possible to provide a so-called depletion layer in the contact layer region by providing it in direct contact with a layer region containing a substance that controls the conductivity. For example, in the first layer (I) 102, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in direct contact with each other.
A J7pn junction can be formed to provide a depletion layer.

In the present invention, the first layer (I) 102 composed of a-3i Ge (H,
For example, a-5i Ge (H,
X) To form the first layer (I) 102 composed of A raw material gas and a raw material gas for introducing hydrogen atoms and/or a raw material gas for introducing halogen atoms are introduced into a deposition chamber in which the internal pressure can be reduced at a desired gas pressure state.

A glow discharge is generated in the deposition chamber, and a-3iGe (
A layer consisting of H, X) may be formed. In addition, in order to contain germanium atoms in the first layer (I) 102 in a non-uniform distribution state, the distribution of germanium atoms at 0 degrees is controlled according to the desired rate of change curve, while a-3iGe (H,X)
What is necessary is to form a layer consisting of. In addition, in the sputtering method, a target composed of silicon atoms, or a target composed of the target and germanium atoms is used in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases. Using two targets or a mixed target of silicon atoms and germanium atoms, He, Ar
A source gas for supplying germanium atoms and a gas for introducing hydrogen atoms and/or halogen atoms diluted with a diluent gas such as layer (I
) 102 is formed. In this sputtering method,
In order to make the distribution of germanium atoms non-uniform, the target may be pattered seven times while controlling the amount of gas Ii 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 rat crystal silicon and polycrystalline germanium or single crystal germanium are housed in a deposition boat as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam. The first layer (I) 102 can be formed in the same manner as in the sputtering method, except that the evaporated material is heated and evaporated by a method such as the EB method, and the flying evaporated material is passed through a desired gas plasma atmosphere. can.

Substances that can be used as the raw material gas for supplying silicon atoms used in the present invention include SiH4, S f2H6,
Silicon hydride (silanes) in a gaseous state or which can be gasified, such as S i, lHt, S i4H, etc., can be cited as being effectively used, especially for ease of handling during layer creation work, silicon atoms S i H4 in terms of supply efficiency, etc.
, S i, H, are listed as preferred.

Substances that can be used as raw material gas for supplying germanium atoms include GeH4, Ge, H,, Ge, H,, Ge
,H,,,G e,H,,,G e,H,+,G e
Germanium hydride in a gaseous state or which can be gasified, such as 7H, , , Ge, H, , , GeyH2, is mentioned as one that can be effectively used. In terms of good atomic supply efficiency, etc., G
Preferred examples include e H,, G e2H, and G e,H.

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 Furthermore, a halogen source Y- which is in a gaseous state or can be gasified and has a silicon atom and a halogen atom as its constituent elements.
Silicon hydride compounds containing the following can also be cited as effective in Kidori 1.

Specifically, the halogen compounds preferably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, C3LF, CfLFBrF, B
Examples include interhalogen compounds such as rF, IF5, IF, ICJI, and 11Br.

As the silicon compound containing a halogen atom, so-called a silane derivative substituted with a halogen atom, there are specific examples, such as S
i,F,,3 i2F,,S i Cl,,S i B
Preferred examples include silicon halides such as r4.

When a photoconductive member characteristic of the present invention is formed by a glow discharge method using such a silicon compound containing halogen atoms, a raw material gas capable of supplying silicon atoms together with a raw material gas for supplying germanium atoms is used. The first layer (I) 1 consisting of a-3iGe containing halogen atoms can be formed on the desired support 101 without using silicon hydride gas.
02 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 supplying germanium atoms, and gases such as Ar, H2, He, etc. are introduced into a deposition chamber in which a photoreceptive layer is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases, thereby depositing them on a desired support 101. 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. The desired gas is also 1i1. ' They may be mixed to form a layer.

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 layer (I) 102 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. 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 other halogen compounds such as HF, HC, HBr, and HI are also used. hydrogen chloride.

S i H2F2, S f H,I,, S i H2C
12,5iHCU,,S i H,Br,,5iHB
r, isohalogen-substituted silicon hydride, and GeHF, ,G
eH,F,,GeH,F,GeHCl,,G
e H2Cl,, G e H3Cl, G e HB r
,,G e H,Br,,G e H,Br,G
Halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides, GeF, GeC, etc.

G e B r4, Ge■4, G e F,, G e
Gaseous or gasifiable substances such as Cl, G e Br, G e IJ germanium halides, 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 (1) 102. Since halogen is also introduced, it is used as a suitable raw material for introducing halogen in undeveloped 11.

In order to structurally introduce a hydrogen atom into the first H(1) 102, in addition to the above, H2 or S i H is used.

Silicon hydride such as S i2H, S taHr, S i4H, 6, etc. with germanium or a germanium compound for supplying germanium atoms, or GeH4, Ge
,H,,G e,H,,G e,H,,,G e,H,
2,Ge6H,,Ge7H,6,Ge,II,,
, Ge, ) 12 ml of germanium hydride and silicon or a silicon compound for supplying silicon atoms coexist in a deposition chamber to generate a discharge.

In a preferred example of the present invention, the amount of hydrogen, the amount of halogen atoms, or the sum of hydrogen atoms and halogen atoms (H+X) contained in the first layer (I) 102 of the photoconductive member to be formed is preferably 0.01 to 4o atom%, more preferably 0.05 to 3o atom%, optimally 0.1 to 2o atom%.
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;
All you have to do is control the discharge force, etc.

In the present invention, in order to provide the layer region (N) containing nitrogen atoms in the first layer (I) 102, the first layer (I) 10
Using the starting material for nitrogen atom introduction in the formation of 2 together with the starting material for forming the first R(I) 102 described above,
It may be contained in the formed layer while controlling its amount.

When the glow discharge method is used to form the layer region (N), the side ζ is a material selected from among the starting materials for forming the first R(I) 102 described above for introduction of nitrogen atoms. Starting materials 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.

Starting materials that can be effectively used as raw material gases for introducing nitrogen atoms used when forming the layer region (N) include nitrogen as a constituent atom, or nitrogen and hydrogen as constituent atoms. For example, nitrogen (N2), ammonia (pi
Nitrogen compounds such as gaseous or gasifiable nitrogen, nitrides and azide compounds may be mentioned, such as H3), hydrazine (H,N N H2), hydrogen azide (HN, ), ammonium azide (NH4NJ), etc. I can do it. In addition to this, in addition to introducing nitrogen atoms, halogen atoms can also be introduced, so nitrogen fluoride (F, N), nitrogen tetrafluoride (F,
Examples include halogenated nitrogen compounds such as Nρ.

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 (02) and ozone (02).
5), -Nitrogen oxide (NO), nitrogen dioxide (N or)
, -nitrogen dioxide (N20), nitrogen sesquioxide (N, Oyo), nitrogen tetroxide (N, 04), nitrogen sesquioxide (N20
ρ, nitrogen dioxide (N O,) whose constituent atoms are silicon atoms, # elementary atoms, and hydrogen atoms, for example, disiloxa 7
(HySiO5il(,), trisiloxa7(H,
Examples include lower siloxanes such as 5iO3iH, 08iH, and the like.

In order to form the layer region (N) by the subinterning method, a monocrystalline or polycrystalline silicon wafer or silicon wafer (Si), N4'7 wafer, or silicon atoms is used during the formation of the first layer (CI) 102. The sputtering may be carried out by using a wafer containing a mixture of Si3N4 as a target and sputtering the wafer in various gas atmospheres.

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 can be diluted with a diluent gas as necessary to create a sputtering target. The silicon wafer may be sputtered by introducing the gas into a deposition chamber and forming a gas plasma of these gases.

Alternatively, silicon atoms and S t3N4 may be used as separate targets, or silicon atoms and Si, N4 14
By using a single combined target, sputtering can be carried out in an atmosphere of a diluent gas such as Spunter River gas or 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, raw wood for introducing nitrogen atoms in the raw material gas shown in the glow discharge example mentioned above is used:
1 gas can also be used as an effective gas in the case of sputtering.

In the present invention, when a layer region (N) containing nitrogen atoms is provided when forming the first fi(I) 102, the distribution concentration of nitrogen atoms contained in the layer region (N) C(N)
In the case of glow discharge, the distribution concentration C(N) is changed in the WJI direction to form a layer region (N) having a desired distribution state (depth profile) in the layer thickness direction.
The starting material gas for the introduction of nitrogen atoms to be changed is
The gas meteor may be introduced into the deposition chamber while being changed appropriately according to a desired rate of change curve.

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

When forming the layer region (N) by a sputtering method, 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 shape 8 (
In order to form a depth profile), first, as in the case of the glow discharge method, a starting material for introducing nitrogen atoms is used in a gas state, and the gas flow rate when introducing the gas into the deposition chamber is adjusted. This can be done by appropriately changing as desired. Second, if a target containing a mixture of silicon atoms and S t3N+ is used as a sputtering target, for example, the mixing ratio of silicon atoms and Si, N, & should be adjusted in the direction of the layer thickness of the target. This is accomplished by making changes in advance. In order to structurally introduce a substance that governs the conduction properties, for example, a group (I) atom or a group V# atom, into the first group (I) 102, during layer formation, The starting material or the starting material for introducing ft5V group atoms may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the first phase (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. Such a number ■
Specifically, starting materials for introducing group atoms include B, I(,, B, H,., B voice 9, B, I
I,,B,II,. , BtH, □, B, H-based boron hydride, B F3, B Cl, , BBr, etc. (7) Hatf
Examples include boron f-genide. In addition, A-view Cl,,G
eC3L3, G e (CHy), I n CUs,
T I Cu, etc. can also be mentioned.

In the present invention, the starting materials for introducing Group V atoms that are effectively used for introducing phosphorus atoms are PH,
The hydrogen north end of P2H4, etc., P H4I, P F,, P
F,,P Cl,,P Cl,,PBr,,PBr,,
Examples include phosphorus halides such as P I. Other than this.

A s H,, A s F,, A s Cl,, A s
B r,, A s F,, SbH,, S b F,,
S b F,, sbc sentence 1, sbc island, B i H3,
BiC, BiBrj, 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 that constitutes the first fi(I) 102 and is unevenly distributed on the side of the support 101 and contains a substance that controls conduction characteristics is as follows: The lower limit is determined as desired depending on the characteristics required of the layer region-L and other layer regions constituting the first layer (I) 102 formed in the layer region-L.

The current is preferably 30λ or more, more preferably 40A or more, and optimally 50A or more. Further, the content of the substance controlling the conductive properties contained in the layer region is 3.
When it is 0 atomic ppm or more, the upper limit of the layer thickness of the layer region is preferably 10IL or less, preferably 8IL.
Hereinafter, the optimum value is preferably 5IL or less.

In the photoconductive member lOO 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, It is provided in order to achieve the objectives of the present invention in terms of electrical pressure resistance, usage environment characteristics, and durability.

Furthermore, in the present invention, since the four layers of amorphous material constituting the first layer (I) 102 and the second layer (II) 103 have a common constituent element of silicon atoms, , both D(I)toz and (II)103 Ir1 layer boundaries [0
In No. 1, chemical stability is sufficiently ensured.

In the present invention, the layer (II) 103 is an amorphous material (hereinafter referred to as r a -(S
1xct-x) y(H,X)+-yJ However, 0<x
, y<1).

a −(S ixc+ −X\) y(H,X:)+−
The second 75103 (II) composed of y is formed by a glow discharge method, a sputtering method, an ion plantation method, an ion blating method, an electron beam method, or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level of equipment capital investment, current manufacturing status, and desired characteristics of the photoconductive member to be produced. Advantages include that it is relatively easy to control the manufacturing conditions for manufacturing the conductive member, and that it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the second layer (II) 103 to be manufactured. A glow discharge method or a sputtering method is preferably employed.

Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in the same system to form the second layer (II) 10.
3 may be formed.

To form the first 1(II) 103 by glow discharge υ, a-(S 1xc1-x) y(H,Xh-
The raw material gas for forming y is mixed with a dilution gas at a predetermined mixing ratio as necessary, and introduced into the first chamber of the vacuum deposition chamber 1 where the support 101 is installed, and the introduced gas is turned into gas plasma by generating a glow discharge, and the first H(
I) a −(S ixC+ −x) y(H
, X)+-y may be deposited.

In the present invention, a-(Sixc+-x)y (H,
X) As the raw material gas for ry formation, most gaseous substances or gasified substances whose constituent atoms are at least one of silicon atoms, carbon atoms, hydrogen atoms, and halogen atoms are used. can be used.

When using a raw material gas that has a silicon atom as one of silicon atoms, carbon atoms, hydrogen atoms, and halogen atoms, for example, a raw material gas that has silicon atoms as a constituent atom and a carbon atom as a constituent atom. If necessary, a raw material gas containing hydrogen atoms and/or a raw material gas containing halogen atoms may be mixed at a desired mixing ratio, or silicon atoms may be used as constituent atoms. The raw material gas and the raw material gas containing carbon atoms and hydrogen atoms or/and the raw material gas containing halogen atoms are mixed at a desired mixing ratio, or silicon atoms are mixed. Use a mixture of a raw material gas containing constituent atoms and a raw material gas containing three constituent atoms: silicon atoms, carbon atoms, and hydrogen atoms, or a raw material gas containing three constituent atoms: silicon atoms, carbon atoms, and halogen atoms. You can.

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. A raw material gas containing carbon atoms as a constituent atom may be mixed with the raw material gas.

In the present invention, halogen #; (f-) contained in the second layer (II) 103 is preferably fluorine, chlorine,
Bromine and iodine are preferred, with fluorine and chlorine being particularly preferred.

In the present invention, raw material gases that can be effectively used to form the second W(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, gases that are effectively used as the raw material gas for forming the second layer (II) 103 are Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, Si, etc., whose constituent atoms are silicon atoms and hydrogen atoms, that are effectively used as the raw material gas for forming the second layer (II) 103.
, H, Si4H, etc., silicon hydride gases such as silanes (Siane), carbon atoms and hydrogen atoms as constituent atoms, e.g. saturated hydrocarbons having 1 to 4 carbon atoms, 2 carbon atoms
~4 ethylene hydrocarbons, acetylene hydrocarbons having 2 to 3 carbon atoms, simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides,
Examples include silicon hydride. Specifically, saturated hydrocarbons include methane (CH4), ethane (C, H,
), propane (c+Hr), n-butane (n -C4
H, ), pentane (CgHu), ethylene hydrocarbons include ethylene (C2H4), propylene (CJ
I4), butene-1 (CaHr), butene-2 (C
4Hρ, inbutylene (C, Hρ, pentene (CgH+
, ), and acetylene hydrocarbons include acetylene (
C, H,), methylacetylene (C, H4), butyne (c, n,), halogens include fluorine,
Halogen gases such as chlorine, bromine, and iodine, and hydrogen halides include FH, Hl, HCu, and HBr. Interhalogen compounds include BrF, C9, F, C3LF, and CU F.
,,B r Fs,BrFIF,IF,,I(11,I
Br.

31 7 Silicon halides include S i F4, S 1rFt,
S I C14,3i CM, B r, S i C1
,Br2.5iCuBr,,5iCJl,I,S i
B r, as the halogen-substituted silicon hydride, SiH
Yuuma, S f H□Cu,, 5il (CJI,, Siuma C1, SiH, Br.

S i ll2B r2.5iHBr,, as silicon hydride, S i H,, S t, n,, S i4H,
, etc., and the like can be mentioned.

Other than these CF, CC! 14, CBr4, CHF3
, CH,F, ,CH,F , CH3C4Q, CH,B
r, CH, I, C2H, Cl, etc. (7) Fluorinated sulfur compounds such as halogen-substituted paraffinic hydrocarbons, SF4, SF, etc., 5t(OH, included, 5i(qI(j)4)
Alkyl silicide such as
Silane derivatives such as halogen-containing alkyl silicides such as (GHJ), SiC, and CH3 can also be cited 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, silicon atom ζ carbon atom and hydrogen atom can be easily included in S, and a calendar of desired properties can be formed.
i (CH;)4 and 5iHCu as a substance containing a halogen atom, S i H yo C or Si 0 statement. Alternatively, a - (SixC
+-x) y The second layer consisting of (cu+H)+-y (
II) 103 can be formed.

To form the second W(II) 103 by the sputtering method, a monocrystalline or polycrystalline silicon wafer, a graphite wafer, or a wafer containing a mixture of silicon atoms and carbon atoms is used as a target. This can be carried out by sputtering in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements, if necessary6. For example, if a silicon wafer is used as a target, carbon atoms and hydrogen atoms or/and A raw material gas for introducing halogen atoms is diluted with a diluting gas as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to form the silicon wafer/\-. All you have to do is sputter. Alternatively, silicon atoms and carbon atoms may be used as separate targets, or hydrogen atoms and/or halogen atoms may be used as needed by using a single target containing silicon raw r- and carbon atoms. Sputtering may be performed in a gas atmosphere containing. In the case of the sputtering method, the second W(II) 103 forming material shown in the glow discharge example described above is used as the raw material gas for introducing carbon jic (-1 hydrogen atoms and I\rogen atoms). can also be used as effective substances.

In the present invention, the diluent gas used when forming the second layer (II) 103 by a glow discharge method or a sputtering method is a so-called rare gas, such as He, Ne, Ar,
etc. can be mentioned as suitable ones.

The second W(11)lo3 in the present invention is carefully formed so that its required properties are provided 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,x)I-y, the conditions for its formation are strictly selected as desired. For example, in order to provide the second layer (II) 103 with the main purpose of improving electrical withstand voltage, a−(SixC+−x
)y (H,X)1-y is made as an amorphous material with pronounced electrically insulating behavior in the environment of use.

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

On the surface of the first layer (I) 102 (7), a-(S izc
+-x)y (second) layer (II consisting of H, Xh-y)
) 103, the support 10 during layer formation
The temperature of 1 is an important factor that influences the structure and properties of the formed layer, and in the present invention, the temperature of a-(SixC1-x)y (H,X)+-y
It is desirable that the temperature of the support at the time of layer formation be closely controlled so that a desired layer can be formed. Second JET (II) for effectively achieving the desired objective in the present invention
In addition to the formation method of 103, the optimum range is selected as appropriate,
The formation of the second layer (II) 103 is carried out, and the temperature of the support during layer formation is preferably 20-400°C 1,1
1 Suitably 50 to 350°C, optimally loo to 300"
It is desirable that it be set to 0.

To form the second layer (II) 103, glow discharge is used to form the second layer (II) 103, since delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods. 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 one of the important factors that influences the characteristics of a −(S ixc+−x )yX+−y that is created.

a having the characteristics for achieving the object of the present invention;
-(Sixc+-x)yX+-y is preferably produced at 1O to 300W, more preferably from 20 to 250W, and optimally from 50 to 200W to effectively create yX+-y with good productivity. is desirable.

The gas pressure in the deposition chamber is preferably between 0.01 and I Torr.
, more preferably, Q, l to Q, about 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. It is not determined by the desired characteristics a − (S 1xc1− x) y ()I,
It is preferable that the optimum value of each generation factor is determined based on the mutual organic relationship so that the second 7i3(II) 103 consisting of X)+-y is formed.

The second in the photoconductive oil phase of the present invention! '(II')1
The carbon atoms contained in 03 are the second layer (II) 1
Similar to the conditions for forming 03, 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. The second D(I
The amount of carbon atoms contained in I) 103 is the same as that in the second layer (I).
I) It can be determined as desired depending on the type of amorphous material constituting 103 and its characteristics.

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

However, 0<a<1), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as "amorphous material").

r a −(S ibC+−b)c Hl−CJ, where 0<b, c<1), and an amorphous compound composed of silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms. quality material (hereinafter ra -(S id C1-d
) e (H,X)te”. However, od, e
<1).

In the present invention, the second layer (II) 103 is a-Sia
When composed of Cl-a, the second layer (II) 1 (J3
The amount of carbon atoms contained in is preferably 1×10 to 9
o atom%, more preferably 1 to 80 atom%, optimally 10 atom%
It is desirable that the content be 75 atomic %. That is,
If you use the above a-3iaC+-ac7)ac7) display,
a is preferably 0.1-=0.99999, more preferably 0.2-0.99, optimally 0.25-0.9.

In the present invention, the second layer (II) 103 is a-(S
When composed of ibC1-b)c Hl-c, the amount of carbon atoms contained in the second layer (II) 103 is preferably 1X10 to 90X10 to 90 atoms, preferably 1
~90 at%, optimally 10~B'00 atoms, and the hydrogen atom content 71 is preferably 1~40 at%, more preferably 2~35 at%, optimally is preferably 5 to 30 atom %, and photoconductive members formed when the hydrogen content is in this range are excellent in practical applications and can be sufficiently applied.

That is, if expressed in the form H to C, b is preferably o, i ~ 0.99999, more preferably 0.1-0.99, optimally 0.15. ~0.
9, C is preferably 0.6 to 0.99, more preferably 0
．． 65 to 0.98, most preferably 0.7 to 0.95.

The second (7) layer (II) 103 is a − (S idc
+-d)e (H,X)1-e,
The content of carbon atoms contained in the second layer (II) 103 is preferably 1 to 90 at%, and optimally 10 to 800 to 80 atoms. , and the content of halogen atoms is preferably 1 to 20 at%, more preferably 1 to 18 at%.
It is desirable that the halogen atom content be in the range of 2 to 15 at. Further, the content of hydrogen atoms, which may be included as necessary, is preferably 19 at % or less, more preferably 13 at % or less.

That is, prior a −(SidC+−d) e (H,X)
If expressed as d and e in v-e, d is preferably 0.1
~0.99999, more preferably 0.1-0.99. Optimally, e is 0.15-0.9, preferably 0.8-0.
99, more preferably 0.82 to 0.99, optimally 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 object of the present invention. It can be determined as desired depending on the intended purpose.

Moreover, the layer thickness of the second layer (It) 103 is the same as that of the layer (II) 1
The amount of carbon atoms contained in 03 and the first W(I)1o
The relationship between layer thickness and thickness of layer 2 must be appropriately determined as desired based on the organic relationship depending on the characteristics required for each layer region. It is also desirable to consider economic efficiency that takes into account productivity and mass production.

The layer thickness of the second 75(II) 103 in the present invention is preferably 0.003 to 30 hi, more preferably 0.003 to 30 hi.
004 to 20 cast, and preferably t to 0.005 to io = 1, N.

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

Examples of the conductive support include NiCr, stainless steel, Ai, Cr, Mo, Au, Nb, Ta, V, Ti, and P.
Examples include metals such as T, 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, NiCr1, A
n, Cr, Mo, Au, Ir, Nb, Ta, V,
Ti, PL, Pd, I n20J, SnO2, I
Conductivity can be imparted by providing a thin film made of T O (In20J+S n O,), etc., or if a synthetic resin film such as a polyester film is used, N
iCr, An, Ag, Pb, Zn, Ni, Au, Cr
A thin film of metal such as lMo, Ir, Nb, Ta, V, Ti', PL, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the above metal, and then Provides conductivity.

The shape of the support 1O1 may be 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. If used as a member for continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape.The thickness of the support 101 is determined as appropriate so that a desired photoconductive member is formed. However, l'T as a photoconductive member
When 1A properties are required, the thickness is made as thin as possible within a range that allows the function as a support to be fully exhibited.

However, in such a case, the thickness of the support 1O1 is preferably set to the thickness of 1O from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.

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

FIG. 15 shows an example of a photoconductive member manufacturing apparatus.

In the figure, raw material gases for forming the photoconductive member of the present invention are sealed in gas cylinders 1102 to 1106. As an example, 1102 is SiH4 gas diluted with He. (Purity 99.999%, hereinafter abbreviated as S i H4/He) Cylinder, 1103 is H
1104 is a cylinder of GeH4 gas (purity 99.999%, hereinafter abbreviated as GeH4/He) diluted with He, and 1104 is a SiF4 gas diluted with He (purity 99.99%).
, hereinafter abbreviated as S s F4/He. ) cylinder, 110
5 is NH, gas (purity 99.999%) cylinder, 110
6 is a H2 gas (purity 99.999%) cylinder.

In order to flow these gases into the reaction chamber 1101, valves 1122 to 1126 of gas cylinders 1102 to 1lo6.
Confirm that the leak valve 1135 is closed, and also check the inflow valves 1112 to 1116 and the outflow valve 11.
After confirming that 17 to 1121 and auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to vent 1 J of air into the reaction chamber 1101° and each gas pipe. Next, at the time of the vacuum gauge, the auxiliary valves 1132, 1133 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, 5IH4/He gas from gas cylinder 1102, G e H4/He gas from gas cylinder 1103, and G e H4/He gas from gas cylinder 1105 are used. NH, gas, valve 1122,1
Open 123.1125 and check the outlet pressure gauge 1127, 11
Adjust the pressure of 28°1130 to 1 kg/crrl',
Inflow valve! 112, 1113.1115 by gradually opening the mass flow controller 11072.1.
10B and '1110, respectively.

Subsequently, the outflow valves 1117, 1118° 1120,
The auxiliary valve 1132 is gradually opened to allow each gas to flow into the reaction chamber 1101.

S i H4/He gas flow rate and G e H at this time
Adjust the outflow valves 1117, 1118 and 1120 so that the ratio of the 4/He gas flow rate to the NH3 gas flow rate becomes the desired value, and adjust the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 becomes the desired value. Main valve 1 while checking the reading.
Adjust the opening of 134. After confirming that the temperature of the base 1137 is set to a temperature in the range of 50 to 400"C by the overheating heater 1138, the power supply 114
is set to a desired power to generate a glow discharge in the reaction chamber 1101, and at the same time, the opening of the valve 1120 is changed appropriately according to a pre-designed change rate curve manually or by applying a method such as an external drive motor. Go N
The flow rate of H and gas is adjusted to ts, thereby controlling the distribution concentration C(N) of nitrogen atoms contained in the formed layer. In this way, 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 (II) 103 on the 02, for example, S i I (4 gas, C, H, Each of these is diluted with a diluent gas such as He as necessary and placed in the reaction chamber 110.
1 and generate glow discharge according to desired conditions.

In order to contain halogen atoms in the second layer (II) 103, for example, SiF4 gas and C7H4 gas are used.

Alternatively, the second D (II), l 03 may be formed in the same manner as above by adding S i I (, gas) to this.

Needless to say, all the 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 out of the reaction chamber 1toi. In order to avoid gas remaining in the gas piping leading from the valves 1117 to 1121 into the reaction chamber 1101, 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 i H gas and C H gas introduced into the reaction chamber 1101 in the case of glow discharge as desired. Alternatively, when forming a layer by sputtering, the sputtering area ratio of the silicon wafer and the graphite wafer is changed when forming the target, or the mixing ratio of the silicon powder and the graphite powder is changed and the target is formed to obtain the desired shape. It can be controlled accordingly. The amount of halogen atoms contained in the second 75(II) 103 can be determined by adjusting the flow rate when the raw material gas for introducing halogen atoms, such as S i F, is introduced into the reaction chamber 1101. It is done accordingly.

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 Shown in Figure 15! 8! An electrophotographic image forming member (sample Notl-l-17
-4) respectively (Table 2).

The distribution concentration of germanium atoms in each sample is @1
FIG. 6 shows the distribution concentration of nitrogen atoms, and FIG. 17 shows the nitrogen atom content distribution concentration.

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

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

Immediately thereafter, a good toner image was obtained on the sample (imaging member) surface by cascading the sample (imaging member) surface with an O-charged developer (including toner and carrier). The toner image on the sample is +5.
When transferred onto transfer paper using OKV's corona charging, clear, high-density images with excellent resolution and good gradation reproducibility were obtained in all samples.

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 to form an electrostatic image. When we evaluated the image quality of toner transfer images, we found that the resolution of all samples was
- Clear, high-quality images with excellent gradation reproducibility were obtained.

Example 2 Samples (sample Nos. 21-1 to 2 Hama-4) as image forming members for electrophotography were prepared using the manufacturing apparatus shown in FIG.
) were created respectively (Table 4).

The content distribution concentration of germanium atoms in each sample is wS
FIG. 16 shows the concentration distribution of nitrogen atoms, and FIG. 17 shows the nitrogen atom content distribution concentration.

When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples provided high quality toner transfer images. In addition, each sample was heated at 38°C and 80% R.
When a repeated usage test was conducted 200,000 times in an environment of H, no deterioration in image quality was observed in any of the samples.

Example 3 Sample Nos. 11-1 and 11-1 of Example 1 were used, except that the conditions for creating the second M(π) 103 were as shown in Table 5.
Each of the Shigeko photographic image forming members (sample No., 11-1-1 to 1
1-1-8.12-1-1-12-1-8.13-1-
24 samples (1 to 13-1-8) were created.

Each of the electrophotographic image forming members obtained in this way is individually installed in a copying machine, and the overall image quality of the transferred image is evaluated for each of the electrophotographic image forming members corresponding to each example.
Table 6 shows the results of durability evaluation after repeated and continuous use.

Example 4 When forming the second layer (II) 103, the same procedure was carried out except that the target area ratio between silicon and graphite was changed and the content ratio of carbon atoms to silicon atoms in the layer (II) was changed. After repeating the developing and cleaning steps about 50,000 times as described in Example 1 for each of the image forming members using the same method as Sample No. 11-1 in Example 1, the image forming member was Upon evaluation, the boiling results shown in Table 7 were obtained.

Example 5 When forming the second layer (II) 103, SiH, gas and CL
Each of the image forming members was prepared in the same manner as in sample amount No. 12-1 of Example 1, except that the content ratio of silicon atoms and carbon atoms in F3(II) was changed by changing the flow rate ratio of horse gas. It was created.

For each image forming member thus obtained, the process up to transfer was repeated approximately 50,000 times in the manner υζ as described in Example 1, and then image evaluation was performed.
Ta.

Example 6 [7] ffiF (II) 103i mino formation, S
Sample amount No. of Example 1 except that the content ratio of silicon atoms and carbon atoms in the layer (II) was changed by changing the flow rate ratio of the i H4) gas, S i F4 gas, CeII, and the gas. Each of the image forming members was created by the same method as No. 13-1. After repeating the image formation, development and cleaning steps as described in Example 0 and 1 about 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 Sample N of Example 1 except that the layer thickness of layer (II) was changed.
Each of the imaging members was prepared in exactly the same manner as in Example No. 11-1. The image forming and phenomenon cleaning steps as described in Example 1 were repeated to obtain the results shown in Table 1θ.

Tables 6 and 10 Common preparation conditions in the above embodiments of the present invention 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 schematic layer MII diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 each illustrate the distribution state of germanium atoms in the photoreceptive layer. Figures 1'J and 1me4 and fJS11 to 14 are theory 1 for explaining the distribution state of nitrogen atoms in the photoreceptive layer, respectively.
Figures 51 and 15 are schematic explanatory diagrams of the apparatus used in the present invention, and Figures 16 and 17 are distributions showing the 0 degree state of the content distribution of each atom in the embodiment of the present invention, respectively. FIG. 100... Light guide face material 101... Support 102... First layer (I) 103... Second layer (II) 104... Light receiving layer Applicant Canon Co., Ltd. agent Private Patent Attorney Yoshi Tani - Figure 1 +05 100 C -11111-C -〇C C Figure 12 C (N) (Original -)%) (+603)

Claims (8)

[Claims] (1) Support for photoconductive member 1. Consisting of an amorphous material containing a v-body and a silicon atom and a germanium element r-,
A first layer exhibiting photoconductivity provided on the support; and a second layer provided on the second layer and made of an amorphous material containing silicon atoms and carbon atoms. and a photoreceptive layer comprising a nitrogen atom in the first layer,
A photoconductive member characterized in that the concentration distribution of the nitrogen atoms in the layer thickness direction is smooth and the maximum concentration distribution is within the first layer. (2) The photoconductive member according to claim 1, wherein the first layer contains hydrogen atoms. (3) The photoconductive member according to claim 1 and barbs 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 controls 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.