JPS60131541A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member superior in sensitivity, etc., by forming on a substrate the first amorphous layer composed of a Ge-contg. region and Si-contg. photoconductive region, and contg. a conductivity governor in a specified concn. distribution, and the second amorphous layer contg. Si and N in succession. CONSTITUTION:The first amorphous layer 102 is formed by laminating on a substrate 101 a layer region 103 contg. Ge, and a photoconductive layer region 104 contg. Si, in succession, and incorporating a conductivity governor, such as B or P, in a concn. distribution in the layer thickness direction having the max. value in the region 104 and contg. more on the side near the substrate 101. An objective photoconductive member 100 is obtained by forming the second amorphous layer 105 contg. Si and N on the layer 102 to form a photoreceptor 107.

Description

[Detailed description of the invention] The present invention is based on light (here, light in a broad sense, ultraviolet light).

The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as visible light, infrared light, X-rays, R-rays, etc.

As a photoconductive material forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it has a high sensitivity and a 8N ratio [photocurrent CI,
/dark current (Id)) has absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness and has the desired dark resistance value, and is non-polluting to the human body during use. In addition, solid-state imaging devices are required to have characteristics such as being able to easily process internal pressure for a predetermined period of 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 8-81) is a photoconductive member that has recently attracted attention, for example, German Publication No. 2746967, German Publication No.
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

A photoconductive member having a photoconductive layer composed of conventional a-81 has excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as humidity resistance, etc. It is necessary to improve the overall characteristics of J! in terms of usage environment characteristics and stability over time. The reality is that there are points that can be improved.

For example, in the case of applying it to an electrophotographic image forming member, when trying to achieve both high light sensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains in the trap during use. When a photoconductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speeds, the responsiveness gradually decreases. There were many cases where this inconvenience occurred.

Furthermore, a-8l 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 incomparable with single conductor lasers currently in practical use. In terms of matching, when using commonly used Rodan lamps and fluorescent lamps as light sources, they are improved in that they can be used effectively for light matching on the long wavelength side. There is still room left 0 Also, if the amount of irradiated light that reaches the support increases without being sufficiently absorbed in the photoconductive layer, the support itself may pass through the photoconductive layer. If the emissivity of the incident light is low, interference due to multiple reflections will occur within the photoconductive layer, which is one of the causes of blurring in images.

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

Furthermore, when the photoconductive layer is composed of a-81 nanoparticles, in order to improve its electrical and photoconductive properties, hydrogen atoms, fluorine atoms, chlorine atoms, etc. Boron atoms, phosphorus atoms, etc. are included in the photoconductive layer as constituent atoms to control the conductivity type, or other atoms are included in order to improve other properties. Depending on the method of inclusion, problems may arise in the electrical or photoconductive properties of the formed layer.

V That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charges from the support side in a dark area is not sufficiently prevented. etc. rarely occur: None. - Therefore, while efforts are being made to improve the properties of the a'-81 material itself, it is necessary to take measures to solve all of the above-mentioned problems while designing the photoconductive member.

The present invention has been made in view of the above points, and is
As a result of comprehensive research and consideration from the viewpoint of applicability and applicability as optical conductors used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that the silicon atom an amorphous material containing at least a small amount of either hydrogen atoms (6) or rhodan atoms (3), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as The layer structure of a photoconductive member having a photoreceptive layer exhibiting photoconductivity is specified as described below. The photoconductive materials designed and manufactured under this technology not only exhibit extremely superior properties in practical use, but also surpass in all respects compared to conventional photoconductive materials, especially for electrophotography. This is based on the discovery that it has extremely excellent properties as a photoconductive material and that it has excellent absorption spectrum properties on the long wavelength side.

The present invention has stable electrical, optical, and photoconductive properties at all times, is an all-environment type with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is resistant to photofatigue. Another object of the present invention is to provide a photoconductive member which is extremely durable, shows no deterioration phenomenon even after repeated use, and has no or almost no residual potential observed. It is an object of the present invention to provide a photoconductive member that has high photosensitivity in the visible light range, has excellent matching with a semiconductor radar, and has a fast photoresponse.

Another object of the present invention is that when applied as an image forming member for electrophotography, the present invention has a charge retention property during charging processing for electrostatic image formation 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 having sufficient properties.

Still another object of the present invention is to provide a photoconductive member for electrophotography that allows easy acquisition of high-quality images with high density, clear halftones, and high resolution without blurring of the image. It is to be.

Yet another object of the present invention is high photosensitivity.

It is also an object to provide a photoconductive member having high 8N ratio characteristics.

The photoconductive member of the present invention includes a support for the photoconductive member, a first layer region (0) composed of an amorphous sidewall containing one germanium atom on the support, and an amorphous layer region containing a silicon atom. a second layer region (8) made of a transparent material and exhibiting photoconductivity; , consists of 7
(a photoreceptive layer consisting of a second layer, the first layer contains a substance (C) that controls conductivity, and the substance (C)
) in the second layer region (8
) Inside the reeds, and? The material (C) is contained in the second layer region (S) K in such a manner that it is distributed more toward the support side.〇It has a layer structure as described above. The photoconductive member of the present invention designed as described above solves all of the above-mentioned problems, and has excellent electrical and optical properties.

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

5 In particular, when applied as an image forming member for electronic use, interference can be sufficiently prevented even when coherent light is used, and there is no influence of residual potential on image formation. It has stable electrical characteristics, high sensitivity, and a high signal-to-noise ratio. It has excellent light fatigue resistance and repeated use characteristics, and has high density, clear halftones, and high resolution. It is possible to stably and repeatedly obtain high-quality images.・、.

Furthermore, the photoconductive member of the present invention has high photosensitivity in the entire visible light range 1, is particularly excellent in matching with semiconductor lasers, and has a fast photoresponse.

Hereinafter, the photoconductive member of the present invention will be described in detail with reference to FIG. 1.

FIG. 1 is a schematic structural diagram schematically shown to explain the layer structure of the photoconductive member of the present invention.

The photoconductive member 100 shown in FIG. 1 has a photoreceptive layer 107 consisting of a first layer (1) 102 and a second layer (II) 105 on a support 101 for the photoconductive member. The negative layer (1)] 02 has a free surface 106 on one end surface.

The first layer (1) 102 includes glumanium atoms and, if necessary, silicon atoms (SI) from the support 101 side.

An amorphous material containing at least one of a hydrogen atom (6) and a halodane atom (a) (hereinafter referred to as r a-G@(81, H,
) A first layer region (G) composed of (abbreviated as J)
103 and a second layer region (8) 104 composed of a-8L(H+X) and having photoconductivity. Controlled substance C
), and the maximum value of the distribution concentration in the layer thickness direction of the substance (C) is in the 10th layer region ψ), and in the second layer region ψ), the maximum value of the distribution concentration in the layer thickness direction It is contained in a state where it is widely distributed.

The germanium atoms in the first point (reduction) are contained in a uniform state in the in-plane direction parallel to the surface of the support, but even if they are uniform in the layer thickness direction, they are non-uniform. It doesn't matter if there is.

In addition, if the distribution state of germanium atoms in the first layer region (03) is non-uniform in the layer thickness direction, the distribution concentration C in the layer thickness direction may be changed to the support side or the second layer region (03). 8
In particular, it is desirable that the distribution of germanium atoms in the first layer region 1 is such that germanium atoms are distributed throughout the entire layer region. is continuously distributed, and the distribution concentration of germanium atoms in the layer thickness direction C(G)
is given a change that decreases from the support side toward the second layer region (S), between the first layer region (G) and the second layer region (S). It has excellent affinity, and as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the edge of the support, almost no germanium atoms are present in the second layer region (S) when using a semiconductor radar or the like. Elements on the long wavelength side that cannot be completely absorbed can be substantially completely absorbed in the first layer region (G), and interference due to reflection from the support surface can be prevented, and 1 It is possible to suppress the reflection at the interface between the layer area eaves) and the layer area (8). A typical example of the distribution state of germanium atoms contained in the layer thickness direction is shown. Indicates the layer thickness of the layer region (G) of
) indicates the position of the end face. That is, in the first layer region O) containing germanium atoms, layers are formed from the tll side toward the ptT side.

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

In the example shown in FIG. 2, the support surface where the tenth layer region (2) containing germanium atoms is formed and the first
The interface position tll where the layer region of ) contacts the surface of )tl
Up to the position, the distribution concentration CI) of germanium atoms becomes C
Germanium atoms are contained in the first layer region formed with a constant value of I, and the position [tI is the concentration c2
It is gradually and continuously decreased by about 1 until reaching the interface position 1T. At the interface position RtT, the distribution concentration of germanium atoms is C#'i, Cs.

In the example shown in FIG. 3, the distribution concentration C of the contained dalmanium atoms is such that the concentration C4 gradually and continuously decreases from the position 1m to the position tTK, and reaches the concentration cs at the position tT. is formed.

In the case of Fig. 4, position t, horizontal position fl t! Until then, the distribution concentration C of germanium atoms is assumed to be a constant value of concentration c6, and the position t! The distribution concentration C is gradually and continuously reduced between the positions t and r, and the distribution concentration C is made substantially zero at the position tT (here, substantially zero means that the amount is below the detection limit). ).

In the case of FIG. 5, the distribution concentration C of germanium atoms is gradually and continuously reduced from the position 1B to the position t, and becomes substantially zero at the position tT.

In the example shown in FIG. 6, the distribution concentration C of germanium atoms is a constant value of concentration C9 between position 1B and position t3, and the concentration C at position flttT. be done. Between the position ts and the position tT, the distribution density C is linearly decreased from the position t3 to the positions t and rK.

In the example shown in FIG. 7, the distribution concentration cB position 1B
Up to position t4, the concentration is c1. Take a constant value of t, position t
From 4 to position 1T, the concentration is c1! It is assumed that the distribution state decreases linearly with the concentration CIs t.

In the example shown in FIG. 8, from position tjl to position tTK
The distribution concentration C of germanium atoms is the concentration CI
From 4 onwards, it decreases in a linear manner, essentially reaching zero.

In FIG. 9, the distribution concentration C of germanium atoms decreases linearly from the concentration Cps to the concentration cps from the position tll to the position t@, and from the position 1 to the position t@. and position 1
An example is shown in which the concentration C11l is increased to a constant value between T and T.

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is the concentration CI? at position 1B? Then, up to the position t6, the #I degree is initially gradually decreased from this #I degree c17, and near the position t6, it is rapidly decreased to the concentration C11l at the position t6.

Between position t6 and position t7, the concentration Cte decreases rapidly at first, and then gradually decreases to reach the concentration Cte at position t7. The concentration is gradually decreased and reaches the concentration C,· at position t=. Position t8 and position 1. In between, degrees Cao and A are reduced 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 region (G)
As described above, some typical examples of the distribution state of germanium atoms contained in the layer thickness direction, in the present invention,
On the support side, there is a part where the distribution concentration C of germanium atoms is high, and on the interface tT side, there is a part where the distribution concentration C is considerably lower than on the support side.The distribution state of germanium atoms is the first. layer area).

The first layer region constituting the original receptor layer constituting the photoconductive member in the present invention is preferably a localized region containing germanium atoms at a relatively high concentration on the support side, as described above. It is desirable to have region (4).

In the present invention 1, the localized region (4) is shown in FIGS.
To explain using the symbols shown in the figure, the interface position t, the direction 5
It is desirable that it be provided within μ.

In the present invention, the localized region (A) is located at the interface position t
, may be the entire layer region (LT) up to 5μ thick, or may be a part of the layer region (LT).

Whether the localized region) is to be a part or all of the layer region (LT) is determined as appropriate depending on the required characteristics 1 of the first layer (1) to be formed.

In the localized region (G), the distribution state of germanium atoms contained therein in the layer thickness direction is such that the maximum value CmX of the distribution concentration of glu1nium atoms is preferably 1000 atoms ppm with respect to the sum with silicon atoms. As mentioned above, preferably 5000 atomic ppm or more, most preferably 1 x 10" atomic ppm or more), 1
-Ai-Screen 415- Layers are formed so as to form a cloth state.

Therefore, in the present invention, the layer region containing germanium atoms) is defined as the distance from the support side, τ (within 5μ (
tIl to 5μ thick layer area + 1'cy maximum value of cloth concentration c
It is preferable to form an mK layer in which max exists.

In the present invention, the content of germanium atoms in the first layer region (←) may be determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 1. l 0 X l 05atomicPP”
% preferably ill '00~9.5 X 105a
to105ato, optimally 500-8 X 10'
It is assumed to be atomic ppm.

In the present invention, the first layer region (b) and the second layer region (8)
) is one of the important factors for effectively achieving the object of the present invention, so the photoconductive member should be designed so that the formed photoconductive member has sufficient desired properties. Sufficient care needs to be taken when

In the present invention, the first point M) layer! T-H1 preferably 3OX~50μ, more preferably 401~4
0μ, optimally 50X to 30μ.

Further, the layer thickness T of the second layer region (S) is preferably 0.5
~90μ, preferably 1~80μ, optimally 2~
It is assumed to be 50μ.

The sum (TB+T) of the layer thickness TB of the first layer region (G) and the layer thickness T of the second important region (provided) is the characteristic required for both layer regions and the characteristic required for the entire photoreceptive layer. It is determined as desired when designing the layers of the photoconductive member based on the organic relationship between the two.

In the photoconductive member of the present invention, the numerical range of (TB+T) is preferably 1 to 100μ, more preferably 1 to 80μ, and most preferably 2 to 50μ.

In a highly preferred embodiment of the present invention, the above layer thickness TB and layer thickness T are preferably T, /T≦1
Appropriate numerical values are selected for each so as to satisfy the following relationship.

In selecting the numerical values of the layer thickness TIl and the layer thickness T in the above case, it is preferable that T! The layer thickness T is such that the relationship l/T≦0.9, optimally TB/T≦0.8, is satisfied!
Preferably, the values of l and layer thickness T are determined.

In the present invention, the content of germanium atoms contained in the tenth layer region (G) is 1 x 105 atomic
ppm or more, the layer thickness TB of the first layer region (G)
It is desirable that the thickness be as thin as possible, preferably 30μ or less, more preferably 25μ or less, optimally 20μ or less.
It is considered to be less than μ.

In the present invention, the halodan atoms (3) contained as necessary in the first layer region (C) and/or second layer region (8) constituting the first layer (1) include: Specific examples include fluorine, chlorine, bromine, and iodine, especially fluorine,
Chlorine may be mentioned as suitable.

In the present invention, K forming the first layer region a) composed of a-Ge (81, H, This is accomplished by a vacuum deposition method that utilizes the discharge phenomenon. For example, by glow discharge method, a-Ge
K forming the first layer region (G) composed of (81, H, Then, a raw material gas for introducing St supply gas capable of supplying silicon atoms (81), a raw material gas for introducing hydrogen atoms (6), and/or a raw material gas for introducing halodane atoms (3) are introduced into the deposition chamber. It is sufficient to generate a glow discharge and form a layer on the surface of a predetermined support that has been placed in a predetermined position in advance. It contains dharmanium atoms, which are distributed non-uniformly. While controlling the distribution concentration C of Iko according to a desired rate of change curve, a layer consisting of a-Ge (Si, H, Or, using a target made of 81 in a mixed gas atmosphere with these gases leaked, or using two pieces of this target and a target made of Ge, or with SI. Q
If desired, using a mixed target of e.
A gas for introducing hydrogen atoms or -/and halodane atoms (3) diluted with a diluting gas such as He or Ar is introduced into a deposition chamber for sputtering to form a plasma atmosphere of the desired gas, if necessary. At the same time, while controlling the gas flow rate of the raw material gas for supplying Ge and/or the raw material gas for supplying 81 according to a desired rate of change curve, the target 9t is sputtered "!I yft,C+tp" In the case of the ion deleting method, for example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in an evaporation cage as evaporation sources, and the evaporation sources are heated using the resistance heating method. , or by heating and evaporating using an electron beam method (FB method), etc. 1. This can be carried out in the same manner as in the case of the sli4' tuttering method, except that the flying evaporates are passed through the desired gas atmosphere.

Substances that can be used as the raw material gas for supplying S1 used in the present invention include 1. SiH4, 812H6, 815
Silicon hydride (silanes) in a gaseous state or that can be gasified, such as HB + Si4H10, can be effectively used, especially in terms of ease of handling during one-layer production work, good 8I supply efficiency, etc. 81H4, 5i2I (6 is preferred).

GeH is a substance that can be used as the raw material gas for supplying Ge.
a, Ge2H6, Ge5HB, Ge4H1o
, Ge5H12, Ge6H1aG@7Hj6 + c
Germanium hydride in a gaseous state or that can be gasified, such as e8H1Q and G119H20, can be effectively used.
GeH4 in terms of supply efficiency, etc.

Preferable examples include Ge2H6 and Ge5H6.

Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gas, ), rhodanides, interhalogen compounds, and halogen-substituted silane derivatives. Preferred examples include gaseous or gasifiable herodane compounds such as @Also, silicon hydride compounds containing a gaseous or gasifiable halogen atom, which are composed of silicon atoms and halogen atoms. As an effective example, I would like to mention non-inventiveness.

Specifically, halodane compounds that can be suitably used in the present invention include fluorine, chlorine, and bromine.

Iodine gas, BrF, C1F, C
lF5, BrF5.

BrF5 + IF5, IF7, ICt, I
Examples include intermetallic compounds such as Br.

Specifically, silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include, for example, 8
Preferred examples include silicon halides such as 1F4, 8i2F4, 81Ct4, and 5IBr4.

When forming the characteristic photoconductive member of the present invention using a glow discharge method using a silicon compound containing a halo r7 atom as described above, KSi can be supplied together with the raw material gas for supplying Ge. The first layer region (G) made of a-81Ge containing halogen atoms can be formed on a desired support without using silicon hydride gas as a source gas.

When creating the first essential region width (containing halogen atoms) according to the glow discharge method, basically, for example, silicon oxide, which will be the raw material gas for 81 supply, and hydrogen, which will be the raw material gas for Ge supply. germanium chloride and Ar + I2 r
A gas such as He is introduced into a deposition chamber in which a gas such as He or the like 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. Therefore, the first layer region (G) is deposited on the desired support.
However, in order to more easily control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer. It may be formed.

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.

K that introduces no-rodan atoms into the layer formed in both the SnoF stumbling method and the ion grating method.
In this case, a gas of the above-mentioned halogen compound or the above-mentioned silicide compound containing halogen atoms may be introduced into the deposition chamber to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as I2, or the above-mentioned silanes and/or damanium hydride gases, is introduced into the deposition chamber for sputtering. What is necessary is to form a plasma atmosphere of the gases.

In the present invention, the above-mentioned Kuno\rodan compound or silicon compound containing Hano-Kuchudan is effectively used as the raw material gas for introducing Nokatsu Rodan atoms, but in addition, HF r HCl + HBr +H
Hydrogen halide such as I, SiH2F2 + 5iH2I
2.

11H2c12, 5iHOt3 v 81H211r
Norodan-substituted silicon hydride such as 2r5IHBr5,
and GeHF3, GeI2F2, GeI5F1
.

GeHBr5, G5H2C4z, GmH5CL
, GeHBr5, GeI2Br2.

GeHBr5, GeHI3. GeI2I2, Ge
Halogen atoms containing hydrogen atoms as one of the constituent elements, such as hydrogenated rumanium such as H51, GeF4
, GeCA4, GeBr4 +GeI4, G
eF2, 9eCt2, GeBrz, GeI2
Gaseous or gasifiable substances such as halides, germanium, etc. may also be mentioned as useful starting materials for forming the 1' layer region (6).

Halodanides containing hydrogen atoms in these substances are the first
When forming the layer region (G), hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced at the same time as halogen atoms are introduced into the layer. used as raw material.

In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, KH2, 81H4, s+2n4.

A rumanium or germanium compound for supplying Go to silicon hydride such as 5i3HB, 8i4H+o,
Or s GeH4+ Ge2H6* Ga3HB +
Ge5H12r Ge5H12rce6)114,
Ge7H+6, Ge7H+6, G112H2
This can also be carried out by causing discharge to occur by causing rumanium hydride such as 0 and silicon or a silicon compound for supplying Sl to coexist in the deposition chamber.

In a preferred example of the present invention, the amount of hydrogen atoms (b) or the amount of halogen atoms (3) or the amount of hydrogen atoms and halogen atoms contained in the first layer region (G) of the photoconductive member to be formed The sum (H+X) is preferably o, oi~40
atomia%, 0.05 to 30ato
ie96, optimally 0.1 to 25 atomia4.

in the first layer region) or/
and the amount of halogen atoms (3) can be controlled, for example, by the temperature of the support or/and by the amount of hydrogen atoms (3) or by the deposition system of the starting material used to contain the halogen atoms (3). It is sufficient to control the amount introduced, discharge power, etc.

In the photoconductive member of the present invention, a substance (q The conduction characteristics of the core layer region (S) and the layer region (Q) can be arbitrarily controlled as desired.

At this time, the second layer region (S) contains the substance (
C] may be contained in the entire region or a part of the layer region of the first layer region), but in any case, it needs to be contained in a state where it is distributed more toward the support side. Thing provided in the second layer region (8) * The layer region (spN) containing (C) is provided as the entire layer region of the second layer region (8), or (8)
The support side end layer region (BE) is provided as a part of the support body side end layer region (BE). In the case of the former, provided as a full-layer region, the distribution concentration C(S) is provided so as to increase linearly or stepwise, or in a curved manner toward the support side.

When the distribution concentration C(S) increases in a curved manner, a substance (C) that controls the conductivity is provided in the layer region (S) so that the conductivity increases monotonically toward the support. is desirable.

When the layer region (SPN) is provided as a part of the second layer region (8), the distribution state of the substance (q) in the layer region (8PN) is in a plane parallel to the surface of the support. It is assumed that the substance (C) is uniform in the layer thickness direction, but it may be uniform or non-uniform in the layer thickness direction.In this case, in the layer region (13PN), the substance (C) is non-uniform in the layer thickness direction. It is desirable that K be provided in a distributed manner so as to form a distributed concentration line similar to that in the case where K is provided in the entire layer region of the first layer region (8).

First layer region (G) K Also when containing a substance (q) that controls conductivity and providing a layer region (GPN) containing the substance (C), second layer region (S) K layer region (SPN)
This can be done in the same way as when providing .

In the present invention, both the first layer region 0) and the second layer region (8) contain a substance (Q) that controls conduction characteristics, and in this case, the substance contained in both layers! (C) may be of the same type or mutually different types.

In the case of containing a substance (C) that controls the conductivity of alt1 in one layer region, the maximum distribution density sound in the layer thickness direction of the substance (C) is found in the second layer region (S). i.e. inside the second layer region (8) or inside the first layer region (G
) is preferably provided at the interface with the

In particular, it is desirable that the maximum distribution concentration is provided at the contact interface with the first layer region ←) or in the vicinity of the interface. ) to control the conduction properties (C).
, the layer region (PN) containing the second ONI region (S
), preferably as an end layer region (Sg) on the support side of the second layer region (8).

When the layer region (PN) is provided so as to span both the first layer region (S) and the first layer region width), the layer region (GPN) of the substance (C) that controls conduction characteristics is There is C(G)max between the maximum distribution concentration C(Gia x) and the maximum distribution concentration C(S)max in the layer region (5PN).
<C(S)max> Substance (
C) is contained in the first layer (1).

A substance (Q) that controls conductivity contained in the layer region (PN)
Examples of impurities include so-called impurities in the semiconductor field, and in the present invention, p-type impurities give p-type conductivity to Sl or GeK, and n-type impurities give i-type conductivity to Sl or GeK. can be mentioned.

Specifically, p-type impurities include atoms belonging to Group Ⅰ of the periodic table (Group 11 atoms), such as B (boron), kl (
Among them, B%Go is particularly preferably used.

Mouth-type impurities include atoms belonging to Group V of the periodic table (Group V atoms), such as P (phosphorus), Am (arsenic), and sb (
(antimony), Bl (bismuth), etc., and particularly preferably used are P and As.

In the present invention, the content of the substance (C) that controls the conduction properties contained in the layer region (PN) K provided in the first layer (1) is determined by the conduction properties required for the layer region (PN). , or the relationship with the characteristics at the contact interface with the layer region of the support or pond with which the layer region (PN) is provided in direct contact, etc., can be selected as appropriate in terms of organic relationships.

In addition, the characteristics of the layer region provided in 1IiK contact with the layer region and the relationship with the characteristics at the contact interface with the other layer region are also considered, and the content of the substance (Q content) that controls the conduction characteristics is taken into consideration. is selected as appropriate.

In the present invention, the content of the substance (C) that controls conduction properties contained in the layer region (PN) is preferably 0.01 to 5 X 1 Q'atomle ppm,
More preferably 0.5 to 1×10 atom c
ppm s optimally 1-5 x 103103ato pp
It is assumed that m.

In the present invention, the layer region (PN) containing the substance (C) that controls the conduction properties is placed in contact with the contact interface between the first layer region (S) and the second layer region (S), or The content of the substance (C) in the layer region (PN) is preferably 30 ppm. As described above, by setting the amount to more preferably 50 atomle ppm or more, optimally 100 atomle ppm or more, for example, when the substance to be contained is the above-mentioned p-type impurity, the polarity of the free surface of the photoreceptive layer is charged. It is possible to effectively prevent the movement of electrons injected from the support side into the second layer region (the second layer region) when subjected to the treatment, and also to prevent the transfer of electrons when the substance to be contained is the n-type impurity. When the free surface of the photoreceptive layer is charged to e-polarity, the movement of holes injected from the support side into the second layer region can be effectively prevented.

In the above-mentioned case, the layer area (K) of the part of the present invention excluding the layer area (pN) under the above-mentioned basic configuration is
A substance that controls conduction characteristics with a polarity different from that of the substance that controls conduction characteristics contained in the layer region (PN) may be included, or a substance that controls conduction characteristics with the same polarity may be contained. may be contained in an amount much smaller than the actual amount contained in the layer region (PN).

In such a case, the content of the substance controlling the conduction properties contained in the layer region (PN) is as follows:
K: is determined as desired depending on the polarity and content of the substance contained, but is preferably o,
ooi~1'000aVomle I)flff1% or more preferably 0.05~F+00atomle ppm'
, optimally 0.1 to 200 atoms ppm.

In the present invention, when the layer region (PN) and the layer region (6) K contain the same kind of substance that controls the conductivity, the □ content in the layer region (6) is preferably 3
It is desirable that the Q'a'to crystal content be 1 eppm or less.

In addition to the above-described case, in the present invention, the first layer (1
), so that 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 contact with each other.・It is also possible to provide a so-called depletion layer in the contact area by providing □
・I can do it. That is, for example, in the first layer [1], the layer region containing the p-type impurity described above and the layer region containing the n-type impurity described above are provided 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.

11 to 24 show typical distribution states of the substance (0) contained in the first layer (1) that controls conduction properties in the layer thickness direction.

In these figures, the horizontal axis shows the distribution concentration C (PR) of the substance (0) in the layer thickness direction, and the vertical axis shows the layer thickness t from the support side of the first layer (1). . tB is the first layer region (G)
The bending resistance position on the support side of , t, is the bending resistance position opposite to the support side of the second layer region (S), and to is the position of the contact interface between the layer region 0) and the layer region (S). show.

FIG. 11 shows the first distribution state of the substance (Ij) in the layer thickness direction that controls the conduction properties contained in the first layer (1).
A typical example is shown.

In the example shown in FIG. 11, the substance fi (C1) is not contained in the layer region (G), and only the layer region (S) K is contained in a constant distribution of concentration C□. In the layer region (8), the substance (G) is contained in the end layer region between 1o and 1. at a constant distribution concentration of C1.

In the example of FIG. 12, the material (C) is uniformly contained in the layer region (S), but the material (C'
) are not included.

The substance (C) has a distribution concentration of C! in the layer region between to and t2. C! is contained at a constant concentration in the layer region between t2 and t. It is contained at a constant concentration of C3, which is much lower than that of C3.

With such distribution concentration C(PN), substance (C) is added to the first layer (
By including 1) in the layer region (S) constituting the layer region (S), it is possible to effectively prevent the charge injected from the layer region (G) into the layer region (8) from moving toward the surface, and at the same time, It is possible to measure improvements in photosensitivity and dark resistance.

In the example shown in Fig. 13, the layer region (G) contains K substance (C) evenly, but the concentration decreases monotonically toward the upper surface from C4 at t to tT. When a substance (0
Contains. The layer region 1G) does not contain any substance (0).

In the case of the examples in Figures 14 and 15, the substance (C) is
This is an example in which it is unevenly contained in the lower end layer region of the layer region (2). That is, in the case of the examples shown in FIGS. 14 and 15, the layer region (8) includes a layer region containing the substance (Q) and a layer region not containing the substance C, in this order. It has a layered structure laminated from the support side.

The difference between the examples in FIG. 14 and FIG. 15 is that in the case of FIG. 14, the distribution concentration c (PN) is between to and 13, and the concentration C1 at the position to is 1. Concentration 0 at position
While it monotonically decreases with respect to i, in the case of FIG. 15, between to and t-4, 1. Concentration C6 at position
This means that it continues to linearly decrease to 9Il1 degrees 0 at the position t4. 14 and 15, the first layer region (Q does not contain the substance (0). In the examples shown in FIGS. 16 to 24, the first A case is shown in which both the layer region (1) and the second layer region (8) contain a substance (b) that controls conductivity.

Insertion of the examples of FIGS. 16 to 22 is the second layer.

The region (8> is a layer region containing the substance (C),
They commonly have a two-layer structure in which layer regions that do not contain the substance (Q) are laminated in this order from the support side.

In the examples shown in FIGS. 16 to 21, the distribution state of the substance (C) in the first layer/region (G) is different from that in the second layer region (8). Interface position t.

Distribution concentration C (PN) decreasing towards the support side
It has a state of change.

23 and 24: In the case of the example, the first layer (1)
The substance (C) is evenly contained in the layer thickness direction over the entire layer region. In addition, in the case of FIG. 23, in the first layer region (G), 1. From the concentration Cf1S at tBK, t
The concentration CSZ at o increases linearly from tB toward t6, and in the second layer region, (8) K, the concentration C*t at to increases to the concentration 0 at tT. It monotonically and continuously decreases toward tTK.

In the case of Fig. 24, in the layer region between tB and tll, the substance (C) is contained at a constant distribution concentration of CW4, and in the layer region between t13 and tT. is the concentration C
□ It decreased linearly and reached OK at tTK.

11 to 24, the distribution concentration C(P) of the substance (C) that controls conductivity in the first layer (1)
As explained in the substitutive case of the variation example of N), in both examples, the substance (C) is Contained in the first layer (I).

In the present invention, the second
To form the layer region (8), the first layer region (8) described above is formed.
G) From among the starting materials for formation (1), starting materials excluding the starting material that serves as the raw material for supplying Ge [starting material phrase for forming the second layer region (S)] are used. This can be carried out according to the same method and conditions as in the case of forming the first layer region (G).

That is, in the present invention, in order to form the second layer region (S) composed of a-8i (H, This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon such as an ion blating method. For example, a -81(H,
To form the second layer region (8) consisting of
Basically, along with the raw material gas for supplying the silicon atoms (Si) described above, if necessary, the raw material gas for introducing hydrogen atoms and/or halodane atoms (T) is The a-81 (HFX) layer may be introduced into a deposition chamber which can be reduced in pressure to generate a glow discharge within the deposition chamber, thereby forming a layer of a-81 (HFX) on a predetermined support surface that has been placed in a predetermined position. In addition, when forming by a sputtering method, for example, when sputtering a target composed of St in an atmosphere of inert gas such as Ar, H gravel, or a mixture of these gases, A gas for introducing hydrogen atoms a◇ and/or halogen atoms (3) may be introduced into the deposition chamber for sputtering.

In the present invention, the amount of hydrogen atoms (6) or the amount of halogen atoms (3) or hydrogen atoms contained in the 20th layer region (S) constituting the first layer (1) to be formed The sum of the amounts of halodane atoms (H×X) is preferably 1 to 4 Q a
tomlc%, more preferably 5-30 atrnl
c, optimally 5 to 25 atomic%.

In the layer region constituting the first layer (1), a substance (Ql) that controls conduction properties (for example, a group II' atom or a group V atom is structurally introduced) During layer formation, the starting material for introducing Group 1 atoms or the starting material for introducing Group V atoms is introduced into the deposition chamber in the form of a gaseous head. In order to form the layer (1), it is good to introduce it together with the starting material of the reservoir.
It is preferable to use materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. -For use, B2H6, m4 horse 01 BS”
91 B5H11tB6H1゜t B6H12t B6
Boron hydride diBF-5+ such as H14 BCL5rB B
Boron halides such as rs etc. are 1-digit. In addition,
htct,, act3. GIL(CH,)3. ”'
i'nC't3t Ttct, 5, etc. can also be mentioned. ``As a starting material for introducing Group 1 atoms, P is effectively used in the present invention for introducing myphosphorus atoms.
H,, hydrogen such as P2H4, phosphorus, PH4I, PF3
．． P.F.

PCl5. PCl5. PBr3. “P′Ir5.
/% l:l jf n ratio of "PIs' etc. is mentioned. This pond, AsH2, AsF3. AsCt3+As
Br3. AsF5. SbH,, SbF5. SbF
5.5bC16, 5bC15°ntH3, ntcz3.
Bier' Wi may also be mentioned as a useful starting material for the introduction of Group V atoms.

In the photoconductive member 100 shown in FIG.
has a free surface 106 and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, electrical use environment characteristics, and durability.

Furthermore, in the present invention, since each of the amorphous materials constituting the first 0M(1) 102 and the second layer ([1) 165 has a common constituent element of silicon atoms, , chemical stability is sufficiently ensured at the laminated interface.

The second method (ω) in the present invention is a silicon atom (St)
and nitrogen atom axis, and an amorphous material containing a hydrogen atom (6) or/and a logon atom (hereinafter referred to as r
It is written as a-(s4N,-x), (HtX),-,J. However, o < x, y < 1).

The formation of the second layer (■) consisting of a-(81xN,-,), (H,

These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the light/tail member to be manufactured. It is relatively easy to control the production rate for producing optical electrical components, it is easy to introduce nitrogen atoms and halogen atoms together with silicon atoms into the second layer (II) to be produced, etc. Due to these advantages, the glow discharge method or the glow discharge method is preferably employed.

Furthermore, in the present invention, the second layer ff1) may be formed by using both the glow discharge method and the four-horn tsuttering method within the same apparatus system.

To form the 20th layer <1) by the glow discharge method a
-(SixNl-X)y (HeX) 1-y
The raw material gas for formation is mixed with diluent gas at a predetermined mixing ratio if necessary, and introduced into a vacuum deposition chamber where a support is installed, and the introduced gas is used to cause glow discharge. This may result in sglazma formation and the formation of K&-(811N1-x) on the first layer (1) already formed on the support.
)y(H+X)(-y).In the present invention, a-(81xN,-x), (H,X
), -, silicon atoms (
ss ), most of the gaseous substances or gasified substances that have at least one of the following atoms: nitrogen atom axis, hydrogen atom (6), and no-rodan atom (3). may be used.

81. When using sulfur as a raw material whose constituent atoms are Si as one of N, H, and X, for example, the raw material whose constituent atoms are sl and the raw material whose constituent atoms are , if necessary, the raw material containing Ht atoms may be mixed with a raw material gas containing S or/and X at a desired mixing ratio, or the raw material gas containing St and N may be used. and a raw material gas containing H as constituent atoms or/and a raw material gas containing N and X as constituent atoms, also at a desired mixing ratio, or a raw material gas containing other constituent atoms, S
A raw material gas containing three constituent atoms: L, N, and H, or S
A raw material having three constituent atoms, t, N, and X, can be used in combination with sulfur.

In addition, a raw material gas KN whose constituent atoms are B, st, and H
The raw materials whose constituent atoms are Si and X may be used as a mixture, or Si and X may be used. A raw material gas containing N as a constituent atom may be mixed with a raw material gas containing N as a constituent atom.

In the present invention, (') is suitable as the halogen atom (2) contained in the second layer [).
In p I, A-sho, especially JfCF, C1 is preferable. In the present invention, raw materials that can be effectively used to form the second layer ω) include those that can be used at room temperature. Mention may be made of substances that are in a gas state or that can be easily gasified under pressure.

When forming the second layer [) by sputtering method,
For example, it would look like this:

First, a target made of an inert gas such as Ar or He or a mixture of these gases as a base is scorched.

At the same time, the raw material gas for nitrogen atom introduction is used for hydrogen atom (b) introduction and/or the raw material ffx4 for introduction of hydrogen atoms (b) according to QK. Second, as a target for Neno and Tsutarinda, 8
One target consisting of i, N, or two targets consisting of a target consisting of Sl and a target consisting of Ejl, N4, or a target consisting of SI and Si, N4. The second layer (r
l) A nitrogen atom axis can be introduced into the atom. On this occasion,
By using the above-mentioned raw material gas for introducing the nitrogen atom axis,
It is easy to arbitrarily control the amount of energy introduced into the second layer (n) by controlling the volume and flow rate.

During the second layer ω) is introduced. The content of the phoneme atomic axis is
By controlling the flow rate when the raw material and gas for nitrogen atomic axis introduction into the deposition chamber, or by controlling the proportion of nitrogen atoms present in the target for nitrogen atomic axis introduction, Adjust when creating the target, or the torture is this 9 cars,
It can be controlled arbitrarily by performing the following actions.

The starting materials used in the present invention as raw material gas for supplying Si include 81H4, Sl□H6, 81, H
8°8 l 4H,. Silicon hydride (silanes) in a gas state or capable of being turned into a gas can be effectively used.In particular, 5IH4 is effective in terms of ease of handling in layer creation work and good S1 supply efficiency. , 812H6 are preferred.

Using these starting materials, the second layer formed by properly selecting the layer formation conditions (KSI)
At the same time, H can also be introduced.

81 Effective starting materials for feedstock include:
In the above silicon hydride pond, a silicon compound containing a rhodane atom (i), a silane derivative substituted with a rhodane atom, specifically, for example, 5IF4゜st, i'6
．． Preferred examples include /% 0 I'' siliconide such as 8% cz4.8LBr4.

Furthermore, 5IH2F2.5IH2I2.8kH2CL2
．． 5tticz,.

7% rhodane-substituted silicon hydride such as 5IR2Br2.81HBr, etc., which has a hydrogen atom as one of its constituents in a gas state or can be gasified, etc./・Rogenide is also effective for the formation of the second layer ω) It can be mentioned as a starting material for supplying SI.

Even when these silicon compounds containing /% o f atoms (3) are used, as described above, by appropriately selecting the layer forming conditions, it is possible to introduce You can.

The silicon oxide compound (containing hydrogen atoms among the above-mentioned starting materials) is extremely useful for controlling electrical or photoelectric properties at the same time as introducing halogen atoms into the layer during the formation of the second layer (If). Since an effective hydrogen atom (6) is also introduced, it is used in the present invention as a suitable starting material for the introduction of hydrogen atoms.

In addition to the above-mentioned materials, effective starting materials that serve as raw materials for introducing halodane atoms used in forming the second layer Ql) in the present invention include -1, fluorine,
Chlorine, bromine, iodine, BrF, Cj
IFt ClF5* BrF5. BrF5p IF7
．． ICt, IBr, IF.

Interhalogen compounds such as HFHHCL, HBr, H
Hydrogen halides such as I can be mentioned.

Nitrogen atoms (lV
+)4 Starting materials that can be effectively used as raw material gases include nitrogen (N2), ammonia (N
H,) eHydrazine (H2NNH2), hydrazine (HN3)? Ammonium azide (NH4N!,
), nitrogen compounds such as gaseous or gasifiable elements, nitrides, and azides can be mentioned. This fil
Nitrogen trifluoride (FAN)
*Nitrogen compounds such as nitrogen tetrafluoride (F4N2) can be mentioned.

In the present invention, the diluent gas used when forming the second layer (j7) by the glow discharge method or the star sintering method is a so-called diluent gas, for example, is, No.

Preferred examples include Ar.

The second layer (II> in the present invention is carefully formed so that its required properties are provided as desired!).

That is, a substance containing H and/or
Properties ranging from electrical conductivity to hand-centered and insulating properties, as well as from photoconductive properties to non-photoconductive properties, are shown in the present invention. has a-(
In order to form stxN, -1)a(singX)t□, the creation conditions are strictly selected according to one's desire. For example, is the second layer (II) electrically resistant? To provide the main purpose of improvement is a − (S l xN 1−=? y
(HTX) 1-y is prepared as an amorphous material with pronounced electrically insulating behavior in the environment of use.

In addition, if a second layer is provided for the main purpose of improving the characteristics of continuous repeated use or the characteristics of use under conditions of use, the electrical insulation of the upper layer may be improved. The degree of a-(S
i, N, -x), (H, X), are created.

a-(81xN 1-X )y on the surface of the first layer (1)
When forming the second layer [) consisting of (Hv In this case, a-(81XNl-x)y having the desired properties
It is desirable that the temperature of the support during layer formation be strictly controlled so that (''*X)1-y can be formed as desired.

In the present invention, the formation of the second layer (II) is carried out by selecting an appropriate range in accordance with the method of forming the second layer ([1) in order to effectively achieve the desired purpose. The temperature is preferably 20 to 400°C, more preferably 50 to 350°C.
°C, optimally 100 to 300 °C. second layer <1
For the formation of 1>, glow discharge method or sputtering method is adopted because delicate control of the composition ratio of atoms making up the layer and control of layer thickness are relatively easy compared to other methods. However, when forming the second layer (fl) using these layer forming methods, the discharge power during layer formation is set at a - (S 1-xN 1
-x )y (Hy In order to effectively create a - (Si, N, x) y (H, % Preferably Vi2.
0 to 250W1, most preferably 5.0 to 200W.

The gas pressure in the deposition chamber is preferably OO1 to l Torrs.
More preferably, it is about 01 to Q, 5 Torr.

In the present invention, the preferable numerical ranges for the support temperature, discharge, and power for forming the second layer (II) include the above-mentioned ranges, but these layer formation factors are independent of each other. The desired characteristics a-(stxN,-x)y(u,x),- are not determined separately.

It is desirable that the optimum value of each layer formation factor be determined based on mutual organic relationships so that a second layer (It) consisting of .

Similar to the conditions for forming the second layer (It), the amount of nitrogen atoms contained in the second layer (II) in the photoconductive member of the present invention has the desired characteristics to achieve the object of the present invention. Of the nitrogen atoms contained in the second layer (■) in the present invention! -1
It can be determined as desired depending on the type and characteristics of the amorphous material constituting layer (II) of (d) and (a).

□That is, the general formula a -('5txN, -X)y(H
,X)1. The amorphous abrasive material shown by □ can be broadly classified as an amorphous material composed of silicon atoms and nitrogen atoms (hereinafter referred to as r = = sj, rtr, l, J. However, O
(a'(,1'''), an amorphous material composed of a teric atom, a 9-element atom, and a hydrogen atom (hereinafter, r a-('
Q:t':'N, -, )eH, -0''. however,'
o(b, c(1), an amorphous material composed of silicon atoms, nitrogen atoms, halide atoms, and optionally hydrogen atoms (hereinafter r a -(5ldN, -d)).

(t(:x);-', written as J. However, O'("d,
e (1).

In the present invention, the second layer (It) is a-8IaN, -
1, the amount of nitrogen atoms contained in the second layer (■) is preferably 1'X10"'6'0 at
omic%, more preferably 1 to 5'Oato'mlC
The optimum amount is 10 to 4'5 atornie%. That is, if it is expressed as 8 of a-8i aN + -a, turtle is preferably 0.4 to 099999, more preferably 0.5 to 099, most preferably 055 to 8,9'- r
:be.

In the present invention, the second layer 0) is '-("bNl-b)
When composed of eH-, the amount of nitrogen atoms contained in the second layer (II) is preferably 1X10-' to 55
atomic range, more preferably '1 to 55 a
tornic chi, 10 to 5 atomic for the highest quotient
%. The acid containing a hydrogen atom is preferably 1
~40 atomic %, good %, optimally 5
It is desired that the photoconductive member be formed in a field with a thick hydrogen content in the range of ~3 Oatomic-4t<4t, which is excellent in practical terms and can be used satisfactorily ( Fathom 6゜ □ That is, the previous a -(StbN': "-,,),, ■■,
-8 display, b is preferable and k is 0.45 to 0999
99, preferably 045 to 0.99, most preferably 045
~0.9, C75; preferably i'< is O6 ~ 0.99, preferably 0.65 ~ 0.98, □ optimally 0.7 ~ 0.
It is 95. □The second layer (It) is a-(81dN
+ ,,,a)e(H,X),-a, the nitrogen atom-containing liquid contained in the second layer (II) is preferably 1×10 3-60
atomic%, preferably 1 to 60 atoms
iC% and imK are 10 to 551F to ITIIC%. /N roIf” Containing 7 atoms - As for the death,
Preferably 1 to 20 atomic%, more preferably 1 to 18 atomic%, optimally 2 to 15 atomic%
mic, and a photoconductive member produced when there is one-rodan atom-containing debris in these ranges can be sufficiently applied to practical applications. The content of hydrogen atoms, which may be contained as necessary, is preferably 19 atomic% or less, more preferably 1 3 atomic% or less.

That is, the previous * - (81, N, - (1) e (H, X)
, -, d is preferably 0.
4 to 0.99999, more preferably 0.4 to 0.99,
Optimally 0145-0.9, e is preferably o, "i
l ~ o, 991 kl, preferably 012 ~ 0.99
, optimally between 85 and 0.9 g.

The number range of the layer thickness of the second M (n) in the present invention is one of the important factors for effectively achieving the object of the present invention.

In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose.

The thickness of the second layer (II) also depends on the amount of nitrogen atoms contained in the layer (If) and the thickness of the first layer (1). It needs to be determined as desired based on the organic relationship depending on the characteristics required for the area.

In addition, it is desirable to consider economic efficiency, including productivity and respectability.

The layer thickness of the second layer (IT) in the present invention is preferably 0.003 to 30μ, more preferably 0.004 to 2μ.
0μ, optimally o, oos to 10μ.

The support used in the present invention may be electrically conductive or electrically insulating. As a conductive support,
For example, N1Cr1 stainless steel, At.

Cr%Mo5Au, Nb, Ta, VXTiXPtS
Examples include metals such as Pd and alloys thereof.

As the electrically insulating support, polyester, polyethylene, I? carbonate, cellulose acetate,
Films or sheets of synthetic resins such as polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, paper, etc. are commonly used. These electrically insulating supports preferably have at least one surface thereof.

It is desirable that the conductive layer be subjected to a conductive treatment and that another layer be provided on the conductive treated front side.

For example, apply N1Cr to the surface of a glass tube.

Als Cr −, Au s Mo % J rs
Nb % Ta s V % Tj, pt.

Pd, In2O, 5no2, ITO (ln203
Conductivity is imparted by providing a WJI film consisting of +5nO2), or if it is a synthetic resin film such as a polyester film, NlCr t, At,
Ag, Pb, Zn, N1, Au.

A thin film of metal such as Cr, Mo, Ir, Nb, Ta5V, Ti, PL, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, deposition, suction, etc., and the surface is laminated with the above metal. As a result, conductivity is imparted to the surface.

The shape of the support may be any shape such as vertical, cylindrical, belt-like, plate-like, etc., and the shape is determined as desired. For example, the photoconductive member 100 of FIG. In the case of continuous high-speed copying, since it is used as a forming member, it is desirable to use an endless belt shape or a cylindrical shape.

The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within the range. In such cases, the thickness is usually set to 10 μ or more in view 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. 25 shows an example of a photoconductive member manufacturing apparatus.

In the figure, gas gompe numbers 202 to 206 include the light of the present invention.
The raw material gas that forms the electrical parts and materials is sealed,
For example, 202 is I (81 diluted with e) I4 gas (purity 99.999%, hereinafter referred to as SiH, /
) Abbreviated as I. )? N, P, 203 is Ge H4 gas diluted with He (purity 99.999%, hereinafter G@H
It is abbreviated as 4A1s. )? SiF diluted with 204ijHe (purity 99.99%, hereafter 81 F)
<7'l (abbreviated as s) Tempeh, 205 is 82H6 gas diluted with H6 (purity 99.999%, hereinafter referred to as Bz
It is abbreviated as H6/he. ) Kimpe, 206dH2 gas (99.999% purity) cylinder.

To allow these gases to flow into the reaction chamber 2011C, make sure that the valves 222 to 226 of the gas cylinders 202 to 206 and the leak pulp 235 are closed, and also close the inflow pulps 212 to 216, the outflow valves 217 to 2211, and the auxiliary valve 232. Make sure .233 is open,
First, the main valve 234 is opened to exhaust the reaction chamber 201 and each gas pipe. Next, the reading on the vacuum gauge 236 is about 5.
When the temperature reaches x10-' torr, the auxiliary valve 232
．． 233, close the outflow pulps 217-221.

Next, to give an example of forming a light receiving layer on the cylindrical substrate 237, s + H from the gas cylinder 202
4/”'e gas, gas cylinder 203 J) 伽HaAe
The gas is adjusted to 1 kg/cfn2 at the outlet pressure 227 and 228 by passing the gas through the noclubs 222 and 223, respectively,
The inlet pulps 212, 213 are gradually opened to allow each to flow into the mass 70 controllers 207, 208. Subsequently, the outflow pulps 217 and 218 and the auxiliary valve 232 are gradually opened to allow the respective gases to flow into the reaction chamber 201.

At this time, S I H4/4 (s gas flow rate and GeI (<
, /11e Adjust the outflow pulp 217, 218 so that the ratio with the gas flow rate becomes the desired value, and while watching the reading of the vacuum gauge 236 so that the pressure in the reaction chamber 201 becomes the desired value. Adjust the opening of the main valve 234. Then, the temperature of the base 237 is increased to 50 to 40 by the heating heater 238.
After confirming that the temperature is set in the range of 0° C., the power source 240 is set to the desired power to generate a glow discharge in the reaction chamber 201 to form a first layer region on the substrate 237 ←
) to form. At the point when the desired layer thickness (first layer region width) is formed, the outflow pulp 218 is completely closed and the gas is transferred from the gas cylinder 205 to the above 8 i T (a/l). (Following the same conditions and procedures except that the e-gas is introduced into the reaction chamber 201 by the same valve operation as the e-gas and the mass 70 controller 210 is controlled according to the desired doping curve, and the discharge conditions are changed as necessary. By maintaining the glow discharge for the desired time,
A second layer region (2) substantially free of rumanium atoms can be formed on the first layer region (1).

In this way, the first layer @tan←) and the second layer area (t)
) is formed on the substrate 237.

The first layer (iris) formed to a uniform thickness as described above
To form the second 1 (II) on top', the first layer (1
), for example by pulping operations similar to those used in the formation of 5I
This is achieved by diluting each of T (4ff) and NH5 with a diluent gas such as He as necessary to generate a glow discharge according to desired conditions. For example, 81F4 gas and C
This is done by adding 2T (4 gas) or 81H4 gas to it and forming the second waste (It) in the same manner as above.

Outflow of the gas necessary to form the Mibi layer, all outflow except the groin, and the groin must be closed. In order to prevent gas from remaining in the reaction chamber 201 and in the gas piping leading from the outflow pulps 217 to 221 to the reaction chamber 201, the outflow pulps 217 to 221 are closed and the auxiliary valve 2 is closed.
32, 233 is opened, the main valve 234 is fully opened, and the system is temporarily evacuated to a high vacuum, as necessary.

The amount of nitrogen atoms contained in the second layer (II) can be determined, for example, by changing the flow rate ratio of dR1H4 gas and NH gas introduced into the reaction chamber 201 in the case of glow discharge, or by changing the flow rate ratio of dR1H4 gas and NH gas introduced into the reaction chamber 201 as desired, or by When forming a layer using /'y'' y, change the ratio of the grooves and ivy areas between the silicon wafer and the silicon nitride plate, or change the mixing ratio of the silicon powder and the silicon nitride powder. □It is possible to adjust the control element depending on the condition by changing the term used to mold the targut.The amount of halodane (3) contained in the second layer ([1) is -. This is done by adjusting the flow meter when the raw material gas for rinsing, for example, 5 tF4 gas is introduced into the reaction chamber 201'.

Further, during layer formation, it is desirable that the base body 237 be rotated at a constant speed by a motor 239 in order to ensure uniform layer formation.

Examples will be described below.

Example 1 A cylinder-shaped At
Each sample as an electrophotographic image forming member was formed on a substrate under the conditions shown in Table 1 (see Table 2).

When forming the layer region (8), the distribution concentration shown in Fig. 26 is formed for each sample by changing the flow-out ratio of B2H6 gas, PR, and gas according to the change rate line drawn in advance. did.

Each sample thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 kV for 0.3 seconds, and immediately irradiated with a light image. A tungsten lung light source was used to emit light of 21 ux-sec through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the photoreceptive layer by cascading an e-chargeable developer (containing toner and carrier) over the surface of the photoreceptive layer of each sample.

When the toner image on the light-receiving layer was transferred onto transfer paper by corona charging at 5.0 kV, each sample had excellent resolution and a clear, high-density image with good gradation reproducibility was obtained.

In the above, the light source is replaced by a tungsten lung.
The image quality of the toner transfer image was evaluated for each sample in the same manner as above except that the electrostatic image was formed using a 0 nm GaAs semiconductor laser (10 mW). Clear, high-quality images with excellent resolution and good gradation reproducibility were obtained.

Example 2 A cylindrical AA was manufactured using the manufacturing apparatus shown in Fig. 25.
Each sample as an image forming member for electrophotography was formed on a certain body under the conditions shown in the third rock (see Table 4).

By changing the flow rate of the 82H6 gas and PH gas according to a pre-designed rate of change line during the formation of the layer region (81) and the layer region (81), the distributed concentration shown in FIG. It was then formed.

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. Also, each sample was heated at 38℃ and 80SR.
No deterioration in image quality was observed in any of the samples after 200,000 repeated use tests were conducted in an environment of H.

Example 3 A cylindrical piece At
Samples (samples/ft31-1 to 37-12) as electrophotographic image forming members were prepared on a substrate under the conditions shown in Table 5 (Table 6).

The content distribution concentration of germanium atoms in each sample is the second
8, and the distribution concentration of impurity atoms is shown in FIGS. 26 and 27.

When each of these samples was subjected to image evaluation in the same manner as in Example 1, all of the samples provided high quality toner transfer images. Father, 38℃, 80S for each sample
When a repeated usage test of 200,000 times was conducted in one RH setting, no deterioration in image quality was observed in any of the samples.

Example 4 Samples A I-1 and 1-2 of Example 1, except that the preparation conditions for the 20th layer (10) were changed to the conditions shown in Table 7.

]-3, each of the electrophotographic imaging members (Samples AI-1-1 to 1-1-8°1-2
-1 to 1-2-8. 24 samples of 1-3-1 to 1-3-8) were created.

Each of the image forming members for photographic use thus obtained was individually placed in a copying machine, corona charged at e5kv for 0.2 seconds, and a light image was irradiated. A tungsten rung is used as the light source, and the light intensity is 1.01 ux-sec! :did. The latent image was developed with a charged developer (containing toner and carrier) and transferred to regular paper. The transferred image was extremely good.

Toner that was not transferred and remained on the electrophotographic imaging member was cleaned with a rubber blade. Even when such steps were repeated over 100,000 times, no image deterioration was observed in any case.

Table 8 shows the results of the overall image quality evaluation of the transferred images of each sample and the evaluation of durability through repeated and continuous use.

Example 5 When forming the second layer (II), by changing the target area ratio of the mixed gas of Ar and PllI (3) and the silicon atoms and silicon nitride, the silicon atoms in the second layer (n) were formed. Each of the image forming members was prepared in exactly the same manner as in Sample Al-1 of Example 1, except for changing the content ratio of nitrogen atoms.For each of the image forming members thus obtained, Example 1 After repeating the steps of image formation, development, and cleaning about 50,000 times as described above, image evaluation was performed, and the results shown in Table 9 were obtained.

Example 6 When forming the second layer (1), the flow rate ratio of 8iH4 gas and NH5 gas is changed to change the content ratio of silicon atoms and nitrogen atoms in the second layer (II). The fruit is 6 except
Each of the one-square acid members was created in exactly the same manner as for sample points 1-2 in Example 1. 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, image-by-image evaluation was performed, and the results shown in Table 10 were obtained. .

Example 7 When forming the second layer (1), SIT (4 gases, 5I
The second layer (n
Each of the image-forming members was prepared in exactly the same manner as the sample plate 1-3 of Example 1, except that the content ratio of silicon atoms and nitrogen atoms in (2) was changed. Each of the image forming members thus obtained was subjected to the image forming, developing and cleaning steps as described in Example 1 about 50,000 times, and then image evaluation was performed, and the results shown in Table 11 were obtained.

Example 8 Each of the image forming members was created in exactly the same manner as in Sample A1-4 of Example 1, except that the layer thickness of the 20th layer (II) was changed. The image forming, developing and cleaning steps as described in Example 1 were repeated to obtain the results shown in Table 12.

□1 Table 12 The common layer formation conditions in the examples of the present invention shown in Table 1 and above are as follows.Substrate temperature: +''Rumanium atom (contains)) containing layer...approximately 200°C Dalmanium atom (G,) not contained Layer...approx. 2
50℃ discharge frequency: 13.56MHz Reaction chamber pressure during reaction: Q, 3 Tart

[Brief explanation of the drawing]

Fig. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and Figs. 2 to 10 are for explaining the entire distribution state of dalmanium atoms in the husbandry layer region. An explanatory diagram of
FIGS. 11 to 24 are explanatory views for explaining the distribution state of impurity atoms in the photoreceptive layer, respectively. FIG. 25 is a schematic explanatory view of the apparatus used in the present invention, and FIGS. 26 to 28. Each figure is an explanatory diagram showing the distribution state of each atom in an example of the present invention. 100... Photoconductive member 101... Support body 102.
・・Photoreceptive layer ---→-C C -11-→-C -11-→-C -C(PN) -C(PN) □C(PN) 11111kaC(PN ) C(PN) -(, (PN) -11111C(PN) C(PN) -C(PN) □C(PN) 11111C(PN) -C( PN)

Claims (1)

[Scope of Claims] (1) A support for a photoconductive member and a first layer region (
G) and a second layer region (8) made of an amorphous material containing silicon atoms and exhibiting photoconductivity are provided in order from the support side, and silicon atoms and nitrogen. a second layer made of an amorphous material containing atoms, the first layer contains a substance (C) that controls conductivity, and the substance (C) The maximum value of the concentration distribution in the layer thickness direction of the substance (
A photoconductive member 0 characterized in that the second layer region (2)) contains C) in a state where it is distributed in a larger amount toward the support side. (2) The first layer region (2) 2. The photoconductive member according to claim 1, wherein silicon atoms are contained in the photoconductive member.・、
. (3) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer region 0) is non-uniform in the layer thickness direction. , (4) The photoconductive member according to claim 1, wherein the distribution state of dalmanium atoms in the first layer region is uniform in the layer thickness direction. (5) The photoconductive member according to claim 1, wherein at least one of the first layer region ←) and the second layer region (S) contains hydrogen atoms. (6) The photoconductive material according to claim 1 or 5, wherein at least one of the first layer region (G) and the second layer region (S) contains a halogen atom. Element, . (7) The photoconductive member according to claim 2, wherein germanium atoms in the first layer region O) are distributed in a distribution state in which breaks are more distributed toward the support side. (8) The photoconductive member according to claim 1, wherein the substance (C) that controls conductivity is an atom belonging to Group Ⅰ of the periodic table. (9) The photoconductive member according to claim J, wherein the substance (C) that controls conductivity is an atom belonging to Group Ⅰ of the periodic table.