JPS60142350A - Photoconductive member - Google Patents

Abstract

PURPOSE:To make electrical, optical and photoconductive characteristics always stable by incorporating carbon atoms into the 1st layer constituting a photoreceptive layer and the 2nd layer contg. a silicon atom and nitrogen atom and distributing a material for controlling conductivity so as to have the max. value of the distributed concn. thereof more on the base side in the 2nd layer region S. CONSTITUTION:A photoconductive member 100 has a photoreceptive layer 107 consisting of the 1st layer 102 and the 2nd layer 103 on a base 101 as a photoconductive member. Said layer 107 has a free surface 106 at one end face. The 1st layer 102 has the layer construction in which the 1st layer region G103 constituted of a-Ge (Se, H, X) and the 2nd layer region consituted of a-Si (H, X) and having photoconductivity are successively laminated. The layer 102 contains carbon atoms and a material for controlling a conduction characteristic. The max. value of the distributed concn. of said material in the layer thickness direction exists in the 2nd layer region S and the material is distributed more on the base 101 side.

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 photoconductive members that are sensitive to electromagnetic waves such as visible light, infrared light, X-rays, gamma 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 is highly sensitive and has a photocurrent (Ip) of 8N ratio.
/dark current (Id)), has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has the desired dark resistance value, and 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 afterimages within a predetermined time.

Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as a-8t) is a photoconductive material that has recently attracted attention.
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

However, the conventional photoconductive member having a photoconductive layer composed of A-8T has a low dark resistance value and a low light sensitivity.

It is necessary to improve the overall properties in terms of electrical, optical, and light guide properties such as photoresponsiveness, use environment properties such as moisture resistance, and even stability. The reality is that there are points that can be further improved.

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 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 response gradually decreases, etc. This often occurred.

Furthermore, a-81 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 difficult to match with semiconductor radars currently in practical use. However, when using commonly used halogen lamps and fluorescent lamps as light sources, there is still room for improvement in that they cannot effectively use light on the longer wavelength side.

In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases,
If the support itself has a high reflectance to the light that passes through the photoconductive layer, interference due to multiple reflections will occur within the photoconductive layer, which is one of the causes of "darkness" in the image. .

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

Furthermore, when forming a photoconductive layer using an A-8L material, in order to improve its electrical and photoconductive properties, hydrogen atoms, fluorine atoms, chlorine atoms, etc., and electrically conductive Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms to control the type, or other atoms are included in order to improve properties, but how these constituent atoms are contained is determined. In some cases, problems may arise with 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 is not sufficient, or the injection of charge from the support side is not sufficiently prevented in the dark area, etc. This often occurs.

Therefore, while efforts are being made to improve the properties of the a-8i 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 focuses on the applicability and applicability of A-81 as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive and intensive research and study from this perspective, we have developed a depleted amorphous material that uses silicon atoms as its base material and contains at least one of hydrogen atoms (H) or halodane atoms (X), so-called hydrogenated amorphous silicon, and halogenated amorphous silicon. Amorphous silicon or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as RA]
-8l (using I(,X)J) and has a photoreceptive layer showing photoconductivity. Conductive members not only exhibit outstanding practical properties, but also
Compared to conventional photoconductive materials, it is superior in all respects, especially as a photoconductive material for electrophotography, and has excellent absorption spectrum characteristics on the long wavelength side. It is based on what we have found to be excellent.

The present invention has electrical, optical, and photoconductive properties that are always constant, and is applicable to all environments with almost no restrictions on usage environments.It has excellent photosensitivity characteristics on the long wavelength side and is resistant to light fatigue. The main object of the present invention is to provide a photoconductive member that is extremely durable, does not exhibit any deterioration phenomenon even after repeated use, and has no or almost no residual potential observed.

Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor radars, and has fast photoresponse.

Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an 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 having sufficient performance.

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

Yet another object of the present invention is high photosensitivity.

It is an object of the present invention to provide a photoconductive member having high 8N ratio characteristics.

The photoconductive member of the present invention comprises a support for the photoconductive member, a 10th printing region (G) made of an amorphous material containing r-lumaeum atoms, and an amorphous material containing silicon atoms. A first layer having a layer structure in which a second layer region (S) exhibiting conductivity is provided in order from the support side, and a second layer made of an amorphous material containing silicon atoms and %N atoms. and a photoreceptive layer consisting of a layer, the first layer containing carbon atoms and a substance (C) that controls conductivity,
The maximum value of the distribution concentration in the layer thickness direction is the second layer region (8)
In the second layer region (8), the second layer region (8) is characterized in that it is contained in a state where it is distributed more toward the support side.

The photoconductive member of the present invention designed to have the above-described layer structure can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. Indicates pressure resistance and usage environment characteristics.

In particular, when applied as an electrophotographic image forming member, interference can be sufficiently prevented even when coherent light is used, and the influence of residual potential on image formation is completely eliminated. High quality with stable electrical characteristics, high sensitivity, and high signal-to-noise ratio, excellent resistance to light fatigue and repeated use, high density, clear halftones, and high resolution. images can be obtained stably and repeatedly.

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

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

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) 103 on a support 101 for the photoconductive member. However, the light-receiving layer 107 has a free surface 106 on one end surface.

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

Amorphous material containing at least one of a hydrogen atom (H) and a halogen atom (X) [hereinafter r a-Go (81, H#X)
A first layer region (G) composed of 10
3 and a second layer region (S) 104 composed of a-st(H+x) and having photoconductivity are laminated in this order.

The first layer (1) 102 contains carbon atoms, and
Contains a substance (C) that controls conduction properties, the substance (C)
In the first layer (1) 102, the maximum value of the distribution concentration in the layer thickness direction is in the second layer region (S), and in the second layer region (S), It is contained in a state where it is distributed more toward the support body 101 side.

The germanium atoms in the first layer region (G) are contained uniformly in the in-plane direction parallel to the surface of the support, but are not uniformly contained in the layer thickness direction. There is no problem even if it is non-uniform.

In addition, if the distribution state of germanium atoms in the first layer region (G) 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. (S
) side, it is desirable to change it gradually, stepwise, or linearly.

In particular, the distribution state of germanium atoms in the first layer region (G) is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration of germanium atoms in the layer thickness direction C (
When G) is given a change that decreases from the support side toward the second layer region (S), the first layer region (G)
It has excellent affinity between the layer region (S) and the second layer region (S), and as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the edge of the support, semiconductor lasers, etc. When used, the first layer region (G) can substantially completely absorb light on the long wavelength side, which is almost completely absorbed by the second layer region (S). Not only can interference due to reflection from the support surface be prevented, but also reflection at the interface between the layer region (G) and the layer region (S) can be sufficiently suppressed.

2 to 10 show typical examples of the distribution state of damanium atoms contained in the first layer region (G) of the photoconductive member of the present invention in the layer thickness direction.

2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer region (G), and tB represents the first layer region (G) on the support side. ), tt is the position of the end surface of the first layer region (G) on the side opposite to the support side.
Indicates the position of the end face. That is, in the first layer region (G) containing the 9-rumanium atoms, the layer is formed from the tB side toward the 11 side.

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

In the example shown in FIG. 2, the interface position 1. where the surface of the support where the germanium atom-containing first layer region (G) is formed and the surface of the first layer region (G) are in contact with each other. thant
Up to the position l, the distribution concentration C of germanium atoms is C1
0 interface, which is contained in the first layer region (G) where germanium atoms are formed while taking a constant value of At the position C, the distribution concentration C of dalmanium atoms is C5.

In the example shown in FIG. 3, the distribution concentration C of the germanium atoms contained is at position 1i1i and from tII to position 11.
The concentration gradually decreases continuously from C4 until reaching position 1.
1, a distribution state is formed such that the concentration becomes C5.

In the case of FIG. 4, the distribution concentration C of germanium atoms is kept at a constant value C6 from position ta to position t2, gradually and continuously decreases between position t2 and position tT, and is gradually and continuously decreased from position ta to position t2. In this case, the distribution concentration C is substantially zero (substantially zero here means that it is less than the detection limit amount).

In the case of FIG. 5, the distribution concentration C of germanium atoms is continuously and gradually decreased from the concentration CB from position tB to position 11, and becomes substantially zero at position 11.

In the example shown in FIG. 6, the distribution concentration C of germanium atoms is a constant value of concentration C9 between position tB and position t3, and is set to concentration C10 at position tT. Between position t3 and position tT, the distribution density C is linearly decreased from position t5 to position 11.

In the example shown in FIG. 7, the distribution concentration C is at the position tB.
The concentration C11 takes a constant value up to position t4, and
4 to position tT, the distribution state is such that the concentration decreases linearly from C12 to C13.

In the example shown in FIG. 8, the distribution concentration C of dalmanium atoms from position tB to position tT is the concentration C14.
It decreases in a linear function so as to substantially reach zero.

In FIG. 9, from position tB to position t5, the distribution concentration C of germanium atoms is higher than the concentration C15*
C1b is linearly decreased, and the positions t5 and t
An example is shown in which the concentration C16 is a constant value between T and T.

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration C17 at the position tB, and the concentration decreases slowly from this concentration C17 until reaching the island position t6, and then rapidly decreases near the position t6. The concentration is reduced to C18 at position t6.

Between position t6 and position t7, the concentration CI? is first rapidly decreased, and then slowly and gradually decreased, and at position t7, the concentration CI? Between the positions t7 and t8, the concentration is gradually decreased very slowly and reaches the concentration C20 at the position t8. Between position t8 and position 11,
The concentration is reduced from C20 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 (9)
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 with a high distribution concentration C of germanium atoms, and on the interface 11 side, the distribution concentration C is high.
The first layer region (G) is provided with a germanium atom distribution having a portion that is considerably lower than that on the support side.

The first layer region (G) constituting the first layer (1) constituting the photoconductive member in the present invention contains germanium atoms at a relatively high concentration on the support side as described above. It is desirable to have a localized area (A) that is

In the present invention, the localized region (A) is
To explain using the symbols shown in the figure, 5 from the interface position tB.
It is desirable that it be provided within μ.

In the present invention, the localized region (A) is located at the interface position t
It may be the entire layer region (Lt) with a thickness of 5 μm from B, or it may be a part of the layer region (LT).

Whether the localized region (A) is a part or all of the layer region (LT) is appropriately determined according to the characteristics required of the photoreceptive layer to be formed.

The localized region (A) has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration of germanium atoms is preferably 1000 atomic ppm or more with respect to the sum with silicon atoms, or more. It is desirable that the layer be formed in such a manner that a distribution state can be obtained, preferably 5000 atomic ppm or more, most preferably 1 x 10' atomic ppm or more.

That is, in the present invention, the layer region (G) in which the atoms are contained has a maximum distribution concentration Cma within 5 μm in layer thickness from the support side (layer region 5 μm thick from ta).
Preferably, it is formed so that x exists.

In the present invention, the content of germanium atoms contained in the first layer region (G) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 10 10 atonue ppm.

More preferably 100 to 9.5 X 10 atoms
c ppm, optimally 500-8 X 105 atoms
ic ppm.

In the present invention, the first layer region (G) and the second 1! ! The layer thickness with the region (S) is one of the important factors for effectively achieving the object of the present invention. Great care must be taken when designing the components.

In the present invention, the layer thickness TB of the first layer region (G) is preferably 301 to 50μ, more preferably 401 to 40μ.
μ, optimally set to 501 to 30 μ.

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

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

In the photoconductive member of the present invention, the above numerical range of (Tm+T) is preferably 1 to 100μ, more preferably 1
~80μ, optimally 2-50μ.

In a more preferred embodiment of the present invention, the above
- Thickness TB and layer thickness T are preferably T, /T≦
It is desirable that appropriate numerical values be selected for each so as to satisfy the relationship of 1.

In selecting the numerical values of layer thickness Tl and layer thickness T in the above case, more preferably TB/T≦0.9, optimally T
It is desirable that the values of layer thickness Tl and layer thickness T be determined so that the relationship B/T≦0.8 is satisfied.

In the present invention, the content of germanium atoms contained in the first layer region (G) is I x 10 atomic
ppm or more, the layer thickness TB of the first layer region (G)
is desirably as thin as possible, preferably 30μ
Hereinafter, the thickness is preferably 25μ or less, most preferably 20μ or less.

In the present invention, the halodane atoms (X) contained as necessary in the first layer region (G) and/or second layer region (S) 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, the first layer region (G) composed of a-Ge (Si+H+X) is formed by vacuum deposition using a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion silating method. done by law. For example, by the glow discharge method, @-G@ (Sl
In order to form the first layer region (G) composed of yH2 ) that can supply 81 raw material gas for supplying hydrogen atoms (H) raw material gas for introducing hydrogen atoms (H) or/and halodan atoms (X)
A raw material gas for introduction is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated within the deposition chamber, thereby causing the gas to flow onto the surface of a predetermined support that has been placed at a predetermined position in advance. It is sufficient to form layers. In order to non-uniformly distribute the dahmanium atoms, the distribution concentration C of the germanium atoms contained in the a-Go(
A layer consisting of SiyH*X) may be formed. In addition, when forming by sputtering method, for example, Ar p
In an atmosphere of an inert gas such as He or a mixed gas based on these gases, a target composed of St, or two targets composed of the target (I' y ) and Ge are used. Alternatively, using a mixed target of Si and Gs, a source gas for supplying Ge or St diluted with a diluent gas such as He or Ar may be used as necessary.
The raw material gas for supply is converted into hydrogen atoms ()I) as necessary.
Or/and a gas for introducing halodane atoms (X) is introduced into a deposition chamber for sputtering to form a plasma atmosphere of a desired gas, and at the same time, the raw material gas for supplying Ge or/
While controlling the gas flow rate of the raw material gas for supplying St and St according to a desired rate of change curve, the target may be stuttered.

In the case of the ion blating method, for example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in an evaporation tray as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam. (FB method), etc., and the flying evaporates are passed through the desired gas plasma atmosphere.
This can be done in the same manner as in the sputtering method.

Substances that can be used as the raw material gas for S1 supply used in the present invention include SiH4#Si2H6,81,)
Silicon hydride (silanes) in a gaseous state or that can be gasified, such as 181S l 4H1, can be effectively used, especially because of its ease of handling during layer creation work, good Si supply efficiency, etc. In this respect, SiH4 and Si□H6 are preferred.

As a material that can be a source gas for supplying Ge, GeH
4y Ge2H6e Go, He# Gl! +4H10
t Ge5H121G@6H14y Ge7H16t
Gaseous or gasifiable damanium hydride such as GeBHIB*Cy8pH2o can be effectively used, especially for its ease of handling during layer forming operations,
In terms of Ge supply efficiency, etc., 4 * Ge2H is used for Ge.
6#Ga5)1B is preferred.

Many halogen compounds are effective as the raw material gas for introducing halodane atoms used in the present invention, such as gases such as halogen gas, halodanides, interhalogen compounds, and halodane-substituted silane derivatives. Preferred examples include halogen compounds that can be converted into gas or gasified.

Furthermore, silicon hydride compounds containing halodane atoms, which are in a gaseous state or can be gasified and whose constituent elements are silicon atoms and HI:I dan atoms, are also mentioned as effective compounds in the present invention. I can do it.

Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine, io+7
Hao f 7 ;) f Su, BrF # C1F t
czIll'3sBrFs t BrF5 e IF
Examples include interhalin compounds such as 5#IF, lIctlIBr, and the like.

Specifically, silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include, for example, 5
IF4 e 512F6 y 5ICA4 # SiB
Preferred examples include silicon halides such as r4.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen is used as a raw material gas capable of supplying 81 along with a raw material gas for supplying Ge. The first layer region (G) made of a-8iG@ containing halogen atoms can be formed on a desired support by using silicon oxide gas.

When creating the first layer region (G) containing halogen atoms according to the glow discharge method, basically, for example, silicon halide, which serves as a raw material gas for supplying Si, and hydrogenation, which serves as a raw material gas for supplying Ge. Germanium and Ar t H2t H
Gases such as E are introduced into the deposition chamber for forming the first layer region (G) at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. A first layer region (G) is deposited on the desired support by
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.

Su/4'? In order to introduce halogen atoms into the layer formed in either the /talling method or the ion silating method, a gas of the above-mentioned halodane compound or the above-mentioned silicon compound containing halodan atoms is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for hydrogen atom introduction, such as H2, or the above-mentioned silanes or/
Gases such as germanium hydride and the like may be introduced into the deposition chamber for A-stutting to form a plasma atmosphere of the gases.

In the present invention, the above-described halodane compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, halogen compounds such as HF, HCl, HBr, rHI, etc. ) f Hydrogen heptaide, 5iH2F, 2 # 5iH2I2
1SiH2Ct2 # 5iHCt3 t 5iH2B
halogen-substituted silicon hydrides such as r2v 5IHBr, and GeHF5 l GeH2F2tGeH3F1 t
GeHCAs + GeH2C42y GsH5CA
tGeHBr.

GeH2Br2 t Gs+H,Br, GeHI3
tGeH2I2. Hydrogenated germanium halides such as GeH, I, halides containing hydrogen atoms as one of their constituent elements, GeF4tGeCL, tG5Br4t
GeI4s GeF2+ GeC12# GeBr2
The layer region of layer 1 (G
) can be mentioned as a starting material for the formation.

Among these substances, halodane containing hydrogen atoms are
At the time of forming the first layer region (G), hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced at the same time as halodan atoms into the layer, so in the present invention, halodane can be preferably introduced. used as raw material.

In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, H2 or SiH4p 5i2H6t
Silicon hydride such as SisH8+ 814H4゜ and germanium or a germanium compound for supplying Go, or GeH4j Ge2H6* Ge5H81Ge4
H1os (yl15H12sGe16H14+ Ge
, HI3eG@aH+atGe2H2o, etc., or by coexisting kermanium and silicon or a silicon compound for supplying Si in the deposition chamber to generate a discharge.

In a preferred example of the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the amounts of hydrogen atoms and halodan atoms contained in the first layer region (G) of the photoconductive member to be formed The sum (H+X) is preferably 0.01 to 40
atomic%, preferably 0.05 to 30 at
omic%, optimally 0.1 to 25 atomic%.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the first layer region (G), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms The amount of the starting material used to contain (X) introduced into the deposition system, the discharge power, etc. may be controlled.

In the photoconductive member of the present invention, the second layer region (S) that does not contain germanium atoms and the first layer region (G) that contains germanium atoms contain a substance (C) that controls conduction properties. ), the layer region (S)
And the conductive properties of the layer region (G) can be controlled as desired.

At this time, the substance (C) contained in the second layer region (S)
) may be contained in the entire layer region (G) or in a part of the layer region, but in either case, it needs to be contained in a state where it is distributed more toward the support side.

That is, the layer region (SPN) containing the substance (C) provided in the second layer region (S) is provided as a full-thickness slope of the second layer region (S), or It is provided as a support side end layer region (SE) as a part of the region (S). In the former case where it is provided as a full-layer region, it is provided so that its distribution concentration C(8) increases linearly, stepwise, or curved toward the support side.

When the distribution concentration 1j[:C(s) increases in a curved manner,
It is desirable to provide in the layer region (S) a substance <C) which controls the conductivity so that it increases monotonically towards the support.

When the layer region (SPN) is provided as a part of the second layer region (S), the distribution state of the substance 5K (C) in the layer region (SPN) is parallel to the surface of the support. It is assumed that the layer is uniform in the in-plane direction, but it may be uniform or non-uniform in the layer thickness direction. In this case, the layer region (SPN
), in order to provide the substance (C) so that it is distributed non-uniformly in the layer thickness direction, the same distributed concentration line as in the case where the substance (C) is provided in the entire layer region of the first layer region (S) is obtained. It is desirable to set it up in a similar manner.

In the case where the first layer region (G) contains a substance (C) that controls conductivity and a layer region (GPN) containing the substance (C) is provided, the second layer region (S) contains a layer. This can be done in the same way as when providing a region (SPN).

In the present invention, when a substance (C) that controls conduction characteristics is contained in both the first layer region (G) and the second layer region (S), the substance contained in both layer regions (C) may be the same species or mutually different species.

However, when both layer regions contain the same type of substance (C) that controls conductivity, the maximum distribution concentration of the substance (C) in the layer thickness direction is in the second layer region (S). That is, it is preferable to provide it inside the second layer region (S) or at the interface with the first layer region (G).

In particular, it is desirable that the maximum distribution concentration is provided at or near the contact interface with the first layer region (G).

In the present invention, as described above, the first layer (1) contains a substance (C) that controls conduction characteristics, and the layer region (PN) containing the substance (C) is formed in the second layer (PN). It is preferably provided as the end layer region (SF) on the support side of the second layer region (S) so as to occupy at least a part of the layer region (S).

When the layer region (PN) is provided so as to span both the first layer region (G) and the second layer region (S), the layer region (GPN) of the substance (C) that controls conduction properties There is C(G)mix between the maximum distribution concentration C(G)max in the layer region (SPN) and the maximum distribution concentration C(8)max in the layer region (SPN).
The substance (C
) is contained in the first layer (1).

A substance (C) that controls conductivity contained in the layer region (PN)
) can include so-called impurities in the semiconductor field, and in the present invention, p-type impurities give p-type conductivity to SN or Ge, and n-type impurities give n-type conductivity to SN or Ge. Type impurities can be mentioned.

Specifically, p-type impurities include atoms belonging to Group ■ of the periodic table (Group ■ atoms), such as B (boron), AL (aluminum), Ga (gallium), In (indium), and Tt ( Among them, BlGIL is particularly preferably used.

Examples of n-type impurities include atoms belonging to Group ■ of the periodic table (Group ■ atoms), such as P (phosphorus), A++ (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) provided in the first layer (1) is determined by the conduction properties required for the layer region (PN). Alternatively, the layer region (PN) can be appropriately selected depending on the organic relationship, such as the relationship with the characteristics at the contact interface with the support or other layer region provided in direct contact with the layer region (PN).

In addition, the characteristics of other layer regions provided in direct contact with the layer region and the relationship with the characteristics at the contact interface with the crystallization layer region are also taken into consideration, and the substance (C) that controls the conduction characteristics is determined. The content is selected appropriately.

In the present invention, the content of the substance (C) that controls conduction properties contained in the layer region (PN) is preferably 0.0
1 to 5 X 10' atomle ppm, more preferably 0,5 to I X 10' atomle ppm N
Optimally, it is 1 to 5 x 10' atomic ppm.

In the present invention, the layer region (PN) containing the substance (C) that controls conduction properties is in contact with the contact interface between the first layer region (G) and the second layer region (S), or the layer region (PN)
occupies at least a part of the first layer region (G), and the content of the substance (C) in the layer region (PN) is preferably 30 atomic ppm or more,
More preferably, the amount is 50 atomic ppm or more, optimally 100 atomic ppm or more, so that, for example, when the substance to be contained is the above-mentioned p-type impurity, the free surface of the photoreceptive layer is subjected to polar charging treatment. When the substance to be contained is the n-type impurity, it is possible to effectively prevent the movement of electrons injected from the support side into the second 1-region (S). When the free surface of the photoreceptive layer is charged to e-polarity, it is possible to effectively prevent the movement of holes injected from the support side into the second layer region (S).

In the above case, the layer region (Z) excluding the layer region (PN) under the above-mentioned basic structure of the present invention has the following properties:
It is also possible to contain a substance that controls conduction properties of a polarity different from the polarity of the substance that controls conduction properties contained in the layer region (PN), or a substance that controls conduction properties of the same polarity. It 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 characteristics contained in the layer region (Z) may be adjusted as desired depending on the polarity and content of the substance contained in the layer region (PN). Although it is determined, the preferred trench depth is 0.001~
1000 atomic ppm1, more preferably 0.
05-500 atomic ppm, optimally 0.05-500 atomic ppm.
1 to 200 atomlc ppm.

In the present invention, when the layer region (PN) and the layer region (Z) contain the same kind of substance governing conductivity, the content in the layer region (Z) is preferably 30 atoms.
ic, ppm or less.

In addition to the above-mentioned cases, in the present invention, the photoreceptive layer contains a substance that controls conductivity with one polarity, and the nine-layer region contains a substance that controls conductivity with the other polarity. It is also possible to provide a so-called depletion layer in the contact region by providing the layer region in direct contact with the contact region. That is, for example, in the photoreceptive layer, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided so as to be in direct contact with each other to form a so-called p-n junction. A depletion layer can be provided.

FIGS. 11 to 24 show typical examples of the distribution state of the substance (C) that controls conduction properties contained in the first layer (1) in the layer thickness direction.

In these figures, the horizontal axis shows the distribution concentration C (PN) of the substance (C) in the layer thickness direction, and the vertical axis shows the layer thickness t from the support side of the first layer (1). . to is the first layer region (G
) and the contact interface between the second layer region (S) and the second layer region (S) are shown.

In addition, tB is the position of the end surface of the first layer (1) on the support side,
tT indicates the position of the end surface of the first layer (1) on the side opposite to the support side.

FIG. 11 shows a first typical example of the distribution state of the substance (C) that controls conduction properties contained in the first layer (1) in the 1-thickness direction.

In the example shown in FIG. 11, the substance (C) is not contained in the first layer region (G), but is contained only in the second layer region (8) at a constant distribution humidity with a concentration C1. ing. Clogged,
In the second layer region (S), the substance (C) is contained in the end layer region between to and t1 at a constant distributed concentration of C1.

In the example shown in Figure 8g12, the second layer region (S) contains the substance (
C) is contained evenly, but in the first layer region (G
) does not contain substance (C).

The substance (C) is contained in the layer region between tO and t2 at a constant distribution concentration of 02, and the layer region between t2 and tT has a constant quality of C5, which is much lower than C2. Contained in high concentrations.

The substance (C) is deposited in the first layer (
By including 1) in the second layer region (S) constituting the layer, it is possible to prevent the charge injected from the first 1-region (G) to the second layer region (8) from moving toward the surface. It is possible to effectively prevent this, and at the same time, it is possible to improve photosensitivity and dark resistance.

In the example of FIG. 13, the substance (C) is evenly contained in the second layer region (S), but the concentration decreases monotonically toward the upper surface from C4 at t to tT. The substance (C) is contained in a state in which the distribution concentration C(+N) changes so that the concentration becomes O at the same time. The first layer region (G) does not contain the substance (C).

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 (8). That is, in the case of the examples shown in FIGS. 14 and 15, the second layer region (S) includes a layer region containing the substance (C) and a layer region not containing the substance (C). and have a layered structure in which they are laminated in this order 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) at the position of t3 is lower than the concentration C5 at the position of tQ between tQ and t5. On the other hand, in the case of FIG. 15, between to and t4, the concentration at t(1) decreases monotonically to 0.
The concentration decreases linearly and continuously from 6 to 0 at the position t4. In the examples shown in FIGS. 14 and 15, the first layer region (G) does not contain the substance (C).

In the examples shown in FIGS. 17 to 24, the first layer region (
A case is shown in which both the conductivity controlling substance (C) is contained in the conductivity controlling substance (C) and the second layer region (S).

In the case of the examples shown in FIGS. 17 to 22, the second layer region (S
) is the layer region containing the substance (C) and the layer region containing the substance (C).
) is common in that they have a two-layer structure in which the layer regions that do not contain layer regions are laminated in this order from the support side. In the examples shown in Figures 17 to 21, the first
The distribution state of the substance (C) in the layer region (G) is the second
The distribution density C(r*) decreases from the interface position t(1) with the layer region (:Y) toward the support.

In the examples shown in FIGS. 23 and 24, the substance (C) is evenly contained in the layer thickness direction over the entire layer region of the first layer (1).

In addition, in the case of FIG. 23, in the first layer region (G), the concentration C2 at tQ is lower than the concentration C2S at tB.
2 to 1. In the second layer region (8), the concentration C22 at to increases linearly toward to.
The concentration decreases monotonically and continuously from tO to tT up to the concentration O at T.

In the case of FIG. 24, in the layer region between 'LB and t14, the substance (C) is contained at a constant distribution concentration of concentration C24, and in the layer region between t14 and 11, the concentration is C25
It decreases more linearly and reaches 0 at tT.

11 to 24, the distribution concentration C(p
As explained in the typical cases of changes in N), in all examples, the substance (C) is Contained in the first layer (1).

In the present invention, to form the second layer region (S) composed of % a-81 (HyX), from among the starting materials (I) for forming the tenth layer region (G) described above, G. Form the first layer region (G) using the starting material [starting material for forming the second layer region (S) (■)] excluding the starting material that will become the raw material gas for supply. It can be carried out according to the same method and conditions as in the case.

That is, in the present invention, the second layer region (S) composed of a-8i (HtX) can be formed by, for example, the glow discharge method, the s/4' stumbling method, or the ion silating method. This is accomplished by a vacuum deposition method that utilizes the discharge phenomenon. For example, a-81(H
In order to form the second layer region (S) consisting of t A raw material gas for introducing atoms (H) and/or for introducing halodane atoms (X) is introduced into a deposition chamber whose interior can be made to have a reduced pressure, and a glow discharge is generated within the deposition chamber. a-31(H,X) on a given support surface with
What is necessary is to form a layer consisting of. In addition, when forming by a sputtering method, for example, when sputtering a tardite made of Si in an atmosphere of an inert gas such as Ar, H@, or a mixed gas based on these gases, hydrogen is A gas for introducing atoms (H) and/or halodane atoms (X) may be introduced into the deposition chamber for snow 4' tuttering.

In the present invention, the amount of hydrogen atoms (1()) or the amount of halodan atoms (X) or the amounts of hydrogen atoms and halodan atoms contained in the second layer region (S) constituting the layer to be formed The sum (H x) is preferably 1 to 40 atoms
More preferably 5-30 atomib%, optimally 5-30%
It is desirable to set it to 25 atomic%.

A layer region containing the substance (C) by structurally introducing a substance (C) that controls conduction properties, for example, a group II atom or a group II atom into the layer region constituting the photoreceptive layer. (PN
), during layer formation, the starting material for introducing the m-th Atsushi or the starting material for introducing the It may be introduced together with the starting material. As the starting material for the introduction of Atsushi No. 1, it is desirable to use a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, as a starting material for introducing Atsuko Atsushi, B2) (61P4H10'B5H9' B5H1l
'Boron hydride, BF, such as B6H1o, P6H42, P6H14.

Examples include boron halides such as BCA3 p BBrs.

In addition, htct, e ahct5e am (cHs
) sp xnct, ertct, etc. can also be mentioned.

In the present invention, the starting materials effectively used for introducing phosphorus atoms are PH, #
Hydrogen ratio adjacent to P2H4 etc. t PH4I I I) F3゜PF5 t Pct, t Pct5# PBr, #
Examples include halodane atoms such as PBr3 p PI. In addition, AsH3* AsF3 eAsCt3 t
AsBr, e AsF5 l 5bH5e SbF3
# SbF5 t8bC15t 5bCt5 t B
iH3s BkCl3 + B1Br3 and the like can also be mentioned as effective starting materials for the introduction of Atsushi No. 2.

In the light guide member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the first layer (I), the first layer (I) is Carbon atoms are also present in the layer (1). The carbon atoms contained in the first layer (1) may be contained in the entire layer area of the first layer (1) without any scratches, or may be contained in a part of the first layer (summer). It may be contained only in the layer region and unevenly distributed.

In addition, the distribution state of carbon atoms is such that even if the distribution concentration C (C) is uniform in the thickness direction of the first layer (■), the distribution concentration C (C) is not uniform in the layer thickness direction. It may be uniform.

In the present invention, when the main purpose of the layer region (C) containing carbon atoms provided in the first 1ψi (1) is to improve photosensitivity and dark resistance 1, The first layer (
All 1 of 1)? The support and the layer (1) or the first layer region (G) and the second layer region (
S) If the objective is to strengthen the adhesion throughout the entire surface, the end layer region of the first layer (1) on the support side or the region near the interface between the first and second layer regions. It is set up so that it occupies the area.

In the former case, the content of carbon atoms contained in the layer region (C) is relatively small in order to maintain high photosensitivity, and in the latter case, in order to ensure the strengthening of the VN property between the layers. It is desirable that a relatively large amount be used.

Also, for the purpose of achieving both the former and the latter at the same time,
The first layer (
1) It is distributed at a relatively low concentration on the free surface side, or the surface W1 region on the free surface side of the first layer (1) does not contain carbon] Toko. What is necessary is to form a distribution state of carbon atoms in the layer region (C).

Furthermore, the support or the first F! If the purpose is to prevent charge injection from the dark region (G) to the 20th layer region (S) and increase the overall dark resistance, the first layer region (
In G), carbon atoms are distributed at a higher concentration at the support side end, or carbon atoms are distributed at a higher concentration of gold near the interface between the first layer region and the second layer region.

25 to 40 show typical examples of the distribution of carbon atoms in the first layer (D).

tB indicates the position of the end surface of the first layer (17) of the support (111), and tT indicates the position of the end surface of the first layer (1) on the opposite side to the support. In the example shown in FIG. , from position tB to position Nt1, the carbon atom distribution concentration C (C) is assumed to be a constant value, and from position j
The carbon atom distribution concentration from i′j t 1 to position tT is C
It is said to be constant at 2.

In the example shown in FIG. 26, the carbon atom distribution concentration is constant at C3 from position fits to position t2, and
Yo i) m, t! Up to i'5, uJ consider atomic distribution concentration ke C
4, and from position t3 to position tT, the carbon atom distribution concentration is set to C5, and the carbon atom distribution concentration is decreased in three stages.

In the example in Fig. 27, the carbon atom distribution is C6 six times from position ta to fnt4, and the carbon atom distribution concentration is C7 from position t4 to position tT.◇ In the example in Fig. 28, from position tB to position The carbon atom distribution concentration is C8 until t5, the carbon atom distribution concentration is C9 from position t5 to position t6, and the carbon atom distribution concentration is C10 from position t6 to position t7. In this way, the carbon atom distribution concentration is increased in three stages.

In the example of FIG. 29, the carbon atom distribution concentration "ecll" is set from position tn to position [Ut7, and from position 1i'7t7 to position t.
The carbon atom distribution concentration up to position Mta is set to C12, and the carbon atom distribution concentration from position Mta to position ffftT is set as t=C+3. The carbon atom distribution concentration is made high on the support side and the free surface side.

In the example shown in FIG. 30, from position ffttm to position t9
Up to this point, the carbon atom distribution concentration is C14, the carbon atom distribution JT'fj degree from position t9 to position tto is C1s, and the carbon atom distribution fμ degree from position ftt+o to position tT is C14.

In the example shown in FIG. 31, from position ts to position 16tN
At t, the carbon atom distribution concentration is set to 016, and from position t11 to position t12t, the carbon atom distribution concentration increases stepwise to C17, and from position Mt12 to position %JtT, the carbon atom distribution concentration decreases to 018.

In the example of FIG. 32, the carbon atom distribution concentration 'frc+q is set from position ta to position lft1st, and from position t15 to position t.
At 14t, the carbon atom distribution concentration is increased stepwise to C20, and from position t14 to position tT, the carbon atom distribution concentration is set to C21, which is lower than the initial concentration.

In the example shown in FIG. 33, the carbon atom distribution concentration is C22 from position 1B to position t15, decreases to carbon atom distribution concentration kc25 from position t15 to position tj6, and the carbon atom distribution concentration is reduced to C22 from position 1B to position tj6.
The carbon atom distribution concentration is 0 from r'ft+6 to position t17.
24, and decreases to a carbon atom distribution concentration tc23 from position t17 to position tT.

In the example shown in FIG. 34, the distribution concentration C (C
) is the distribution concentration from 0 to C from position tB to position Wtr.
It monotonically increases continuously up to 25.

In the example shown in FIG. 35, the distribution density of carbon atoms is 1.
In (c), at position tB, the distribution density is C26, which monotonically and continuously decreases from the distribution density C26 until reaching position t18, and becomes the distribution density C27 at position tjQ. Between position NtlB and position 1iftT, the distribution concentration C (C) of carbon atoms monotonically increases continuously from position tea, and becomes the distribution concentration C2B at position fftt.

The example in Figure 36 is relatively similar to the example in Figure 35, but the difference is that no carbon atoms are contained at position IF/119 and position t20. Between position tB and position ti9, the distribution concentration at position tfrttn monotonically decreases from distribution concentration C29 at position t19 to distribution concentration O at position t19, and between position t20 and position fiftT, the distribution concentration at position t2o decreases. The distribution density increases continuously by a single X from 0 to 030 at position tB.

In the light guide member of the present invention, Figs.
As a typical example is shown in the figure, more carbon atoms are contained on the lower and upper surfaces of the photoreceptive layer, and less carbon atoms are contained toward the inside of the first layer (1). In addition, the distribution concentration of carbonaceous atoms in the layer thickness direction c
(c) + 'y+; By continuously changing, for example, the first layer (1) is made to have high photosensitivity and dark red resistance.

In addition, in FIGS. 34 to 36, by continuously changing the distribution concentration C, (C) of carbon atoms, hf (change in refractive index) in the layer thickness direction due to the inclusion of carbon atoms This effectively prevents interference caused by coherent light such as laser light.

In the example shown in FIG. 37, the position fft21 is lower than the position tB.
The carbon atom concentration is assumed to be C31, and from position tH to position 1
The carbon atom concentration increases to iJ't22 and reaches a peak value C32 at position t22. The carbon atom concentration decreases from position if t22 to position t25, and at position fi￥tT, the carbon atom concentration C
It will be 31.

In the example shown in FIG. 38, the carbon atom concentration is C33 from position tB to position t24, increases sharply from position t24 to position t25, and at position t25, the carbon atom concentration reaches the peak value C34 and reaches position M From t25 to position tT, the carbon atom concentration decreases to almost zero.

In the example shown in FIG. 39, from position 1B to position t26, the carbon atom concentration gradually increases from C35 to C56, and at position t26, the carbon atom concentration reaches a peak value C36. The carbon atom concentration rapidly decreases from position t26 to position tl, and reaches a carbon atom concentration C55 at position 11.

In the example shown in FIG. 40, the carbon atom concentration is C37 at position tB, decreases to one position t27, becomes carbon atom concentration C38, and remains constant at carbon atom concentration C28 from position 18tz7 to position fRt2a. The carbon atom concentration increases from position t2s to position t29, and at position t29, the carbon atom concentration reaches a peak value C59'? Take t. The carbon atoms decrease from position t29 to position 11, and the carbon atom concentration becomes C38 at position tT.

In the present invention, even if the layer region (C) occupies the entire area of the first layer (1) or does not occupy the entire area of the 10th layer (1), the layer thickness To of the layer region (C) If the proportion of the first layer (1) in the layer thickness T is sufficiently large, the upper limit of the content of carbon atoms contained in the layer region (C) will be sufficiently smaller than the above value. desirable.

In the case of the present invention, VC is such that when the thickness of the layer region (C) is equal to or more than two-fifths of the thickness T of the first layer (I), The upper limit of the amount of carbon atoms contained in the layer region (C) is the sum of silicon atoms, germanium atoms, and carbon atoms [hereinafter referred to as r'r ('s 1Gec)]
, J], preferably 30 atomic
It is preferably less than 20 atomic%, most preferably less than 1° atomic%.

In the present invention, the layer region (C) containing carbon atoms constituting the first layer (1) contains carbon atoms at a relatively high concentration on the support side and near the free surface, as described above. In the former case, the support and the 10th layer (1
), and the acceptance potential can be improved.

Upper nr2 Xi is here! ll Castle (B) is shown in Figures 25 to 4.
Explaining using the symbols shown in FIG. 0, it is desirable to provide within 5 μm from the interface position tB or free surface tT.

In the present invention, the localized region (B) is located at the interface position t
Bma'fL is the entire layer area up to 5μ thick from one free surface (
LT), or may be part of a layer region (LT).

Localized region (B) t? Whether it is a part or all of the layer region (Lt) is determined as appropriate depending on the characteristics required of the layer to be formed.

The localized region (B) has the maximum distribution concentration Cma of carbon atoms as the distribution state of the carbon atoms contained therein in the layer thickness direction.
XZ>', preferably 5 Q O,, atomfc p
pm or more, more preferably 800 atomic ppm
Above, optimally 1000 atomic ppm or more,
It is desirable that the layers be formed in such a way that a distribution state can be achieved.

That is, in the present invention, the layer region (C) containing carbon atoms has a maximum distribution concentration Cmax within 5 μm in layer thickness from the support side or free surface (layer region with a thickness of 5 μm from tll or tT). It is desirable that it be formed so that it exists.

In the present invention, even if the layer region (C) occupies the entire area of the first layer or does not occupy the entire area of the first layer (1),
If the ratio of the layer region (C) to the layer thickness T of the first layer (1) of the layer J'jL T o is large enough, the region of J (C
The upper limit of the content of carbon atoms contained in ) is desirably set to be sufficiently smaller than the above value.

In the case of the present invention, when the ratio of the layer thickness To of the PINfi region (C) to the layer thickness T of the first layer (1) is two-fifths or more, the layer region <C> h contained in
j'j, the upper limit of +J1 of elementary atoms is T (SiGeC)
preferably 30 atomic% or less, more preferably 20 atomic% or less, and Hlt has lO
atomlc% or less.

In the present invention, in order to achieve the object of the present invention more effectively, the distribution concentration curve of carbon atoms in the layer thickness direction in the layer button tt: (C) K is It is desirable that # atoms be contained in the layer region (C) so that the layer region (C) is smooth and continuous. In addition, the effects described below are greatly exhibited by arranging the distribution S1 degree curve so that its maximum distribution concentration cmhX is located inside the 10th layer (1).

In the present invention, the maximum distribution concentration cm&X is preferably provided in the vicinity of the surface of the fi first layer (I) opposite to the support (the free surface 1&1Il in FIG. 1). In this case, by appropriately selecting the maximum distribution concentration cm□, the total effect of injecting charges from the VCC coating surface into the inside of the photoreceptive layer when the photoreceptive layer is subjected to i-torture treatment from the free surface side can be reduced. It can be prevented.

In addition, in the vicinity of the free surface described by nfI, carbon atoms are contained in the first 0M (1) K so that the distribution concentration of carbon atoms decreases sharply from the maximum distribution concentration Cm1lX toward the free surface. Durability in a humid atmosphere can be further improved.

When the distribution concentration curve of carbon atoms is within the radial distribution concentration Cma By containing carbon atoms, it is possible to improve the adhesion between the support and the light-receiving layer and to prevent rough injection.

In the present invention, carbon atoms are desirably contained in the central layer region of the first layer (1) in an amount that does not reduce photosensitivity even though it strives to increase dark resistance.

In the present invention, the maximum distribution concentration cmax of carbon atoms is
For T (81 GeC), preferably 67 atoms
c% or less, more preferably 50 atom1c% or less,
Optimally, it is set to 40 atomie% or less.

In the present invention, the M region (
The content of carbon atoms contained in C) depends on the characteristics required for the layer region (C) itself, or when the layer region (C) is provided in direct contact with the support, the content of the carbon atoms in the support In terms of organic relationships, such as the relationship between properties at the contact interface with
It can be selected as appropriate.

In addition, when another layer region is provided in direct contact with the layer region (C'), the characteristics of the crystallized layer region and the characteristics at the contact interface with the crystallized layer region are determined. The carbon atom content is appropriately selected taking into consideration the relationship.

The amount of carbon atoms contained in the layer region (C) may be adjusted as desired depending on the properties required of the photoconductive member to be formed, or may be adjusted as desired depending on T (SiGeC). 001-50 atomlc%, more preferably 0.002-40 atomic9! +, optimally 0.
003 to 30 atomic%.

In the present invention, in order to provide the layer region (C) containing carbon atoms in the first layer (D), all the starting materials for introducing carbon atoms are added during the formation of the first layer (1). It may be used together with the starting material for forming the first layer (1) and contained in the formed layer while controlling its amount.

When using the entire glow-release method to form the layer region (C), a starting material for introducing carbon atoms is added to a material selected as desired from among the starting materials for forming the first layer (1). Added. As the starting material for introducing carbon atoms, most of the gaseous substances containing at least carbon atoms or gasified substances that can be gasified can be used.

For example, a raw material gas containing silicon atoms (St), a raw material gas containing carbon atoms (C) and hydrogen atoms (H) or/and halogen atoms (X
) is mixed with a raw material gas containing constituent atoms at a desired mixing ratio, or a raw material gas containing silicon atoms (81) tl- constituent atoms is mixed with carbon atoms (C) and hydrogen atoms (
H) A raw material gas containing all constituent atoms is also mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and silicon atoms (St), carbon atoms (C ) and hydrogen atoms (H) as constituent atoms.

Alternatively, a raw material gas containing silicon atoms (Sl) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing carbon atoms (C).

Examples of those having C and H as constituent atoms include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like.

Specifically, as a saturated hydrocarbon, methane (CH4)
, mtan (C2H6) + 76o / mtan (C,
H8), n-butane (n-C4H1o) + 'methane (C5H12) + ethylene hydrocarbon,
Ethylene (C2H4), Propylene (C3H6), Butene-1' (C4H8) *Butene-2 (C4H8)
, isobutylene (C4H8), pentene (C5H10
) Acetylene hydrocarbons include acetylene (C
2H2), methylacetylene (C,H4), butyne (C
4H6), etc.

In addition to these, alkyl silicides such as 81(CH,)4.5l(C□H5)4 can be cited as raw material gases containing 8i, C, and H as constituent atoms.

In the present invention, the layer region (C) may further contain oxygen atoms and/or nitrogen atoms in addition to carbon atoms in order to enhance the effects obtained by carbon atoms.

For example, oxygen (02) is used as a raw material gas for introducing oxygen atoms to uniformly increase the oxygen atoms in the entire layer region (C).

Ozone (03), -nitrogen oxide (No), nitrogen dioxide (N
o2), -nitrogen dioxide (N20), sesquioxide phoneme (
N2O5) *Trinitrogen tetraoxide (N204), nitrogen trioxide (N205), nitrogen trioxide (No6), silicon atom (st), oxygen atom (0), hydrogen atom (H) and all constituent atoms, e.g. , disiloxane (H3SiO8In
, ) , ) Disiloxane (H,5iO8iH20S
Examples include lower siloxanes such as iH3).

Nitrogen atoms (N) used when forming layer region (C)
A starting material that can be effectively used as a raw material gas for introduction is nitrogen (N2) having N as a constituent atom or N and H as constituent atoms.

Ammonia (N)I, ), hydrazine (H2NNH2
), water azide 1 (HN3), + ammonium azide (NH4N3) e (D In addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced, so all nitrogen halodide compounds such as nitrogen trifluoride (F3N) and nitrogen tetrafluoride (F4N2) can be mentioned. .

In order to form the entire layer region (C) containing carbon atoms using the mother tuttering method, a single crystal or polycrystalline 81 wafer and a C wafer, or a wafer containing a mixture of 81 and C can be formed. As a result, sputtering may be performed in all of these various gas atmospheres.

For example, if a Sl wafer is used as a target, all of the raw material gas for introducing carbon atoms and optionally hydrogen atoms or/and halodane atoms is diluted with a diluent gas as necessary, and Suno J. A gas plasma of these gases is formed in a chamber for ivy and the entire Si wafer is heated. All you have to do is tumble.

Alternatively, Sl and C can be used as separate targets, or by using a combined target of 81 and C (DfjJ), in an atmosphere of diluent gas as a gas for snow ivy, or At least a hydrogen atom (H) or/
and sputtering in a gas atmosphere containing halogen atoms (X) as constituent atoms.

As the raw material gas for carbon atom introduction, it can be used as the raw material gas for carbon atom introduction among the raw material gases shown in the glow discharge example described above, or as a gas that is also effective in the case of sputtering.

In the present invention, when a layer region (C)' containing carbon atoms is provided when forming the first layer (1), the distribution concentration of carbon atoms contained in the layer region (C) C (C) Change the distribution state in the thickness direction of the entire layer (dept
In order to form a layer region (C) with f profile), in the case of a glow discharge, the gas of the starting material for the introduction of carbon atoms, which is to be changed in distribution concentration C (C), is adjusted to its total desired gas flow rate. This is accomplished by introducing the material into the deposition chamber while changing it appropriately according to the rate of change curve. For example, the opening of a predetermined needle pulp provided in the middle of the gas passage system may be gradually changed by any commonly used method such as manual operation or an external drive motor.

At this time, the rate of change in the flow rate does not need to be linear; for example, using a microcomputer, etc., the rate of change in the flow rate does not need to be linear.
It is also possible to obtain a desired content curve by fully controlling the temperature according to the h-line.

When forming the layer region (C) by the snow or tuttering method, the distribution concentration C (C) of carbon atoms in the layer thickness direction is changed in the layer thickness direction to obtain the desired distribution state (d
epth profile) To create the entire
As in the case of the glow discharge method, this is accomplished by using a starting material for introducing carbon atoms in a gaseous state and appropriately changing the gas flow rate when introducing the gas into the entire deposition chamber as desired.

Second, if a mixed target of St and C is used as a target for snow or vine ring, for example, the mixing ratio of SI and C should be changed in advance in the layer thickness direction of the target. It is achieved by letting it happen.

In the light guide section 100 shown in FIG. 1, the second layer (It) 1 formed on the first layer (1) 102
05 has a free surface of 106Tt and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated usage characteristics, electrical pressure resistance, usage environment characteristics, and durability.

Further, in the present invention, each of the amorphous materials forming the first layer (■) 1O2 and the second layer (n) tO5 has all the common constituent elements of silicon atoms. Therefore, chemical stability is sufficiently ensured at the laminated interface.

The second layer (II) in the present invention consists of silicon atoms (8
1), nitrogen atom (N), and hydrogen atom (H) as necessary
or/and halogen atom (X) after ib amorphous material, [a-(s+xN1-X), (HlX)i-y
'

However, it is composed of O<x, y<l].

The formation of the second layer (II) composed of a(S i 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 photoconductive member to be manufactured. Advantages include that it is relatively easy to control the manufacturing conditions for manufacturing the M member, and that it is easy to introduce all nitrogen atoms and herodanium atoms together with silicon atoms into the second layer (n) to be manufactured. Therefore, a glow discharge method or a sputtering method is preferably employed.

Furthermore, in the present invention, the second layer (II) can be formed by using both the glow discharge method and the star sparkling method in the same system.
may be formed.

To form the second layer ([1) by glow discharge method, '-(SixNl-x)V(HlX)+--All raw material gases for forming Y, dilution gas as needed, and a predetermined uniform mixing ratio. The tl-fc sludge is mixed in the vacuum deposition chamber where the support is installed, and the introduced tl-fc scum is turned into gas plasma by generating a glow discharge, and the tl-fc residue that has already been formed on the support is converted into gas plasma. a-(StxNl-X)F(
HIX) 1-y may be deposited.

In the present invention, a-(SlxNl-x)y(H,X)
, as a raw material gas for forming y, silicon atoms (Si) are used.
, nitrogen atom (N), hydrogen atom (H), halogen atom (X
) Any gaseous substance or gasifiable substance having at least one constituent atom of the following may be used.

When using all the raw material gases including St as one of Si, N, H, and X, for example, S I
A raw material gas containing all till constituent atoms, a raw material gas containing all N constituent atoms, and a raw material gas containing H as constituent atoms or/and a raw material gas containing X as constituent atoms as necessary? Alternatively, a raw material gas containing Si\ as a constituent atom, a raw material gas containing all N and N constituent atoms, or/and a raw material gas containing N and xB constituent atoms, and the total This can also be done by mixing at a desired mixing ratio, or by mixing a raw material gas with siy structure atoms and a raw material gas with all three constituent atoms of 81, N and H, or three of Sl, N and X. It can be used in combination with a raw material gas having constituent atoms.

Separately, N is added to the raw material gas containing Sl and H as constituent atoms.
A raw material gas having 81 and X as constituent atoms may be mixed and used, or a raw material gas having all N atoms as constituent atoms may be mixed and used.

In the present invention, F 2 , C1, Br, and I are preferable as the herodane atoms (3) contained in the second layer ω), and F 2 and C1 are particularly preferable.

In the present invention, the second layer (It)'? Possible raw material gases that can be effectively used for total formation include ′
Examples include substances that are in a gaseous state at normal temperature and pressure, or substances that can be easily gasified.

Snow 4 When the second layer (II) is entirely formed by the vine ring method, the following procedure is performed, for example.

Firstly, when sputtering a target made of Sl in an atmosphere of an inert gas such as Ar or He or a mixed gas consisting entirely of these gases, a raw material gas for introducing nitrogen atoms (N) is used. All, hydrogen atoms as necessary (
H) It may be introduced into a vacuum deposition chamber where sputtering is performed together with a raw material gas for introduction and/or for introduction of halodan atoms (X).

Secondly, 813 is used as a target for sputtering.
A target composed of N4, or a target composed of Si and a target composed of Si3N4, or a target composed of sl, sl, and N4) (by using H) Second layer (If)
Nitrogen atoms (N) can be introduced into it. On this occasion,
If all the raw material gases for introduction of nitrogen atoms (N) are used together, the flow rate can be controlled. The amount of nitrogen atoms (N) introduced into the second layer (If) can be arbitrarily controlled. is easy.

The content of enzyme atoms (N) introduced into the 20th layer (II) can be determined by controlling the total flow rate of the raw material gas for introducing nitrogen atoms (N) into the deposition chamber, or by controlling the flow rate of the raw material gas for introducing nitrogen atoms (N) into the deposition chamber, or The ratio of nitrogen atoms (N) contained in the target for introducing atoms (N) can be adjusted as desired by adjusting the proportion of nitrogen atoms (N) contained in the target for introducing atoms (N), or by doing both. It can be controlled.

The starting materials used as the raw material gas for supplying St used in the present invention are 5IH4, Si2H6, Si, H8
Gaseous or gasifiable silicon hydride (silanes) such as ゜514H1゜ can be used effectively, especially in terms of ease of handling in layer creation work and good St supply efficiency. , 5IH4, and 512H6 are preferred.

If all of these starting materials are used, H as well as hydrogen can be introduced into the second layer (n) formed by appropriately selecting the layer forming conditions.

Effective starting materials that serve as raw material gas for S1 supply include:
In addition to the silicon hydride mentioned above, a halogen atom (X)? A silicon compound containing a so-called silane conductor converted into fff with a halogen atom, specifically, for example, 5IF41St2F6.5
Preferred examples include silicon halides such as iC14 and SiBr4.

Furthermore, Sl■I2F2,5iH2I2.5IH2Ct
Halodane 1ti-substituted silicon hydride such as 2.5IHCt3゜5IH2Br2, 5sHBr5, etc., which is in a gaseous state or can be gasified, and which is one of the total constituents of hydrogen atoms, is also effective for forming the second layer (■). It can be used as a starting material for supplying St.

Even when these silicon compounds containing halogen atoms (X)'f- are used, X can be introduced together with Si into the second layer (11) to be formed by appropriately selecting the layer forming conditions as described above. You can.

In addition to forming the second layer (II), the halogen atom (X) can be introduced into the layer to control the electrical or photoelectric properties of the above-mentioned starting material. Since hydrogen atoms (H), which are extremely effective in
In the present invention, it is used as a suitable starting material for introducing a halogen atom (X).

In addition to the above-mentioned materials, examples of effective starting materials as raw material gas for introducing halogen atoms (X) used in forming the second layer (II) in the present invention include fluorine, chlorine, bromine, etc. , iodine halogen gas, BrF,
CtF, CIF BrF, BrF, , HF
3゜51 5 IF7 * ICt+ Interhalogen compounds such as IBr,
HF.

Hydrogen halides such as HCI, HBr, HI?
I can list them.

The starting material that can be effectively used as a raw material gas for introducing nitrogen atoms (N) used in forming the second layer (It) is all Nt constituent atoms or N and H atoms. For example, nitrogen (N2) as all constituent atoms.

Ammonia (NH5), hydrazine (f(2NNH2)
), hydrogen azide (IN3), ammonium azide (
Gaseous or gasifiable nitrogen such as NH4N3) and nitrogen compounds such as nitrides and azides can be used.

In addition to this, nitrogen trifluoride (F
, N), and nitrogen tetrafluoride (F4N2).

In the present invention, the diluent gas used when forming the second layer (n) by a glow discharge method or a sputtering method is a so-called rare gas, such as He.

Suitable examples include Ne, Ar, and the like.

The second layer (n) in the present invention is carefully formed so as to give the required properties as desired, i.e., 81, N, H or/and X as necessary, and the constituent atoms Depending on the conditions in which it is created, the material has a structure that ranges from crystalline to amorphous, and its electrical properties range from conductive to semiconductive to insulating, as well as photoconductive properties. In the present invention, a-(
The selection of the conditions for its creation is made strictly as desired so that S i xNl-X)y(H,X), -y is formed. For example, if the second layer (n) is provided with the main purpose of improving the pressure resistance of the spiracle of all vehicles, a - (S l x N,
L x )y (H+

In addition, if a second layer (II) is provided for the purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation will be relaxed to a certain extent, and it will have a certain degree of resistance to the irradiated light. As an amorphous material with full sensitivity, a-
(S'xNl-z)y (Hlx)1- is created.

a-(SixN1-x)y(H
, In the invention, a-(S l xNt -x
)y (H,

In the present invention, the optimum temperature range is appropriately selected in accordance with the method of forming the second layer (If) in order to effectively achieve the desired purpose, and the formation of the second layer (n) is performed. is carried out, preferably from 20 to 400°C, more preferably from 50 to 35°C.
The temperature is preferably 0°C, most preferably 100 to 300°C. The glow discharge method is used to form the second layer (II) because it is relatively easy to finely control the composition ratio of atoms constituting the layer and control the layer thickness compared to other methods. However, when forming the second layer (n) using these layer forming methods, the discharge power during layer formation should be adjusted in the same manner as the support temperature described above. is created a-(
It is one of the important factors that influences all the characteristics of slxN,-,)y(MIX)1-y.

It has the characteristics that enable the object of the present invention to be achieved.”
The power conditions for effectively producing "'xNl -x)y(HlX)1-y" with good productivity are preferably 10 to 300W, more preferably 20 to 250W.

Optimally, it is set at 50 to 200W.

The gas pressure in the deposition chamber is preferably 001 to ITorr1.
More preferably, it is about 0.1 to 0.5 Torr.

In the present invention, the values in the above-mentioned ranges are mentioned as the preferable numerical ranges of the support temperature and the discharge power for forming the second layer (II)'. , are not determined independently and separately, but are mutually organically related so that a second layer (n) consisting of a-(81xN, -X), (MIX), -y with desired characteristics is formed. It is desirable that the optimum value of each layer creation factor be determined based on the properties of the layers.

The amount of nitrogen atoms contained in the second layer (II) in the photoconductive member of the present invention is determined to have the desired characteristics to achieve the object of the present invention, as well as the conditions for forming the second layer (n). This is an important factor in the formation of the resulting second layer (II).

The amount of hydrogen atoms contained in the second layer (II) in the present invention can be determined as desired depending on the type and characteristics of the amorphous material constituting the second layer (1). C.It is something that can be determined.

That is, the general formula a-(stxNl-,), (MIX)
, -y can be roughly divided into amorphous materials composed of silicon atoms and nitrogen atoms [hereinafter referred to as r
It is written as a-81aN1-aJ. However, 0 (a (1
], an amorphous material composed of silicon atoms, nitrogen atoms, and hydrogen atoms [hereinafter referred to as ra-(si, N,-,), H,-
0”.

However, 0〈bl c〈1〕, an amorphous material composed of silicon atoms, nitrogen atoms, Harigan atoms, and hydrogen atoms as necessary [hereinafter ra-(stdN,-,)e(u,x
), -e”. However, it is classified as O(d % e (1).

In the present invention, the second layer (II) is a-8f aNl
-a, the amount of nitrogen atoms contained in the second layer (It) is preferably i x 10"" to 60
atomic%, more preferably 1-50 atomic%
The optimum content is 10 to 45 atomie%.

That is, if we use the expression a-8i aNl-a above,
a is preferably 0.4 to 0.99999, more preferably 0.5 to 0.99, most preferably 0.55 to 0.9.

In the present invention, the second layer (rl) is '-""'bNl
-b) cHl When composed of -c, the second layer (I
The amount of nitrogen atoms contained in I) is preferably l
lO”-3 to 55 atomic%, more preferably 1 to 55 atomic%, optimally lO to 55
It is assumed to be atomia%. The content of hydrogen atoms is preferably 1 to 40 atomic atoms, more preferably 2 to 3 atomic atoms.
5 atomic %, optimally 5-30 atomic
The photoconductive member formed when the hydrogen atom-containing urine is present in these ranges can be effectively applied as an excellent material.

That is, if expressed as "S'bNl-b)cHl-e", b is preferably 0.45 to 0.99999, more preferably 045 to 099, optimally 0.45 to 09, and C is preferably 0.6-099, more preferably 065-0.
98, optimally 0.7-095.

The second layer (II) is a-(st,lN1-.1)cl
('LX), -e, the second layer (I
The content of nitrogen atoms contained in I) is preferably l
X 10-6 to 60 atom lc%.

More preferably 1 to 6 Q atomlc%s and optimally lo to 55 atomic. The content of heron atoms is preferably 1-20 atomic%, more preferably 1-18 atomic%, optimally 2-1
5 atomlc%, and photoconductive members prepared when the halodan atom content is within this range can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably l 9 atom
It is desirable that the content be less than 1%, more preferably less than 13%.

That is, the original a-(sldNl-d)e'(H+X), -
If expressed as d and e of 0, d is preferably 0.4 to 0.
．． 99999, more preferably 0.4-0.99, optimally 0.45-0.9, e preferably 0.8-0.99
, more preferably 0.82 to 0.98, optimally 0.85
~0.98.

The number range of the layer thickness of the second layer (II) 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 (It) also depends on the amount of nitrogen atoms contained in the layer (II) and the thickness of the tenth 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 take into consideration economic efficiency, which takes into account productivity and mass production.

The layer thickness of the second layer (■) in the present invention is preferably 0.003 to 30 μm, more preferably 0.004 to 2 μm.
〇8 The optimum value is 0.005 to 10μ.

The support used in the present invention may be electrically conductive or sleep-insulating. As the conductive support, for example,
NiCr% Stainless steel, At, 'Cr, Mo
, Au, NbXTa, V, TiXPt5Pd, or alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbanate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. be done. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side6. For example, if it is glass, the surface , NiCr1Al
, Cr, Mo, Au, Ir, Nb, Ta, V, TI, P
t, Pd.

In,,O,,S nO2, ITO(In203+ 5
Magnetic conductivity can be imparted by providing a thin film consisting of NiCr, A/, %Ag, P, etc., or by using a synthetic resin film such as a polyester film.
b, Zn, Nl, Au, Cr.

A thin film of metal such as Mo, IrNb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal described above to make the surface conductive. gender is given.

The shape of the support 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 yen shown 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 is appropriately determined so as to form the desired light guide member, but if flexibility is required as a photoconductor, the thickness of the support may be determined to be sufficient for its function as a support. It is made as thin as possible within the range of performance. However, in such a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is preferably IOμ or more.

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

FIG. 41 shows an example of a photoconductive member manufacturing apparatus.

In the gas chambers 202 to 206 in the figure, a raw material gas for forming the photoconductive member of the present invention is sealed.
F4 gas (purity 99.999, hereinafter referred to as S i F 4
/ abbreviated as He)? 203 is G diluted with He.
eF4 gas (purity 99.999%, hereinafter referred to as GeF4/
204 is C2H4 gas (purity 99
．． 99%, hereinafter abbreviated as C2H4) Dempe, 205ke II
B2H6 gas diluted with e (purity 99.999%, hereinafter referred to as B2H6/1 (abbreviated as e)) is diluted with H2 gas (purity 99.999%). 206 is H2 gas (purity 99.999%).

To allow these gases to flow into the reaction chamber 201, make sure that the gas valves 202 to 206, the leak valves 222 to 226, and the leak valve 235 are closed. ~221, after confirming that the auxiliary pulps "j" 232 and 233 are open, first open the main pulp 234 and open the reaction chamber 201.
and exhaust the inside of each gas pipe. Next, when the reading on the vacuum gauge 236 reaches approximately 5X I O-'torr, the auxiliary pulps 232, 233 and the outflow pulses f217 to 221 are closed.

Next, when a light-receiving layer is formed on the cylindrical substrate 237, when one side tone is raised, S i F is released from the gas pump 202.
4/He gas, Ga Fa/He from gas cylinder 203
Gas, C2H4 gas from gas cylinder 204, H2 gas from gas cylinder 206? , pulp 222.223°224
．． 226 and outlet pressure gauge 227°228.2
The pressure of 29, 231 was adjusted to 1 kg/crn2, and the inflow pulps 212, 213, 214, 216 were gradually opened.
Mass flow control 207 +208.209.
211 to make each one a dealer.

Subsequently, the outflow pulp 217, 218, 219° 221
, gradually open the auxiliary pulse f232 to supply each gas to the reaction chamber zolVcm. S i F a/ at this time
He gas am and G e F 4/He gas flow rate and c2H
The outflow pulps 217, 218, 219, 221 are all adjusted so that the ratio between the 4 gas flow rate and the H2 gas flow rate becomes the desired value, and the vacuum gauge 236 is adjusted so that the pressure inside the reaction chamber 201 becomes the desired value. Adjust the opening of the main valve 234 while checking the reading. Then, the temperature of the base body 237 becomes higher than that of the heating heater 2.
After confirming that the temperature is set in the range of 50 to 400° C. by 38, the power source 240 is set to the desired power to generate glow emission in the reaction chamber 201, and the substrate 237 is heated.
A first layer region (G) is formed thereon. first to the desired layer thickness.
All the pulps are completely closed at the time when the layer region (G) is formed. S i F 4/He gas dempek
5IH4/He (SiH4 purity 99,999%) Instead of Gimpe, 5IH4/He gas is used as impeline, B 2
Using Hb7'f (e gas cylinder line, C2H4 gas cylinder line), perform all the valve operations similar to those for forming the first layer region (G), set the desired glow discharge conditions, and perform glow discharge for the desired time. By maintaining this, it is possible to form a second layer region (S) substantially free of r-rumanium atoms on the first layer region (G).

In this way, the first layer region (G) and the second layer region (S
) is formed on the substrate 237.

In order to completely form the second layer (II) on the first layer (1) formed to a predetermined layer thickness as described above, first layer (1) 1
7) By the same pulping operation as in the formation, e.g.
The H4 gas and NH gas are each diluted with a diluent gas such as He as required, and glow ink is generated according to desired conditions. In order to contain halodan atoms in the second layer (n), for example, SiF4 gas and C
This is done by adding 2H4 gas or sti+4 gas to it and forming the second layer (n)k in the same manner as above.

It goes without saying that all pulps other than the gas-escaping pulp necessary for forming each layer are closed, and when forming all of the layers, the gas used to form the previous layer is inside the reaction chamber 201. Outflow pulp 217-221 to reaction chamber 20
In order to avoid remaining in the gas piping leading to 1,
Optical pulp 217-221t-close, auxiliary pulp 232
, 233, fully open the main valve 234, and temporarily evacuate the system to a high vacuum, as necessary.

For example, the atom atom contained in the second layer (■) is
In the case of glow discharge, the flow rate ratio of 5IH4 gas and NH gas introduced into the reaction chamber 201 is changed as desired, or in the case of layer formation by sputtering, the target is entirely formed, the silicon-free wafer and nitrided. It can be controlled as desired by changing the sputtering area ratio of the silicon plate or by changing the entire mixing ratio of silicon powder and silicon nitride powder to form the entire target. Herokane atoms (X) contained in the 20th layer (If)
) indicates the raw material gas for introducing halogen atoms, for example Si
bk, m when F4 gas is introduced into the reaction chamber 201
l k fil.

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 Al
Each sample as an electrophotographic image forming member was formed on a substrate under the conditions shown in Table 1 (see Table 2).

The concentration distribution of impurity atoms (P) in each sample is shown in Figure 42, and the concentration distribution of carbon atoms is shown in Figure 42.
3A and 43B. The distribution a degree of each atom was controlled by changing the light intensity ratio of each corresponding gas according to a change rate line set in advance d1.

All of the samples obtained in this way were charged using the charged u-light experimental device Kvtf.
L■5. OkV "Corona zone for 3 seconds!" was performed, and the entire light image was irradiated in a reconnaissance manner. The light image was made using a tungsten lamp light source, and a 21ux-light scene was irradiated through a transmission type test chart.

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

The toner image on the photoreceptive layer is processed by 5. When transferred onto paper using OkV corona charging, each sample had excellent resolution and a clear, high-density image with good gradation reproducibility was obtained.

In the above, the light source is 81 instead of a tungsten lamp.
0nm (1) GaAs-based semiconductor radar (10mW)')
The image quality of each sample was evaluated in the same manner as above, except that the toner was used to form a static element, and it was found that each sample had excellent resolution and good gradation reproducibility. A clear image of Takashina Satoshi was obtained.

Example 2 A cylindrical A7 was manufactured using the manufacturing apparatus shown in Fig. 41.
Each sample as an electrophotographic image forming member was entirely formed on a substrate under the conditions shown in Table 3 (see Table 4).

The 'N4 distribution concentration of impurity atoms in each sample is shown in FIG. 42, and the distribution concentration of carbon atoms is shown in FIG. 44.

Each of these samples was subjected to all image evaluation tests similar to those in Example 1, and all samples provided high quality toner transfer images. In addition, each sample was heated at 38°C and 80°C.
When all samples were tested for repeated use 200,000 times in an environment of H, no deterioration in image quality was observed in any of the samples.

Example 3 A cylinder-shaped Al
Samples (Samples JK 31-1 to 37-12) as electrophotographic image forming members were prepared on a substrate under the conditions shown in Table 5 (Table 6).

The concentration distribution of impurity atoms in each sample is shown in Figure 42, and the concentration distribution of carbon atoms is shown in Figures 43A and 43B.
As shown in Figures 44 and 44.

The same 111 samples as in Example 1 were used for each of the samples.
When tested in a single image measurement test, all samples produced high quality toner transfer images. Also, for each sample, 38℃,
When a repeated use test was conducted 200,000 times in an environment of 80 degrees RH, no deterioration in image quality was observed in any of the samples.

Example 4 A cylindrical At
All samples (Samples A41-1 to A46-16) as electrophotographic image forming members were prepared on a substrate under the conditions shown in Table 7 (Table 8).

The flow rate ratio of GeH4 gas at the time of forming the first layer region (G) is changed according to a pre-designed change rate line, and the first layer region (G) is formed so that the Go distribution concentration shown in FIG. 45 is obtained. The flow rate ratio of B2H6 gas and PH3 gas during the formation of the 20th layer region (S) was changed according to a pre-designed rate of change line to obtain the impurity distribution concentration shown in FIG. A second layer region (S) was formed.

Further, the η ratio of C2H4 gas at the time of forming the first layer region (G) is changed according to a pre-designed rate of change line to form the fourth layer region (G).
The first
Layer region (G) Th was formed.

When image evaluation was performed on each of these samples in the same manner as in Example 1, high-quality images could be obtained for all samples φ.

Example 5 A cylindrical At
Samples (Samples A51-1 to A56-12) as electrophotographic image forming members were prepared on the substrate under the conditions shown in Table 9 by controlling the flow rate ratio of each gas in the same manner as in Example 1. table).

The concentration distribution of impurity atoms in each sample is shown in FIG. 42, the distribution concentration of carbon atoms is shown in FIG. 44, and the distribution concentration of ri-rumanium atoms is shown in FIG. 45.

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, for each sample, 38℃, 80%
When a repeated use test was conducted 200,000 times in an RH environment, no deterioration in l1ilj image quality was observed in any of the samples.

Example 6 A! shown in Figure 41! ! ! A sample (Sample A 61 -1 to 610-13) were all prepared (Table 12).

The concentration distribution of impurity atoms in each sample is shown in Figure 42, and the concentration distribution of carbon atoms is shown in Figures 43A and 43B.
and FIG. 44, and FIG. 45 shows the distribution concentration of dalmanium atoms.

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°C.
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 7 Samples Al1-1 and 12-111 of Example 1 were used, except that the conditions for forming the second layer (II) were as shown in Table 13.
According to the same conditions and procedures as in 3-1, each of the electron thickness imaging members (sample 11-1-1 to 11-1-8.12) was prepared.
-1-1~12-1-8.13-1-1~13-1-8
24 samples) were created.

The husband ζ of each image forming member for photocopying thus obtained was individually placed in a copying machine, and a corona electric current was applied at θ5 kV for 020,000 hours to irradiate a light image. A tungsten lamp tube was used as the light source, and the light intensity was 1.01 ux.

The latent image was developed with a charged developer (containing toner and carrier) and transferred to regular paper.

The transfer was extremely good. Toner that was not transferred and remained on the four-layer imaging member was cleaned with a rubber grade.

Even if this process is repeated over 100,000 times,
No image deterioration was observed in either 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 8 When forming the second layer (II), by changing the target area ratio of the mixed gas of Ar and NH, the silicon wafer, and the silicon nitride, the ratio of silicon atoms and nitrogen atoms in the second layer (n) was changed. Sample Ah of Example 1 except for changing the content ratio,
Each of the imaging members was entirely prepared in exactly the same manner as in 1-2. For each of the image forming sections thus obtained, the image forming, developing, and cleaning steps as described in Example IK were repeated approximately 50,000 times, and then image evaluation was performed, and the results shown in Table 9 were obtained. .

Example 9 When forming the second layer (II), 5IH4 gas and NH,
An image forming member was prepared in exactly the same manner as in Sample Al1-3 of Example 1, except that the gas flow ratio was changed to completely change the content ratio of silicon atoms and nitrogen atoms in the second layer (II). I created each of them. For each image forming member thus obtained, the process up to transfer was repeated approximately 50,000 times using the method described in Example 1, and then image evaluation was performed.
Example 1O During the formation of the second layer (II), b + H4 gas,
Sample 1i 11-4 of Example 1 except that the flow ratio of SiF4 gas, NH, and gas was changed to completely change the content ratio of silicon atoms and nitrogen atoms in the second layer (It). Each of the imaging members was made in exactly the same manner. After repeating the image forming, developing, and cleaning steps as described in Example 1 approximately 50,000 times for each image forming member thus obtained, image evaluation was performed, and the results shown in Table 11 were obtained.

Example 11 Each of the image forming members was created in exactly the same manner as in Sample Al1-5 of Example 1, except that the layer thickness of the second layer (n) was changed. As described in Example 1, the process numbers of image formation, development, and cleaning were repeated, and the results shown in Table 12 were obtained.

Table 8 Table 10 Special 111 system 0-142350 (Table 14 of 2) Common layer forming conditions for the embodiments of the present invention shown in Table 18 and above are shown below.

Substrate temperature: germanium atom (Ge) containing layer...
...About 200℃ germanium atom (Go)-free layer...
・About 250℃ Discharge frequency: 13.56 MHz Reaction chamber pressure during reaction: 0.3 Torr

[Brief explanation of the drawing]

FIG. 1 is a schematic layer configuration diagram for explaining the layer configuration of the photoconductive part of the present invention, and FIGS. 2 to 10 each illustrate the distribution state of germanium atoms in the 10th layer region CG). 11 to 24 are explanatory diagrams for explaining the distribution state of impurity atoms, and FIG. 25 to 40 are explanatory diagrams for explaining the distribution state of carbon atoms, respectively. Figures 42, 43A, and 43B are schematic explanatory diagrams of the equipment used.
44 and 45 are explanatory diagrams showing the distribution state of each atom in the embodiment of the present invention, respectively. 100... Photoconductive member 101... Support body 102.
...First layer (1) 103...First layer region (G)
104...Second layer region (S) 105...Second layer (10107...Photoreceptive layer 1111→-C C-□--→-C-C-C(PN) -C(PN) C(PN) -(:(PN) □C(PN) □C(PN) --C(PN) -C(PN) -C(PN) -C(PN) -C(PN ) -C(PN) -(, (PN) -C(PN) Whistl/ C[C) C(C) -C(C> , C(C) -C(C) C(C) Shiku( -) ((Cn

Claims (9)

[Claims] (1) A support for a photoconductive member, a first layer region (G) made of an amorphous material containing germanium atoms, and a first layer region (G) made of an amorphous material containing silicon atoms and exhibiting photoconductivity. A photoreceptive layer consisting of a first layer having a layer structure in which two layer regions (S) are provided in order from the support side, and a second layer made of an amorphous material containing silicon atoms and nitrogen atoms. and the first layer contains carbon atoms, and
The conductivity controlling substance (C) is contained in a layer in which the maximum value of the concentration distribution in the layer thickness direction is in the second layer region (S) and the second layer region (S) is
In the layer region (S), the photoconductive member is characterized in that the content is distributed more toward the support side. (2) The photoconductive member according to claim 1, wherein the first layer region (G) contains silicon atoms. (3) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is non-uniform in the layer thickness direction. (4) Claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is uniform in the layer thickness direction.
The photoconductive member described in . (5) The photoconductive member according to claim 1, wherein at least one of the first layer region (G) and the second layer region (S) contains hydrogen atoms. (6) The photoconductive member 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. . (7) The distribution state of kermanium atoms in the layer region (G) of i'1 is such that the distribution state is such that more of the kermanium atoms are distributed toward the support side. Element. (8) The photoconductive member according to claim 1, wherein the substance (C) that governs conductivity is an atom belonging to group Ⅰ of the periodic table. (9) 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.