JPS60136751A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain stable electrical, optical, and photoconductive characteristics, all-environmental type resistance, high sensitivity characteristics especially in the long wavelength region, and superior durability, and freedom from residual potential by forming a photoreceptor layer having a specified structure made of a-Si (H, X) on a substrate. CONSTITUTION:The photoconductive member 100 consists of a substrate 101 and a photoreceptor 102 formed on it, and the photoreceptor layer 102 consists of the first layer 103 comprising the first layer region G made of amorphous Ge (a-Ge), and the second photoconductive layer region S made of a-Si, and the second layer 104 made of a-SiC formed in this order from the substrate 101. The layer 103 contains N, and a conductivity governor kappa in a concn. distribution in the layer thickness direction having the max. value in the region S and in this region S, the distribution increases toward the side of the substrate 101. The photoconductive member of such a structure is improved in elctrical, optical photoconductive, voltage withstanding, and evey environment withstanding characteristics, high in sensitivity and S/N ratio, good in matching with a semiconductor laser, and high in light responsivity, and it can stably form a high-quality image.

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.

Photoconductive materials that form photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, and document reading devices have high sensitivity and low signal-to-noise ratio [photocurrent (Ip)].
/dark current (Id)), has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, and has a desired dark resistance value,
Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use and being able to easily dispose of afterimages within a predetermined time. Especially 1
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. 5718 describes an application as an image forming member for electrophotography, and German Published Publication No. 2933411 describes an application to a charging conversion/reading device.

However, the conventional photoconductive member having a photoconductive layer composed of A-8L has poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are points that can be further improved in terms of environmental characteristics and furthermore, stability over time, where it is necessary to improve overall characteristics.

For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed and measured that residual potential remains during use. When a photoconductive member is used repeatedly for a long period of time, fatigue due to repeated use may accumulate, resulting in the so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speeds, the responsiveness gradually decreases. There were many cases in which points were caused due to such inconveniences.

Furthermore, A-8L has a relatively small absorption coefficient in the long wavelength region compared to the short wavelength region in the visible light region, making it suitable for matching with semiconductor radars currently in practical use. Furthermore, when a commonly used halodane lamp or fluorescent lamp is used as a light source, there remains room for improvement in that the light on the longer wavelength side cannot be used effectively.

Additionally, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases,
When the support itself has a high reflectance for light transmitted through the photoconductive layer, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "picketing" 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 laser is used as the light source.

Furthermore, when the photoconductive layer is composed of a-S 1 material,
In order to improve its electrical and photoconductive properties, hydrogen atoms or halodane atoms such as fluorine atoms and salt purple atoms are used, and boron atoms and phosphorus atoms are used to control the electrical conductivity type, or other properties are improved. Therefore, other atoms are contained in the photoconductive layer as constituent atoms, but depending on how these constituent atoms are contained, problems may arise in the electrical or photoconductive properties of the formed layer. There are cases.

That is, for example, the lifetime of photocarriers generated in the formed photoconductive layer by light irradiation is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, etc. This often occurs.

Therefore, while efforts are being made to improve the properties of the A-81 material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the above points, and has applicability and applicability to the A-8I as an optical four-electronic member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive and intensive research studies from this perspective, we have developed an amorphous material that uses silicon atoms as its base material and contains at least either hydrogen atoms (H) or halodane atoms (X). , halodanized amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter, a-81(H, A photoconductive member designed and produced with the layer structure of the photoconductive member specified as explained below has not only demonstrated extremely superior properties in practical use, but also has superior properties compared to conventional photoconductive members. In particular, we found that it has outstanding properties as a photoconductive material for electrophotography, and that it has excellent absorption spectrum properties on the long wavelength side. Based on.

The present invention has stable electrical, optical, and photoconductive properties at all times, is an all-environment type with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is resistant to light fatigue. The main object of the present invention is to provide a photoconductive member which is extremely durable, shows no deterioration phenomenon even after repeated use, and has no or almost no residual potential observed.

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 lasers in particular, and has fast photoresponse.

Another object of the present invention is that when applied as an image forming member for electrophotography, the present invention can be used to form a sheet for electrostatic image formation, to the extent that ordinary electrophotography methods can be applied very effectively. It is an object of the present invention to provide a photoconductive member having sufficient charge retention ability.

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

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 signal-to-noise ratio characteristics.

The photoconductive member of the present invention comprises a support for the photoconductive member, a first layer region (G) made of an amorphous material containing germanium 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 carbon atoms. The first layer contains a nitrogen atom and a conductivity controlling substance (C) is added to the first layer.
In the layer, the maximum value of the distribution concentration in the layer thickness direction is in the second layer region (S), and the second layer region (S)
It is characterized in that it is contained in a state where it is distributed in a larger amount on the side of the support.

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 image forming member for electrophotography, it is possible to sufficiently prevent interference even when using coherent light, and there is no influence of residual potential on image formation, and the electrical High quality with stable optical characteristics, high sensitivity, high signal-to-noise ratio, light fatigue resistance, repeated use characteristics, 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 radar, and has fast response.

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 showing the layer structure of the photoconductive member of the present invention.

A photoconductive member 100 shown in FIG. 1 has a photoreceptive layer 107 consisting of a first layer (1) 102 and a second layer (II) 105 on a support 101 for the photoconductive member. death,
The light-receiving layer 107 has a free surface 106 on one end face.

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

An amorphous material containing at least one of a hydrogen atom (H) and a halodane atom (X) [hereinafter referred to as r a-Ge (Si, H, X)
A first layer region (G) 103 composed of
and a-81(H,X) and has photoconductivity.
It has a layer structure in which layer regions (S) 104 are laminated in order.

The first layer (I) 102 contains nitrogen atoms;
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.

Dalmanium 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 uniform in the layer thickness direction. There is no problem even if it is uneven.

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 dalmanium atoms in the first layer region CG) is such that dalmanium atoms are continuously distributed in the entire layer region, and the distribution concentration of dalmanium atoms in the layer thickness direction C is given a change that decreases from the support side towards the second layer region (S), the first layer region (S)
G) and the second layer region (8), and by making the distribution concentration C of dalmanium atoms extremely large at the edge of the support, as will be described later. , when using a semiconductor radar, etc., the light on the long wavelength side, which is almost completely absorbed by the second layer region (S), is transferred to the tenth layer region (G).
), it is possible to absorb substantially completely, prevent interference due to reflection from the support surface, and sufficiently prevent reflection at the interface between layer region (G) and layer region (S). It can be held down.

2 to 10 show typical examples of the distribution state of damanium atoms contained in the first layer region CG) of the photoconductive member in 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 i represents the first layer region (G) on the support side. ), and tT indicates the position of the end surface of the first layer region (G) on the side opposite to the support side. That is, the first layer region (G) containing germanium atoms is formed as a layer from the tB side toward the tT side.

FIG. 2 shows a first typical example of the distribution state of dalmanium 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. 1 more
．． Up to the position, the distribution concentration C of Dal 1 atoms is C1
Germanium atoms are contained in the first layer region (G) where germanium atoms are formed, taking a constant value, and the concentration is gradually and continuously decreased from the position t1 to the interface position C2. .

At the interface position tT, the distribution concentration C of dalmanium atoms
is assumed to be C3.

In the example shown in FIG. 3, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration C4 from the position ti to the multi-position 11, and reaches the concentration CIi at the position 11. forming a state.

In the case of FIG. 4, position 1. is lower than position ta. ! Then, the distribution concentration C of kermanium atoms is assumed to be a constant value of concentration C6,
The distribution concentration C is gradually and continuously reduced between position t2 and position tT, and at position tT, the distribution concentration C is substantially zero (here, substantially zero means that the amount is below the detection limit). Deol).

In the case of FIG. 5, the distribution concentration C of dalmanium atoms is continuously and gradually reduced from the concentration C8 from the position tB to the multiple positions tT, and becomes substantially zero at the position tT.

In the example shown in FIG. 6, the distribution concentration C of germanium i particles is a constant value of the concentration C between the position tB and the position t3, and the concentration C10 at the position 11. Between position t3 and position t, the distribution concentration C decreases linearly from position t3 to position tT.In the example shown in FIG.
From position 1Ett4 to position 1Ett4, the concentration Ctt is a constant value, and from position t4 to position trt, the concentration decreases linearly from C12 to C13.

In the example shown in FIG. 8, from position tm to position tT, the distribution concentration C of germanium atoms decreases linearly from the concentration C14 to substantially zero.

In FIG. 9, from the position ta to the position tl, the distribution concentration C of dalmanium atoms decreases linearly from the concentration cps to the concentration Cl11, and between the position B ts and the position tT, An example is shown in which the concentration C1g is set to a constant value.

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration cty at a position t11, and this concentration C17 is initially decreased until reaching a position t6, and then the concentration C is gradually reduced to a position t. In the vicinity, the concentration decreases rapidly to a concentration C11l at position t6.

Between position t6 and position t7, the concentration is first rapidly decreased, and then gradually decreased to reach CI9 at position t7, and between position t7 and position t8, it is extremely slowly decreased. The concentration is gradually decreased to reach the concentration CtO at position t8. Between position t8 and position tT,
The concentration is reduced to substantially zero from C20 according to a curve shaped as shown in the figure.

As described above, according to FIGS. 2 to 10, the first layer region (G)
As described above, some typical examples of the distribution state of germanium atoms contained in the layer thickness direction, in the present invention,
On the support side, there is a part with a high distribution concentration C of germanium atoms, and on the interface tT side, the distribution concentration C is high.
The first layer region (G) K is provided with a distribution state of germanium atoms 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 preferably contains Mannobe germanium atoms on the support side at a relatively high concentration as described above. It is desirable to have a localized region body).

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

In the present invention, the localized region (A) is located at the interface position t
It may be the entire layer region (L?) up to 5μ thick from B, or it may be a part of the layer region (ILT).

Whether the localized region (A) should be a part or all of the layer region (L?) is determined as appropriate depending on the characteristics required of the layer to be formed.

In the localized region (A), the maximum value CmJLK of the germanium atom distribution in the shallow layer is the sum of the silicon atoms, as the distribution state of the dalmanium atoms contained therein in the layer thickness direction.
Preferably 1 Q 00 atomic ppm or more,
It is desirable that the layer be formed so as to obtain a distribution state such that T/c is preferably 5000 atomic ppm or more, most preferably 1 x 10' atomic ppm or more.

That is, in the present invention, the first layer region (G) containing germanium i particles has a maximum distribution concentration cm within 5 μm in layer thickness from the support side (layer region from 1 to 5 μm thick).
It is preferable that it is formed so that ax exists.

In the present invention, the content of germanium atoms contained in the first layer region (G) is determined as desired so as to effectively achieve the object of the present invention, but is preferably 1-10 X 10 atomic ppms, preferably 100 to 9.5
m.

Optimally 500-8 X 10 atomic ppm
It is desirable that this is done.

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

In the present invention, the layer thickness TB of the first layer region (G) is preferably 301 to 50μ, more preferably 4°
It is desirable that μ is optimally set to 50× to 30 μ.

Further, the layer thickness T of the second layer region (S) is preferably 0.5
~90μ, more preferably 1~80μ, optimal VC is 2~
It is desirable that the thickness be 50μ.

The sum (TB+T) of the layer thickness T of the first layer region CG) and the layer thickness T of the 20th layer region (S) is determined based on the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. It is determined as desired when designing the layers of the photoconductive member based on the organic relationship between them.

In the photoconductive member of the present invention, the above (T n + T
) is preferably 1 to 100μ, more preferably 1 to 8011s, and most preferably 2 to 50μ.

In a more preferred embodiment of the present invention, the above layer thickness TB and layer thickness T are preferably TB/'r≦1
When satisfying the following relationship, it is desirable to select appropriate numerical values for each of them.

In selecting the numerical values of the layer thickness TB and the layer thickness T in the above case, the layer thickness should be selected so that the relationship TB/T≦09 is more preferably satisfied, and optimally, TB/T≦0.8. Thick TB
Preferably, the values of and the layer thickness T are determined.

In the present invention, the content of germanium atoms contained in the first layer region (G) is 1 x 105 atanle.
ppm or more, the layer thickness TB of the first layer region (G)
It is desirable that the thickness be made thin, preferably 30μ or less, more preferably 25μ or less, and optimally 20μ or less.

In the present invention, as a halogen atom (X) contained as necessary in the 10th layer region (G) spanning/and the second layer region (S) constituting 10N (1), Specific examples include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred.

In the present invention, in order to form the first layer region (G) composed of a-Ge (Sl, Lu), a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion silating method is used. This is accomplished using a vacuum deposition method.

For example, a-Ge(St +H
In order to form the first layer region CG) composed of 1X), basically G
raw material gas for e supply and silicon atoms (S
The raw material gas for supplying 81 that can supply hydrogen atoms (H
) A raw material gas for introduction and/or a raw material gas for introducing halogen atoms (X) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber. What is necessary is to form a layer on the surface of a predetermined support that is placed at a predetermined position. To make the germanium atoms non-uniformly distributed, the distribution concentration C of the contained damanium atoms is
a-Ga(S) while controlling it according to the desired rate of change curve.
1 +H+X) may be formed.

In addition, when forming by the S/4' stumbling method, for example, a tar-nod made of Sl in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, or A target r7 composed of the target and Ge
Or, use two pieces of G, El and G.

If necessary, use a mixed target of H
e, a raw material gas for Ge supply or a raw material gas for S1 supply diluted with a diluent gas such as Ar, along with a gas for introducing hydrogen atoms (H) or/and halogen atoms (X) as necessary, The gas is introduced into a deposition chamber for sputtering to form a plasma atmosphere of a desired gas, and the flow rate of the raw material gas for supplying Ge and/or the raw material gas for supplying Si is controlled according to a desired rate of change curve. Alternatively, the target may be sputtered.

In the case of the ion grating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline dalmanium or single crystal germanium are deposited as evaporation sources, respectively. - This evaporation source is heated and evaporated by a resistance heating method, an electron beam method (EB method), etc., and the flying evaporated material is passed through a desired gas glazma atmosphere.
This can be done in the same manner as in the sputtering method.

A substance that can be used as the raw material gas for S1 supply used in the present invention is 5lH4r 812I (6,5I3
Silicon hydride (silanes) in a gaseous state or that can be gasified such as H81S14H+O can be effectively used. In particular, 5iH4r is easy to handle during layer creation work, and has good Sl supply efficiency. 5I2H6 is preferred.

GeH is a substance that can be used as the raw material gas for supplying Ge.
4.Gl! +2H6r Ge4H6, Ga4H1g +
Ge5F112.

Ge6H1a, Ge7H+61G118H18, G
Gaseous or gasifiable hydrogenation gas such as e9H2o
Rumanium can be used effectively, and GeH4, Ga2H6, and G55HB are particularly preferred in terms of ease of handling during layer formation work and good Ge supply efficiency.

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 gases, halogenides, interhalodane compounds, and halogen-substituted silane derivatives. Preferable mention may be made of halogen compounds in the state or which can be gasified.

Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention.

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

Iodine halogen gas, BrF, CLF, CL
F3. BrF5゜BrF5 r IF5, IF7
+, IC4, IBr, and other interhalogen compounds.

As a silicon compound containing a halodane atom, so-called a silane derivative substituted with a halogen atom, specific Ku
IF4 + Si2F6, 5iC64r SiBr4
Preferred examples include silicon halides such as the following.

When a photoconductive member characteristic of the present invention is formed by a glow discharge method using such a silicon compound containing a halodane atom, hydrogen is used as a raw material gas capable of supplying St together with a raw material gas for supplying Ge. The first layer region (G) consisting of &-8IGs containing halogen atoms can be formed on a desired support without using silicon oxide gas.

According to the glow discharge method, the first one containing nologon atoms
When creating the day area (G), basically, for example, S1
Silicon halide, which serves as a raw material gas for supplying, germanium hydride, which serves as a raw material gas for Ge supply, and Ar r H2r.
A gas such as He is 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. By doing this, it is possible to form the desired VC first layer region (G) on the support, but in order to more easily control the ratio of hydrogen atoms introduced, these gases may be further added. A layer may also be formed by mixing a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms.

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

In order to introduce halogen gas into the layer formed by either sputtering method or ion silating method,
It is sufficient to introduce a gas of the above-mentioned halodane compound or a silicon compound containing the above-mentioned halodane atoms into the deposition chamber to form a plasma atmosphere of the gas.

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

In the present invention, the above-mentioned halogen compounds or silicon compounds containing halogen atoms are effectively used as the raw material gas for introducing halogen atoms.
In addition, hydrogen halides such as HF r HCl and HBrt[, SiH2F2, 5lH2I2 rSiH
2Ct2, 5lHC15, 5jH2Br2, 5IH
Halogen-substituted silicon hydride such as Br5, and GeHF5
, GeHBr5.

GeHBr5, GcHC4, GeH2Ct2,
GeHBr5. GeHBr5゜GeHBr5, Ge
HBr5, GeHI, 5, GeHBr5, G
Halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides such as eH51, GeF4
+GeCl4, GeBr4, Ge1a + G
Gaseous or gasifiable substances such as germanium halides such as eF2 r Ge9H2o GeBr2+GeI 2 and the like can also be mentioned as useful starting materials for the formation of the first layer region CG).

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

In order to structurally introduce hydrogen atoms into the first layer region CG), in addition to the above, H2, SiH4, 5I2H6rSi
Silicon hydride such as 5HQ, 514H1, etc. with a germanium or darmanium compound for supplying Ge, or GeH4r Ga2H6r Ge3HB, Ge
4H10,Ge5H12゜Ga6H14T Ge7H1
This can also be carried out by causing discharge by causing dalmanium hydride such as 6r GeBHlB or Ge2H2p and silicon or a silicon compound for supplying St to coexist in the deposition chamber.

In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the amount of hydrogen atoms and halogen atoms contained in the first layer region (G) of the photoconductive member to be formed The sum (H+X) is preferably O, 01 to 40 a
tomic%, preferably 0.05 to 30 ato
mic%, optimally 0.1 to 25 atomlc%.

In order to control the amount of hydrogen atoms (H) and/or halodane 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 can be controlled. 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 dalmanium atoms and the first layer region (G) that contains germanium atoms contain a substance that controls conduction properties ( C), the second layer region (
The conduction properties of S) and the first layer region (G) can be controlled arbitrarily as desired.

At this time, the substance (C) contained in the second layer region (S)
) may be contained in the entire first 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 the entire layer region of the second layer region (S), or the layer region (SPN) containing the substance (C) is provided in 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 C(s) increases in a curved manner, a substance (C) for controlling conductivity is provided in the second layer region (S) so that the conductivity increases monotonically toward the support side. is desirable.

When the layer region (SPN) is provided as a part of the second layer region (S), the distribution state of the substance (C) in the layer region (SPN) is parallel to the surface of the support. Although it is assumed to be uniform in the in-plane direction, it may be uniform or non-uniform in the layer thickness direction. In this case, the layer area (SPN)
In K, in order to provide the substance (C) so that it is distributed non-uniformly in the layer thickness direction, it is necessary to provide 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). It is desirable to provide a

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

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

However, when both layer regions contain the same type of conductivity controlling substance (C>), the layer Jl of the substance (C)
The maximum distribution concentration in the direction is in the second layer region (S), that is, in the interior of the second layer region (S) or at the interface with the first layer region CG). preferable. Especially,
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 the conduction properties.
) layer region (PN) t-1 second layer region (S)
Preferably, the second layer occupies at least a portion of the layer area.
It is provided as an end layer region (SE) on the support side 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)max 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).
<C(g)maxThe material (
C) is contained in the first layer (I).

A substance (C) that controls conductivity contained in the layer region (PN)
) can include impurities known in the field of conductors, and in the present invention, p-type impurities give p-type conductivity to Si or Ge, and p-type impurities give n-type conductivity to Si or Ge. This type of impurity can be mentioned.

Specifically, p-type impurities include atoms belonging to group Ⅰ of the periodic table (group W atoms), such as B (boron), ht (
Aluminum), Ga (gallium), In (indium), Tt (thallium), etc., and 3% Ga is particularly preferably used.

Examples of n-type impurities include atoms belonging to Group I of the periodic table (Group V atoms), such as P (phosphorus), As (arsenic), and sb (
(antimony), bismuth (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 layer region of the pond are also considered, and the substance (C) that controls the conduction characteristics is determined. Containing Nil is fully selected.

In the present invention, the content of the substance (C) that controls the conduction properties referred to in the no region (PN) is preferably O,
01-5 X 10' atomic ppm, more preferably 0,5-1 X 10' atomic PPm
% is preferably set to 1 to 5 x 105105 at 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 no region (G) of Kintei 1 and the second layer region (S), or the layer region (PN) P.N.
) 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 By setting the amount to 50 atomic ppm or more, optimally 100,100 atomic ppm or more, for example, when the substance to be contained is the above-mentioned p-type impurity, when the free surface of the photoreceptive layer is subjected to polar charging treatment, It is possible to effectively block the movement of electrons injected from the support side into the second layer region (S), and when the substance to be contained is the n-type impurity, the photoreceptor layer When the free surface of A has been subjected to an anti-polarity treatment, the transfer of holes injected from the support side into the second layer region (G)
tJrk can be effectively prevented.

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 characteristics of a polarity different from the polarity of the substance that controls conduction characteristics contained in the PN layer, or a substance that controls conduction characteristics of the same polarity. 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 conductive properties contained in the layer region (Z) can be adjusted as desired depending on the polarity of the substance contained in the layer region (PN) and the stitching. It is determined appropriately, but preferably from 0.001 to
1000 atomic ppm, more preferably 0.0
5-500 atomic ppm, optimally 0.1
It is desirable to set it to 200 atomic ppm.

In the present invention, when the layer region (PN) and the rigid region (Z) contain the same type of substance governing conductivity, the content in the layer region (Z) is preferably 30 ato
It is desirable to set it to mic ppm or less.

In addition to the above-mentioned cases, in the present invention, the first layer (1
), a layer region containing a substance controlling conductivity having one polarity and a layer region containing a substance controlling conductivity having the other polarity are provided so as to be in direct contact with each other. , it is also possible to provide a so-called depletion layer in the contact region. That is, for example, in the 10th layer (1), a so-called p-n junction is formed by providing the layer region containing the p-type impurity and the layer region containing the n-type impurity in direct contact with each other. can be formed to provide a depletion layer.

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 of the first layer from the support side. In the figure, tn is the position of the end surface of the first layer region CG) on the support side, d is the position of the end surface of the second layer region (S) on the opposite side, and Lo is the position of the end surface of the layer region CG) and the layer region (
The position of the contact interface of S) is shown.

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 layer thickness direction.

In the example shown in the Ml1 diagram, the substance (C) is not contained in the first layer region (G), but is contained only in the second layer region (S) at a constant distribution concentration of C1. There is. That is, 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 concentration CI.

In the example of FIG. 12, the first layer region (G) contains a substance (C
) is contained without any scratches, but the ff120 layer region (
S) does not contain substance (C).

Then, the material (C) is t (in the layer region between 1 and t2,
The distribution concentration is constant at 02 and is contained at once, and the layer region between L2 and tT has a constant concentration d of C3, which is much lower than C2.
It is contained in degrees.

ko(D'f4 fx distribution a W C(PN) te substance (C) in the first layer (1) t-the second layer region (
By including it in S), the second layer region CG) is more concentrated than the first layer region CG).
If it is possible to effectively prevent the charge injected into the layer region (S) from moving toward the surface ml, it is possible to improve the photosensitivity and dark resistance at 1 DJ.

In the example of Fig. 13, the material (C
) is included without any scratches, but once in to
The material (Li) is contained in a state where the distribution 4 degrees C (PN) is changing so that it monotonically decreases from 4 toward the upper surface and reaches d degrees O at tT. Region (G) does not contain 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 (S). 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). However, it has a layered structure in which the layers are stacked in this order from the support side.

The difference between the examples shown in FIG. 14 and FIG. 15 is that in the case of FIG. In contrast, in the case of Fig. 15, between to and t4, the concentration C at the to position decreases monotonically to 0.
The concentration decreases linearly and continuously until the concentration reaches 0 at the position of 6 to Ct4.

Also in the case of the examples shown in FIGS. 14 and 15, the first layer region CG
) does not contain substance (C).

In the examples shown in FIGS. 16 to 24, the second layer region (
S) is a layer region where the substance (C) is completely contained and a layer area where the substance (C) is completely contained.
A common feature is that the layer region that does not contain C) has a two-layer structure in which the layer region is laminated in one layer from the support side. In the examples shown in FIGS. 17 to 21, the distribution state of the substance (C) in the first layer region CG) is different from that at the interface with the second layer region (S). This means that the distribution concentration C (pN) decreases from position fi\to toward the support.

In the examples shown in FIGS. 23 and 24, the substance CC) is contained in the entire layer region of the first layer (1) in the layer thickness direction without any scratches.

In addition, in the case of FIG. 23, in the first layer region (G), the concentration CZS at to is one degree higher than the concentration CZS at tB.
tn j P) increases linearly towards t6 until X,
In the second layer region (S), the concentration Ca at to
The concentration decreases monotonically and continuously from to to tr from t to the concentration O at tT.

In the case of FIG. 24, in the layer region between ts and ttsO, the substance (C) is contained at a constant distribution concentration of concentration C24, and in the layer region between t13 and tT, the concentration CXS It decreases linearly and reaches 0 at LT.

11 to 24, the distribution concentration C(P) of the substance (C) that controls conductivity in the first layer (I)
As explained in the typical cases of changes in N), in all examples, the substance (C) is distributed such that the maximum distribution concentration of the substance (C) is in the second layer region (S). Contained in the first layer (1).

In the present invention, in order to form the second layer region (S) composed of a-8i (Hr , forming the first layer region (G) using the starting material [starting material for forming the second layer region (S) ([1)]) excluding the starting material that becomes the raw material gas for supplying Go It can be carried out in the same manner and according to the same steps as in the case of

That is, in the present invention, in order to form the second layer region (S) composed of a-8t (H,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon such as a ball method, a sputtering method, or an ion blating method. For example, in the glow discharge method, a"5i(H,X)
A second layer region (S) consisting of t- is formed by
Basically, along with the raw material gas for Si supply that can supply the silicon atoms (St) described above, hydrogen atoms (St) are used as needed.
H) Introducing the raw material gas for introduction and/or the introduction of no-rodan atoms (X) into a deposition chamber whose interior can be reduced in pressure,
A glow discharge is generated in the deposition chamber to form a layer of a-6i (H, In addition, in the case of forming by sputtering method, for example, when TARDAT made of SI is sludged or sputtered in an atmosphere of an inert gas such as Ar r He or a mixed gas containing these gases, hydrogen atoms are A gas for introducing (H) or/and rhodan atoms (X) may be introduced into the deposition chamber for sputtering.

In Book 9f3 Akira, the first 79 formed (1)
The amount of hydrogen atoms (H) or the amount of halodane atoms (X) or the sum of the amounts of hydrogen atoms and no-rodan atoms (H+X) contained in the second layer region (S) constituting the is preferably 1~
40 atoms 1a% r, preferably 5-3 Q at
omic%, preferably 5 to 25 atomic%.

A substance (C) that controls conductivity, for example, a group Ⅰ atom or a group V atom, is structurally introduced into the layer region constituting the first layer <1). To form the contained layer region (PN), during layer formation, the starting material for the introduction of the group I atoms or the starting material for the introduction of the group It may be introduced together with the starting materials for forming the layer (1). As the starting material for such introduction of Group (I) atoms, it is desirable to employ materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Such a number ■
Specifically, starting materials for introducing boron atoms include B2H6, B4H10, B5H91B5H.
Hydrogenation #1 element such as H1B6H10r B6H12r B6H44, BF5.

Examples include boron halides such as BCl3 + BBr3.

In addition, ALC4, GaCl2, Ga(CH5
+InC65+Ttct3 etc. can also be mentioned.

As a starting material for introducing a group V atom, PH3r is effectively used in the present invention for introducing a phosphorus atom.
Hydrogen ratios such as P2H4, PH4I, pp'3.

PF5 * PCl3 + PCl3 r PBr3
Examples include nologonated phosphorus such as r PBr3 r PH5. In addition, AsH3r AIIF! , 1AsC23
, AsBr3 r AsF5 r SbH3, SbF3
．． 5bFs rSbC15, 5bC65, BiH3, B
Effective starting materials for introducing Group I atoms, such as 1Cl3 and B1Br3, can be listed below.

In the photoconductive member of the present invention, the first layer (1) is added for the purpose of increasing light sensitivity and darkening resistance, as well as improving the adhesion between the support and the first layer (1). Nitrogen atoms are contained in the zero layer (1). The nitrogen atoms contained in the layer (1) of the conduit may be contained in the entire layer of the first layer (1) without any scratches, or may be contained in a part of the first layer (1) of the former 1). It may be contained and unevenly distributed only in the layer region.

In addition, the distribution state of nitrogen atoms is such that even if the distribution concentration C(N) is uniform in the layer thickness direction of the first layer (I), the distribution concentration C(N) is uneven in the layer thickness direction. It may be uniform.

In the present invention, when the main purpose of the nitrogen atom-containing no-head layer (N) provided in the first layer (1) is to improve photosensitivity and dark resistance, the first layer (1) is The support and the first layer (1) are provided so as to occupy the entire layer area of the layer (1).
Or, if the main purpose is to strengthen the adhesion between the first layer region (G) and the second layer region (S), the support side end of the first layer (1) layer region or first and second
It is provided so as to occupy an area near the layer area interface.

In the former case, the M content of nitrogen atoms contained in the interlayer region (N) is made relatively small in order to maintain high photosensitivity, and in the latter case, the content of nitrogen atoms in the interlayer region (N) is made relatively small in order to maintain high photosensitivity. It is desirable to have a relatively large amount for measurement purposes.

Also, in order to achieve both the former and the latter at the same time,
A relatively 46 degree distribution on the support side and a relatively low concentration distribution on the free surface side of the first layer, or a surface JvI region on the free surface side of the first layer. This can be achieved by forming a distribution state of nitrogen atoms in the layer region (N) that does not actively contain nitrogen atoms.

Furthermore, when the purpose is to increase the apparent dark resistance by preventing charge injection from the support or the first layer region (G) to the second layer region (S), the first layer region (G) layer area CG)
The first step is to distribute nitrogen atoms at a high concentration on the edge of the support.
Nitrogen atoms are distributed at a high concentration near the interface between the first layer region and the second layer region.

FIGS. 25 to 40 show typical examples of the overall distribution of nitrogen atoms in the first #(1).

It should be noted that symbols used throughout the description of these figures have the same meanings as used in FIGS. 11 to 24.

In the example shown in FIG. 25, the nitrogen atom distribution concentration C1 is constant from the position tB to the υ position 1°, and the position U t
The nitrogen atom distribution concentration C2 is constant from tT to position tT.

In the example shown in FIG. 26, the nitrogen atom distribution concentration Cs is a constant value from position ts to position 1°, and the nitrogen atom distribution concentration C4 is constant from position t2 to position t3, and the nitrogen atom distribution concentration C4 is constant from position ts to position t3.
From position t-7, the nitrogen atom distribution concentration is C, which is 3
The nitrogen atom distribution concentration is reduced in stages.

In the example of FIG. 27, position 1. From position t4 to position t4, the nitrogen atom distribution concentration is C6, and from position t4 to position D, the nitrogen atom distribution concentration is C7.

In the example of FIG. 28, the nitrogen atom distribution concentration is C from position t11 to multiple positions tS, the nitrogen atom distribution concentration is C9 from position ts to position t6, and the nitrogen atom distribution concentration CIG is from position t6 to position fftT. In this way, the nitrogen atom distribution concentration is increased in three stages.

In the example of FIG. 29, the nitrogen atom distribution concentration is C1l from position tB to multi-position t7, the nitrogen atom distribution concentration is -2 from position t7 to position t8, and the nitrogen atom distribution concentration C13 is set from position t8 to position tT. The nitrogen atom distribution concentration is made high on the support side and the free surface side.

In the example shown in FIG. 30, position 1. From position t9 to position t, the nitrogen atom distribution concentration is C14.
The nitrogen atom distribution concentration CtS is set up to lo, and the nitrogen atom distribution concentration C14 is set from position t1° to position d.

In the example shown in FIG. 31, the nitrogen atom distribution concentration is 016 from position tB to position tll, and from position 111 to position t1.
Nitrogen atom distribution concentration up to 2 C1? and stepwise increase,
The nitrogen atom distribution concentration is reduced to C1l from position t1m to position tT.

In the example of FIG. 32, the nitrogen atom distribution concentration is C19 from position tm to position t1g, the nitrogen atom distribution concentration is increased stepwise with CXO from position tts to position t14, and the nitrogen atom distribution concentration is increased stepwise from position tts to position t14.
The nitrogen atom distribution concentration from 14 to position ty is lower than the concentration in W period C! It is set as l.

In the example shown in FIG. 33, the nitrogen atom distribution concentration from position ti to position tis is C10, the nitrogen atom distribution concentration is reduced to C113 from position tts to position tta, and the nitrogen atom distribution concentration C24 from position 1 ftss to position t17.
The nitrogen atom distribution concentration is increased stepwise from the position till to approximately 1 ft., and is decreased to czs.

In the example shown in FIG. 34, the distribution concentration C(N
) increases continuously and monotonically from position fits to position tT with a distribution of 44 degrees from 0 to cps.

In the example shown in FIG. 35, the distribution concentration C(N
) is at position 1. , the distribution concentration (41) monotonically and continuously decreases from the distribution concentration Cts until reaching the position till, and becomes the distribution concentration Cat at the position tie. In between, the distribution concentration C(N) of nitrogen atoms increases continuously and monotonically from the position tla, and becomes the distribution concentration CZS at the position tT.

The example in FIG. 36 is relatively similar to the example in FIG. 35, but differs from the example in position tll and position t2. It does not contain any nitrogen atoms.

Position 1. and the position tie, the distribution concentration C9 at the position tm continuously monotonically decreases from the distribution concentration C9 at the position till to 0t, and between the position t2o and the position t7, the distribution concentration at the position t! There is a continuous monotonous increase from the distribution concentration O at ◎ to the distribution concentration C3G at position tm.

In the photoconductive member of the present invention, as typical examples are shown in FIGS. 34 to 36, more nitrogen atoms are added to the lower surface and/or upper surface of the first layer (1). For example, by containing fewer nitrogen atoms toward the inside of the first layer (1) and continuously changing the distribution concentration C(N) of nitrogen atoms in the layer thickness direction, The first layer (1) is designed to have high light sensitivity and high dark resistance.

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

In the example shown in Figure 8g37, position 1jfttiJ:D position t! 1, the nitrogen atom concentration is C1l, and the position t! 1
It increases from position 1 ft., i, and once the nitrogen atom at position tzx reaches the peak value C32. From position tI to position fig t
The nitrogen atom concentration decreases at zs i and reaches the nitrogen atom concentration CSX at position t7.

In the example shown in FIG. 38, position 1. The nitrogen atom concentration is C13 from position txa to position Rtt.
The nitrogen atom concentration rapidly increases to Cs, and at position t's the nitrogen atom concentration takes a peak value Cs4t-, and decreases from position t's to position C until the nitrogen atom concentration becomes almost zero.

In the example shown in FIG. 39, from position fftts+ to position row t
The nitrogen atom concentration gradually increases from Cps to CSS until knee, and at position ff1t*s, the nitrogen atom concentration reaches the peak value a.
It becomes SS. The nitrogen atom concentration rapidly decreases from position Mtzs to position tT, and reaches the nitrogen atom concentration CSS at position tT.

In the example shown in FIG. 40, position 1. and the nitrogen atom concentration C
St and position t! The nitrogen atom concentration decreases up to 7 and becomes the nitrogen atom concentration CSS. The nitrogen atom concentration is constant at Ca1l from the position toy to the position txs. from position tzs to position t
The nitrogen atom concentration increases until o, and reaches a peak value Ca11 at position t29. from position two to position 11
The nitrogen atom 4 degree decreases until 1iffitt and becomes the nitrogen atom 4 degree Ca1l.

In the present invention, even if the layer region (N) occupies the entire area of the first layer (1) or does not occupy the entire area of the first layer (1), the layer thickness To of the layer region (N) If the proportion of the first layer (1) in the no thickness T is sufficiently large, the upper limit of the content of nitrogen atoms contained in the layer region (N) will be sufficiently smaller than the above value. desirable.

In the case of the present invention, when the ratio of the layer thickness To of the layer region (N) to the layer thickness T of the first layer (1) is two-fifths or more, the layer region (N) The upper limit of the amount of nitrogen atoms contained in N) is preferably 3° atomic% or less with respect to the sum of the three atoms of silicon atoms, glumanium atoms, and nitrogen atoms [hereinafter referred to as r T (S1 GeN) J]. , more preferably 20 atomic% or less, optimally 10 atomic%
It is desirable that it be atomic% or less.

In the present invention, the layer region (N) containing nitrogen atoms constituting the first /l) contains nitrogen atoms at a relatively high concentration near the support side and the free surface side, as described above. In the former case, it is desirable to further improve the adhesion between the support and the first layer and to improve the acceptance potential. I can do it.

The above localized region CB) can be explained using the symbols shown in FIGS. 25 to 40, such as the interface position tB or the free surface t
In the present invention, the localized region CB) is preferably provided within 955 degrees of the interface position 1.
．． Or the entire layer area up to 5μ thick from the free surface tT (LT
), or as part of the father, j-layer region LT).

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

The localized region (B) has the maximum distribution concentration Cm of nitrogen atoms as the distribution state of the nitrogen atoms contained therein in the layer thickness direction.
It is desirable that the layer be formed in such a manner that the distribution of ax is preferably 500 atomic ppm or more, more preferably 800 atomic ppm or more, and optimally 1000 atomic ppm or more.

That is, in the present invention, the layer region (N) containing nitrogen 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 tl or tT). It is desirable that the structure be formed in such a way that it exists.

In the present invention, even if the layer region (N) occupies the entire area of the first layer (1) or does not occupy the entire area of the first layer (1), the layer thickness T of the layer region (N) If the ratio of , to the layer thickness T of the first layer (1) is sufficiently large, the upper limit of the content of nitrogen atoms contained in the layer region (N) is made sufficiently smaller than the above value. is desirable.

In the case of the present invention, when the ratio of the layer thickness T of the layer region (N) to the layer thickness T of the first layer (1) is two-fifths or more, the layer region The upper limit of the amount of nitrogen atoms contained in (N) is preferably 3 to T(SiGeN).
0 atomic or less, preferably 20 atoms
ia% or less, preferably 10 atomic% or less.

In the present invention, in order to more effectively achieve the object of the present invention, the distribution concentration line of nitrogen atoms in the layer thickness direction in the layer region (N) is smooth in the entire region. It is desirable that the layer region (N) contains methane atoms in a continuous manner. Furthermore, if the distribution concentration line is designed so that its maximum distribution concentration Cmax exists inside the first layer (1), the effects described below will be exhibited significantly.

In the present invention, the maximum distribution concentration Cmax is preferably provided near the surface of the first layer (1) opposite to the support (the free surface side in FIG. 1). . In this case, by appropriately selecting the maximum distribution concentration Cmax, it is possible to effectively prevent charges from being injected from the free surface side of the photoreceptive layer into the interior of the photoreceptive layer when the free surface side of the photoreceptive layer is subjected to the stripping treatment. You can.

Further, in the vicinity of the free surface, nitrogen atoms are contained in the 10th layer (I) so that the distribution concentration of nitrogen atoms decreases more sharply than the maximum distribution concentration Cmax toward the free surface. Furthermore, durability in a humid atmosphere can be further improved.

When the nitrogen atom distribution concentration curve has the maximum distribution concentration Cmax inside the first layer (1), the distribution concentration curve is further designed so that the maximum value of the distribution concentration exists on the support side, By containing nitrogen atoms, it is possible to improve the adhesion between the support and the first layer (1) and to prevent charge injection.

In the present invention, nitrogen 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 nitrogen atoms is
For T(SlGeN), preferably 67 atoms
It is desirable that the content be lc% or less, more preferably 50 atomla% or less, most preferably 40 atomla% or less.

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

In addition, when another layer area is provided in direct contact with the layer area (N), the relationship with the characteristics of the original layer area and the characteristics at the contact interface with the layer area of the song should also be considered. and the nitrogen atom content is appropriately selected.

The amount of nitrogen atoms contained in the layer region (N) is appropriately determined as desired depending on the characteristics required for the light guide to be formed, but is preferably 0. 001-50 atomic%, more preferably 0.002-40 atomic%, optimally 0.0
It is desirable that the content be 0.03 to 30 atomc%.

In the present invention, in order to provide the layer region (N) containing nitrogen atoms in the first layer (1), a starting material for introducing nitrogen atoms is added during the formation of the first layer (1). M may be used together with the starting material for forming the first layer (1) to contain M in a limited amount in the formed layer.

When a glow discharge method is used to form the layer region (N), a starting material for introducing nitrogen atoms is added to a starting material selected as desired from among the starting materials for forming the first layer (1). It will be done. As the starting material for introducing nitrogen atoms, most of the gaseous substances containing at least nitrogen atoms or gasified substances that can be gasified can be used.

For example, a raw material gas containing silicon atoms (Si), a raw material gas containing nitrogen atoms (N), and hydrogen atoms (H) or/and halogen atoms (X
) f: Either a raw material gas containing constituent atoms is mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Sl) and nitrogen atoms (N) and hydrogen atoms (
H) is also mixed with a raw material gas having constituent atoms at a mixing ratio of J, or 7 silicon atoms (Si)'e
A raw material gas containing tM atoms and a silicon atom 1':Si
), nitrogen atoms (N), and hydrogen atoms (H) can be mixed and used.

Father, apart from silicon atoms (Si) and hydrogen atoms (I (
) is added to the raw material gas whose constituent atoms are nitrogen atoms (N).
A mixture of raw material gases containing t-component atoms may be used.

Nitrogen atoms (N) used in forming the layer region (N)
It becomes raw material gas for 4 uses! Starting materials that are usefully used as a catalyst include, for example, nitrogen (N2,
Ammonia (NI5), hydrazine (H2NNH2)
.

Hydrogen azide (I(Ns), ammonium azide (NI)
Mention may be made of gaseous or gaseous nitrogen such as (4N5), nitrogen compounds such as nitrides and azides.

In addition to this, nitrogen trifluoride (
F3N), and nitrogen tetrafluoride (F4N2).

In the present invention, in addition to nitrogen atoms, in order to further enhance the effect obtained by pixel atoms, in the layer region (N),
Furthermore, it can contain oxygen atoms. As the raw material gas for introducing oxygen atoms into the layer region (N), for example, oxygen (02) is used.

ozone (03), -nitric oxide (NO), nitrogen dioxide (NO2).

-Nitrogen dioxide (N20), nitrogen sesquioxide CN20s)
rtrinitric oxide (N204) rnitric oxide (N2
05) + Nitrogen trioxide (NO5), silicon atom (S
i), an oxygen atom (0), and a hydrogen atom (■()), for example, disiloxane (H5SiO3IH3)
, ) disiloxane (H3SiO8iH20SiH3
) and other lower siloxanes.

S・9. To form the layer region (N) containing nitrogen atoms by the Kring method, a single crystal or polycrystalline Sl wafer or a Si3N4 wafer, or a St and Si3N4 wafer is used.
Sputtering may be carried out by using a wafer containing a mixture of these as a target in a 1M gas atmosphere.

For example, if a Si wafer is used as a target, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluting gas as necessary, and a deposition chamber for sputtering is prepared. The St wafer may be sputtered by introducing the St wafer into the St wafer and forming a gas plasma of these gases.

Separately, by using Si and S1SN4 as separate targets, or by using a single target containing a mixture of St and Si5N4, the dilution gas can be used as a gas for the gas. Sputtering is performed in an atmosphere or in an atmosphere surrounded by a gas containing at least hydrogen atoms CH) or/and halodane atoms (X) as constituent atoms. As a raw material gas for introducing nitrogen atoms,
The raw material gas for introducing nitrogen atoms into the raw material gas shown in the above-mentioned example of glow sleep can also be used as an effective gas in the case of snow dusting.

In the seventh invention, when forming the first layer (1), if a layer region (N) containing nitrogen atoms is provided, distribution of tetraatomic atoms contained in the layer region (N). Concentration C(N)+1
- Change the distribution in the thickness direction to obtain the desired thickness distribution g (d
epth profile) Yc; i4 layer area (N)? i- In the case of glow discharge, the gas of the starting material for introducing nitrogen atoms whose distribution concentration [C(N) is to be changed is changed as appropriate according to the desired rate of change curve. This is done by placing four people in the deposition chamber while For example, hands! The opening of the constant needle pulp provided in the middle of the gas flow path system may be changed sideways by any method commonly used in I7I or an external drive motor. At this time, the rate of change of the flow rate does not need to be linear; for example, it may follow a rate of change curve designed in advance using a microcomputer, etc.
Control the prize 1. It is also possible to obtain a desired ownership rate curve.

When forming the layer region (N) by the x sputtering method, the distribution of the 4-group atoms in the layer thickness direction is changed once C(N) is changed in the layer thickness direction to obtain the desired distribution state of the cap atoms in the layer thickness direction. (
depth profile) To form f, first, as in the case of the glow discharge method, a starting material for introducing nitrogen atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is ) by appropriately changing Ji'Ml.

Second, sputtering targets, such as St
If a mixed target of 5151J4 and 5151J4 is used, this can be done by changing the mixing ratio of Sl and Si3N4 in advance in the thickness direction of the targate.

In the photoconductive member 100 shown in FIG. 1, a second layer (11) 10 is formed on a first layer (1) 102.
5 has a free surface and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, electrical pressure resistance, usability, and durability.

Furthermore, in the present invention, since each of the amorphous materials constituting the first layer (1) 102 and the second layer (10105) has a common constituent element of silicon atoms, Luobao of chemical stability is the main component.

The second layer in the present invention (10 is a silicon atom (St
), a carbon atom (C), and optionally a hydrogen atom (H) or/and a halodane atom (X) [hereinafter r a-(SixC1-x)yotx)1-y J However, it is composed of 0 (x, y (denoted as 1)).

The formation of the second layer composed of a-(SlzCl-x)yCkLX)1-y is performed by a glow discharge method, a sputtering method, an ion plantation method, an ion grating method, an electron beam method, etc. These manufacturing methods are interpreted and adopted as appropriate depending on factors such as mounting conditions, the level of equipment capital investment, manufacturing scale, and the characteristics desired for the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for producing a photoconductive member having silicon atoms, and carbon atoms and halodane atoms can be easily introduced into the second layer (10). Due to these advantages, the glow discharge method or the sputtering method is preferably employed.

Furthermore, in the present invention, the second layer ω)t- may be formed by using both the glow discharge method and the sputtering method in the same apparatus system.

To form the second layer (a) by glow discharge method,
-(SixC1-x)y(HrX)ty-The raw material gas xf for forming y is mixed with a dilution gas at a predetermined mixing ratio as necessary, and a deposition chamber for vacuum deposition where a support is installed. The introduced gas is turned into gas lazma by suppressing the generation of glow emission, and a-(81xC1-x)y( H2
X)+-3' may be deposited.

In the present invention, a-(SlXC1-z)y('',X)
As the raw material gas for +-y formation, silicon atoms (St
), carbon atom (C), hydrogen atom (H), halogen atom (
Most gaseous substances or gasified substances containing at least one of X) as a constituent atom can be used.

8i, C, H, and X, when using a raw material gas with another constituent atom, for example, a raw material gas with Sl as a constituent atom, a raw material gas with C as a constituent atom, and a raw material gas with another constituent atom as necessary. Accordingly, a raw material gas containing H as a constituent atom and/or a raw material gas containing X as a constituent atom may be mixed at a desired mixing ratio, or a raw material gas containing SL as a constituent atom and C and H
A raw material gas containing St as constituent atoms and/or a raw material gas containing x6 constituent atoms may be mixed at a desired mixing ratio, or a raw material gas containing St as constituent atoms and/or a raw material gas containing x6 constituent atoms may be mixed with Si, C, and H. A raw material gas having three constituent atoms or a raw material gas having three constituent atoms of St, C, and X can be mixed and used.

Separately, C is added to the raw material gas containing St and H as constituent atoms.
A raw material gas containing 'kti& atoms may be mixed and used, or a raw material gas containing 81 and X as constituent atoms may be mixed with ff1l+ gas containing C as constituent atoms.

In the present invention, F, CL, Br are suitable as the halodane atoms (X) contained in the second layer 01).
.

(2) Particularly desirable are F and CL.

In the present invention, materials that can be used effectively as the raw material gas to form the second layer (n) include those that are in a gaseous state at room temperature and normal pressure, or substances that can be easily gasified. I can do it.

In the present invention, what is effectively used as the raw material gas for forming the second 0m (■) is S
iH4r 512H6r 5I5HB r 814”1
Silicon hydride gas such as silanes (8i 1ane) such as silanes (8i 1ane), saturated hydrocarbons containing C and H as constituent atoms, for example having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, carbon atoms 2-3 acetylenic hydrocarbons, single rodan,
Examples include hydrogen halide, inter-rhodan compounds, silicon hydride, halodane-substituted silicon hydride, and silicon hydride.

Specifically, methane (CFL4) is used as a saturated hydrocarbon.
.

Ethane (C2I (6)
, n-butane (1o to n-C4), penta7 (C
sH + z) r: c tyrene thread hydrocarbons include ethylene (C2H4) r globylene (Ca),! ten-1 (C4)18), butene-2 (C4Ha).

Isobutylene (CaHa) *Pentene (CsHlo)
, As the acetylene hydrocarbon, acetylene (C2
H2).

Methylacetylene CC5Ha) sgutin CCaHb)
, No. As a single substance, halogen gas of fluorine, chlorine, bromine, and iodine;
.

As the HI, HCtjHBr1 interhalon compound, B
rF, CLF, ClF5, C6Fs, B
rF5, BrF5, IF7゜IF5 *IC
1.IBr 1 sip'415 as silicon oxide
12F6 r 5iCt4, 5IC63Br r 5
iCt2Br2 +5lC2Br5, 5iCt3I
, 5lBr4 , /~Ol' :/ As the substituted silicon hydride, 81H2F2 , 5iH2C62, 5iHCj
5 r81) I5Ct, 81) 15Br, 8i)
As 12Br2, 5lHBr5, and silicon hydride,
Examples include silanes (S-an6) such as 5L)14, 5t2Ha, 5t4u1o, and the like.

In addition to these, CF4, CCl2, CBr4,
(JIF3.

CH2F2, CH3F, CH3CA, CH
Halodane-substituted paraffinic hydrocarbons such as 3Br, CH3I, C2H3Ct, fluorinated sulfur compounds such as NSF4 rSF6, 5l(CH5)4.

Alkyl silicides such as 5i(CzHs)4 and 5iCt(C
Hs)3.

s+ct2 (cm,)2, 5lct5cu5 etc.
Silane derivatives such as f7-containing 'l-alkyl iride can also be cited as effective.

These second layers (m-forming substances contain silicon atoms, carbon atoms, and log atoms in a predetermined composition ratio in the IQ) and hydrogen atoms as necessary. They are selected and used as desired when forming the second layer (11).

For example, 5l can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and can form a layer with desired characteristics.
(CH3)4 and (D 5iHCt3 , 5lH2Ct2 , 5iC24
Alternatively, 8-(SixC1-x)y(c
A second layer (IDt-) consisting of t+H)+-3' can be formed.

To form the second layer (lI) by the sputtering method, target binding of a single crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Sl and C is required. Depending on the situation, sputtering may be performed in various gas atmospheres containing halodane atoms and/or hydrogen atoms as constituent elements.

For example, if a Sl wafer is used as a target, the raw material gas for introducing C and H or/and The Si wafer may be sputtered by forming a gas plasma of these gases.

Separately, by using Sl and C as separate targets or by using a single plate of mixed Sl and C, it is possible to use a gas atmosphere containing hydrogen atoms or halodane atoms as necessary. This is done by 4-tutting. The material that becomes the raw material gas for introducing C, H, and can be used as

In the present invention, the diluting gas used when forming the second layer (It)'t by the Starzterling method is a so-called rare gas, such as Ha, Ne, etc.
.

Preferred examples include Ar.

The second layer (10) in the present invention is carefully formed to provide the desired properties.

That is, a substance whose constituent atoms are St, C1, H or/and X as required, has a structure ranging from crystalline to amorphous depending on its preparation conditions, and in terms of electrical properties,
In the present invention, it exhibits properties ranging from conductivity to semiconductivity to insulating properties, and properties ranging from photoconductive properties to non-photoconductive properties, so in the present invention, it has desired properties depending on the purpose. The preparation conditions are strictly selected as desired so that a-(SizCl-x)y(HlX)+-y is formed. For example, to provide the second layer (II) 'ii-'-with the main purpose of improving the gas pressure resistance, a-(Sl
zCl-,x)y(LX)1-y is made as an amorphous material with pronounced electrically insulating behavior in the environment of use.

In addition, if a second layer (ID) is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation will be relaxed to a certain extent, and the sensitivity to the irradiated light will be increased to a certain degree. As an amorphous material having a-(
SixC1-x)y(HlX)1-y is created.

a-(stxcl-x)y(H
, ,
a-(stxcl,)y(H+
It is desirable that the temperature of the support at the time of layer formation be properly controlled so that X) 1-y can be formed as desired.

In the present invention, the formation of the second layer (■) is carried out by selecting an appropriate temperature range in accordance with the method of forming the second layer (IO) in order to effectively achieve the desired purpose. but preferably 20 to 400°C, more preferably 50 to 350°C,
The optimum temperature is preferably 100 to 300°C. For forming the second layer (n), the layer ′! i-Glow discharge method and sputtering method are advantageous because delicate control of the composition ratio of constituent atoms and control of layer thickness are relatively easier than other methods. , When forming the second layer (II) using these layer forming methods, the discharge power during layer formation is set at a-(SizCl-x)yXl- similar to the support temperature described above. It is one of the important factors that influences the properties of 3'.

a- having the characteristics for achieving the object of the present invention;
(81 engineering C1-x) Discharge tJ for yXi-y to be created efficiently and effectively? The power condition is preferably 10~
300W, suitable for 20~250W, optimally 50W
It is desirable that the power is set at ~200W.

The gas pressure in the deposition chamber is preferably 0. (11 to 1 Torr
, y) It is preferably 0.1 to 0.5 Torr and 8 degrees.

In the present invention, the values in the above-mentioned ranges are mentioned as the preferable numerical ranges of the support temperature reaction and discharge power for creating the second layer (n), but these layer creation factors are as follows:
The desired characteristic a is not independently and separately determined.
- (81xC1-X) y (H, .

The amount of carbon atoms contained in the second layer 01) in the photoconductive member of the present invention is the same as the production conditions of the second layer (II), and the amount of carbon atoms contained in the second layer 01) is the same as the production conditions of the second layer (II). This is an important factor in the formation of the second layer (1[).

The number of carbon 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 suspension constituting the second layer (II). It is.

That is, the general formula a-(S l x C1-x)y
(H2X) The amorphous material represented by 1-y can be broadly classified as an amorphous material composed of silicon atoms and carbon atoms [hereinafter referred to as "B-siBcl-aJ". However, 0
(a (1), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms [hereinafter ra-(Si1.C+
-b) Written as cHt-cJ. However, 0 (b, c
(1), an amorphous material composed of silicon atoms, carbon atoms, halodane atoms, and hydrogen atoms as necessary [hereinafter referred to as I
It is written as ``a-(Sl dc, -d)e(HlX)+-eJ.However, it is classified as 0<d, e<1:).

In the present invention, the second layer (II) is a-811LC1
-, the amount of carbon atoms contained in the second layer (IQ is preferably IXI O-3 to 90 at
omic%, preferably 1 to 80 atomic%,
The optimum range is 10 to 75 atomic%. That is, if we use the representation of a in a-8iaC1-B above, a is preferably 0.1 to 0.99999, more preferably 0.2 to 0.99, and most preferably 0.25 to 0. It is .9.

In the present invention, the second layer (If) is a-(SlbC+
-b) When composed of cHt-0, the second layer (In
The number of carbon atoms contained in is preferably lXl0-'
~90 atomic%, preferably 1~90 atomic%
90 atomic%, optimally 10-80 atom
It is desirable to set it to lc%.

The content of hydrogen atoms is preferably 1 to 40 atoms.
The hydrogen content is preferably 2 to 35 atomic %, most preferably 5 to 30 atomic %, and the photoconductive member formed when the hydrogen content is within these ranges is practical. It is considered to be excellent and can be fully applied.

That is, if expressed as a-(811)C1-b)cH+-c, b is preferably 0.1 to 0.99999, preferably 0.1 to 0.99, and most preferably 0.15~0.
9, C is preferably 0.6 to 0.99, more preferably 0
．． 65 to 0.98, most preferably 0.7 to 0.95.

The second layer (ID is a-(Sl, 1C1-a)e(I(
+X)1-e, the content of carbon atoms contained in the second layer (10 is preferably lX
l O~90 atomlc%s 1~9 for favorable treatment
Q atomic, optimally 10-80 atomic
It is symbolically expressed as c%. )\The content of rodan atoms is preferably 1 to 2 Q atomic %, more preferably l to 1 g atomic %, optimally 2 to 1
It is desirable that the content be 5 atomic %, and the photoconductive member produced when the halogen atom-containing lid is in this range can be sufficiently applied in practice.

The content of hydrogen atoms contained as necessary is preferably 19 atomic% or less, more preferably 13 atomic%.
It is desirable that it be less than mlc%.

That is, the previous a-(81(1C+-4)e(H,X)1-
In the display of d and e, d is preferably 0.1 to 0.
．． 99999, more preferably 0.1-0.99, optimally 0.15-0.9, e preferably 0.8-0.99
, preferably 0.82 to O.99, optimally 0.8
It is desirable that it is 5 to 0.98.

The number range of the layer thickness of the second layer (It) in the present invention is one of the xM 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.

In addition, the layer thickness of the second Im 01) is determined according to the requirements for each layer region, also in relation to the amount of carbon atoms contained in the layer (It) and the layer thickness of the first layer (1). It is necessary to appropriately determine the organic relationship according to the desired characteristics.

In addition, it is desirable to consider the economical aspects including productivity and mass production.

The layer thickness of the second layer in the present invention is preferably 0.0
It is desirable that the thickness be 0.03 to 30μ, more preferably 0.004 to 20μ, and optimally 0.005 to 10μ.

The support used in the present invention may be electrically conductive or electrically insulating. As the conductive support, for example,
N1Cr, stainless steel, AL, Cr.

Me, Au r Nb, Ta, V r T
Examples include metals such as i r Pt r Pd and alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, dU propylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. used. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is made of glass, NiCr is applied to its surface.

) d-, Cr1Mo, Au, Ir, Nb
, Ta, V * Tl + Pt, Pd,
In2O3, 5n02, ITO(In2O5+5
Conductivity can be imparted by providing a thin film consisting of N1Cr, At, Ag, etc., or if it is covered with a synthetic resin film such as a polyester film.
Pb.

Zn, Ni, Au r Cr + Mor
Ir r Nbr Ta + V + Tl, Pt
Thin films of metals such as
Conductivity is imparted to the surface by providing the surface with ivy ring or the like, or by laminating the surface with the metal. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and its shape is determined by r')r'A, for example, in the photoconductive member 100 of FIG. When used as an image-shaped spherical member for electrophotography, it is preferable to use an endless belt-like or cylindrical shape for continuous high-speed copying. The thickness of the support is appropriately determined so as to form the desired light guide structure, but if flexibility is required as a photoconductive member, the function of the support is Anything that is within the range of being emitted will be vomited as thinly as possible. However, in such a case, the thickness is preferably 10 μm or more in view of manufacturing and handling of the support, mechanical strength, etc.

An outline of an example of the method for manufacturing a photoconductive member of the present invention will be briefly described.

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

In the gas cylinders 202 to 206 in the figure, the raw material gas for forming the photoconductive member of the present invention is sealed.
As an example, 202 is Si diluted with He.
F4 gas (purity 99.999%, hereinafter abbreviated as SiF4) cylinder, 203 is GeF4 diluted with He (
99.999% purity, hereinafter abbreviated as GeF4/He) cylinder, 204 is NH5 gas (purity 99.99%, hereinafter NH
(abbreviated as 3)? 205 is 82H diluted with He.
6 gas (purity 99.999%, hereinafter referred to as B2H6/He
206 is f (e gas (purity 99.99)
9%) It is a cylinder.

In order to flow these gases into the reaction chamber 201, make sure that the pulps 2-226 and leak pulp 235 of the gas cylinders 202-206 are closed, and also check that the inflow pulps 212-216 and the outflow pulp 217 are closed. ~221, confirm that the auxiliary pulps 232 and 233 are surrounded,
First, the main pulp 234 is opened to exhaust the reaction chamber 201 and each gas pipe. Next, the vacuum gauge 236 is about 5
When Xi reaches 0 torr, reserve pulp 232
, 233, k exit valve 7'' 217-221 is closed.

Next, as an example of forming a light-receiving layer on the cylindrical substrate 237, pslF4/
He gas, gas cylinder 203, il) GeF4/H
e is gas, gas cylinder 204 is fiNH3 gas, gas cylinder 206 is H2 gas t1 PALZO 222, 223゜22
4.226, outlet pressure dirge 227°228.
The pressure of 229, 231 was adjusted to 1 Kg/crn2, and the inflow pulp 212, 213, 214, 216't - Gradually
Mff, mass flow controller 207;

208, 209, and 211, respectively.

Subsequently, the outflow pulp 217, 218, 219° 221
, the auxiliary pulse f232 is gradually opened to allow each gas to flow into the reaction chamber 201. At this time, S l F4/He gas flow rate, GeF47He gas flow storm, NH5 gas flow rate, and B
2. Adjust the outflow pulp 217, 218, 219, 221 so that the ratio with Adjust the aperture of main pulse f234 while checking the reading. Then, the temperature of the base body 237 is increased by the heating heater 238.
After confirming that the temperature is set at a temperature in the range of 50 to 400 tl, the electric power is set to the desired power to generate a glow discharge in the reaction chamber 201 and discharge it onto the substrate 237. Form the first layer region (G) 'e layer. Completely close all the pulps at the time when the first layer region (G) is formed to the desired layer thickness. SiF4/)Le gas + W 5tHa/le (5tu4 purity 99.999%)
) Instead of a cylinder, 5lH4/1EIe is Sugenpeline, B2H4/He gas ♂ Empeline N C2H41!
By performing the same pulping operation as in the formation of the first layer region (G) using a sponpe line, setting the desired glow discharge conditions, and maintaining the glow discharge for the desired time, the A second layer region (S)' which does not substantially contain germanium atoms can be formed on the layer region (G).

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

In order to form a second Iwi (11)' on the first layer (1) formed to a desired layer thickness as described above, the same pulp as that for forming the first layer (1) is used. Depending on the operation, for example, 5SH4 gas and C2H4 gas may be converted to H as necessary.

This is achieved by diluting the liquid with a diluent gas such as the like and generating a glow discharge according to desired conditions.

The second layer (in order to contain halodane atoms in the mountain, for example, 5lF4 gas and C2H4 gas, or this with SiH2
This is done by adding a gas and forming the second layer (n) in the same manner as above.

Needless to say, all the outflow pulps other than the outflow pulp of the gas necessary for forming each layer are closed, and the gas used for forming the previous layer, except for forming each counterfeit, is inside the reaction chamber 201 and the outflow pulp is closed. From 217 to 221 to reaction chamber 201
In order to avoid remaining in the gas piping leading to the interior, the flow and output pulps 217 to 221 are closed, and the auxiliary pulps 232,
233t-Opening operation An operation of fully opening the main pulp 234 and evacuating the system to a high vacuum is performed as necessary.

The amount of carbon atoms contained in the second layer (II) is, for example, SiH4f! in the case of glow discharge. and C2H4
The ratio of the gas to the lid introduced into the reaction chamber 210 can be changed according to the desired amount, or if the layer is formed using a 9-layer ring, the sputtering area ratio of the silicon wafer and the graphite wafer can be changed when forming the target. Alternatively, it can be controlled as desired by changing the mixing ratio of silicon powder and graphite powder and molding the target. Second layer (contained in the mountains)
- The amount of rodan atoms (X) is determined by adjusting the filling area 1c when a raw material gas for halogen atoms, for example SiF4 gas, is introduced into the reaction chamber 201.

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

Examples will be described below.

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

The concentration distribution of impurity atoms (B or P) in each sample is shown in Figure 42, and the concentration distribution of desired element atoms is shown in Figure 43.
This is shown in Figures A and 43B. The distributed concentration of each atom was controlled by changing the flow rate ratio of each corresponding gas according to a pre-designed change rate line.

Each sample thus obtained was placed in a charging exposure experimental device, corona charged at 15.0 kV for 0.3 see, and immediately irradiated with a light image. For light region 1, a tungsten lung light source was used, and a light intensity of 21 ux-sec was irradiated through a transmission type test chart.

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

When one image of the toner on the photoreceptive layer was transferred onto transfer paper by corona charging at e5.0 kV, each sample had excellent resolution and a clear, high-density image with good gradation reproducibility was obtained.

In the above, the light ff is replaced by an 810 nm GaAa semiconductor laser (10 mW) in place of the tungsten lung.
The image quality of the toner transfer image was evaluated for each sample in the same manner as above, except that the electrostatic image was formed using A clear, high-quality image was obtained.

Example 2 A cylindrical At
Each sample as an electrophotographic image forming member was formed on a substrate under the conditions shown in Table 3 (see Table 4).

The content distribution concentration of impurity atoms in each sample is shown in FIG. 42, and the content distribution concentration of nitrogen atoms is shown in FIG. 44.

When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples provided toner transfer images of good quality. Also, 38C18Q% for each sample)
In the LH environment, a 200,000-time test was conducted, and no deterioration in image quality was observed in any of the samples.

Example 3 A cylindrical AA was produced using the manufacturing apparatus shown in Fig. 41.
Samples (Samples A 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 crab atoms is shown in Figures 43A and 43B.
As shown in Figures 44 and 44.

When each of these samples was subjected to the same image quality evaluation test (1) as in Example 1, all samples gave high quality toner transfer images. Also, for the valley sample, 38℃, 80%R
When a repeated use test was conducted 200,000 times in an environment of f(), no deterioration in image quality was observed in any of the samples.

Example 4 Using the manufacturing apparatus shown in FIG. 41, samples (Samples A 41-1 to 46-16) as electrophotographic image forming members were prepared on a cylindrical substrate under the conditions shown in Table 7. (Table 8).

The flow rate ratio of GeH4 gas during formation of the first layer region (G) is changed according to a pre-designed change rate line to form a layer region (G)' such that the Go distribution concentration shown in FIG. 45 is obtained. ,
In addition, B2H6 gas and P during the formation of the second layer region (S)
A layer region (S)' was formed by changing the flow rate ratio of H5 gas according to a pre-designed change rate line so as to have the impurity distribution concentration shown in FIG.

Further, the flow rate ratio of NH31f gas during the formation of the first layer region (G) was changed according to a pre-designed rate of change line to form the 43rd layer region (G).
The first layer region (G) was formed so as to have the N distribution concentration shown in Figures A and 43B.

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

Example 5 Using the manufacturing apparatus shown in FIG. 41, an electrophotographic image forming member was produced on a cylindrical M substrate under the conditions shown in Table 9 by controlling the valley gas flow ratio in the same manner as in Example 1. Samples (Samples A61-1 to 56-12) were prepared as (No. 10).
.

The concentration distribution of impurity atoms in each sample is shown in FIG. 42, the concentration distribution of chamber atoms is shown in FIG. 44, and the distribution concentration of germanium atoms is shown in FIG. 45.

When each of these samples was subjected to the same artist evaluation test as in Example 1, all samples gave high quality toner transfer image preservation. In addition, each sample was heated at 38°C and 80°C.
When a repeated use test of 200,000 times was performed on the change in %RH, no deterioration in image quality was observed in any of the samples.

Example 6 Shown in Figure 41! ! ! Samples (sample 7ilL61-1 to 610-610-1) were prepared as image forming members for electrophotography by controlling the flow rate ratio of each gas in the same manner as in Example 1 under the conditions shown in Table 11 on a cylindrical A4 substrate using a manufacturing device. 13) All were prepared (Table 12).

The content distribution of impurity atoms in each sample is shown in Fig. 42, and the content distribution of desired element atoms is shown in Fig. 43A and 43i.
3 and 44, and the content distribution of 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, 3B℃, 80%R
When a repeated use test of 200,000 times was carried out on H's circular inspection, no deterioration in quality was observed in any of the samples.

Example 7 Second layer (sample Jlh 11-1 + 12 of Example 1 except that the conditions for creating IQ were as shown in Table 13)
-1 According to the same conditions as +13-1 and method 11@, each of the true-use forming members (sample conditions 11-1-1~
11-1-8.12-1-1 to 12-1-8.13-1
-1 to 13-1-8) were created.

Thus obtained /4'rl! The image forming members for child photographs were individually installed in a copying machine, and the transferred images were obtained for each image forming member for Hiroko photographs corresponding to each example under the same conditions as described in each example. We evaluated the overall image quality and the durability after repeated continuous use.

Table 14 shows the results of the overall image quality evaluation of the transferred image of each sample and the evaluation of durability after repeated and continuous use.

Example 8 The second layer ([1] except that the target area ratio of silicon atoms and graphite was changed and the content ratio of silicon atoms and carbon atoms in the second layer (II) was changed. , and image forming parts were prepared in exactly the same manner as in Sample Al1-2 of Example 1.

Each of the imaging members thus obtained was subjected to approximately 5 cycles of grading, development, and cleaning as described in Example 1.
After repeating the process 10,000 times, image evaluation was performed and the results shown in Table 15 were obtained.

Example 9 When forming the second layer (100 layers, 5it (4 gas and C2H)
Image formation was performed in exactly the same manner as in Sample A 11-3 of Example 1, except that the content ratio of silicon atoms and carbon atoms in the second layer (II) was changed by changing the flow rate ratio of the 4 gases. Each member was created.

After repeating the steps up to transfer approximately 50,000 times using the method described in Example 1 for each acid-forming member thus assembled, image evaluation was performed, and the results shown in Table 16 were obtained.

Example 10 When forming the second layer (IQ layer), 5iI (a gas, 5lF
4 gas, C2j (exactly the same as sample Jii 11-4 of Example 1 except that the starvation ratio of the 4 gases was changed and the content ratio of silicon atoms and carbon atoms in the second j so (II) was changed. The image forming member and the member were each created by the same method.For each of the image forming members thus obtained, the image forming and cleaning steps described in Example 1v were repeated approximately 50,000 times. After that, image evaluation was performed, and the results shown in Table 17 were obtained.

Example 11 Image shapes h1 and 0 were created in exactly the same manner as for sample Al1-5 of Example 1, except that the second layer (ID layer #Lt) was changed. The steps of cultivating seedlings, developing, and cleaning were repeated to obtain the results shown in Table 18.

Common layer forming conditions in the Examples of the present invention shown in Table 14 and Table 18 are shown below.

Substrate temperature: Dalmanium atom (Ge)-containing layer... approx. 200°C Germanium atom (Ge) non-containing layer...
・・About 2500 Discharge frequency: l 3.55 MHz Reaction chamber pressure during reaction: 0.3 Torr

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the light guide member of the present invention, and FIGS. 2 to 10 show the distribution state of damanium atoms in the first layer region (G), respectively. 11 to 24 are explanatory diagrams for explaining the first layer C.
25 to 40 are explanatory diagrams for explaining the distribution state of nitrogen atoms, respectively, and FIG. 41 is a schematic explanatory diagram of the apparatus used in the present invention. 42, 43A, 43B, 44, and 45 are explanatory views showing the distribution 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 (II) 107... Photoreceptor no-111-C C -----→-C C -1111 〇-11111 C(PN) -C(PN) -C(PN) 11◆C(PN) □C(PN>C(PN) 11111 C(PN) - C(PN) C(PN) C(PN) 11111伽C(PN ) -C(PN) -(,(PN) C(N) C(N) -C(N) -G( N) -C(N) C(~)

Claims (1)

[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. A second layer region (S) exhibiting photoconductivity is provided in order from the support side, and has a nine-layered first layer and a second layer made of an amorphous material containing silicon atoms and carbon atoms. The first layer contains a substance (C) that contains nitrogen atoms and controls conductivity, and the maximum distribution concentration in the layer thickness direction is in the second layer region. A photoconductive member characterized in that (S) is contained in the reed and in the second layer region (S), 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 dalmanium atoms in the first layer region CG) 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 halodan atoms. (7) The photoconductive member according to claim 2, wherein the distribution state of germanium atoms in the m10 layer region (G) is such that more germanium atoms are distributed toward the support side. (8) The photoconductive member according to claim 1, wherein the substance (C) that controls conductivity is an atom belonging to Group Ⅰ of the periodic table. (9) The photoconductive member according to claim 1, wherein the substance (C) that controls conductivity is an atom belonging to Group Ⅰ of the periodic table.