JPS60140262A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain good and stable electrical, optical and photoconductive characteristics, good photosensitive characteristic on a long wavelength side and excellent mechanical strength and durability by providing a photoreceptive layer having the specific layer constitution consisting of a-SiGe(H, X) on a base. CONSTITUTION:A photoconductive member has a base 101 and a photoreceptive layer 107 consisting of the 1st layer 102 of the layer constitution provided with the 1st layer region G103 constituted of an amorphous material contg. a Ge atom thereon and the 2nd layer region S104 constituted of an amorphous material contg. an Si atom and having photoconductivity successively from the base 101s side and the 2nd layer 105 constituted of an amorphous material contg. an Si atom and O atom. An N atom is incorporated into the 1st layer 104 and a material governing conductivity is incorporated therein in such a way that the max. value of the distributed concn. in the layer thickness direction exists in the region S104 and is distributed much on the base 101 side in the region S104. If the layer 107 having such layer constitution is provided, the electrical, optical and photoconductive characteristics, electrical withstand voltage characteristic and using environment characteristics are improved and the image having high density and high quality is stably and repeatedly obtainable.

Description

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

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

As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive and has a low signal-to-noise ratio [photocurrent (Ip
)/dark current (Id)), has absorption spectral characteristics that match the spectral characteristics of the electromagnetic waves to be irradiated, has fast photoresponsivity, and has a desired dark resistance value.
Solid-state imaging devices are required to have characteristics such as being harmless to the human body during use and being able to easily process afterimages within a predetermined time. Particularly, in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus (7) used in an office as a business machine, the above-mentioned harmlessness during use is an important point.

Based on these points, amorphous silicon (hereinafter referred to as a-81) is a photoconductive material that has recently attracted attention.
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

However, the conventional photoconductive member having a photoconductive layer composed of A-81 has poor electrical, optical, and photoconductive properties such as lucid resistance and one-way photosensitivity, and moisture resistance. The reality is that there are points that can be further improved, such as the need to improve overall characteristics in terms of usage environment characteristics and also in terms of stability over time.

For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use, and this type of When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speeds, the response gradually decreases, etc. This often occurred.

Furthermore, a-81 has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, making it difficult to match with semiconductor lasers currently in practical use. Furthermore, when using commonly used halogen lamps and fluorescent lamps as light sources, there is still room for improvement in that they do not effectively use light on the long wavelength side. There is.

Also, if the light irradiated with L1 is not absorbed sufficiently in the photoconductive layer and the negative light reaching the support increases, the support itself becomes the light guide 1! If the reflectance of the light passing through the layer is high, interference due to multiple reflections will occur in the photoconductive I-tube, resulting in E)! This is one of the factors that causes the "jaggedness" of the ll image.

In order to increase the resolution, the influence of radiation becomes larger as the irradiation spot () is made smaller, and this becomes a big problem, especially when a semiconductor laser is used as the light source.

Furthermore, when forming a photoconductive layer using an a-8i material, in order to improve its electrical and photoconductive properties, hydrogen atoms, fluorine atoms, salt purple atoms, and other hydrogen atoms, as well as electrical Boron atoms, phosphorus atoms, etc. are contained in the photoconductive shell as constituent atoms to control the conduction type, and other atoms are contained in the photoconductive shell to improve the properties. Depending on how it is contained, problems may arise in the electrical or photoconductive properties of the formed layer.

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

Therefore, while efforts are being made to improve the properties of the a-Si 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-mentioned points, and is characterized by the applicability and applicability of A-8L as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive research and consideration from this perspective, we have discovered an amorphous material that uses silicon atoms as its base material and contains at least either hydrogen atoms (H) or NO10 atoms, so-called hydrogenated amorphous silicon, NO10 atoms. hydrogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as [a]
-81 (H, Conductive materials are not just simple materials that exhibit outstanding practical properties;
It is superior in all respects to conventional photoconductive materials, and has particularly excellent properties as a photoconductive material for electrophotography, as well as absorption spectrum characteristics on the long wavelength side. It is based on the points that have been found to be superior to

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 that is extremely durable, does not exhibit any deterioration phenomenon even after repeated use, and has no or almost no residual potential observed.

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

Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having sufficient performance.

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

Yet another object of the present invention is high photosensitivity.

The present invention also aims to provide a photoconductive member having high signal-to-noise ratio characteristics.

The photoconductive member of the present invention includes a support for the photoconductive member, a first layer region O) made of an amorphous material containing germanium atoms, and an amorphous material containing silicon atoms on the support. a photoreceptive layer comprising photoconductive atoms and a second layer composed of an amorphous material containing photoconductive atoms, the first layer containing photoconductive atoms and a photoconductive layer; The substance (C) for controlling properties is contained in a layer in which the maximum value of the distribution U degrees in the layer thickness direction is in the second layer region (8) and in the 20th layer region (S), on the support side. It is characterized by the fact that it is contained in a state where it is mostly distributed in the opposite direction.

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, particularly excellent matching with semiconductor radar, and fast photoresponse.

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

Figure 1 is a schematic configuration diagram schematically shown to explain the layer configuration of the photoconductive member of the present invention.

The photoconductive member 100 shown in FIG. 1 has a photoreceptor N107 consisting of a first Jilt (l) 102 and a second layer (n) 105 on a support 101 for the photoconductive member. , the light-receiving layer 107 has a free surface 106 on one end surface.

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

An amorphous material containing at least one of a hydrogen atom (b) and a halogen atom (g) (hereinafter referred to as ja-Ge(Si, H, X)
A first layer region (G) composed of (abbreviated as J) 10
3 and a-8t(H,X) and a second layer region (S) 104 having photoconductivity are laminated in this order.

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

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

In addition, if the distribution state of germanium atoms in the first layer region (G) is non-uniform in the layer thickness direction, the distribution concentration C in the layer thickness direction may be changed to the support side or the second layer region. (S
) Gradually towards the side or Ste.

It is desirable to change it linearly or linearly.

In particular, the distribution state of germanium atoms in the first layer region (b) is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration of germanium atoms in the layer thickness direction C (G
) decreases from the support side toward the second layer region (S), the difference between the first layer region (G) and the second layer region (S) The second layer region (S) when a semiconductor radar or the like is used, has excellent affinity, and by extremely increasing the distribution concentration C of germanium atoms at the end of the support 111 as described later. In the first layer region (G), the long wavelength 11i light that is hardly absorbed can be substantially completely absorbed in the first layer region (G), and interference due to reflection from the support surface can be prevented. At the same time, reflection at the interface between the single layer region (G) and the layer region (S) can be sufficiently suppressed.

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

2 to 10, the horizontal axis represents the distribution concentration C of dalmanium atoms, the vertical @ represents the layer thickness of the first layer region (G), and tB 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, in the first layer region (G) containing germanium atoms, the layer formation appears from tJll+ toward the 1T side.

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

In the example shown in FIG. 2, the interface position 1Δt! where the surface where the layer region (G) of &) 1 containing the relmanicum atoms is formed and the surface of the first layer region (G) are in contact with each other. lyosi1
, the distribution of germanium atoms is once C(G)
is contained in the first 1 m region (G) where germanium atoms are formed, and gradually and continuously decreases from position t1 to limit C2 to interface position t, while taking a constant value where 0 overlaps. has been done. At the interface position 1T, the distribution concentration C of germanium atoms is 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 position tB to position t7, and reaches the concentration Cs at position tT. It forms a distribution state.

In the case of FIG. 4, from position 1B to position t! Until now, the distribution concentration Mlc of germanium atoms was kept at a constant value iJ degrees c6, and gradually and continuously decreased between the position t2 and the positions IN and tT, and at the position t, the distribution concentration C became substantially It is assumed that the amount is zero (substantially zero here means that the amount is less than the detection limit).

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

In the example shown in FIG. 6, the distribution by-product C of germanium atoms is a constant concentration C- between the positions tB and t3, and the concentration CI+) at the position tT. Between position @t s and position t7, the distribution concentration C is linearly linearly distributed at position 1. It has been reduced to almost inversion RtT.

In the example shown in FIG. 7, the distribution concentration C is at the level RtB
A constant value of the concentration CU is maintained until the position t4.
Concentration el up to 1T position! The distribution state decreases in a linear function up to the concentration C1l.

In the example shown in FIG. 8, the distribution concentration C of germanium atoms from the position tII to the multi-position 1T is the concentration C14.
It decreases in a linear manner, virtually reaching zero.

In FIG. 9, position t! From l to position ts, the distribution change C of germanium atoms decreases linearly with the slope C15t from the concentration CIS, and the position lit t s
An example is shown in which the concentration CXS is kept at a constant value between and the position tT.

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is at the intensity Ctt at the position tll, and at first it gradually decreases from the concentration C1t until it reaches the position ML t s. The concentration decreases rapidly near the position , and the concentration becomes C at the position ta.

Position t6 and position 1. At first, the concentration is rapidly decreased, and then slowly and gradually decreased until the concentration C1l at position t1 and eL is gradually decreased extremely slowly between position t7 and position t. Concentration C at t$
leading to poetry. Between position ts and position 1T, the concentration C
, is reduced according to a curve shaped as shown in the figure so as to become more substantially zero.

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 portion with a high distribution concentration C of germanium atoms, and on the interface tT side, the distribution concentration C is high.
1i A distribution of germanium atoms is provided in the first layer region (G) with a portion that is considerably lower than that on the side of the support.

The first layer region @1 constituting the first layer (1) constituting the photoconductive member in the present invention preferably contains germanium atoms at a relatively high concentration on the support side as described above. It is desirable to have a localized area (4) that is

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

In the present invention, the localized region (4) is located at the interface position t
It may be the entire layer region (LT) up to 5μ thick, or it may be a part of the layer region (1, T).

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

As for the distribution state of the germanium atoms contained in the localized region in the layer thickness direction, the maximum value Cma of the distribution concentration of the germanium atoms is preferably 1000 atomjc ppm or more with respect to the sum of the germanium atoms and the silicon atoms. It is desirable that the layer be formed so as to achieve a distribution state of preferably 5000 atomic ppm or more, most preferably I X 1 'O' atomic ppm or more.

That is, in the present invention, the first layer region (2) containing germanium atoms has a maximum distribution concentration cm within 5 μm in layer thickness from the support side (region # from 1 to 5 μm thick).
It is preferable that it be formed so that hx exists.

In the present invention, the content of germanium atoms contained in the first layer region (Q) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 10 X 10'atomie ppm%, more preferably 100 to 9.5 X 105atom1e
ppm.

Optimally 500-8 X 105 atomic ppm
It is desirable that this is done.

In the present invention, the layer thickness of the first layer region 4 and the second layer region (S) is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the photoconductive member to ensure that the desired properties are fully imparted to the photoconductive member.

In the present invention, the layer thickness T1 of the first layer region (2) is preferably aol to 50μ, more preferably 40X to 40μ.
It is desirable that μ is optimally set to 501 to 30 μ.

Further, the layer thickness T of the second layer region (S) is preferably 0.5
~90μ, more preferably 1-80μ, optimally 2-5
It is desirable that the value be 0μ.

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

In the photoconductive member of the present invention, the numerical range of (T, 10T) is preferably 1 to 100μ, more preferably 1 to 80μ, and most preferably 2 to 50μ. desirable.

In a highly preferred embodiment of the present invention, the above layer thickness Tll and layer thickness T are preferably T, /T≦1
When satisfying the following relationship, it is desirable to select appropriate numerical values for each of them.

In selecting the numerical values of layer thickness TB and layer thickness T in the above case, preferably TB/T≦0.9, optimally T
The relationship ll/T≦0.8 is satisfied. 5. Layer thickness T.

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 I x 10 atoms
ppm or more, the layer thickness T of the first layer region (G)
It is desirable that B be as thin as possible, preferably 30μ or less, more preferably 25μ or less, optimally 20μ or less.
It is desirable that it be less than μ.

In the present invention, the halogen atoms (3) contained as necessary in the first layer region (G) and/or second layer region (S) constituting the first layer (1) include: Specifically, 7. Examples include fluorine, chlorine, bromine, and iodine, especially fluorine,
Chlorine may be mentioned as suitable.

In the present invention, to form the first layer region (G) composed of a-Go (Si, H, X), a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion grating method is used. It is made by a vacuum deposition method. For example, a-Go(81
, H, (Source gas for supplying 81 that can supply sB, raw material gas for introducing hydrogen atoms (b) or/and halogen atoms (3
) A raw material gas for introduction is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the nucleus deposition chamber, and a predetermined support member that has been set at a predetermined position in advance is It is fine if a layer is formed on the surface. In order to non-uniformly distribute germanium atoms, the distribution concentration C of the contained germanium atoms is controlled according to a desired rate of change curve.
A layer consisting of -Go(81,H,X) may be formed.

In addition, when forming by sputtering method, for example, Ar
, In an atmosphere of an inert gas such as He or a mixed gas based on these gases, use a target made of St, a target made of G, or two targets made of the target and Go. or using a mixed target of Sl and Go, if necessary, a raw material gas for supplying Ge diluted with a diluent gas such as He or Ar, or S1
The raw material gas for supply is converted into hydrogen atoms α◇ or / as necessary.
A gas for introducing a halogen atom flash is introduced into a deposition chamber for sputtering to form a desired gas atmosphere, and a gas flow section for the source gas for supplying Ge and/or the source gas for supplying Si is introduced. The target may be sputtered while being controlled according to a desired rate of change curve.

In the case of the ion silating method, for example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition date as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam method. This can be carried out in the same manner as in the sputtering method except that the evaporated material is heated and evaporated by (FB method) or the like and the flying evaporated material is passed through a desired gas plasma atmosphere.

Substances that can be used as raw material gas for supplying Si used in the present invention include SiH4, Si□H6, Si3H8
゜5i4H,. Silicon hydride (silanes) in a gaseous state or which can be gasified, such as SiH4, etc., can be effectively used. 812H6 is preferred.

GeH is a substance that can be used as the raw material gas for supplying Ge.
a lGa2H61Go, H81Ge4H1o + G
e5H12e Ge6H14 Ge 7 Hlb +
Germanium hydride in a gaseous state or that can be gasified, such as Ge a H4s * Ge 9 ) 12o, can be effectively used, especially because of its ease of handling during layer creation work, good Ge supply efficiency, etc. In terms of GeH4+Ge
Preferable examples include 2H6, Ge, and H8.

Many halogen compounds are effective as the raw material gas for the 41 halogen atoms used in the present invention, such as d halogen gas, halides, halide intergun compounds, silane derivatives substituted with octalogones, etc. Gaseous or gasifiable halogen compounds are preferably mentioned.

Furthermore, 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.

Examples of halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, C1F + CJF3 * BrF
5 *BrF, , IF, , IF, , ICt
, IBr, and other interhalogen compounds.

Specifically, as a silicon compound containing a halogen atom, so-called a silane derivative substituted with a halogen atom, for example, 5
iF4e Si2F6. SiC Noa * 5iBra
Silicon halides such as the following are preferred.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using silicon compounds containing various halogen atoms, hydrogenation as a raw material gas capable of supplying Si together with a raw material gas for supplying Ge is necessary. a-5IGo containing halogen atoms on a desired support without using silicon gas
A tenth layer region (G) consisting of the following can be formed.

According to the glow discharge method, when creating the R region (0) of turtle 1 containing halogen atoms, basically, for example, silicon halide, which becomes the raw material gas for supplying St, and hydrogenated silicon, which becomes the raw material gas for supplying Ge. Germanium and Ar e 12 +
)le and other gases are introduced into the deposition chamber forming the first layer region (Q) at a predetermined mixing ratio and gas flow pattern,
The first layer region (G) can be formed on a desired support by generating a glow discharge and forming a plasma atmosphere of these gases, but it is possible to control the introduction ratio of hydrogen atoms. In order to make the measurement even easier, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer.

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

In both the sputtering method and the ion silating method, in order to introduce NO-logon atoms into the formed layer, a gas of the aforementioned NO-logne compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. The gas may be introduced into the atmosphere to form a plasma atmosphere of the gas.

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

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, )(F, HC), Hydrogen halides such as HBr, HI, 5IH2F2.5iH2I2.5iH
2CJ2゜5IHCノ, , 5IH2Br2.5iH
Halogen such as Br5 fj4. silicon hydride, and GeH
F, , Gel12F2 t GeH,5F1 ,
GeHCノ.

GeH2C12+ Ge1 (5C), GeHBr3 +
GeH2C12* GeHBr3GeHI3. Gs
Hydrogenated germanium halides such as H212, GeH3I, halides containing hydrogen atoms as one of their constituent elements, Ge14m, GeC, GeBr4. Ge
I4.

GeF2, GaCno2, GeBr2. Ge1
Gaseous or gasifiable substances such as germanium halides such as 2, etc. may also be mentioned as useful starting materials for forming the first layer region (Q).

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

In order to introduce hydrogen atoms into the first layer region (G) in a barrel-like manner, in addition to the above, H2 or silicon hydride such as 5iH4e 812H6゜513H8,5i4H,o is added to germanium for supplying Go. Or a germanium compound, or GeH4* Ge2H61Ge5f (B t ”4
Hj01 Ge5H12+G@6H44+G@yH16
This can also be achieved by causing germanium hydride such as 1GesH1B1Ge2H61 and silicon or a silicon compound for supplying St to coexist in the deposition chamber to generate discharge.

In a preferred embodiment of the present invention, the amount of hydrogen atoms (3) or the amount of halogen atoms (3) contained in the 8g1 layer area (G) of the photoconductive member to be formed, or the amount of hydrogen atoms and halogen atoms (3) The sum (H+X) is preferably 0, 01 to 4
0 atomic%, more preferably 0.05-30at
omla'L optimally 0.1-25 atomic%
It is desirable that this is done.

In order to control the amount of hydrogen atoms (b) and/or halogen atoms (g) contained in the first layer region (b), for example, the support temperature or/and hydrogen atoms α◇ or halogen atoms ( It is sufficient to control the amount of the starting material used to contain (g) into the deposition system, the discharge power, etc.

In the photoconductive member of the present invention, the second layer region (S) that does not contain germanium atoms and the first layer region (B) that contains germanium atoms contain a substance (Q) that controls conduction properties. By containing , the conductive properties of the J6 region (S) and the layer region (G) can be arbitrarily controlled as desired.

At this time, the substance (Q) contained in the second layer region (S)
may be contained in the entire layer region (G) or 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 (0) provided in the second layer region (S) is provided as the entire layer region of the second layer region (8), but also It is provided as a support side end layer region (BE) as a part of the region (S).When it is provided as a full layer region of the former, its distribution degree C(s) is directed toward the support side, It is provided so as to increase linearly, stepwise, or curvedly.

When the distribution concentration C(s) increases in a curved manner, it is desirable to provide a substance (C) for controlling conductivity in the layer region (S) so that the conductivity increases monotonically toward the support.

When the layer region (SPN) is provided as a part of the second layer region (S), the distribution state of the substance (0) in the layer region (SPN) is in the plane parallel to the surface of the support. Although it is assumed to be uniform in the inward direction, it may be uniform or non-uniform in the layer thickness direction.In this case, in the layer region (SPN), the material (0 In order to provide such a distribution, it is desirable to provide the same distributed concentration as in the case of providing in the entire layer region of the first layer region (S).

When the layer region (G) of @1 contains a substance (Q) that controls conductivity to provide a layer region (GPN) containing the substance (C), a layer region (GPN) containing the substance (C) is provided in the second layer region (S). This can be done in the same way as when providing a region (SPN).

In the present invention, when both the first layer region (G) and the second layer region (S) contain a substance (0) that controls conduction characteristics, the substance (0) contained in both layer regions is 04 They may be of the same species or may be of different species.

However, when both layer regions contain the same kind of conductivity controlling substance (0), the maximum distribution concentration of the substance (C) in the layer thickness direction is in the second layer region (S). There is, that is, the second
It is preferable to provide it so as to fall inside the layer region (S) or at the interface with the first layer region (G).

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

In the present invention, as described above, the first layer (1) contains a substance (0) that controls conduction characteristics, and the layer region (PN) containing the substance (Q) is It is preferably provided as the support side end layer region (sg) of the second layer region (S) so as to occupy at least a part of the layer region (S).

When the layer region (PN) is provided so as to span both the first layer region (B) and the second layer region (S), a substance that controls conduction characteristics (the layer region (GPN) of There is C(a)max between the maximum distribution lead degree C(0)max in the layer region (SPN) and the maximum distribution lead degree C(s)max in the layer region (SPN).
The substance (
b) is contained in the first layer 0).

A substance (0) that controls conductivity contained in the layer region (PN)
Examples of impurities include so-called impurities in the semiconductor field, and in the present invention, p-type impurities give St or Go p-type conductivity, and n-type impurities give n-type conductivity. Type impurities can be mentioned.

Specifically, p-type impurities include atoms belonging to group 1 of the periodic table (group m atoms), such as B (boron) and A (
Among them, B and Ga are 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) and 1A8 (arsenic).

Sb (antimony), Bi (bismuth), etc. are used, and P and As are particularly preferably used.

In the present invention, a substance that controls the conduction properties contained in the layer region (PN) provided in the first layer (1) (the content is the conduction properties required for the layer region (PN), Or, the relationship with the characteristics at the contact interface with the support or other layer region that the R region (PN) is provided in direct contact with, etc.
This can be achieved by making appropriate selections based on organic relationships. 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 layer are also taken into consideration, and a substance (containing Q) that controls conduction characteristics is selected. The amount is selected accordingly.

In the present invention, the content of the substance (C) that controls conduction properties contained in the layer region (PN) is preferably 0.01 to 5 x 10' atoms ppm, more preferably 0.5～I XI O' atomlc p
pm, optimally 1-5X10'atomic ppm
It is desirable that this is done.

In the present invention, a layer region (PN) containing a substance (Q) that controls conduction properties is placed in contact with a contact interface between a first layer region (G) and a second layer region (S), or a layer region ( PN) occupies at least a part of the first layer region (G), and the content of the substance (PN) in the layer region (PN) is preferably 30 atomic ppm or more, more preferably More than 50 atomic ppm, optimally
f 100 atoms 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, the second It is possible to effectively block the movement of electrons injected into the layer region (S), and when the substance to be contained is the n-type impurity, the free surface of the photoreceptive layer has e-polarization. When subjected to charging treatment, the movement of holes injected from the support side into the second layer region (S) can be effectively prevented.゛In such a case, the layer/region (Z) in the portion excluding the layer region (PN) under the above-mentioned basic structure of the present invention has conductive properties contained in the layer region (PN). It is also possible to contain a substance that governs conduction properties with a polarity different from that of the substance that governs it, or a substance that governs conduction properties with the same polarity as the polarity of the substance that is contained in the layer region (PN). It may be contained in an amount much smaller than the amount of .

In such a case, the content of the substance controlling the conductive properties contained in the layer region (Z) is
) is determined as desired depending on the polarity of the substance contained in the substance and the natural landscape, but preferably o,
It is desirable that the amount is 0.00 to 1000 atomic ppm, more preferably 0.05 to 500 atomic ppm, and optimally 0.1 to 200 atomic ppm.

In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance governing conductivity, the content in the layer region (Z) is preferably 130a.
It is desirable that the amount be less than tomic ppm.

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. A so-called depletion layer can also be provided in the contact region. That is, for example, in the 10th layer (), the layer region containing the pm impurity and the layer region containing the n-type impurity are provided so as to be in direct contact with each other to create a so-called p-nm coupling. A depletion layer can be provided by forming a depletion layer.

FIGS. 11 to 24 show typical examples of the distribution state of the substance (0) in the layer thickness direction that controls the conduction characteristics contained in the first layer.

In the diagram, the horizontal axis shows the distribution concentration C (PH) of the substance (C) in the layer thickness direction, and the vertical axis shows the layer thickness t from the support side of the light-receiving layer. t6iL indicates the position of the contact interface between layer region (G) and layer region (S).

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

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

In the example shown in FIG. 11, the substance (0) is not contained in the first layer region (G), but is contained only in the second layer region (S) with a constant distribution of moldiness at a concentration C1. ing.

That is, the second layer region (S) is to and 1. The substance (C) is contained in the end layer region between the two at a constant distributed concentration with a concentration C1.

In the example of FIG. 12, the second layer region (S) contains a substance (C
) is contained without any scratches, but the first layer region (6)
does not contain the substance (Q).

The substance (0 is 1) is contained in the layer region between 1 and t2 at a constant concentration with a distribution concentration of C, and to and t.

In the layer region between, C3 is contained at a constant concentration of C3, which is much lower than C3.

With such a distribution concentration C(PN), the substance (0 is the first 0M (1
) in the 20th waste region (S) constituting the
To effectively prevent the charge injected from the first layer region (b) to the second layer region (S) from moving toward the surface, and at the same time improve photosensitivity and dark resistance. I can do it.

In the example of FIG. 13, the substance (C) is contained in the second layer region (S) without any scratches, but the concentration decreases monotonically in the upper surface direction from C4 at t to t. The substance (C) is contained in a state in which the distribution concentration C (PM) is changing so that the concentration becomes 0 at the same time. The first layer region (6) does not contain any substance (0).

In the case of the example shown in FIGS. 14 and 15, the substance (0) is unevenly contained in the lower end layer region of the layer region (S) of @2. In the case of the example shown in Figure 15, the second layer region (S) consists of a layer region containing the substance (Q) and a layer region not containing the substance (0), which are laminated in this order from the support side. It has a layered structure.

The difference between the examples in FIGS. 14 and 15 is that in the case of FIG. 14, the distribution degree C(PN) is 1. Between to and t3, the function Cs at the position of to decreases monotonically to 0 at the position of t3, whereas in the case of Fig. 15, between to and 14, Concentration C6 at position to
This means that the concentration decreases linearly and continuously by 4 degrees until the concentration reaches 0 at the position t4. Also in the examples shown in FIGS. 14 and 15, the first layer region (G) does not contain the substance (C).

In the examples shown in FIGS. 16 to 24, a case is shown in which a substance (Q) that controls conductivity is contained in both the first rfI region (G) and the second layer region (S). It will be done.

In the case of the examples shown in FIGS. 16 to 22, the second layer region (S
) is the layer region containing the substance (C) and the layer region containing the substance (0
They commonly have a two-layer structure in which the layer region that does not contain is layered in this order from the support side. In the examples shown in FIGS. 17 to 21, the distribution state of the object 'J(('10) in the first layer region (G) is different from that in the second layer region (S). interface position t.

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

In the case of the examples shown in FIGS. 23 and 24, the entire photoreceptive layer @
The substance (C) is contained in the layer thickness direction over the entire area without any scratches.

In addition, in the case of FIG. 23, in the first layer region (G), IAfects at tll increases linearly from tIl to C23 at to, and the second layer region (G) increases linearly from tIl toward to. In the layer region (S), once C in to
The concentration decreases monotonically and continuously from n to 0 at tT (from 1 to 1T).

In the case of FIG. 24, in the layer region between t14 and t14, the substance (Q is contained in a constant distribution concentration of Cu, and t1
In the layer region between 4 and tT, the concentration C decreases linearly with respect to tT and reaches 0 at tT.

11 to 24, the distribution concentration C (PM
) As explained above, in all examples, the maximum distribution concentration of the substance (0) is in the second layer region (
As in S), the substance (0) is contained in the photoreceptive layer.

In the present invention, the second
To form the layer region (S), a starting material (1) for forming the 10th layer region (G), excluding the starting material for the raw material gas for supplying Go, is used. It can be carried out using the starting material (■) for forming the second layer region (S) and according to the same method and conditions as in the case of forming the first layer region (G).

That is, in the present invention, a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion grating method is used to form the second layer region (S) composed of a-ss(u+x). It is made by vacuum deposition method.

For example, by the 1g p-discharge method, a −S l (H*
In order to form the second layer region (S) composed of the silicon atoms (
◇A raw material gas for introduction and/or introduction of halogen atoms is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber. A layer consisting of a-8t(H,X) may be formed on the supporting surface of. In addition, when forming by sputtering method, for example, S is formed in an atmosphere of an inert gas such as Ar or H@, or a mixed gas containing these gases as a base.
When sputtering a target composed of t, a gas for introducing hydrogen atoms (I) and/or halogen atoms (3) may be introduced into the deposition chamber for sputtering.

In the present invention, the amount of hydrogen atoms (b) contained in the second layer region (S) constituting the first layer (1) to be formed, or the amount of halogen atoms (3), or The sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 1 to 40 a
tomle % + more preferably 5 to 3 oatomlc
It is desirable that e161 is optimally set at 5 to 25 atomfc.

A substance (C) that controls conduction properties, for example, a group atom or a group V atom, is structurally introduced into the layer region constituting the first layer (1) to contain the substance (C). In order to form a layer region (PN) in which a first layer is formed, a starting material for introducing atoms of the uSm group or a starting material for introducing atoms of group Ⅰ is added in a gaseous state to a deposition chamber during layer formation. It may be introduced together with other starting materials for forming (1). Possible starting materials for introducing such group-group atoms include ′-
It is desirable to use a material that is gaseous at room temperature and pressure, or at least can be easily gasified under layer-forming conditions. As a starting material for introducing such a group atom, specifically, for introducing a boron atom, B2) f6. B4H1o, B
5117. B5H11゜B6I■101 B6H12
Boron hydride such as 1B6I114, BF, , BCi,
.

Examples include boron halides such as BBr3.

In addition, AJCJIs r GaCnos, ca(c
Hs)x I InCl, , T1Cl, etc. can also be mentioned.

In the present invention, effective starting materials for the introduction of Group V atoms include PH5 for the introduction of phosphorus atoms.
*Hydrogen ratios such as P2H4, PH4I, PF3゜P
F5. PC! , , pc! , , PBr, ,
PBr3. Examples include phosphorus oxides such as PI and the like. In addition, Ash3+ AsF3.

AsCノ, , AgBr3 , A4F5 , SbH3, S
bF3, SbF5, SbCノ.

sbc! , l BIH,, BiCnos + BIBr
It can be mentioned as an effective starting material for introducing Group Ⅰ atoms such as a.

In the photoconductive member of the present invention, the first layer (1 ) contains nitrogen atoms. The nitrogen atoms contained in the first layer (1) are
It may be contained in the entire layer area of the first layer (1) without any scratches, or it may be contained in only a part of the layer area of the first layer (1) and unevenly distributed.

Further, the distribution state of the nine element atoms may be uniform or non-uniform in the layer thickness direction of the first layer (1) once the distribution C(N) is in the thickness direction of the first layer (1).

In the present invention, when the main purpose of the layer region (c) containing nitrogen atoms provided in the first layer (1) is to improve photosensitivity and dark resistance, the layer region (c) provided in the first layer (1) is (j) is provided so as to occupy the entire layer area, and strengthens the adhesion between the support and the first layer (1) or the first layer area (b) and the second layer area (S). In the case where the main purpose is to measure, the layer is provided so as to occupy the end layer region of the first layer (1) on the side of the support or the region near the interface between the first and second layer regions.

In the former case, the content of nitrogen atoms in the layer region is made relatively small in order to maintain high photosensitivity, and in the latter case, the content of nitrogen atoms in the layer region is made relatively small to ensure that the adhesion between the layers is strengthened. Therefore, it is desirable to have a relatively large amount.

Also, for the purpose of achieving both the former and the latter at the same time,
The first layer (
1) Nitrogen is distributed at a relatively low concentration on the free surface side, or nitrogen atoms are not actively contained in the interface layer region on the free surface side of the first layer (1). What is necessary is to form a distribution state of atoms in the layer region.

Furthermore, if 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), silk 1 layer area (6)
Nitrogen atoms are highly distributed at the end of the support, or the first
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 distribution of nitrogen atoms in the entire first layer (1).

tll is the position of the end surface of the first layer (1) on the support side, t
T indicates the position of the end face of the 10th layer (1) on the side opposite to the support side.

In the example shown in FIG. 25, the nitrogen atom distribution concentration CI is a constant value from position tIl to position t1, and the positions M, t
The nitrogen atom distribution concentration CS is assumed to be constant from s to l11tT.

In the example shown in FIG. 26, the nitrogen atom distribution concentration Cs is a constant value from position 1B to position t3, and position 1. The nitrogen atom distribution concentration is C4 up to the position tm, and the concentration is C4 up to the position t8.
From to position 1T, the nitrogen atom distribution concentration CS is 3
The nitrogen atom distribution concentration is reduced in stages.

In the example of FIG. 27, the nitrogen atom distribution attitude is C· from position 1B to position 1fiLt*t, and from position ff t a to position t,
up to the nitrogen atom distribution concentration C1.

In the example of FIG. 28, position 1. From position ts to position fit ta, the nitrogen atom distribution concentration is C-, from position ts to position fit ta, nitrogen atom distribution concentration C9, and from position t6 to position tT, nitrogen atom distribution concentration C16. In this way, the nitrogen atom distribution concentration is increased in three stages.

In the example of Figure 29, place @1. From position tyt, the nitrogen atom distribution concentration is set to C1l, from position t7 to position k t s, the nitrogen atom distribution concentration is set to C1g, and at position 1. The nitrogen atom distribution concentration from position t to position t is CtS. The nitrogen atom distribution concentration is made high on the support side and the free surface side.

In the example shown in FIG. 30, the nitrogen atom distribution concentration is C14 from position tB to position t9, and from position t9 to position R1.
, , the nitrogen atom distribution concentration is set to 6, and the nitrogen atom distribution concentration is set to 4 from position t'10 to position tTi.

In the example shown in FIG. 31, the nitrogen atom distribution concentration CtS is set from position tB to position tll, and from position to to position tll.
The nitrogen atom distribution concentration is increased stepwise to cy, and is decreased to C1l from position tst to position #tT.

In the example of FIG. 32, the nitrogen atom distribution degree C1l is set from position t to position to, the nitrogen atom distribution degree is increased stepwise from position tts to position J4, and position jIft,
, the nitrogen atom distribution concentration is set to a concentration C*1 that is lower than the initial concentration from the position to the position.

In the example shown in FIG. 33, from position tll to position tll
The nitrogen atom distribution concentration is set to CB up to CB, the nitrogen atom distribution decreases to Cn from position ttg to position tl11, increases stepwise to nitrogen atom distribution concentration C14 from position t1 to position mark, and from position Rt1v to position 1T1. The nitrogen atom distribution concentration is reduced to Cu.

In the example shown in FIG. 34, the distribution concentration C of nitrogen atoms monotonically increases continuously from the distribution concentration 0 to C from the position tIl to the position t.

In the example shown in FIG. 35, when the distribution concentration of nitrogen atoms is C(ro)hiro, position ft, the distribution acupuncture degree C is monotonous until the distribution concentration CsI reaches the position tts. Continuously decreasing to position 1. The distribution density is C. position t
Between is and position t, the distribution of spiritual element atoms increases monotonically and continuously at position C, and at position tT, the distribution concentration becomes cm. ing.

The example in FIG. 36 is relatively similar to the example in FIG. 35, but the difference is that at position tn and position 1,
It does not contain nitrogen atoms.

Between position tm and position tlG, the distribution density C at position t8 monotonically decreases continuously from the distribution density C at position txs to 0 at position txs, and between position tm and position tT, the distribution density C at position t8 monotonically decreases.
Distribution concentration C at 1tIl from 0
It monotonically increases continuously up to 8o.

In the photoconductive member of the present invention, as typical examples thereof are shown in FIGS. 34 to 36, the lower surface and/or upper bottom side of the photoreceptive layer contains more nitrogen atoms, and The first layer (1) contains fewer nitrogen atoms toward the inside, and the distribution concentration of nitrogen atoms in the layer thickness direction C(
By continuously changing N), for example, the first ffi
(1) High light sensitivity and high dark resistance are being achieved.

In addition, in FIGS. 34 to 36, by continuously changing the distribution humidity CH of nitrogen atoms, the change in refractive index in the layer thickness direction due to the inclusion of nitrogen atoms is made gradual, and the laser beam is This effectively prevents interference caused by coherent light such as.

In the example shown in FIG. 37, the nitrogen atom concentration is C31 from position t to position -, increases from position tn to position tni, and reaches a peak value of 03m at position to. The nitrogen atom concentration decreases from the position tax to the positions t, , f, and becomes the nitrogen atom concentration C11 at the position tT.

In the example shown in FIG. 38, the position @t! Up to 4 is the nitrogen atom concentration CSS, and from position (itB to position t'
The nitrogen atom concentration rapidly increases to s, takes a peak value C114 at position tgs, and decreases from positions tM and tss to position 1f-t until the concentration of 9 elemental atoms becomes almost zero.

In the example shown in FIG. 39, from position tll to position t.

The nitrogen atom concentration gradually increases from 038 to cs6, and the nitrogen atom concentration reaches a peak value CI6 at position tss. The nitrogen atom concentration rapidly decreases from position t's to position tT, and reaches the nitrogen atom concentration CSS at position 1T.

In the example shown in FIG. 40, the nitrogen atom concentration C at position tB
The nitrogen atom density decreases from at to the position to, and remains constant at the nitrogen atom concentration C3a from the position tar to the position tll, where the nitrogen atom concentration becomes CSS. The nitrogen atom concentration increases from the position t's to the position t*ef, and at the snow 9 position, the nitrogen atom concentration reaches a peak value Ca1l. The nitrogen atom concentration decreases from position tse to position t and trench, and becomes nitrogen atom concentration cs- at position tT.

In the present invention, whether the layer region (2) occupies the entire area of the first layer (1) or even if it does not occupy the entire first layer (1), the layer thickness of the layer region (2) ' If the proportion of the first layer (1) of ro in the layer thickness T is sufficiently large, the upper limit of the content of nitrogen atoms contained in the layer region (b) will be sufficiently smaller than the above value. is desirable.

In the case of the present invention, the layer region (the thickness To of the first layer is 0
) accounts for two-fifths or more of the layer thickness T, the upper limit for the amount of nitrogen atoms contained in the layer region (b) is silicon atoms, germanium atoms, nitrogen atoms. Preferably 30 atoms or less, more preferably 20 atoms or less, optimally 1
It is desirable that the number be 0 atomie1 or less.

In the present invention, the layer region (g) containing nitrogen atoms constituting the first layer (1) contains nitrogen atoms λ at a relatively high concentration on the support side and near the free surface, as described above. In the former case, the support and the first layer (1
> It is possible to further improve the adhesion between the two and to improve the receptive potential. □ The localized region (B) can be explained using the symbols shown in FIGS. 25 to 40.
It is desirable that it be provided within μ.

In the present invention, the localized region (B) is the interface position 1
M or t may be the entire layer region (LT) up to 5μ thick, or may be a part of the layer region (LT).

Whether the localized region (B) is a part or all of the layer region (L,) is appropriately determined according to the characteristics required of the light-receiving layer to be formed.

In the localized region (B), the distribution state of the nitrogen atoms contained therein in the layer thickness direction is the maximum value C of the distribution concentration of nitrogen atoms.
Preferably 500 atoms m&x or more, more preferably 800 atoms ppm or more,
It is desirable that the layer be formed in such a way that the distribution state is optimally 1000 atomic ppm or more.

That is, in the present invention, the maximum value Cmax of the distribution concentration in a layer region containing nitrogen atoms (wherein is within 5 μm in layer thickness from the support side or free surface side (layer region 5 μ thick from 1B or tT) It is desirable that the structure be formed in such a way that it exists.

In the present invention, whether the layer region (2) occupies the entire area of the first layer (1) or even if it does not occupy the entire first layer (1), the layer thickness of the layer region (2) ' When the proportion of the first layer (1) of ro in the layer thickness T is sufficiently large, the upper limit of the content of nitrogen atoms contained in the layer region (to) is made sufficiently smaller than the above value. is desirable.

In the case of the present invention, when the ratio of the layer thickness To of the layer region (6) 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 g) is preferably 30 atomic% or less, more preferably 2 to T(81GeN)7.
Less than 0 atomic, optimally 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 (b) is smooth in the entire region. It is desirable that the nitrogen atoms be contained in the layer regions in a uniform and continuous manner. Further, by designing the distribution disease severity line so that its maximum distribution concentration Cmax exists within the 10th layer (1), the effects described below are significantly exhibited.

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 the case of nickel, by appropriately selecting the maximum distribution concentration cmax, when the photoreceptive layer is subjected to charging treatment from the free surface side, charge is effectively prevented from being injected from the surface into the interior of the photoreceptor layer. You can.

In addition, in the vicinity of the free surface side, nitrogen atoms are contained in the first layer (1) so that the degree of distribution of nitrogen atoms sharply decreases toward the free surface side by the maximum distribution concentration CmaX. In particular, durability in a humid atmosphere can be further improved.

When the nitrogen atom distribution concentration curve has the maximum distribution concentration Cm1LX inside the first layer (1), further design the distribution concentration curve 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 photoreceptive layer 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 a range 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 preferably 67a for T(SiGeN).
tomic% or less, more preferably it: 50 at
omic% or less.

Optimally, it is desirable to set it to 40 atomle% or less.

In the present invention, the layer region provided in 10-(1) (
The content of nitrogen atoms contained in the layer region (6) depends on the properties required for the layer region (6) itself, or when the layer region (6) is provided in direct contact with the support, the nitrogen atom content 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 region is provided in direct contact with the layer region (b), the relationship between the characteristics of the layer region of the layer and the characteristics at the contact interface with the layer region of the layer is also determined. The content of purchased atoms is selected accordingly.

The dose line of nitrogen atoms contained in the layer region (b) can be determined as desired depending on the characteristics required of the photoconductive member to be formed, but it is preferably 0.001 to T(81GeN). 50 atomic%, more preferably 0.002 to 40' atomic%, optimally o, o
It is preferable that the amount is between o a and 30 atoms.

In the present invention, in order to provide a layer region 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). It may be used together with the starting material for forming the first layer (1) and contained in the formed layer while controlling its amount.

When the glow discharge method is used to form the layer region, a starting material for nitrogen atom introduction is added to the starting materials selected as desired from among the starting materials for forming the first 0M(]) light. . As the starting material for introducing nitrogen atoms, most of the gaseous substances containing at least atoms of atoms or the gasified substances that can be gasified can be used.

For example, a raw material gas whose constituent atoms are silicon atoms (old), a raw material gas whose constituent atoms are silicon atoms (g), and a raw material gas whose constituent atoms are hydrogen atoms (H) or/and halogen atoms (3) as necessary. A raw material gas containing silicon atoms (81) as constituent atoms and a raw material gas containing nitrogen atoms (e) and hydrogen atoms (b) as constituent atoms may be used by mixing them at a desired mixing ratio. Alternatively, a raw material gas containing silicon atoms (St) and silicon atoms (Sl), !, may be mixed at a desired mixing ratio. It is possible to use a mixture of a raw material gas consisting of elementary atoms and hydrogen atoms.

Also, separately, silicon atoms (si) and hydrogen atoms (b)
It is also possible to mix and use a raw material gas having constituent atoms of and a raw material gas having constituent atoms of sulfur atoms (b).

A starting material that is effectively used as a raw material gas for introducing nitrogen atoms (N2) used in forming the layer region is, for example, nitrogen (N2).

Ammonia (NJ(,), hydrazine (H2NNH2
), hydrogen azide ()IN, ), ammonium azide (NH4N, ), etc., gaseous or gasifiable nitrogen, nitrogen compounds such as nitrides and azides may be mentioned. In addition to this, in addition to the introduction of nitrogen atoms (c), nitrogen trifluoride (
F! IN).

Examples include halogenated nitrogen compounds such as elemental tetrafluoride (F4N2).

In the present invention, the layer region (g) may further contain oxygen atoms in addition to nitrogen atoms in order to further enhance the effect obtained by nitrogen atoms. Examples of raw material gases for introducing oxygen atoms into the layer region (b) include oxygen (02), ozone (03), -nitrogen oxide (No), -nitrogen dioxide (No2), and -nitrogen dioxide. (N20) *Nitrogen sesquioxide (N204), nitrogen sesquioxide (N205), nitrogen trioxide (NO3), whose constituent atoms are silicon atom (si), oxygen atom (0), and hydrogen atom (b), e.g. , disiloxane (H3SIO8
i) 13) , ) disiloxane ('ll5SiO8i
Examples include lower siloxanes such as H20SiH5).

To form a layer region containing nitrogen atoms by the horn 9 tuttering method, a monocrystalline or polycrystalline Sl wafer or a 513N4 wafer h-1 or st and 81,N
This may be carried out by using a target of wafer 1- containing a mixture of 4 and 4 as a target, and by spraying or taring them in various gas atmospheres.

For example, if 81W-- is used as a target, the raw material gas for introducing nitrogen atoms and hydrogen atoms and/or halogen atoms as necessary is diluted with a diluting gas as necessary for sputtering deposition. These gases are introduced into the chamber to form a gas plasma of the above-mentioned 81 water.
All you have to do is sputter.

Alternatively, 81 and 5t3N4 may be used as separate targets, or a mixed target of Sl and 513N4 may be used in an atmosphere of dilution gas as a sputtering gas or at least hydrogen atoms (I (
This is accomplished by sputtering in a gas atmosphere containing l or/and halodane atomic flash as constituent atoms. As the raw material gas for introducing nitrogen atoms, the raw material gas for introducing nitrogen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, when a layer region (b) containing nitrogen atoms is provided when forming the 10th layer (1), the layer region (b) containing nitrogen atoms is provided.
A desired distribution state in the layer thickness direction (dapth
In the case of glue discharge, the starting material gas for nitrogen atom introduction whose distribution concentration C(N) is to be changed is prepared by changing the gas flow rate to the desired change. This is accomplished by introducing it into the deposition chamber while changing the rate appropriately according to the rate curve. For example, the opening of a predetermined needle pulp provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manually or using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a rate-of-change curve designed in advance to obtain a desired content rate curve.

When forming the layer region (b) by the S-arm tuttering method, the desired distribution state (d) of nitrogen atoms in the layer thickness direction is achieved by changing the distribution lesion C (b) of nitrogen atoms in the layer thickness direction.
epth profile), first, as in the case of the glow discharge method, the starting material for introducing crab atoms is used in a gaseous state, and the gas when introducing the gas into the deposition chamber is PJ flow rate? This can be done by changing it appropriately as desired.

Secondly, Snow'? For example, if a mixed target of St and 813N4 is used as a target for vine ringing, this can be achieved by changing the mixing ratio of Sl and Si3N4 in advance in the layer thickness direction of the target. Ru.

In the photoconductive member 100 shown in FIG.
- layer (1) second layer (II) formed on 102
105 has a free surface 106, which is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.

The second layer (It) in the present invention consists of silicon atoms (S
t ), an oxygen atom (0), and optionally a hydrogen atom (b) or/and a halogen atom (referred to as [a-(ssXol-x)y(H+X)1-yJ However, it is composed of O<x, y<1).

a-(S1.01-x)y(HlX)1-7
The formation of the 20th layer (n) consisting of: glow discharge method;
This is accomplished by the Nu-Taira method, Taling method, electron beam method, ion implantation method, ion grating method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, the level of equipment capital investment, and the desired characteristics of the photoconductive member to be manufactured. The second waste material (20), which produces oxygen atoms and halogen atoms together with silicon atoms, is relatively easy to control the production conditions for producing a conductive member.
II) Glow discharge method or Suba because of its advantages such as ease of introduction.

The taring method is preferably employed.

Furthermore, in the present invention, the glow discharge method and the suba-turning method are used together in the same system to generate the second m (Jl).
may be formed.

To form the second layer (It) by glow discharge method, a − (s t xo 1-x) y (u+ x) I
The raw material gas for L y formation is mixed with a dilution gas at a predetermined mixing ratio as necessary, and the stem, which is a support installation, is introduced into the deposition chamber, and the introduced gas is used to generate a glow discharge. By doing so, the first layer (1), which has already been formed on the support, is formed into a
), (H,X), -, may be deposited.

In the present invention, a-(Slxol-y) 0ttx)
1-. As the p material for formation, silicon atoms (Sl
), oxygen atoms), hydrogen atoms, and halogen atoms (3). obtain.

81.0. When using a raw material gas t4p with ss 2 constituent atoms as one of H, Depending on , 0 and Hf: a raw material gas having constituent atoms or/and a raw material gas having 0 and X as constituent atoms, also,
Either mix at a desired off-shore ratio, or mix a raw material gas with %81 as constituent atoms and a raw material gas with St, O and H as constituent atoms. It can be used in combination with a raw material gas having two constituent atoms.

In addition, a raw material whose constituent atoms are Si and H is
A raw material gas having 414 constituent atoms of St, X and 't' may be mixed with a raw material gas having 0 constituent atoms. You can use it as well.

In the present invention, the nitrogen contained in the second layer (11)
Suitable rodan atoms (3) are F, Ct, and B.
r, I, especially F, CL are preferred.

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

Further, when forming the second layer (II) by sputtering, the method is as follows.

Firstly, when sputtering a target composed of 81 in an atmosphere of an inert gas such as Ar or He or a mixed gas made entirely of these gases, a raw material gas for introducing oxygen atoms (0) is used. Gold, hydrogen atom depending on the hair @
It is better to put them into a vacuum deposition chamber where sputtering is performed together with the raw material gas for introduction and the introduction of #'i/ and no-rodan atoms oC).

Second, SiO as a target for sputtering
A tar P composed of □), or a tar f Tsu) composed of Sl and a target composed of 8102, or 81,! : By using a target composed of SiO□, oxygen atoms (oxygen atoms) can be introduced into the second layer (11) to be formed. At this time, if the above raw material gas for introducing oxygen atoms (0) is also used,
By controlling the flow rate, it is easy to arbitrarily control the amount of oxygen atoms (0) introduced into the second layer (1).

The content of oxygen atoms (0) introduced into the second layer (It) is determined by the flow rate when the raw material gas for introducing oxygen atoms (0) is introduced into the deposition chamber. Alternatively, the proportion of oxygen atoms contained in the target for oxygen atomization can be adjusted at the time of preparing the target, or by doing both, the proportion of oxygen atoms contained in the target can be adjusted as desired. The starting materials η that can be controlled as the raw material gas for supplying Sl used in the present invention include 81H4, Sl□H6181, H
8,814H. Silicon hydride (silanes) in a gaseous state or which can be gasified, such as silanes, are considered to be effective in use, especially for their ease of use in scrap preparation work and good efficiency in dispensing. S tl (41Sl 2H6) is mentioned as a good book.

Using these starting materials 5&l, H can also be introduced along with 81 into the second layer (U) formed by appropriate selection of the layer formation Φ conditions.

In addition to the above-mentioned silicon hydride, effective starting materials that can be used as raw material gas for supplying Sl include silicon compounds containing silane atoms, and, of course, silane island conductors disguised as b' with halogen atoms. , Specifically, the example is 5IF4°R12F6 #
Silicon halides such as 81Ct4181Br4 are preferred.

Furthermore, 5IH2F2, 81H2f2 t 5jH2
C42t 81HC1s.

Halogens such as FllH2Br2 and 5IHRr5
Formation of hydrogen atoms in a gaseous state or that can be gasified, such as f-conversion water purple silica purple! ! Rodanide, which is one of the iI elements, can also be cited as an effective starting material for supplying Sl for the formation of the second layer (IN).

Even when these silicon compounds containing halogen atoms (3) are used, X can be introduced together with 81 into the second layer (It) to be formed by appropriately selecting the layer forming conditions as described above. I can do it.

Among the above-mentioned starting materials, the silicon halide compound containing hydrogen atoms has electrical or photoelectric properties at the same time as the halogen atoms (3) are introduced into the layer during the formation of the second layer (II). Since the extremely effective hydrogen atom (6) is also introduced into the l1iIl grip 1, it is a particularly preferred halogen atom in the present invention.
Used as a starting material for introduction.

'4 In addition to the above-mentioned materials, effective starting materials p that can be used as the raw material gas for introducing halogen atoms used in forming the second layer (II) in the present invention include, for example, fluorine, , bromine 1g halogen gas, RrF ,
C1F, ClF5, BrF5, BrF5
, BF3.

IF7 * Interhalodan compounds such as IC2 and IBr, B
F.

Hydrogen halide t-S of 14CL, HBr, Hl@ can be removed.

Second! The starting materials that can be effectively used as the raw material gas for introduction (oxygen atoms used in forming (II)) include 0 as a constituent atom or N and O as constituent atoms. For example, oxygen (02).

Maison (o5) +-Nine element oxide (No), Dioxide (NO2) r-Dioxygen (N20) + Sesquioxide (N203) e Phosphorine tetroxide (N204) +
Nitrogen pentazoate (N205) + nitrogen trioxide (No3)
e For example, a disiloxane (disiloxane) whose constituent atoms are a silicon atom (si), an oxygen atom (0), and a hydrogen atom (6)
) I, 5iO8IH, ) , To1J Siloxa7 (H3
In the present invention, the diluent gas used when forming the second layer (II) by the gloglofrost method or the sputtering method is as follows: 11i1 Noble gas, e.g. He H
Ne.

Ar or the like can be suitably used for purification.

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

In other words, depending on the SI and O1 requirements, there are a few that have H or Fi (lit) as constituent atoms, and depending on the conditions of creation, the structure can take a form from crystalline to amorphous, and electrically conductive. There are few issues between properties, semiconducting properties, and insulating properties.
Also, since it exhibits both photoconductive and non-photoconductive properties,
In the present invention, a
-(SIXOl-x)y(H, For example, in order to provide the second layer (It) tl- with the main purpose of improving the electrical withstand voltage, a-(stx
o, -X)y(a,x), is prepared as a highly amorphous material with electrically insulating behavior in the environment of use.

In addition, when a second layer (IT) is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to a certain extent, and it resists the irradiated light to a certain extent. As an amorphous negative material with a sensitivity of
-(S1xO,-x)y(H,x),- is created.

a-(Slxol-X
)y(H+X), the second m (It) consisting of -y
When forming a layer, the supporting body temperature # during layer formation is a factor that affects the structure and properties of the formed layer, and in the present invention, a-(stxo ,
-x)y(H+x)+-, is desired; II; It is desirable that the temperature of the support at the time of layer cropping is strictly controlled to ensure that the powder is easily produced.

In the present invention, the formation of the second layer (II) is carried out by appropriately selecting the optimum range in accordance with the method of forming the second waste (U) in order to effectively achieve the desired purpose. However, tF
Preferably 20 to 400°C, more preferably 50 to 350°C
℃, preferably 6100 to 300℃.

For the formation of the second layer (It), glow emission is used because delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods. However, when forming the second layer (IT)' using these layer forming methods, it is important to is created a-(8
1x01□)A(H,X), -A It is one of the important factors that influences the characteristics of

a having the characteristics for achieving the object of the present invention;
−(S i xol −x )y (Hs X),
The discharge conditions for producing -y efficiently and effectively are preferably lO~300W, more preferably 20~~250W%, preferably 50~200W. It is something.

The gas pressure in the deposition chamber is preferably Id O, 01 ~ ITo
More preferably, it is about 0.1 to 0.5 Torr.

In the present invention, the values within the above-mentioned ranges are considered desirable values for the support temperature and discharge power for creating the second Fi layer (II), but these layer creation factors are , d is not independently and separately determined, but the desired properties a-(sixo,-X)y(n,x),-.

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

The amount of oxygen atoms contained in the second layer (II) in the optical St member of the present invention is determined to have the desired characteristics to achieve the object of the present invention, as well as the conditions for forming the second layer (IJ). This is an important factor in the formation of the second layer (II) obtained.

The amount of oxygen atoms contained in the second layer ([I) in the present invention may be determined as desired depending on the nature and characteristics of the amorphous material constituting the second M (II). It can be determined by

That is, the general formula a-(siXol-X)y(HIX)
, -3' can be roughly divided into amorphous lateral laterals (hereinafter referred to as laterals), which are composed of silicon atoms and oxygen atoms.
Arranged as r a-8l, 0l-aJ. However, 0(a(1)
, an amorphous material composed of silicon atoms, oxygen atoms, and hydrogen atoms (hereinafter referred to as l"'a-(SibOl-b), H
It is written as l-6J.

However, 0〈b, c〈1), an amorphous material composed of a silicon atom, an oxygen atom, a halogen atom, and a hydrogen atom depending on the heart (hereinafter referred to as ra-(stdol-,)eQI,X)
, -e'. However, it is classified as 0(d, e(1)).

In the present invention, the second layer (It)! 1-81a01
-a, the row λ in the representation of a of oxygen atoms contained in the second layer (■), @ -S l aol -a, is preferably tL<ke0, 33~0.99999
The preferred range is 0.5 to 0.99, and the most preferred range is 06 to 0.
It is 9.

In the present invention, the second layer (II) is a-(S l
bol-b) cHl-0, the second layer (
The amount of oxygen atoms contained in It), a-(SibOl
-B)6 I(1-c) b is preferably 0.33 to 0.99999, more preferably 0.5 to
0.9, optimally flo, 6-0.9, e preferably 0.6-0.99, more preferably 0.65-0.98,
Optimally, it is desirable that it is between 0.7 and 0.95.O Second! (II) or a-(Si, 101-d)s(
HIX) 1-e, the second layer (I
The content of oxygen atoms contained in I) is a-(
ss, 1o1-a (HIX), -6 d, if expressed as a, d is preferable, 0.33 to 0.99999, preferably 0.5 to 0.99, optimally 0.6-0.9
, e is preferred, Fio, 8 to 0.99, preferably #'i 0.82 to 0.99, optimally 0.85 to 0.9.
8 is desirable.

The number range of M rhinoceros in the second m (II) in the present invention is:
This is one of the important factors for effectively achieving the purpose of the present invention.

The layer thickness of the second layer (It), which is appropriately determined as desired according to the intended purpose so as to effectively achieve the purpose of the present invention, is based on the density of oxygen atoms contained in the layer (U). Also in relation to the layer thickness of the first layer (1), there is a polishing process that is appropriately determined according to the desire, with various approximations depending on the characteristics given to each N region. .

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

The layer thickness of the second layer (n) in the present invention is u', fj
f 0.003 to 30 μ, preferably 0.00
It is desirable that the thickness be 4 to 20μ, optimally Uo, and 005 to 10μ.

The support used in the present invention may be blue-electric or electrically insulating. Examples of the conductive support include LD, NiCr + stainless steel, and At.

Cr, Me, Au, Nb, Ta,
Examples include alloys of V, TI, Pt, and Pd%.

Examples of the electrically insulating support include films or sheets of synthetic resin such as polyester, polyethylene, polycargonate, cellulose acetate, polypropylene, polycyclized vinyl, polycyclized vinylidene, polystyrene, polyamide, glass, ceramic, paper, etc. is used by hunting spies. These electrically insulating supports are preferably subjected to fL box treatment on at least one surface thereof, and the electrically conductive surface side is
Preferably, other layers are provided.

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

Al, Cr, Mo, Au, Ir, Nb,
Ta, ,V,TI.

Pt, Pd, xn2o, 5n02,
By providing a film consisting of ITO (In205 + l; In02), conductivity and properties are imparted.
iCr, AL, Ag, Pb, Zn.

N1, Au, Cr, Mo, Ir,
Nb, Ta, V, TI.

A thin film of gold M such as PT is applied to the surface by full vacuum deposition, electron beam evaporation, or sputtering, or the surface is laminated by prepolymerization to impart conductivity to the surface. The shape of the support may be cylindrical, belt-like, plate-like, etc. Its shape is determined depending on the user's wishes, but for example, if the light-enabled part 100 shown in Fig. 1 is used as a combination member for a cylindrical blade, in the case of continuous high-speed printing, It is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is determined as appropriate to form a photoconductive part of the desired thickness. As long as it is within the l# range where it is fully utilized, it will be used as much as possible. However, in such a case, from the viewpoints of Jky B of the support body, handling, mechanical strength, etc., the shooting distance is set at 10 μJ or more.

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

W, Figure 41 shows the manufacturing speed of the light guide and the part ≠ -1 negative 10l+.

Gas cylinders 202 to 206 in the figure KIrJ1 are filled with raw material gases for forming the optical fibers of the present invention.As an example, for example, gas cylinders 202 to 206 diluted with 2 oz. 111/& 99.999%
, hereinafter S I F a, /l (abbreviated as a) cylinder, 2
03 is Ge F4 gas (contained [99,
999%, hereinafter abbreviated as GeFa/Ha. ) cylinder, 2
04 is NH, gas (purity 99, 99%, hereinafter referred to as NH) cylinder, B2H6 diluted with 205 dHa (purity i99.999%, hereinafter abbreviated as B2Hb/'ff@) - One pump, 206dH2 (purity 99.999
．． 1) is Nbe.

To allow stiff gas to flow into the gold reaction chamber 201, make sure that the valves 222 to 226 of the pumps 202 to 206 and the leak valve 235 are closed, and also close the inflow valves 212 to 216 and the &lfj palf. Recognizing that 217-221 and auxiliary valves 232 and 233 are open,
First, close the main valve 234 to υ■4 and open the reaction chamber 201. And the inside of the gas piping is antagonized. Next, when the reading of the vacuum [1236] reaches approximately 5 x 10-' torr, the auxiliary valves 232 and 233 and the outflow valves 217 to 221 are closed.

Next, an example of the case where the photoreceptor N is completely formed on the cylindrical differential body 237 is as follows: gas cylinder 202 and SiF
4. /) 1g gas, 203 p G4! F4
/He gas, gas pump 204 and 5NI (, gas, gas pump 206 and 2 gas, valve 222.223
.

224 and 22.6 gold respectively lHt+ and outlet pressure r-di2
Adjust the pressure at 27°228, 229, 231 to 1k11/F2, gradually open the inlet valves 212, 213, 214, 216, and then turn the mass flow controllers 207°208.
209 and 211 respectively.

Subsequently, the outflow valves 217, 218, 219° 221
, the auxiliary valve 232 is gradually opened to allow each gas to flow into the reaction group 201 . s l F4 at this time. “il
e gas flow rate, GeF J1m gas flow ■, and Nil.

Outflow valves 217, 218, 219, 221t are set so that the ratio of gas flow rate to %H2f gas gruel becomes the desired value.
Also, adjust the opening of the main valve 234 while checking the vacuum It 236 reading so that the pressure inside the reaction chamber 201 reaches the desired value. After confirming that the temperature of the base body 237 is set to rIM degrees in the range of 50 to 400°C by the heating heater 23.8, the power supply 23.
40 to a desired force to generate a glow discharge in the reaction chamber 201 to form a first layer region V←Lt- on the base 237.
Form. At the point when r5 [first #region 0 at the desired throat] is formed, all valves are completely closed. 5
IF4/i (e is Sugonbe 5IF4/'He (Fi
tH4 purity 99.9994) % p instead of z
HH4/')If! Gas is pump line, B2H〆He is Sue? Using the cylinder line, NH, and gas cylinder line, perform the same valve operation as in the formation of the first layer region O),
By maintaining the glow discharge for a desired period of time by disguising the desired glow discharge t+=, a second layer region 1) containing substantially no rumanium atoms is formed on the first layer region 1). A layer region (S)t- can be formed.

In this way, the first layer region O) and the second layer region (SS
A first layer (1) is formed on the base body 237.

In order to form the second i (It) on the first layer (1) formed to a predetermined layer thickness as described above, the first layer (I)
For example, Fi
This is accomplished by diluting each of H4f and No with a diluent gas such as He as necessary to generate a glow in %I according to desired conditions. In order to contain halogen atoms in the second layer (...), for example, 8iF4 gas and No.
The second layer (n)t- is formed in the same manner as above by adding gas or KSIH4.

It goes without saying that all outflow valves 1 outside the palladium l for the outflow of gas required when forming each layer are closed, and when forming each layer, it is necessary to In order to prevent the gas from remaining in the reaction chamber 201 and in the gas piping leading from the outflow nozzles 217 to 221 to the reaction chamber 201, the outflow nozzles 217 to 221 are closed and the auxiliary nozzles 232 and 233 are opened. If necessary, the main pulp 234 is completely drained and evacuated to the internal high vacuum of the system.

The proportion of oxygen atoms contained in the second layer (II) is changed according to the flow ratio t4i''J of SiH4 gas and NO gas introduced into the reaction chamber 201 in the case of glow discharge, Alternatively, when forming a layer by sputtering, use a silicon unihat 5 when forming a tartar layer.
It can be controlled as desired by changing the sputtering area ratio of the IO2 plate or by changing the combination of silicon powder and 8102 powder to form the target. The amount of halogen atoms contained in the second 0M (It) is adjusted to adjust the flow rate when the raw material gas for the No. 4 μλ element, for example, 5IF4f, is introduced into the reaction chamber 201. It is achieved by this.

Further, during layer formation, it is desirable to rotate the substrate 237 at a constant speed by a motor 239 in order to ensure uniform II-AN formation.

Examples will be explained below.

Example 1 Each sample as an image forming member for electron η was formed on a cylinder-shaped At substrate under the conditions shown in Table 1 using the structural apparatus shown in FIG. 41 (see Table 2).

The thickness of the concentration distribution of impurity atoms (B or p) in each test is shown in Figure 42, and the concentration distribution of nitrogen atoms d
Figure 43A and! As shown in Figure 43B.

The distribution concentration of each atom was controlled by varying the flow rate ratio of each corresponding gas according to a predetermined variation line.

Each sample thus obtained was placed in a 4-electrophotometer experimental device.■5. Corona charging was performed at OkV for 0.3see, and a light image was irradiated beforehand. The light image was irradiated using a tungsten lamp light source and a 21ux-sea light ax tracing the length of a transmission type test chart.

Thereafter, a good toner ii[u] was obtained on the photoreceptive layer surface by cascading an e-chargeable developer (including toner and carrier) over the photoreceptive layer surface of each sample. The toner image t on the photoreceptive layer is 5. When transferred onto transfer paper using an OKV corona charger, both excellent samples had good resolution and clear, high-density images with good reproducibility were obtained.

In the above, the light source is 81 instead of a tungsten lamp.
A two-sided evaluation of the toner transfer image was performed for each trial in the same manner as in 81 above, except that an electrostatic image was formed using a 0 nm GaAa semiconductor laser (10 mW). For both samples, W = Image power, clear, high-quality images with good reproducibility (Q).

Example 2 A cylinder-shaped At
Each sample as an electronic mirror forming member was entirely formed on the substrate under the conditions shown in Table 3 (see Table 4).

The concentration distribution of impurity atoms in each size is shown in FIG. 42, and the distribution concentration of tetraatomic atoms is shown in FIG. 44.

When each of these samples was subjected to the same image evaluation test as in Example 1, all tests yielded toner transfer images of excellent quality. Also, for each sample, 38℃, 80%
When a 200,000-cycle test was carried out under RH conditions, 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 for electrophotographic images (Torium 31-1 to 37-12) were prepared on the I body under the conditions shown in Table 5 (Table 6).

The content distribution concentration of impurity 5/A in the famous sample is 4th.
In FIG. 2, the concentration distribution of nitrogen atoms is shown in FIGS. 43A, 43B, and 44.

When each of these samples was subjected to the image correction test of Example 1, all of the samples gave toner transfer images of high quality η. Also, for each sample, 38℃, 80%
When we conducted a 200,000-reuse test using RH salt-burning, no deterioration in image quality was observed in any of the TL samples.

Example 4 The cylindrical At
Samples (41-1 to 46-16) as image forming portions for electrophotography were prepared on the substrate under the conditions shown in Table 7 (Table 8).

The flow rate ratio of Ge H4 gas at the time of forming the first layer region (G) is changed according to a rate of change line drawn in advance, so that the distribution concentration of dallmanium atoms shown in FIG. 45 is obtained.
G), and B at the time of forming the second first working area (S>).
By changing the flow rate ratio of 2H6 gas and PH3 gas according to a pre-designed rate of change line, the impurity content 41 shown in FIG.
Island regions (8) were formed so that the concentration was 1.

Further, the flow rate ratio of NH3 gas at the time of forming the first layer region (G) is changed according to a change rate line drawn in advance, and the
Layer region 0) was formed so as to have the distribution concentration of the atomic atoms shown in FIGS. 43 and 43B.

When images of Example 1 and recycle were evaluated for each of these samples, images of sieve hooks could be obtained for each sample.

Example 5 Using the custom equipment shown in Fig. J1141, an image forming member for electrophotography was prepared on a cylindrical At substrate by controlling the flow rate ratio of each gas under the conditions shown in Table 9 in the same manner as in Example 1. Samples (Samples A31-1 to A56-12)' were prepared (Table 10).

Distribution concentration of impurity atoms in each sample #'1s42
Furthermore, the content distribution degree of nitrogen atoms is shown in FIG. 44, and the content distribution concentration of r-luminium atoms is shown in FIG. 45.

When each of these samples was subjected to the same W11 image evaluation test as in Example 1, all of the samples provided toner transfer images of high quality. Also, for each sample, 38℃, 8
When we conducted a 200,000-item repeated use test on 0% RHC), all samples showed ii! No decrease in Il image quality η was observed.

Embodiment 6 A cylinder-shaped At
Samples (Samples A61-1 to 610-13) as electrophotographic image forming members were prepared on the substrate under the conditions shown in Table 11 by controlling the flow rate ratio of each gas for the Example 1 and P1 strains (
Table 12).

#-1 No. 42 for the content distribution of impurity atoms in each sample
In addition, the content distribution of g atoms is shown in Figure 43A, #4.
38 and H44, and the germanium atom content distribution # degree is shown in 8145.

Each of these samples was subjected to the same image evaluation test as in Example 1, and all of the samples produced high-quality toner transfer images. Also, for each phase, 38°C p 8 o
When we conducted a 200,000-time test at Narasaki, SNU, all samples were L! No decline in the threat of IJ statues was observed.

Example 7 Sample Al1-1.12-1.1 of Example 1 except that the conditions for creating the second layer ([1) were as shown in Table 13.
Each of the electrophotographic imaging members (samples Al1-1-1 to 11-1-8
．． 12-1-1~12-1-8゜13-1-j~13-
A sample of 24 micrometers (1-8) was prepared.

thus? ←The husband and wife of each electrophotographic image forming member were installed as copies individually, and e5kv and 0.2seer! 1
A light image was irradiated using a ``corona'' @ turtle. A tungsten lamp was used as the source, and the light intensity was set to 1.01 ut-see to create a 0 latent image ■ Chargeable developer (including toner and carrier)
The image was developed by a printer and transferred to regular paper. The transferred image was extremely good.

Any toner that remained on the electrophotographic imaging member without being washed was cleaned with a rubber blade. Even when this process was repeated 100,000 times, no deterioration of the image was observed in any case.

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

Example 8 When forming the second layer (II), the target area ratio of Ar and No mixed gas, silicon wafer and 5tO2 was changed,
Each of the I-formed members was prepared in exactly the same manner as in Sample 11-2 of Example 1, except that the content ratio of silicon atoms to oxygen atoms in the second M (It) was changed. It was created. After repeating the image forming, developing, and cleaning steps approximately 50,000 times as described in Example 1 for each of the fC and image forming members thus obtained, image evaluation was performed, and the results shown in Table 15 were obtained. Ta.

Example 9 When forming the second layer (■), the content ratio of silicon atoms and limiting atoms in the second Id (II) was changed by changing the flow ratio of 5IH4 gas and NO gas. Each of the image forming members was created in exactly the same manner as in Sample Al1-3 of Example 1 except for the following changes. For each image forming member thus obtained, the process up to transfer was repeated approximately 50,000 times using the method described in Example 1, and then image evaluation was performed.
The results shown in Table 6 were obtained.

Example 10 When forming the second layer (II), SIH, gas, 5IF
The second layer (II) was formed by changing the flow rate ratio of 4 and NO.
Each of the image forming portions was created in exactly the same manner as for sample Al1-4 of Example 1, except that the content ratio of silicon atoms and oxygen atoms in the sample was changed. After repeating the steps of image formation, development, and printing about 50,000 times as described in Example 1 for each image forming member thus obtained, 1i
I11 times the revised price f: 1] and obtained the results shown in Table 17.

Example 11 Each of the image forming members was prepared in exactly the same manner as in Sample A 11-5 of Example 1, except for changing the N thickness of the second layer (It). Imaging and viewing 5 as described in Example 1
The imaging and cleaning steps were repeated to obtain the results shown in Table 18.

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

Substrate temperature: Glumanium atom (Go) containing layer...
・・・・・・・・・ About 200℃ germanium atom (G
e) Non-containing content... Approximately 250℃ discharge frequency:
13.56 MHz Reaction chamber internal pressure 20.3 Torr

[Brief explanation of the drawing]

FIG. 1 is a schematic explanatory diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. The explanatory diagrams, FIGS. 11 to 24, respectively show the impurity atoms,
Figures 25 to 40 show the distribution state of nitrogen atoms 'fI
:i51', Scattered diagram for clarity to Figure 41 Fi is a schematic explanatory diagram of the apparatus used in the present invention, and Figures 42 to 45
Each figure is an explanatory diagram showing the distribution state of each atom in an example of the present invention. 100... Photoconductive member 101... Support body 102.
...First layer (1) 103...First row area (to)
)104...Second layer region 1(s) 105...Second layer (II) 106...Free surface 107...Photoreceptive layer-111-C -1-→-C ---→-C -C(PN) -C(PN) 11111◆C(PN) C(PN) □C(PN) -C(PN) -C(PN) -C(PH C(PN) -C(PN) -C(/'N) -C(PN) C(PH) □C(PN) C(N) C(N) C(N) 11111- C(N) 1-------C7N)

Claims (9)

[Claims] (1) A support for a photoconductive member, and a first layer region (6) made of an amorphous material containing germanium atoms on the support and an amorphous material containing silicon atoms. A second layer region (S) composed of a layer structure and exhibiting photoconductivity is composed of a first layer of a layer structure provided in order from the support side and an amorphous material containing silicon atoms and oxygen atoms. a photoreceptive layer consisting of a second layer, the first layer contains a nitrogen atom, and a conductivity controlling substance (0 is defined as 0, and the maximum value of the distribution concentration in the layer thickness direction is the second layer). A photoconductive member characterized in that the content is present in the layer region (S), 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 silicon atoms are contained in the iml layer region (G). (3) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is non-uniform in the layer thickness direction. (4) Claim 1, wherein the distribution state of germanium atoms in the first layer region (b) 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 (6) 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 tenth layer region (G) and the second layer region (S) contains a halodan atom. . (7) The photoconductive member according to claim 2, wherein the distribution state of germanium atoms in the first 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 that controls conductivity (0 is an atom belonging to Group Ⅰ of the periodic table). (9) The photoconductive member according to claim 1, wherein the substance governing conductivity* (Q is an atom belonging to Group Ⅰ of the periodic table).