JPH0548466B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on light (here, light in a broad sense, ultraviolet light).
rays, visible rays, infrared rays, X-rays, and gamma rays).
Photoconductive materials for electrophotography that are sensitive to various types of electromagnetic waves
Regarding. Solid-state imaging devices or electronics in the image forming field
Photoconductivity in photographic image forming members and document reading devices
As a photoconductive material forming a layer, it has high sensitivity and
High signal-to-noise ratio [photocurrent (Ip)/dark current (Id)]
Matched to the spectral characteristics of the emitted electromagnetic waves
It has absorption spectrum characteristics and fast photoresponsiveness.
It must have a desired dark resistance value, and it must have a desired dark resistance value.
It is harmless to the human body, and solid-state imaging
In the device, afterimages can be easily processed within a predetermined time.
Characteristics such as being able to do the following are required. Special
Electronic photography used in offices as business machines
In the case of an electrophotographic image forming member incorporated into a device
The above-mentioned non-hazardous aspects of use are important.
be. Based on these points, light guide has recently been attracting attention.
Amorphous silicon (hereinafter referred to as a-Si) is used as an electrical material.
For example, German Publication No. 2746967
Publication No. 2855718 describes an image forming unit for electrophotography.
German publication number 2933411 describes its application to wood.
Application to electrical conversion and reading devices is described. However, the conventional photoconductive layer composed of a-Si
The photoconductive member has dark resistance, photosensitivity, and photoresponse.
electrical, optical, photoconductive properties such as properties, and moisture resistance
In terms of usage environment characteristics such as durability, and stability over time,
In this respect, further improvements are needed to improve the bonding characteristics.
The reality is that there are things that can be improved. For example, when applied to an electrophotographic imaging member
Attempts were made to achieve high light sensitivity and high dark resistance at the same time.
Conventionally, when using the product, there is no residual
Cases where a potential remains are often observed, indicating that this type of photoconductivity
If parts are used repeatedly for a long time, they will
Accumulation of fatigue due to
starts to emit a flash phenomenon or repeatedly occurs at high speed.
Inconveniences such as a gradual decrease in responsiveness when used
There were many cases where problems occurred. Furthermore, compared to the short wavelength side of the visible light region, a-Si
Therefore, the absorption in the wavelength region longer than the wavelength region on the long wavelength side is
It has a relatively small absorption coefficient and is currently in practical use.
In matching with a conductor laser, or
The light source is a commonly used halogen lamp or fluorescent lamp.
In this case, it is not possible to effectively use light on the long wavelength side.
In this respect, there is still room for improvement.
There is. In addition, if the irradiated light is in the photoconductive layer,
The amount of light that reaches the support is large.
The support itself passes through the photoconductive layer.
When the reflectance of light is high, the photoconductive layer contains
Interference due to multiple reflections occurs in the image, causing
This is one of the factors that causes this. This effect is due to the fact that the illumination spot is
The smaller the size, the larger the size, especially for semiconductor lasers.
This is a big problem when using the light source as a light source. Furthermore, when the photoconductive layer is composed of a-Si material,
in order to improve its electrical and photoconductive properties.
Hydrogen atoms, fluorine atoms, chlorine atoms, etc.
and boron atoms for control of electrical conduction type.
, phosphorus atoms, etc., or other properties to improve properties.
are contained in the photoconductive layer as constituent atoms, respectively.
However, how these constituent atoms are contained
Therefore, the electrical or photoconductive properties of the formed layer may
Sexual problems may occur. That is, for example, when a formed photoconductive layer is exposed to light,
The lifespan of the resulting photocarrier in this layer is
Insufficient or dark areas, the support side
This may occur due to insufficient prevention of charge injection.
There are many cases of cheating. Therefore, efforts have been made to improve the properties of the a-Si material itself.
On the other hand, when designing photoconductive materials, the above-mentioned
It is necessary to devise ways to solve all of these problems.
be. The present invention has been made in view of the above points, and includes a
- Light used in electrophotographic imaging members for Si
Applicability as a conductive member and its applicability perspective
As a result of comprehensive and intensive research studies, we found that silico
hydrogen atom (H) or halogen atom
Contains at least one of atoms (X)
Amorphous amorphous material, so-called hydrogenated amorphous silica
silicon, halogenated amorphous silicon, or
Halogen-containing hydrogenated amorphous silicon [hereinafter
“a-Si(H,X)” is used as a generic notation for these.
A photoreceptor that exhibits photoconductivity and is composed of
A photoconductive member having layers, the layer structure of which will be explained later.
A light guide specifically designed and created to
Electrical components have shown extremely superior properties in practical use.
rather than traditional photoconductive materials in every respect.
Dredging, especially photoconductive materials for electrophotography
It has extremely excellent properties as
Excellent absorption spectrum characteristics on the long wavelength side
It is based on the discovery that The present invention always has electrical, optical, and photoconductive properties.
Stable and almost unrestricted by usage environment
Compatible with all environments and has excellent photosensitivity characteristics on the long wavelength side
In addition, it has excellent resistance to light fatigue, and can withstand repeated use.
No deterioration phenomenon occurs even when the product is used, and there is no or almost no residual potential.
To provide a photoconductive member for electrophotography that is not observed
The main purpose is to Another object of the present invention is to provide light sensitivity in the entire visible light range.
It has a high degree of accuracy and is especially good for matching with semiconductor lasers.
We propose a photoconductive member for electrophotography that has a fast photoresponse.
It is to provide. Another object of the invention is to provide an imaging member for electrophotography.
When used as a
Bands for electrostatic imaging to the extent that they can be effectively applied.
Electrophotographic light with sufficient charge retention ability during electrophotographic processing
An object of the present invention is to provide a conductive member. Still another object of the present invention is to
Blurred images with clear tones and high resolution
Electronic technology that makes it easy to obtain high-quality images without
An object of the present invention is to provide a photoconductive member for photography. Yet another object of the present invention is high photosensitivity,
Providing a photoconductive member for electrophotography with high signal-to-noise ratio characteristics.
It is also about offering. The electrophotographic photoconductive member of the present invention (hereinafter simply referred to as
(referred to as "photoconductive member") is a photoconductive material for electrophotography.
A support for the member, and on the support, 1 to 10 × 10^Five
Amorphous material containing atomic ppm germanium atoms
Layer region (G) with a layer thickness of 30 Å to 50 μ made of material
contains silicon atoms (contains germanium atoms)
layer thickness 0.5~90μ composed of amorphous material
A second layer region (S) is provided in order from the support side.
Layer thickness of 1 to 100μ showing photoconductivity of eclipsed layer structure
the first layer of silicon atoms and 1×10^-3~
It is made of an amorphous material containing 60 atomic% of nitrogen atoms.
and a second layer with a layer thickness of 0.003 to 30μ.
and a receptor layer, and the first layer has a 0.001~
Contains 50 atomic% oxygen atoms and conducts
The distribution concentration of the substance (C) that controls properties in the layer thickness direction
When the maximum value of is 30 atomic ppm or more, the second layer region
in the second layer region (S) and in the second layer region (S).
In this case, the maximum value is on the support side.
It is characterized by containing in the state. It was designed to have the layer structure described above.
The photoconductive member of the present invention overcomes all of the above-mentioned problems.
Excellent electrical, optical, and photoconductive solutions
Indicates physical characteristics, electrical voltage resistance, and usage environment characteristics. Especially when applied as an electrophotographic imaging member.
In some cases, interference must be sufficiently prevented even when using coherent light.
In addition to being able to prevent residuals from forming images,
It is completely unaffected by potential and its electrical characteristics are stable.
It is highly sensitive and has a high signal-to-noise ratio.
It has excellent light fatigue resistance, repeated use characteristics, and high concentration.
Clear halftones and high resolution
High-quality images can be obtained stably and repeatedly.
Ru. Furthermore, the photoconductive member of the present invention is transparent in the entire visible light range.
It has high photosensitivity and is especially compatible with semiconductor lasers.
It has excellent optical performance and fast photoresponse. Hereinafter, according to the drawings, the photoconductive member of the present invention will be explained.
This will be explained in detail. FIG. 1 illustrates the layer structure of the photoconductive member of the present invention.
FIG. The photoconductive member 100 shown in FIG.
On top of the support 101 for use, a first layer ()
102 and a second layer ( ) 105
layer 107, the light-receiving layer 107 has a free surface 1
06 on one end face. The first layer ( ) 102 is formed from the support 101 side.
Germanium atoms and optionally silicon atoms
(Si), hydrogen atoms (H), and halogen atoms (X).
Amorphous materials containing at least one (hereinafter referred to as “a-Ge
(Si, H, X))
Consists of layer region (G) 103 and a-Si (H,X)
second layer region (S) 104 having a photoconductive layer
It has a layered structure in which these are laminated in order. The first layer ( ) 102 contains oxygen atoms
Contains a substance (C) that controls conduction properties.
However, the substance (C) is present in the first layer () 102.
, the maximum value of the distribution concentration in the layer thickness direction is the second
in the layer region (S) and in the second layer region (S)
In the case of
Contained in the form of Germanium source in the first layer region (G)
In the in-plane direction parallel to the surface of the support
is contained in a uniform state, but in the layer thickness direction,
It may be uniform or non-uniform. Also, germanium in the first layer region (G)
When the distribution state of atoms is non-uniform in the layer thickness direction,
The distribution concentration C in the layer thickness direction is determined from the support side or
or gradually toward the second layer region (S) side, or
or stepwise or linearly.
is desirable. In particular, germanium in the first layer region (G)
The distribution state of umium atoms is germanium in the entire layer region.
Atoms are continuously distributed, and the layer thickness of germanium atoms is
Distribution concentration C in the direction is from the support side to the second layer region
If a decreasing change toward (S) is given,
In this case, the first layer region (G) and the second layer region
(S) and has excellent affinity with
As shown in the figure, germanium atoms are formed at the end of the support.
By extremely increasing the distribution concentration C, semiconductor
Second layer region when using a body laser etc.
(S) absorbs almost no light on the long wavelength side,
Substantially complete absorption in the first layer region (G)
interference due to reflection from the support surface.
In addition to being able to prevent
Reflection at the interface between (G) and the second layer region (S)
I can hold it down enough. FIG. 2 to FIG. 10 show the light guide in the present invention.
Gel contained in the first layer region (G) of the electrical member
A typical example of the distribution state of manium atoms in the layer thickness direction is
shown. In Figures 2 to 10, the horizontal axis is germanium.
The vertical axis represents the distribution concentration C of umium atoms in the first layer region.
Indicates the layer thickness of (G), t_Bis the first layer region on the support side
The position of the end face of area (G) is t_Tis opposite to the support side
The position of the end face of the first layer region (G) on the side is shown. Immediately
First, the first layer region containing germanium atoms
(G) is t_BT from the side_TLayering takes place towards the sides. In FIG. 2, the content contained in the first layer region (G) is shown.
The first distribution state of germanium atoms in the layer thickness direction
A typical example is shown. In the example shown in Figure 2, the germanium atom
Surface on which the first layer region (G) containing is formed
and the surface of the first layer region (G) are in contact with each other.
Placement_BMoret₁Up to the position of the germanium atom,
Cloth density C is C₁germanium while taking a certain value
Contained in the first layer region (G) where umium atoms are formed
and position t₁Rather than concentration C₂The interface position t_Tleading to
has been gradually and continuously reduced. Interface position t_T
The distribution concentration C of germanium atoms is C₃
It is said that In the example shown in Figure 3, the contained
The distribution concentration C of rumanium atoms is at position t_BMore position_T
Concentration C up to_Fourgradually and continuously decreasing from
position t_Tconcentration C at_FiveForm a distribution state such that
are doing. In the case of Figure 4, position t_BMore position₂until then
The distribution concentration C of rumanium atoms is the concentration C₆and a constant value
and position t₂and position t_Tgradually between
Continuously decreased position t_T, the distribution concentration C
is substantially zero (here, substantially zero and
is below the detection limit). In the case of Figure 5, the distribution concentration of germanium atoms is
Degree C is position t_BMore position_TConcentration C up to₈Yoriren
Continuously gradually decreased, position t_Tsubstantially in
It is considered to be zero. In the example shown in Figure 6, germanium atoms
The distribution concentration C of is given by the position t_Band position t₃In between,
Concentration C₉is a constant value, and the position t_TIn the case of concentration
C_Tenbe done. position t₃and position t_TThe distribution concentration is between
C is linearly positioned at t₃More position_Tdecreased to
There have been a few. In the example shown in FIG. 7, the distribution concentration C is
position t_BMore position_Fouruntil the concentration C₁₁Take a constant value of
position t_FourMore position_Tuntil the concentration C₁₂More concentration C₁₃to
It is assumed that the distribution state decreases linearly. In the example shown in FIG. 8, the position t_BMore position_T
Until , the distribution concentration C of germanium atoms is
Degree C₁₄It decreases linearly to more effectively reach zero.
There are a few. In Figure 9, position t_BMore position_Fiveuntil
Then, the distribution concentration C of germanium atoms is the concentration C₁₅
More concentration C₁₆is linearly decreased until the position t_Five
and position t_TBetween, the concentration C₁₆with a constant value of
An example is shown. In the example shown in FIG.
The distribution concentration C of mu atoms is at position t_Bconcentration C at₁₇in
Yes, position t₆This concentration C until it reaches₁₇the beginning
is gradually decreased, and t₆around the position of
is sharply decreased at position t₆Then the concentration C₁₈considered to be
Ru. position t₆and position t₇At first, the relationship between
decreased, and then slowly decreased gradually
position t₇At concentration C₁₉and position t₇and position t₈between
is very slowly and gradually reduced to position t.₈to
, the concentration C₂₀leading to. position t₈and position t_TBetween
Then, the concentration C₂₀In the figure, so that it becomes more substantially zero.
It is reduced according to a curve of the shape shown. As described above, from FIGS. 2 to 10, the first layer region
Layer thickness of germanium atoms contained in region (G)
As we have explained some typical examples of direction distribution states,
In addition, in the present invention, gel is formed on the support side.
It has a part with a high distribution concentration C of manium atoms, and
face t_TOn the support side, the distribution concentration C is
germanium, which has a considerably lowered area compared to
The distribution state of atoms is provided in the first layer region (G).
It is. First layer constituting the photoconductive member in the present invention
The first layer region (G) constituting () is preferably
As mentioned above, there are germanium atoms on the support side.
Localized region containing relatively high concentration (A)
It is desirable to have In the present invention, the localized region (A) is shown in FIG.
To explain using the symbols shown in Figure 10, the interface
position t_BIt is preferable to set the distance within 5μ.
It is. In the present invention, the localized region (A) is a field
surface position t_BFull layer area up to 5μ thick (L_T) is said to be
In some cases, the layer region (L_T) is considered part of
In some cases. The localized region (A) is transformed into a layered region (L_T) as part of
Whether it is all or all depends on the layer being formed
It is determined as appropriate according to the characteristics. The localized region (A) is the gelatin contained therein.
As the distribution state of Ni atoms in the layer thickness direction, germanium
The maximum value Cmax of the distribution concentration of nium atoms is silicon
Preferably 1000atomic for the sum with atoms
ppm or more, more preferably 5000 atomic ppm or more,
Optimally 1×10^FourIt seems that it is more than atomic ppm.
Layers are formed so that they can be distributed. That is, in the present invention, germanium atoms
The first layer region (G) contained is from the support side
Within 5μ for layer thickness (t_BThe distribution concentration is in the layer area of 5μ thick from
It is formed so that there is a maximum value Cmax of degree.
preferable. In the present invention, contained in the first layer region (G)
The content of germanium atoms is determined according to the aim of the present invention.
Make appropriate decisions according to your wishes so that the objectives are effectively achieved.
preferably from 1 to 10×10^Fiveatomic
ppm, more preferably 100-9.5×10^Fiveatomic
ppm, optimally 500 to 8×10^Fiveconsidered to be atomic ppm
Ru. In the present invention, the first layer region (G) and the second layer
The layer thickness of the region (S) effectively achieves the purpose of the present invention.
This is one of the important factors for achieving
The resulting photoconductive member has sufficient desired characteristics.
In order to ensure that sufficient care is taken when designing photoconductive materials,
needs to be paid. In the present invention, the layer thickness of the first layer region (G)
T_Bis preferably 30Å to 50μ, more preferably 40
It is set to Å~40μ, optimally 50Å~30μ. Further, the layer thickness T of the second layer region (S) is preferably
is 0.5 to 90μ, more preferably 1 to 80μ, optimally
It is said to be 2 to 50μ. Layer thickness T of the first layer region (G)_Band second layer area
The sum of the layer thicknesses T of (S) (T_B+T) is required for both layer regions.
Required characteristics and characteristics required for the entire photoreceptive layer
Based on the organic relationship between the
It is determined as desired during layer design. In the photoconductive member of the present invention, the above (T_B
The numerical range of +T) is preferably 1 to 100μ, etc.
The thickness is preferably 1 to 80μ, most preferably 2 to 50μ. In a more preferred embodiment of the present invention,
Above layer thickness T_BAnd the layer thickness T is preferably
T_B/T≦1, for each
It is desirable that appropriate values be selected accordingly. Layer thickness T in the above case_Band the value of layer thickness T
In selecting T, more preferably T_B/T≦0.9,
Optimally T_B/T≦0.8 so that the relationship is satisfied
Layer thickness T_Band the value of the layer thickness T is determined. In the present invention, contained in the first layer region (G)
The content of germanium atoms is 1×10^Five
In the case of atomic ppm or more, the first layer region
(G) layer thickness T_BIt is desirable to make it as thin as possible.
preferably 30μ or less, more preferably 25μ or less
Below, the optimum value is 20μ or less. In the present invention, the first layer ()
1 layer region (G) or/and second layer region (S)
Halogen atom (X) contained as necessary in
Specifically, fluorine, chlorine, bromine, and iodine
Among them, fluorine and chlorine are particularly preferred.
It can be mentioned as follows. In the present invention, composed of a-Ge (Si, H, X)
To form the first layer region (G), for example
Glow discharge method, sputtering method, or ionic
Vacuum that utilizes discharge phenomena such as amplating method
It is made by a deposition method. For example, glow discharge method
According to
In order to form layer region 1 (G), basically
For Ge supply that can supply Rumanium atoms (Ge)
Raw material gas and, if necessary, silicon atoms (Si)
Raw material gas for Si supply, hydrogen atoms that can supply
(H) Raw material gas or/and halogen atom for introduction
(X) The internal pressure of the raw material gas for introduction can be reduced.
The gas is introduced into the deposition chamber at the desired pressure and the deposition is carried out.
Create a glow discharge in the room and set it in a predetermined position.
If a layer is formed on the surface of a predetermined support,
good. To distribute germanium atoms unevenly
is the distribution concentration C of germanium atoms contained in
a-Ge while controlling according to the desired rate of change curve.
A layer consisting of (Si, H, X) may be formed.
In addition, when forming by sputtering method, for example
For example, use an inert gas such as Ar or He, or a base of these gases.
composed of Si in a low-temperature mixed gas atmosphere.
The target, or the target and Ge
Using two of the targets, or with Si.
Using a mixed target of Ge as needed
Ge supply diluted with diluent gas such as He, Ar etc.
or raw material gas for Si supply as needed.
Depending on the hydrogen atom (H) or/and halogen atom
(X) Deposition chamber for sputtering introduction gas
to form a plasma atmosphere of the desired gas.
At the same time, the raw material gas for supplying Ge or/and
The gas flow rate of the raw material gas for Si supply is adjusted to the desired rate of change curve.
Splash the target while controlling according to the line.
It would be better to do it by tuttering. In the case of ion plating, for example,
Crystalline silicon or single crystal silicon and polycrystalline germanium
aluminum or single crystal germanium as evaporation sources, respectively.
The evaporation source is housed in a evaporation boat as a
Thermal method, electron beam method (EB method), etc.
The flying evaporates are heated and evaporated into the desired gas.
Except for passing through the plasma atmosphere, spatter
This can be done in the same way as the ring method.
Ru. Raw material gas for supplying Si used in the present invention
Possible substances include SiH_Four,Si₂H₆,Si₃H₈，
Si_FourH_Tensilicon hydride in a gaseous state or capable of being gasified, such as
Elements (silanes) are listed as being effectively used.
In particular, ease of handling during layer creation work and Si supply
SiH in terms of good feeding efficiency, etc._Four,Si₂H₆is preferable
It is mentioned as Substances that can be used as raw material gas for Ge supply include:
GeH_Four,Ge₂H₆,Ge₃H₈,Ge_FourH_Ten,Ge_FiveH₁₂,Ge₆
H₁₄,Ge₇H₁₆,Ge₈H₁₈,Ge₉H₂₀gas state such as
Or germanium hydride, which can be gasified, can be used effectively.
It is mentioned as being used, especially for layer creation work.
In terms of ease of handling and good Ge supply efficiency,
GeH_Four,Ge₂H₆,Ge₃H₈are listed as preferable.
can be lost. For introducing halogen atoms used in the present invention
Many halogenated gases are effective as raw material gases for
For example, halogen gas, halogen
compounds, interhalogens, halogen-substituted
Gaseous or gasifiable materials such as silane derivatives
Preferred examples include rogene compounds. Furthermore, silicon atoms and halogen atoms
Constituent gaseous or gasifiable halo
Silicon hydride compounds containing gen atoms are also effective.
In the present invention, the following can be mentioned. Halogen compounds that can be suitably used in the present invention
Specifically, the substances include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF₃，
BrF_Five,BrF₃,IF₃,IF₇, ICl, IBr, etc.
Intermediate compounds can be mentioned. Silicon compounds containing halogen atoms, so-called halogens
Examples of silane derivatives substituted with carbon atoms include
For example, SiF_Four,Si₂F₆,SiCl_Four, SiBr_Fouretc.
Silicon rogenide is preferred.
I can do it. Adopts silicon compounds containing such halogen atoms
The characteristic light guide of the present invention is produced by the glow discharge method.
When forming electrical parts, raw material gas for Ge supply is required.
Hydrogenation as a raw material gas that can supply Si along with gas
can be deposited on the desired support without the use of silicon gas.
A first layer region made of a-SiGe containing rogen atoms
It is possible to form a region (G). According to the glow discharge method,
When creating the layer area (G) of layer 1, basically the example
For example, silicon halide, which is the raw material gas for supplying Si,
Germanium hydride, which is the raw material gas for Ge supply
and Ar,H₂, He and other gases at a predetermined mixing ratio.
Form the first layer region (G) so that the flow rate is
This is introduced into a deposition chamber where a glow discharge is generated.
By forming a gas plasma atmosphere of
to form a first layer region (G) on a desired support.
However, it is possible to control the introduction ratio of hydrogen atoms.
to these gases to make it even easier to measure
Hydrogen gas or silicon compound gas containing hydrogen atoms
They may also be mixed in desired amounts to form a layer. In addition, each gas can be used not only as a single species but also in a predetermined mixing ratio.
There is no problem in using a mixture of multiple types. Sputtering method, ion plating method
In either case, halogen atoms are present in the layer formed.
In order to introduce the above-mentioned halogen compound or the above-mentioned
Deposition chamber of silicon compound gas containing halogen atoms
to form a plasma atmosphere of the gas.
Just do it. In addition, when introducing hydrogen atoms, hydrogen atom guide
Necessary raw material gas, e.g. H₂, or the above
Gases such as silanes and/or germanium hydride
The gas is introduced into a deposition chamber for sputtering.
All that is required is to form a plasma atmosphere of gases. In the present invention, raw materials for introducing halogen atoms
The halogen compounds or halogens listed above as gases
Silicon compounds containing gen are used as effective ones.
In addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH₂F₂,SiH₂
I₂,SiH₂Cl₂,SiHCl₃,SiH₂Br₂,SiHBr₃etc.
rogane-substituted silicon hydride and GeHF₃, GeH₂F₂，
GeH₃F, GeHCl₃, GeH₂Cl₂, GeH₃Cl,
GeHBr₃, GeH₂Br₂, GeH₃Br, GeHI₃, GeH₂
I₂, GeH₃Germanium hydrogenated halides such as I,
Halogenation in which hydrogen atoms are one of the constituent elements, such as
matter, GeF_Four, GeCl_Four, GeBr_Four, GeI_Four, GeF₂，
GeCl₂, GeBr₂, GeI₂germanium halides such as
Substances that are in a gaseous state or can be gasified, such as
As an effective starting material for forming the first layer region (G)
I can list the following. Halides containing hydrogen atoms in these substances
When forming the first layer region (G), halogen is added in the layer.
At the same time as the introduction of electron atoms, electrical or photoelectric properties can be improved.
Hydrogen atoms, which are extremely effective for control, are also introduced, so
In the present invention, a suitable raw material for introducing halogen is
used. Hydrogen atoms are structurally introduced into the first layer region (G).
In addition to the above, press H₂, or SiH_Four,Si₂
H₆,Si₃H₈,Si_FourH_TenSupplying Ge such as silicon hydride
germanium or germanium compounds for
Or, GeH_Four,Ge₂H₆,Ge₃H₈,Ge_FourH_Ten，
Ge_FiveH₁₂,Ge₆H₁₄,Ge₇H₁₆,Ge₈H₁₈,Ge₉H₂₀etc
silicon to supply germanium hydride and Si
or a silicon compound in the deposition chamber.
This can also be done by causing a discharge. In a preferred embodiment of the invention, the light guide formed
Hydrogen contained in the first layer region (G) of the electrical member
The amount of atoms (H) or the amount of halogen atoms (X) or
The sum of the amounts of hydrogen atoms and halogen atoms (H+X) is favorable.
Preferably 0.01~40atomic%, more preferably 0.05~
It is said to be 30 atomic%, optimally 0.1 to 25 atomic%. Hydrogen atoms contained in the first layer region (G)
Control the amount of (H) or/and halogen atom (X)
For example, support temperature or/and hydrogen atom
(H) or to contain a halogen atom (X)
Introducing into the deposition system the starting materials used for
It is sufficient to control the amount, discharge force, etc. In the photoconductive member of the present invention, germanium
Second layer region (S) containing no atoms, germanium
In the first layer region (G) containing nium atoms,
Containing a substance (C) that controls conduction properties
Accordingly, the second layer region (S) and the first layer region
The conduction characteristics of the region (G) can be arbitrarily controlled as desired.
Rukoto can. At this time, the above contained in the second layer region (S)
The substance (C) covers the entire first layer region (G) or
It may be contained in some layer areas, but in any case
It is also contained in a state where it is distributed more towards the support side.
need to be That is, the setting in the second layer region (S)
Layer area (SPN) containing the substance (C) to be eclipsed
is provided as the entire layer area of the second layer area (S).
or supported as part of the second layer region (S).
Provided as a support side end layer region (SE). Before
If the area is set up as a full-level area for the
The fabric density C(S) is linear toward the support side.
increase in a straight line or in a stepwise manner or in a curved manner
It is set up as follows. When the distribution concentration C(S) increases in a curved manner,
The conductivity increases monotonically toward the support side.
The substance (C) that controls
It is desirable to provide one. layer region (SPN) into the second layer region (S),
If provided as part of the layer area (SPN)
The distribution state of the substance (C) inside is determined by the surface of the support.
In the in-plane direction parallel to the plane, it is considered to be uniform.
However, in the layer thickness direction, there is no difference whether it is uniform or non-uniform.
I can't support it. In this case, in the layer region (SPN),
The material (C) is set so that it is distributed non-uniformly in the layer thickness direction.
In order to
It is set so that the distribution concentration line is the same as when it is set in
It is desirable to Material that controls conductivity in the first layer region (G)
A layer containing the substance (C) by containing (C)
Even when providing a region (GPN), the second layer region
Proceed in the same way as when creating a layer region (SPN) in (S).
I can do it. In the present invention, the first layer region (G) and the first layer region (G)
The conduction properties can be controlled in either of the two layer regions (S).
When containing substance (C), it is contained in both layer regions.
The substances (C) to be treated may be of the same type but different from each other.
Also good. However, the same type of conductivity is controlled in both layer regions.
When containing a substance (C) that
The maximum distribution concentration in the layer thickness direction of (C) is the second
in the layer region (S), i.e. the second layer region (S)
or at the interface with the first layer region (G)
It is preferable to provide the same. In particular, the maximum distribution
The concentration is at the contact interface with the first layer region (G) or at the contact interface with the first layer region (G).
It is desirable to provide it near the interface. In the present invention, as described above, the first layer ()
Containing a substance (C) that controls conduction characteristics inside
The layer region (PN) containing the substance (C) is
occupies at least a part of the layer area (S) of
Preferably, the support of the second layer region (S)
Provided as the body side end layer region (SE). The layer region (PN) is the first layer region (G) and the second layer region (G).
When provided so as to straddle both layer regions (S) of
includes a layer region of material (C) that controls the conduction properties.
The maximum distribution concentration C(G)max at (GPN),
Maximum distribution concentration C(S) in the layer region (SPN)
max, C(G)max<C(S)max.
The substance (C) is the first layer so that the relational expression holds true.
Contained in parentheses. Control the conductivity contained in the layer region (PN)
As a substance (C), it is called in the semiconductor field.
In the present invention, impurities can be mentioned.
gives p-type conductivity to Si or Ge
p-type impurity and n-type impurity that provides n-type conduction characteristics
I can name things. Specifically, as a p-type impurity,
Atoms belonging to the group (Group atoms), for example, B (B)
element), Al (aluminum), Ga (gallium), In
Especially suitable are Tl (thallium), etc.
B and Ga are used for this purpose. As an n-type impurity, it belongs to group of the periodic table.
atoms (group atoms), e.g. P (phosphorus), As (arsenic)
element), Sb (antimony), Bi (bismuth), etc.
Particularly preferably used are P and As. In the present invention, provided in the first layer ()
to control the conductive properties contained in the layer region (PN).
The content of the substance (C) required in the layer region (PN) is
The required conduction properties or the layer area (PN) are
a support or other layer area provided in contact with the
organic relationships, such as the relationship with the properties at the contact interface.
It can be selected as appropriate depending on the gender. Also, before
of other layer areas provided in direct contact with the recording area.
properties and properties at the contact interface with other layer regions
The relationship between substances that control conduction properties is also taken into consideration.
The content of (C) is appropriately selected. In the present invention, contained in the layer region (PN)
The content of the substance (C) that controls the conduction properties of
Preferably 0.01~5×10^Fouratomic ppm, more preferred
is 0.5~1×10^Fouratomic ppm, optimally 1-5×
Ten³Considered to be atomic ppm. In the present invention, the substance controlling the conduction properties
The layer region (PN) containing (C) is the first layer region.
In contact with the contact interface between the region (G) and the second layer region (S)
or a part of the layer region (PN) is the first layer region.
occupy at least a part of the area (G), and
Content of the substance (C) in the layer region (PN)
, preferably 30 atomic ppm or more, more preferably
is at least 50 atomic ppm, optimally 100 atomic ppm
By doing the above, for example, the substance to be included
If the quality is the p-type impurity mentioned above, the self-reflection of the photoreceptive layer
When the support surface is polarized and charged,
The transfer of electrons injected into the second layer region (S) from
It is possible to effectively prevent the above-mentioned
If the substance to be used is the above-mentioned n-type impurity, the light receiving
When the free surface of the capacitor layer is subjected to polar charging treatment
Injected into the second layer region (S) from the support side.
can effectively prevent the movement of holes.
Ru. In the above case, the above-mentioned basic structure of the present invention
The layer area excluding the layer area (PN) below the formation
In the region (Z), there is a conduction contained in the layer region (PN).
conduction characteristics with a polarity different from the polarity of the material that governs its properties.
It may contain a substance that controls sex, or
is the material that governs the conduction properties of the same polarity in the layer region
much less than the actual amount contained in (PN).
It may be contained in a small amount. In such a case, the material contained in the layer region (Z)
The content of the substance that governs the conduction properties varies depending on the layer region.
The polarity and content of the above substances contained in the range (PN)
It shall be determined as appropriate according to the desire.
but preferably 0.001 to 1000 atomic ppm, more preferably
Suitably 0.05~500atomic ppm, optimally 0.1~
It is estimated to be 200 atomic ppm. In the present invention, a layer region (PN) and a layer region
(Z) contains a substance that controls the same kind of conductivity.
In the case where the content in the layer region (Z) is
Preferably, it should be 30 atomic ppm or less. In the above case
In addition to the above, in the present invention, in the first layer ()
In addition, a substance that controls conductivity with one polarity is
Containing layer region and conductivity with the other polarity
Direct contact with the layer containing the substance that controls the
A so-called depletion layer is provided in the contact region.
You can also do that. That is, for example the first layer ()
Therein, the layer region containing the p-type impurity and the layer region containing the p-type impurity.
in direct contact with the layer region containing n-type impurities.
A depletion layer is formed by forming a so-called p-n junction.
Can be set up. In Figures 11 to 24, in the first layer ()
layer of substance (C) that controls conduction properties contained in
A typical example of the distribution state in the thickness direction is shown. In these figures, the horizontal axis is the layer thickness of material (C)
The distribution concentration C(PN) in the direction, the vertical axis is the first layer
The layer thickness t from the support side in parentheses is shown. t_B
is the position of the interface between the support and the layer region (G), t₀is a layer
The position of the contact interface between the region (G) and the layer region (S), t_T
indicates the position of the end face of the layer region (S). FIG. 11 shows the amount contained in the first layer ().
Distribution of substance (C) that controls conduction properties in the layer thickness direction
A first typical example of the condition is shown. Shown in Figure 11
In this example, the substance (C) is in the first layer region (G).
is not contained in the second layer region (S).
, concentration C₁Contained in a uniformly distributed concentration.
Clogging, the second layer region (S) is t₀and t₁end layer between
The substance (C) in the area has a concentration C₁with a constant distribution concentration of
Contains. In the example of FIG. 12, in the first layer region (G),
Substance (C) is contained evenly, but
The substance (C) is not contained in the second layer region (S).
do not have. And the substance (C) is t₀and t₂layer between
In the area, the distribution concentration is C₂is contained at a constant concentration, t₂
and t_TThe layer region between C₂The concentration is much lower than that of
degree C₃Contained at a certain concentration. Substance (C) is first distributed with such distribution concentration C(PN).
Contained in the second layer region (S) constituting the first layer ()
By having the second layer region (G), the second layer region (G)
Transfer of charges injected into the layer region (S) toward the surface
At the same time, it can effectively prevent the movement of light.
Improvements in sensitivity and dark resistance can be measured. In the example of FIG. 13, the first layer region (G) contains a material.
Although (C) is uniformly contained, t₀in
concentration C_Fourt decreases monotonically toward the upper surface._Tto
The distribution concentration C(PN) changes so that the concentration becomes 0 at
Substance (C) is contained in the form of
The substance (C) is contained in the first layer region (G).
do not have. In the case of the examples in Figures 14 and 15, the substance
(C) is in the lower end layer region of the second layer region (S).
This is an example where it is unevenly contained. That is, the 14th
In the case of the example shown in the figure and FIG. 15, the second layer region
(S) is a layer region containing substance (C);
The layer regions that do not contain substance (C) are arranged in this order.
It has a layered structure in which layers are stacked from the support side. In the case of the examples in Figures 14 and 15, different
The point in Figure 14 is that the distribution concentration C(PN) is t₀
and t₃In between, t₀Concentration C at position_FiveMoret₃rank
While the concentration decreases monotonically to 0 at
So, in the case of Figure 15, t₀and t_FourIn between, t₀of
Concentration C at position₆Moret_FourLinear to concentration 0 at position
This is a continuous decline. Figure 14
In the case of the example shown in FIG.
Quality (C) is not included. In the examples shown in FIGS. 17 to 24, the first
The information is transmitted to both the layer region (G) and the second layer region (S).
When a substance (C) that controls conductivity is contained
is shown. In the case of the examples shown in FIGS. 17 to 22, the second layer
Region (S) is a layer region containing substance (C).
area and the layer area that does not contain substance (C) are supported.
It has a two-layer structure laminated in this order from the body side.
What they have in common is that Among them, Figures 17 to 2
In the example in Figure 1, both are the first layer region.
The distribution state of substance (C) in (G) is the second layer
Interface position t with region (S)₀towards the support side
It has a changing state of the distribution concentration C(PN) which is decreasing.
That's what I'm doing. In the case of the examples in Figures 23 and 24, the first layer
Substance (C) in the layer thickness direction over the entire layer area of ()
It contains all kinds of things. In addition, Figure 23
In the case, in the first layer region (G), t_BAt
concentration C_{twenty three}Moret₀Concentration C at_{twenty two}until t_BMoret₀
increases linearly towards the second layer region (S).
In this case, t₀Concentration C at_{twenty two}Moret_Tconcentration at
t to 0₀Moret_Tdecreases monotonically and continuously toward
ing. In the case of Figure 24, t_Band t₁₃In the layer area between
So, the concentration C_{twenty four}Contains substance (C) at a constant distribution concentration of
possessed, t₁₃and t_TIn the layer region between
C_{twenty five}more linearly decreasing, t_Treaches 0 at
ing. In the above figures 11 to 24, the first layer
() of the substance (C) that controls conductivity in
We will explain a typical example of a change in the distribution concentration C(PN).
As explained, in each example, the substance (C)
such that the maximum distribution concentration of is in the second layer region (S)
The substance (C) is contained in the first layer ( ). In the present invention, it is composed of a-Si(H,X).
To form the second layer region (S), the above-mentioned step
In the starting material () for forming the layer region (G) of
The starting material, which becomes the raw material gas for G supply, is removed.
Starting material [Starting material for forming the second layer region (S)
()] to form the first layer region (G).
may be carried out in the same manner and under the same conditions as when
come. That is, in the present invention, a structure composed of a-Si(H,X)
For example, to form the second layer region (S)
Glow discharge method, sputtering method, or ionic
Vacuum that utilizes discharge phenomena such as amplating method
It is made by a deposition method. For example, glow discharge method
, the second composed of a-Si(H,X)
To form the layer region (S), basically the above-mentioned steps are performed.
A raw material for Si supply that can supply silicon atoms (Si)
Hydrogen atoms (H) are introduced as necessary along with the feed gas
or/and raw material for introducing halogen atoms (X)
A gas is introduced into a deposition chamber whose interior can be reduced in pressure.
A glow discharge is generated in the deposition chamber, and a predetermined
a on a predetermined support surface installed in a fixed position.
A layer consisting of -Si(H,X) may be formed.
In addition, when forming by sputtering method, for example
For example, inert gas such as Ar, He, etc.
composed of Si in a mixed gas atmosphere based on
When sputtering a target, hydrogen atoms
(H) or/and halogen atom (X) introduction gas
If the gas is introduced into the deposition chamber for sputtering,
good. In the present invention, the first layer () to be formed is
Hydrogen contained in the constituent second layer region (S)
The amount of atoms (H) or the amount of halogen atoms (X) or
The sum of the amounts of hydrogen atoms and halogen atoms (H+X) is
Preferably 1 to 40 atomic%, more preferably 5 to 40 atomic%
It is set at 30 atomic%, optimally from 5 to 25 atomic%. There is a conductive characteristic in the layer region constituting the first layer ().
Substances that control the properties (C), such as group atoms or
Alternatively, group atoms may be structurally introduced to form the substance.
To form a layer region (PN) containing (C)
is the starting material for the introduction of group atoms during layer formation.
Alternatively, the starting material for introducing group atoms may be in a gaseous state.
In the deposition chamber, another layer is added for forming the first layer ().
It may be introduced together with the starting material. Like this
As a potential starting material for the introduction of group atoms
is gaseous or at least layer-forming at normal temperature and pressure.
Materials that can be easily gasified under certain conditions are used.
is desirable. Starting materials for the introduction of such group atoms
Specifically, for the introduction of boron atoms,
B₂H₆,B_FourH_Ten,B_FiveH₉,B_FiveH₁₁,B₆H_Ten,B₆H₁₂，
B₆H₁₄Boron hydride, BF etc.₃, BCl₃,BBr₃etc.
Examples include boron halides. In addition,
AlCl₃,GaCl₃, Ga(CH₃)₃,InCl₃, TlCl₃etc. are also listed
You can get it. As a starting material for the introduction of group atoms,
It is effectively used for introducing phosphorus atoms.
So, PH₃,P₂H_FourHydrogenated phosphorus, PH etc._FourI, P.F.₃，
P.F._Five, PCl₃, PCl_Five, PBr₃, PBr_Five, P.I.₃etc. halogen
Examples include phosphorus chloride. In addition, AsH₃,AsF₃，
AsCl₃, AsBr₃,AsF_Five,SbH₃,SbF₃,SbF_Five，
SbCl₃,SbCl_Five, BiH₃, BiCl₃, BiBr₃etc. also group
Listed as effective starting materials for atom introduction
I can do it. In the photoconductive member of the present invention, high photosensitivity and
High dark resistance, furthermore, support and first layer ()
For the purpose of improving the adhesion between
An oxygen atom is contained in (). first layer
The oxygen atoms contained in () are the first layer ()
It may be evenly contained in the entire layer area, or
is contained only in some layer regions of the first layer ().
It may also be unevenly distributed. In addition, the distribution state of oxygen atoms is such that the distribution concentration C(O) is
The first layer () is uniform in the thickness direction.
However, the distribution concentration C(O) is non-uniform in the layer thickness direction.
It's okay to be. In the present invention, provided in the first layer ()
The layer region (O) containing oxygen atoms is photosensitive.
If the main purpose is to improve the power and dark resistance,
It is set so that it occupies the entire layer area of the first layer ().
, the support and the first layer ( ) or the first layer region
(G) and the second layer region (S)
If the main purpose is to measure the
The support side end layer region of the layer () or the first and second layer regions
It is provided so as to occupy the area near the interface between the two layer regions.
Ru. In the former case, the oxygen contained in the layer region (O)
The atomic content is relatively low to maintain high photosensitivity.
In the latter case, the strength of the adhesion between the layers
It is desirable that the amount be relatively large in order to reliably measure the
stomach. Also, the purpose of achieving both the former and the latter at the same time.
In order to
relatively on the free surface side of the first layer ().
Distribute to low concentration or first layer ()
Oxygen atoms are actively added to the surface region on the free surface side of the
The distribution of oxygen atoms in the layer is such that it is not included in the layer.
It may be formed in the area (O). Furthermore, the support or the first layer region (G)
to prevent charge injection into the second layer region (S).
If the purpose is to increase the apparent resistance,
Highly concentrated acid is applied to the support side end of the first layer region (G).
The elementary atoms are distributed in the first layer region and the second layer region.
Oxygen atoms are distributed at a high concentration near the interface of the area. Figures 25 to 40 show the entire first layer ().
A typical example of the distribution state of oxygen atoms as a body is shown.
It can be done. Please note that we do not wish to explain any of these figures.
Symbols used without reference are shown in Figures 2 to 10.
It has the same meaning as when used. In the example shown in FIG. 25, the position t_BMore position₁
Until the oxygen atom distribution concentration is C₁is assumed to be a constant value,
position t₁from position t_TThe oxygen atom distribution concentration is up to C₂Toichi
It is said to be fixed. In the example shown in FIG. 26, the position t_BMore position₂
Until the oxygen atom distribution concentration is C₃is assumed to be a constant value,
position t₂More position₃Until the oxygen atom distribution concentration is C_Fourand
and position t₃from position t_TUp to the oxygen atom distribution concentration
is C_FiveThe oxygen atom distribution concentration is reduced in three stages.
I'm letting you do it. In the example in Figure 27, position t_BMore position_Fourup to oxygen
The atomic distribution concentration is C₆and position t_Fourfrom position t_Tup to acid
The elementary atom distribution concentration is C₇It is said that In the example in Figure 28, position t_BMore position_Fiveup to oxygen
The atomic distribution concentration is C₈and position t_Fivefrom position t₆up to acid
The elementary atom distribution concentration is C₉and position t₆from position t_Tto
The oxygen atom distribution concentration is C_TenIt is said that in this way
The oxygen atom distribution concentration is increased in three stages. In the example of Figure 29, position t_BMore position₇up to oxygen
The atomic distribution concentration is C₁₁and position t₇from position t₈up to acid
The elementary atom distribution concentration is C₁₂and position t₈from position t_Tto
The oxygen atom distribution concentration is C₁₃It is said that Support side
and the oxygen atom distribution concentration becomes higher on the free surface side.
It's there. In the example shown in FIG. 30, position t_BMore position₉
Until the oxygen atom distribution concentration is C₁₄and position t₉mosquito
ra position t_TenOxygen atomic distribution concentration up to C₁₅and position
t_Tenfrom position t_TThe oxygen atom distribution concentration up to C₁₄as
There is. In the example shown in FIG. 31, the position t_Bfrom position t₁₁
The oxygen atom distribution concentration up to C₁₆position t₁₁from position
t₁₂The oxygen atom distribution concentration is up to C₁₇increased in stages with
Set, position t₁₂from position t_TThe oxygen atom distribution concentration is up to
C₁₇and is decreasing. In the example in Figure 32, position t_Bfrom position t₁₃up to oxygen
The atomic distribution concentration is C₁₉and position t₁₃from position t₁₄to
Oxygen atom distribution concentration is C₂₀and increase in stages,
Placement₁₄from position t_TThe oxygen atom distribution concentration is reduced to the initial concentration.
Concentration less than degree C_{twenty one}It is said that In the example shown in FIG. 33, the position t_Bfrom position t₁₅
The oxygen atom distribution concentration is up to C_{twenty two}and position t₁₅Kara position
Placement₁₆Oxygen atomic distribution concentration up to C_{twenty three}decrease to
Placement₁₆from position t₁₇Oxygen atomic distribution concentration up to C_{twenty four}and stages
increase position t₁₈from position t_TUp to oxygen atoms
Cloth density C_{twenty three}has been reduced to. In the example shown in Figure 34, the distribution concentration of oxygen atoms is
The degree C(O) is the position t_BMore position_TThe distribution density becomes
degree 0 to C_{twenty five}It continues to monotonically increase up to . In the example shown in Figure 35, the distribution concentration of oxygen atoms is
The degree C(O) is the position t_B, the distribution concentration C₂₆in,
The distribution concentration C₂₆From position t₁₈It's monotonous until
continuously decreases to position t₁₈distribution concentration C₂₇Tonatsu
ing. position t₁₈More position_TIn between, oxygen
The distribution concentration of atoms C(O) is given by the position t₁₈more consecutively
increases monotonically, position t_TThe distribution concentration C at₂₈and
It's summery. In the example in Figure 36, compare with the example in Figure 35.
Similar but different in position t₁₉and position
t₂₀Because it does not contain oxygen atoms,
be. position t_Band position t₁₉Between position t_Bdistribution in
Concentration C₂₉More position₁₉Continuous until distribution concentration 0 in
decreases monotonically, and the position t₂₀and position t_Tbetween the positions
t₂₀The distribution density at position t from 0_Bdistribution density in
degree C₃₀It continues to monotonically increase up to . In the photoconductive member of the present invention, FIGS.
As a typical example is shown in Fig. 36, the first layer
( ) on the lower surface and/or upper surface side.
containing oxygen atoms and inside the first layer ()
In order to
, the distribution concentration C(O) of oxygen atoms in the layer thickness direction is
By continuously changing, for example, the first layer
Efforts are being made to increase the light sensitivity and dark resistance of (). In addition, in Figures 34 to 36, acid
Continuously changing the distribution concentration C(O) of elementary atoms
In the layer thickness direction due to the inclusion of oxygen atoms,
Coherence of laser light, etc. by slowing the change in refractive index
It effectively prevents interference caused by light. In the example shown in FIG. 37, the position t_BMore position_{twenty one}
Until the oxygen atomic concentration is C₃₁and position t_{twenty one}Kara position
Placement_{twenty two}increases to position t_{twenty one}The oxygen atomic concentration peaks at
value C₃₂become. position t_{twenty two}from position t_{twenty three}Oxygen atomic concentration up to
degree decreases and position t_TThe oxygen atomic concentration C₃₁becomes. In the example shown in FIG. 38, the position t_Bfrom position t_{twenty four}
Until the oxygen atomic concentration is C₃₃and position t_{twenty four}from position
t_{twenty five}increases rapidly until position t_{twenty five}The oxygen atomic concentration is
mark value C₃₄and position t_{twenty five}from position t_Tup to oxygen source
The concentration decreases until it is almost zero. In the example shown in FIG. 39, position t_Bfrom position t₂₆
The oxygen atomic concentration is up to C₃₅from C₃₆slowly increasing to
addition, position t₂₆The oxygen atom concentration is the peak value C₃₆Tona
Ru. position t₂₆from position t_TThe oxygen atomic concentration rapidly increases until
decrease position t_TThe oxygen atomic concentration C₃₅becomes. In the example shown in FIG. 40, the position t_Boxygen atom in
Concentration C₃₇at position t₂₉The oxygen atomic concentration decreases until oxygen
Atomic concentration C₃₈The position t₂₉from position t₂₈up to oxygen source
Child concentration C₂₈is constant. position t₂₈from position t₂₉to
The oxygen atom concentration increases and the position t₂₉Oxygen atomic concentration at
is the peak value C₃₉Take. position t₂₉from position t_Tup to acid
The elementary atom concentration decreases at position t_TThe oxygen atomic concentration C₃₈and
Become. In the present invention, the layer region (O) is the first layer.
() or the first layer ()
Even if it does not occupy the entire area, the layer thickness T of the layer region (O)₀
The proportion of the first layer () in the layer thickness T is sufficiently large.
If the oxygen atoms contained in the layer region (O)
The upper limit of the content of
It is desirable to In the case of the present invention, the layer thickness T of the layer region (O)₀but
The ratio of the first layer () to the layer thickness T is 5
In the case where it is more than 2/2, in the layer area (O)
The upper limit for the amount of oxygen atoms contained in silicon
Three atoms: Con atom, germanium atom, and oxygen atom
For the sum (hereinafter referred to as "T (SiGeO)"),
Preferably 30 atomic% or less, more preferably
It should be less than 20 atomic%, optimally less than 10 atomic%.
It can be done. In the present invention, the acid constituting the first layer ()
The layer region (O) containing elementary atoms is as described above.
The proportion of oxygen atoms on the support side and near the free surface increases.
It has a localized region (B) containing relatively high concentration.
It is desirable that the former be provided as a
In some cases, close contact between the support and the first layer ()
Further improving sexual performance and improving receptive potential
can be measured. The above localized region (B) is shown in FIGS. 25 to 40.
To explain using the symbols shown in , the interface position t_BAlso
is the free surface t_TIt is desirable to set the distance within 5μ.
stomach. In the present invention, the localized region (B) is a field
surface position t_Bor free surface t_TFull layer area up to 5μ thick
Area (L_T), or the layer area
(L_T). The localized region (B) is transformed into a layered region (L_T) as part of
Whether it is all or all depends on the layer being formed
It is determined as appropriate according to the characteristics. The localized region (B) is the oxygen source contained therein.
The distribution concentration of oxygen atoms is expressed as the distribution state in the layer thickness direction.
The maximum value Cmax of the degree is preferably 500 atomic ppm
or more, more preferably 800 atomic ppm or more, optimal
The distribution pattern is said to be more than 1000 atomic ppm.
The layer is formed in such a way that it can be layered. That is, in the present invention, oxygen atom-containing
The layer area (O) is located from the support side or free surface.
Within 5μ for layer thickness (t_Bor t_T(from 5μ thick layer area)
is formed such that there is a maximum value Cmax of the distribution concentration at
It is desirable that In the present invention, the purpose of the present invention can be achieved more effectively.
of oxygen atoms in the layer region (O) to achieve
The distribution concentration line in the layer thickness direction is
The layer area is smooth and continuous.
It is desirable that (O) contains an oxygen atom.
Also, the distribution concentration line has its maximum distribution concentration Cmax
is designed to exist inside the first layer ()
By doing so, the effects described later will be clearly demonstrated.
Ru. In the present invention, the maximum distribution concentration Cmax
is preferably opposite to the support of the first layer ().
Provided near the paired surface (free surface side in Figure 1)
It is desirable to be able to do so. In this case, the maximum distribution concentration
By appropriately selecting Cmax, the free surface side of the photoreceptive layer can be
When subjected to charging treatment, the inside of the photoreceptive layer is
to effectively prevent charge from being injected into the
I can do it. In addition, near the free surface, oxygen atoms
Maximum distribution concentration Cmax when the distribution concentration is towards the free surface
Oxygen atoms are included in the first layer so that they decrease more steeply.
This increases durability in humid atmospheres.
It can be further improved. The distribution concentration curve of oxygen atoms is the maximum distribution concentration Cmax
in the first layer (), further
The distribution is divided so that the maximum value of the distribution concentration is on the side of the support.
Design the fabric concentration curve to contain oxygen atoms.
and the adhesion and charge between the support and the first layer.
Injection prevention can be improved. In the present invention, oxygen atoms are present in the first layer ()
In the central layer region, efforts are made to increase the dark resistance.
However, it is contained in an amount that does not reduce photosensitivity.
It is desirable to In the present invention, the maximum distribution concentration of oxygen atoms
Cmax is preferably for T(SiGeO)
67 atomic% or less, more preferably 50 atomic% or less
The optimum value is 40 atomic% or less. In the present invention, provided in the first layer ()
The content of oxygen atoms contained in the layer region (O) is
Characteristics required for the layer region (O) itself or the layer
When the region (O) is provided in direct contact with the support
In this case, the characteristics of the contact interface with the support
Make appropriate selections in terms of organic relationships such as relationships.
I can do that. In addition, other layer regions may be directly contacted with the layer region (O).
If a region is provided, the characteristics of the other layer region
and the characteristics at the contact interface with other layer regions.
The content of oxygen atoms is selected appropriately, taking into account the relationship
be done. The amount of oxygen atoms contained in the layer region (O) is
Depending on the characteristics required for the photoconductive member to be formed.
Although it can be determined appropriately according to the desire, T (SiGeO)
preferably 0.001 to 50 atomic%, more preferably
Ideally 0.002~40atomic%, optimally 0.003~
It is assumed to be 30 atomic%. In the present invention, oxygen atoms are added to the first layer ().
To provide a contained layer region (O), a first layer
The starting material for introducing oxygen atoms during the formation of ()
Used with starting materials for the formation of the first layer ()
and contain the amount in the formed layer while controlling the amount.
Just do it. Glow discharge method is used to form the layer region (O)
If present, starting materials for the formation of the first layer ()
Oxygen atoms selected from among
Starting material for introduction is added. Such an oxygen source
At least an oxygen source is used as a starting material for the introduction of oxygen.
A gaseous substance whose constituent atoms are atoms that can be gasified
Most of the gasified substances used are
can be done. For example, a material whose constituent atoms are silicon atoms (Si).
Raw material gas and raw material containing oxygen atoms (O) as constituent atoms
gas and, if necessary, hydrogen atoms (H) or
A raw material gas containing rogen atoms (X) as constituent atoms.
Use by mixing at the desired mixing ratio, or
A raw material gas containing silicon atoms (Si) and an acid
The constituent atoms are elementary atoms (O) and hydrogen atoms (H).
and raw material gas at the desired mixing ratio.
or silicon atoms (Si) as constituent atoms.
raw material gas, silicon atoms (Si), and oxygen atoms
The three constituent atoms are (O) and hydrogen atom (H)
It can be used in combination with raw material gas. Also, separately, silicon atoms (Si) and hydrogen atoms
Oxygen atoms in the raw material gas whose constituent atoms are (H)
Mix and use raw material gas containing (O) as a constituent atom
You may do so. Specifically, for example, oxygen (O₂), ozone (O₃),
-Nitric oxide (NO), nitrogen dioxide (NO₂), diacid
Nitrogen (N₂O), nitrogen sesquioxide (N₂O₃), tetradic acid
Nitrogen (N₂O_Four), nitrogen pentoxide (N₂O_Five), trioxide
Nitrogen (NO₃), silicon atoms (Si) and oxygen atoms
Example where (O) and hydrogen atom (H) are constituent atoms
For example, disiloxane (H₃SiOSiH₃), Toshiroki
Sun (H₃SiOSiH₂OSiH₃) and other lower siloxanes
etc. can be mentioned. Oxygen-containing oxygen atoms are produced by sputtering.
To form the layer region (O), single crystal or polycrystalline
Si wafer or SiO₂Wafer or Si
SiO₃A wafer containing a mixture of
These are used as targets in various gas atmospheres.
This can be done by sputtering. For example, using a Si wafer as a target
Then, oxygen atoms and optionally hydrogen atoms or/
and raw material gas for introducing halogen atoms.
Dilute with diluting gas as necessary to make it suitable for sputtering.
A gas plasma of these gases is introduced into the deposition chamber.
The Si wafer is sputtered by forming
That's fine. Also, separately, Si and SiO₂target different from
as or Si and SiO₂A single target mixed with
By using the
in an atmosphere of diluent gas as a gas or at least
Hydrogen atom (H) or/and halogen atom (X)
Sputtering in a gas atmosphere containing constituent atoms
It is done by ringing. Introduction of oxygen atom
As raw material gas for
The raw material gas for introducing oxygen atoms into the raw material gas shown in
gas is also effective in sputtering.
can be used. In the present invention, when forming the first layer ()
A layer region (O) containing oxygen atoms is provided in
In this case, the amount of oxygen atoms contained in the layer region (O) is
Create a desired layer by changing the fabric concentration C(O) in the layer thickness direction.
Layer with depth profile
To form the region (O), in the case of glow discharge
is the oxygen atom whose distribution concentration C(O) should be changed
Select the starting material gas for introduction and its desired gas flow rate.
while changing the deposition chamber as appropriate according to the rate of change curve of
This is accomplished by introducing the For example, manually
Or a commonly used external drive motor etc.
If it is installed in the middle of the gas flow path system by some method.
The opening of a predetermined needle valve is gradually changed.
All you have to do is perform the following operations. At this time, the rate of change in flow rate is
It does not have to be linear; for example, it can be done using a microcomputer, etc.
flow according to a pre-designed rate of change curve.
You can also control the amount and obtain the desired content curve.
Ru. Form layer region (O) by sputtering method
In this case, the distribution concentration of oxygen atoms in the layer thickness direction C(O)
is changed in the layer thickness direction, and the location of oxygen atoms in the layer thickness direction
To form the desired depth profile,
Firstly, as with the glow discharge method, acid
The starting material for introducing elementary atoms is used in a gaseous state, and the
Adjust the gas flow rate when introducing gas into the deposition chamber as desired.
Therefore, it can be achieved by changing it appropriately. Second, the target for sputtering,
For example, Si and SiO₂using a mixed target with
Si and SiO₂The mixing ratio with
The thickness of the target layer is changed in advance.
This is accomplished by In the photoconductive member 100 shown in FIG.
A second layer formed on the first layer ( ) 102
( ) 105 has a free surface 106 and is mainly moisture resistant.
performance, continuous repeated use characteristics, electrical pressure resistance, usage environment
Achieves the objectives of the present invention in terms of environmental characteristics and durability
established for the purpose of Further, in the present invention, the first layer ( ) 102
and the second layer ( ) 105
each have a common constituent element, silicon atoms.
chemical stability at the laminated interface.
have been sufficiently ensured. The second layer () in the present invention is made of silicon raw material.
(Si), nitrogen atom (N), and hydrogen as necessary
Contains an atom (H) or/and a halogen atom (X)
amorphous material (hereinafter referred to as “a-(Si_xN_1-x)_y(H,X)
_1-y”. However, it is composed of 0<x, y<1).
It can be done. a-(Si_xN_1-x)_y(H,X)_1-yThe second consists of
The layer () is formed by glow discharge method, sputtering
This is done by the magnetic method, electron beam method, etc.
Ru. These manufacturing methods depend on manufacturing conditions, equipment capital investment, etc.
load level, manufacturing scale, and the photoconductive member being manufactured.
Selection is made as appropriate depending on factors such as desired characteristics.
A photoconductive member having the desired properties
It is relatively easy to control the manufacturing conditions for manufacturing
Along with silicon atoms, nitrogen atoms and halogens
Introducing atoms into the second layer to be created ()
The glow discharge method or the flash discharge method has the advantage of being easy to perform.
A puttering method is preferably employed. Furthermore, in the present invention, glow discharge method and spa
The second method can be used in conjunction with the Tuttering method within the same system.
A layer ( ) may be formed. Forming the second layer () by glow discharge method
To do this, a-(Si_xN_1-x)_y(H,X)_1-yRaw materials for forming
The gas is mixed with a predetermined amount of diluent gas as needed.
Mix and introduce into a vacuum deposition chamber where a support is installed.
The introduced gas causes a glow discharge.
The gas is turned into a gas plasma by
a-(Si_x
N_1-x)_y(H,X)_1-yAll you have to do is deposit it. In the present invention, a-(Si_xN_1-x)_y(H,X)_1-y
As raw material gas for formation, silicon atoms (Si),
Nitrogen atom (N), hydrogen atom (H), halogen atom
A group consisting of at least one of (X) as a constituent atom
Gasified substances or substances that can be gasified
Most of them can be used. Si is one of the constituent atoms among Si, N, H, and
When using a raw material gas that is
A raw material gas with constituent atoms and a raw material with N atoms as constituent atoms.
raw material gas and, if necessary, raw material containing H as a constituent atom
gas or/and source gas containing X as a constituent atom
Use by mixing at the desired mixing ratio, or use Si as a structure.
A raw material gas with constituent atoms and N and H with constituent atoms.
raw material gas or/and N and X as constituent atoms
This is also mixed with the raw material gas at the desired mixing ratio.
Or, a raw material gas containing Si as a constituent atom
and a raw material gas whose constituent atoms are Si, N, and H.
or an element whose constituent atoms are Si, N, and X.
It can be used in combination with a raw material gas. In addition, there is also a raw material gas whose constituent atoms are Si and H.
Used by mixing raw material gas containing N as a constituent atom.
It is also possible to use a raw material gas containing Si and X as constituent atoms.
Used by mixing raw material gas containing N as a constituent atom.
You may do so. In the present invention, the second layer () contains
Suitable halogen atoms (X) are F, Cl,
Br, I, with F, Cl being particularly desirable.
Ru. In the present invention, forming the second layer ()
It can be used as a raw material gas that can be effectively used for
The gas is in a gas state at room temperature and pressure, or it is easily
Examples include substances that can be gasified. Form the second layer () by sputtering method
In this case, for example, the following is done. Firstly, inert gas such as Ar, He or
In a mixed gas atmosphere based on these gases
Sputtering a target made of Si with
When the raw material gas for introducing nitrogen atoms (N) is
or/and halo for hydrogen atom (H) introduction depending on
Sputtering with raw material gas for introducing Gen atoms (X)
It is best to introduce it into the vacuum deposition chamber where the ring is performed.
stomach. Second, it can be used as a target for sputtering.
TeSi₃N_FourA target composed of or Si
Configured targets and Si₃N_FourA tar made up of
Two pieces of Getu or Si and Si₃N_Fourcomposed of
The second layer formed by using targets
Nitrogen atoms (N) can be introduced into ().
Ru. At this time, the above raw material for introducing nitrogen atoms (N)
If gas is used together, the flow rate can be controlled.
of nitrogen atoms (N) introduced into the second layer ()
It is easy to arbitrarily control the amount. Nitrogen atoms (N) introduced into the second layer ()
The content of the raw material gas for introducing nitrogen atoms (N) is
Control the flow rate when introduced into the deposition chamber, or
is contained in the target for nitrogen atom (N) introduction.
The proportion of nitrogen atoms (N)
or both.
optionally controlled as desired
I can do it. Raw material gas for supplying Si used in the present invention
The starting material is SiH_Four,Si₂H₆,Si₃H₈，
Si_FourH_Tensilicon hydride in a gaseous state or capable of being gasified, such as
Elements (silanes) are listed as being effectively used.
In particular, the ease of handling the layer creation work and the efficiency of Si supply are improved.
SiH in terms of good rate etc._Four,Si₂H₆is preferable
It can be mentioned. By using these starting materials, the layer formation conditions can be changed.
The second layer formed by appropriate selection
() Along with Si, H can also be introduced into (). It can be used as an effective starting material as raw material gas for supplying Si.
In addition to the silicon hydride mentioned above, halogen atoms
Silicon compounds containing (X), so-called halogen atoms
Substituted silane derivatives, specifically e.g.
SiF_Four,Si₂F₆,SiCl_Four, SiBr_FourSilicon halides such as
can be cited as preferred. Furthermore, SiH₂F₂,SiH₂I₂,SiH₂Cl₂,SiHCl₃，
SiH₂Br₂,SiHBr₃halogen-substituted silicon hydrides, such as
Hydrogen atoms in a gaseous state or capable of being gasified, such as
Halides containing as one of the constituents are also effective
Starting material for supplying Si for the formation of the second layer () and
I can list it as follows. Silicon compounds containing these halogen atoms (X)
When using layer formation conditions, as mentioned above,
In the second layer () formed by careful selection
X can be introduced together with Si. Halogen containing hydrogen atoms in the above starting materials
The silicon oxide compound is added to the layer during the formation of the second layer ().
At the same time as introducing halogen atoms (X) into
Hydrogen atoms are extremely effective in controlling photoelectric properties.
Since (H) is also introduced, it is suitable in the present invention.
used as a starting material for the introduction of halogen atoms (X).
used. When forming the second layer () in the present invention
Raw material gas used for introducing halogen atoms (X)
Effective starting materials include those listed above.
In addition, for example, fluorine, chlorine, bromine, and iodine
Logen gas, BrF, ClF, ClF₃,BrF_Five,BrF₃，
IF₃,IF₇, interhalogen compounds such as ICl, IBr, HF,
Hydrogen halides such as HCl, HBr, HI, etc.
I can do that. Nitrogen used in forming the second layer ()
It can be used as a raw material gas for introducing atoms (N).
Starting materials that are effectively used include N as a constituent atom.
Or, for example, nitrogen whose constituent atoms are N and H
(N₂), ammonia (NH₃), hydrazine (H₂
NNH₂), hydrogen azide (HN₃), ammonium azide
Umu (NH_FourN₃) etc. gaseous or gasifiable
Nitrogen compounds such as nitrogen, nitrides and azides are listed.
Rukoto can. In addition, the introduction of nitrogen atoms (N)
In addition to the introduction of halogen atoms (X), it is also possible to introduce halogen atoms (X).
From this point of view, nitrogen trifluoride (F₃N), nitrogen tetrafluoride
(F_FourN₂) and other halogenated nitrogen compounds.
I can do it. In the present invention, the second layer () is treated by glow discharge.
Used when forming by sputtering method or sputtering method.
The diluent gas used is so-called noble gas, for example.
He, Ne, Ar, etc. are preferred.
I can do it. The second layer () in the present invention satisfies its requirements.
carefully shaped to give the desired characteristics.
will be accomplished. That is, Si, N, H or/and X as necessary.
The composition of the substances used as constituent atoms depends on the conditions for their creation.
Structurally, it takes forms ranging from crystals to amorphous.
In terms of electrical properties, it ranges from conductive to semiconducting to insulating.
properties ranging from photoconductive to non-photoconductive.
Since each exhibits electrical properties, in the present invention,
a-(Si_xN_1-x)_y
(H,X)_1-yas desired so that a
The selection of the creation conditions is made strictly. For example,
The main purpose of the second layer () is to improve electrical voltage resistance.
To provide a-(Si_xN_1-x)_y(H,X)_1-ymessenger
Amorphous material with remarkable electrically insulating behavior in a commercial environment
Created as a material. In addition, improvements in continuous repeated use characteristics and usage environment characteristics
A second layer () is provided with the main purpose of
In some cases, the degree of electrical insulation mentioned above is relaxed to some extent.
and has a certain degree of sensitivity to the light that is irradiated.
a-(Si_xN_1-x)_y(H,X)_1
-yis created. a-(Si) on the surface of the first layer ()_xN_1-x)_y(H,
X)_1-yWhen forming the second layer () consisting of the layer
The temperature of the support during formation depends on the structure of the layer being formed and
It is an important factor that influences the characteristics, and in the present invention,
In this case, a-(Si_xN_1-x)_y
(H,X)_1-ylayered so that it can be created as desired.
It is desirable that the temperature of the support during formation be strictly controlled.
stomach. The desired objectives of the present invention are effectively achieved.
Depending on the method of forming the second layer () to
The optimal temperature range is selected and the shape of the second layer ()
formation is carried out, preferably at temperatures between 20 and 400°C.
The temperature is preferably 50 to 350℃, optimally 100 to 300℃.
It can be done. The formation of the second layer () constitutes the layer
Fine control of the atomic composition ratio and layer thickness is
Because it is relatively easy compared to the law,
- It is advantageous to use the discharge method or sputtering method.
However, the second layer () can be formed using these layer formation methods.
If the temperature of the support is
When the discharge power is created a-(Si_xN_1-x)_y
(H,X)_1-yOne of the important factors that influences the characteristics of
It is. Characteristics for achieving the purpose of the present invention
a-(Si_xN_1-x)_y(H,X)_1-yis more productive
As a discharge power condition to be effectively created
is preferably 1.0~300W, more preferably 2.0~
250W, ideally 5.0~200W.
It's a good thing. The gas pressure in the deposition chamber is preferably 0.01 to 1 Torr,
More preferably, it is about 0.1 to 0.5 Torr.
Delicious. In the present invention, in order to create the second layer (),
Desired numerical ranges for support temperature and discharge power
The values in the range mentioned above are listed as
The layer creation factors for are determined independently and separately.
a-(Si_xN_1-x)_y
(H,X)_1-yA second layer () is formed, consisting of
Create each layer based on mutual organic relationships so that
It is desirable that the optimal value of the factor can be determined. The second layer () in the photoconductive member of the present invention
The amount of nitrogen atoms contained depends on the composition of the second layer ().
The desired features to achieve the objectives of the invention as well as the conditions for formation
The second layer (in which the properties are obtained) is formed.
It is a factor. Nitrogen contained in the second layer () in the present invention
The amount of elementary atoms makes up the second layer (amorphous)
Depending on the type of material and its characteristics, as appropriate.
It can be determined by That is, the general formula a-(Si_xN_1-x)_y(H,X)_1-y
Amorphous materials shown in can be roughly divided into silicon
Amorphous material composed of atoms and nitrogen atoms (hereinafter referred to as
After that, “a-Si_aN_1-a”. However, 0<a<1),
Composed of silicon atoms, nitrogen atoms, and hydrogen atoms
amorphous material (hereinafter referred to as “a-(Si_bN_1-b)_cH_1-c"and
write down However, 0<b, c<1), silicon atoms and
Nitrogen atoms, halogen atoms, and hydrogen atoms if necessary
An amorphous material (hereinafter referred to as “a-(Si_d
N_1-d)_e(H,X)_1-e”. However, 0<d, e<
1). In the present invention, the second layer () is a-Si_a
N_1-aContained in the second layer () when composed of
The amount of nitrogen atoms used is preferably 1×10^-3~
60 atomic%, more preferably 1-50 atomic%, maximum
It is preferable to set it to 10 to 45 atomic%.
It is. That is, the previous a-Si_aN_1-aIn the display of a of
If carried out, a is preferably 0.4 to 0.99999, more preferably
is between 0.5 and 0.99, optimally between 0.55 and 0.9. In the present invention, the second layer ( ) is a-(Si_b
N_1-bcH_1-cIf the second layer consists of ()
The amount of nitrogen atoms contained is preferably 1×10^-3
~55 atomic%, more preferably 1~
55 atomic%, optimally 10-55 atomic%
is desirable. As the content of hydrogen atoms
preferably 1 to 40 atomic%, more preferably
Usually 2-35 atomic%, optimally 5-30 atomic%
It is desirable that hydrogen atoms be in these ranges.
The photoconductive member formed when the content is
It can be fully applied as an excellent thing in actual situations.
Ru. That is, the previous a-(Si_bN_1-b)_cH_1-cIf you do it with the display
b is preferably 0.45 to 0.99999, more preferably 0.45
~0.99, optimally 0.15-0.9, c preferably 0.6
~0.99, more preferably 0.65~0.98, optimally 0.7~
A value of 0.95 is desirable. The second layer () is a-(Si_dN_1-d)_e(H,X)_1
-eincluded in the second layer ().
The content of nitrogen atoms is preferably 1×
Ten^-3~60 atomic%, more preferably 1-60 atomic
%, optimally 10 to 55 atomic%. Halogen
The content of atoms is preferably 1 to 20 atomic%,
More preferably 1 to 18 atomic%, optimally 2 to 18 atomic%
It is assumed to be 15 atomic%. Halogen in these ranges
Photoconductive members created when there is an atomic content
It can be fully applied in practice. as needed
The preferred content of hydrogen atoms is
or less than 19 atomic%, more preferably 13 atomic%
% or less. That is, the previous a-(Si_dN_1-d)_e(H,X)_1-ed,
If expressed as e, d is preferably 0.4 to 0.99999,
More preferably 0.4 to 0.99, optimally 0.45 to 0.9, e
is preferably 0.8 to 0.99, more preferably 0.82 to
0.99, optimally 0.85 to 0.98. Number range of layer thickness of second layer () in the present invention
are important for effectively achieving the purpose of the present invention.
This is one of the important factors. According to the intended purpose so as to achieve the purpose of the present invention
can be determined as appropriate and desired. Also, the layer thickness of the second layer () is
The amount of nitrogen atoms contained and the thickness of the first layer ()
In relation to
According to the desired organic relationship according to the characteristics
It needs to be decided accordingly. In addition, it is possible to add economic considerations that take into account productivity and mass production.
It is desirable that considerations also be made in terms of cost efficiency. The layer thickness of the second layer () in the present invention is preferably
preferably 0.003 to 30μ, more preferably 0.004 to 20μ, most preferably
A suitable value is 0.005 to 10μ. The support used in the present invention is electrically conductive.
It may also be electrically insulating. As a conductive support
For example, NiCr, stainless steel, Al, Cr,
Metals such as Mo, Au, Nb, Ta, V, Ti, Pt, Pd, etc.
Or an alloy of these may be mentioned. As the electrically insulating support, polyester, polyester, etc.
Liethylene, polycarbonate, cellulose acetate
Tate, polypropylene, polyvinyl chloride, poly
Vinylidene chloride, polystyrene, polyamide, etc.
Synthetic resin film or sheet, glass, ceramic
Tsuku, paper, etc. are usually used. electrical insulation of these
The sexual support preferably has at least one surface thereof.
is conductively treated, and the other side is on the conductively treated surface side.
Preferably, layers are provided. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Pd,In₂O₃, SnO₂,ITO(In₂O₃+SnO₂) etc.
Conductivity is imparted by providing a thin film of
or synthetic resin film such as polyester film.
For ilms, NiCr, Al, Ag, Pb, Zn, Ni,
Gold such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc.
Vacuum evaporation, electron beam evaporation, sputtering
Provided on the surface with a ring etc., or attached with the metal mentioned above.
The surface is laminated to make it conductive.
Granted. The shape of the support body may be cylindrical or base.
It can be of any shape such as a bolt shape or a plate shape, and can be shaped as desired.
For example, the shape shown in Fig. 1 is determined by
Photoconductive member 100 as an electrophotographic image forming member
If you use it for continuous high-speed copying, do not use it.
Preferably, the end is belt-shaped or cylindrical. support
The thickness of the body is adjusted so that the photoconductive member is formed as desired.
Flexibility as a photoconductive member may be determined as appropriate.
If this is required, the function as a support is sufficient.
It is made as thin as possible within the range that can be achieved.
Ru. However, in such cases, the manufacturing and handling of the support
From the viewpoint of handling and mechanical strength, it is usually 10μ or more.
It is said that Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be described.
Let me explain about the abbreviation. Figure 41 shows an example of a photoconductive member manufacturing apparatus.
vinegar. Gas cylinders 202 to 206 in the diagram are
Raw material gas for forming bright photoconductive members is sealed
For example, 202 is
SiF diluted with He_FourGas (purity 99.999% or less)
SiF_Four/He is abbreviated. ) cylinder, 203 diluted with He
GeF_FourGas (purity 99.999%, hereinafter referred to as GeF)_Four/He
It is abbreviated as ) cylinder, 204 is NO gas (purity 99.99
%, hereinafter abbreviated as NO. ) cylinder, 205 is rare in He
interpreted B₂H₆Gas (purity 99.999%, below B₂H₆/
Abbreviated as He. ) cylinder, 206 is H₂Gas (purity
99.999%) cylinder. To flow these gases into the reaction chamber 201
Valves 222-22 of gas cylinders 202-206
6. Check that the leak valve 235 is closed.
Also check the inlet valves 212-216 and outlet valves.
Lubes 217-221, auxiliary valves 232, 233
Make sure that the main bar is opened and
Open the tube 234 to access the reaction chamber 201 and each gas pipe.
Exhaust the inside. Next, the reading on the vacuum gauge 236 is approximately 5×
Ten^-6When it becomes torr, the auxiliary valves 232, 23
3. Close the outflow valves 217-221. Next, a light-receiving layer is formed on the cylindrical substrate 237.
For example, if the gas cylinder 202
More SiF_Four/He gas, from gas cylinder 203
GeF_Four/He gas, NO gas from gas cylinder 204,
H from gas cylinder 206₂, valve 222,2
23, 224, and 226 respectively and check the outlet pressure gauge.
The pressure of 227, 228, 229, 231 is 1Kg/cm²
and adjust the inflow valves 212, 213, 214,
By gradually opening 216, the mass flow control
Inside trollers 207, 208, 209, 211
Let each of them flow in. Subsequently, the outflow valve 21
7,218,219,221, auxiliary valve 232
are gradually opened to allow each gas to flow into the reaction chamber 201.
let SiF at this time_Four/He gas flow rate and GeF_Four/
He gas flow rate, NO gas flow rate and H₂Ratio to gas flow rate
the outflow valves 217, 21 so that the value is the desired value.
8,219,221, and also the reaction chamber 20
Vacuum gauge 236 so that the pressure inside 1 reaches the desired value.
Adjust the opening of the main valve 234 while checking the reading.
Arrange. Then, the temperature of the base body 237 becomes higher than that of the heater 2.
38, the temperature is set in the range of 50 to 400℃.
After confirming that the power supply 240 is the desired power
to generate a glow discharge in the reaction chamber 201.
Then, a first layer region (G) is formed on the base body 237.
Ru. The first layer region (G) is formed to a desired layer thickness.
Completely close all valves at this point. SiF_Four／SiH gas cylinder_Four/He(SiH_Fourpurity
99.999%) SiH instead of cylinder_Four/He gas bong
Veraine, B.₂H₆/He gas cylinder line, NO gas
of the first layer area (G) using the bombe line.
Perform the same valve operation as for formation to obtain the desired glow release.
Set the current conditions to maintain glow discharge for the desired time.
By doing so, the germanium is deposited on the first layer region (G).
Second layer substantially free of nium atoms
A region (S) can be formed. In this way, the first layer region (G) and the second layer
The first layer () consisting of the region (S) is the base
237. First layer formed to a predetermined thickness as described above
() to form a second layer () on top of the first
by the same valve operation as in the formation of the layer ().
For example, SiH_Fourgas, NH₃each as necessary
and dilute He etc. according to the desired conditions.
– is achieved by creating an electrical discharge. second
To contain halogen atoms in the layer (),
For example, SiF_Fourgas and NH₃gas or this
SiH_Four2nd layer as above adding gas
This is done by forming (). Gas outflow valve required when forming each layer
Needless to say, close all outflow valves except for
Also, when forming each layer, there is no difference in the formation of the previous layer.
The used gas is inside the reaction chamber 201 and the outflow valve 21
Inside the gas piping from 7 to 221 to inside the reaction chamber 201
Outflow valve 21 to avoid residual
7 to 221, and auxiliary valves 232 and 233.
Open the main valve 234 fully and clean the system once.
Perform operations to evacuate to high vacuum as necessary. The nitrogen atomic weight contained in the second layer () is an example
For example, when using glow discharge, SiH_Fourgas and
N.H.₃Flow rate ratio of gas introduced into reaction chamber 201
be changed as desired or sputtered.
When forming a layer by
Spatters between silicon wafer and silicon nitride plate when
Either change the area ratio or use silicon powder and nitride silicon.
Molding targets by changing the mixing ratio of recon powder
can be controlled as desired by
come. Halogen source contained in the second layer ()
The amount of molecules (X) depends on the raw material gas for introducing halogen atoms.
e.g. SiF_FourWhen introduced into the reaction chamber 201
This is done by adjusting the flow rate of Also, while forming layers, make sure that the layer formation is uniform.
In order to achieve this, the base body 237 is moved at a constant speed by a motor 239.
It is preferable to rotate it by degrees. Examples will be described below. Example 1 By the manufacturing equipment shown in Fig. 41, cylinder
For electrophotography under the conditions shown in Table 1 on an Al substrate of
Samples as image forming members (Sample Nos. 1-1 to 6-
13) respectively (Table 2). Containment of impurity atoms (B or P) in each sample
The distribution concentration is shown in Figure 42, and the content distribution of oxygen atoms is shown in Figure 42.
The concentrations are shown in Figures 43A and 43B. each
The distribution concentration of atoms is determined by determining the flow rate ratio of each corresponding gas in advance.
By varying the rate of change according to the designed rate of change line.
controlled. Each sample material obtained in this way was placed in a charged exposure experimental device.
Corona charging was performed for 0.3 seconds at 5.0 kV.
A light image was immediately irradiated. The light source is tungsten run
A transmission type test using a light source with a light intensity of 21ux・sec
It was irradiated through a tochiat. Immediately thereafter, use a charged developer (toner and
(including Yaliar) on the surface of the photoreceptive layer of each sample.
Good coverage on the photoreceptive layer surface by cladding
I got a nice toner image. Toner image on photoreceptive layer
was transferred onto transfer paper using 5.0kV corona charging.
However, each sample has excellent resolution and excellent gradation reproducibility.
A clear, high-density image was obtained. In 1 above, the light source is replaced by a tungsten lamp.
810nm GaAs semiconductor laser (10mW)
Same as above except that the electrostatic image was formed using
Image quality evaluation of toner transfer images for each sample
When we performed this, all samples had excellent resolution.
Clear, high-quality images with good gradation reproducibility can be obtained.
Ta. Example 2 By the manufacturing equipment shown in Fig. 41, cylinder
For electrophotography under the conditions shown in Table 3 on an Al substrate of
Samples as image forming members (Sample Nos. 21-1 to 26-
10) respectively (Table 4). The distribution concentration of impurity atoms in each sample is
In Figure 42, the content distribution concentration of oxygen atoms is shown in Figure 44.
As shown in the figure. For each of these samples, the same procedure as in Example 1 was carried out.
When we conducted an image evaluation test, all samples showed
It gave a high quality toner transfer image. Also, for each sample
200,000 in an environment of 38℃ and 80%RH relative humidity.
After several repeated usage tests, we found that none of the
No deterioration in image quality was observed in the sample. Example 3 By the manufacturing equipment shown in Fig. 41, cylinder
For electrophotography under the conditions shown in Table 5 on an Al substrate of
Samples as image forming members (Sample No. 31-1 to 36-
16) respectively (Table 6). The distribution concentration of impurity atoms in each sample is
In Figure 42, the content distribution concentration of oxygen atoms is shown in Figure 43.
This is shown in Figures A, 43B and 44. For each of these samples, the same procedure as in Example 1 was carried out.
When we conducted an image evaluation test, all samples showed
It gave a high quality toner transfer image. Also, for each sample
The test was repeated 200,000 times in an environment of 38℃ and 80%RH.
When we conducted a reuse test, all samples showed
No deterioration in image quality was observed. Example 4 By the manufacturing equipment shown in Fig. 41, cylinder
For electrophotography under the conditions shown in Table 7 on an Al substrate of
Samples as image forming members (Sample Nos. 41-1 to 46-
16) respectively (Table 8). GeH when forming the first layer region (G)_Fourgas flow
The quantity ratio is changed according to a pre-designed change rate line.
The layer area is divided so that the Ge distribution concentration shown in Fig. 45 is obtained.
(G) and also the formation of the second layer region (S)
Time B₂H₆Gas and PH₃Design the gas flow ratio in advance
Figure 42 shows the change according to the rate of change line.
The second layer region (S) is
was formed. Also, when forming the first layer region (G), the amount of NO gas
The flow rate ratio is varied according to a pre-designed rate of change line.
In addition, the O distribution concentration shown in Figures 43A and 43B
The first layer region (G) was formed so that A similar picture as in Example 1 was drawn for each of these samples.
Image evaluation revealed that all samples were of high quality.
Images can be obtained. Example 5 By the manufacturing equipment shown in Fig. 41, cylinder
Example 1 and the conditions shown in Table 8 were prepared on a
Form an image for electrophotography by controlling the flow rate ratio of each gas in the same way.
Samples as parts (sample Nos. 51-1 to 56-12)
(Table 10). The distribution concentration of impurity atoms in each sample is
In Figure 42, the content distribution concentration of oxygen atoms is shown in Figure 44.
In the figure, the content distribution concentration of germanium atoms is 45th.
As shown in the figure. For each of these samples, the same procedure as in Example 1 was carried out.
When we conducted an image evaluation test, all samples showed
It gave a high quality toner transfer image. Also, for each sample
The test was repeated 200,000 times in an environment of 38℃ and 80%RH.
When we conducted a reuse test, all samples showed
No deterioration in image quality was observed. Example 6 By the manufacturing equipment shown in Fig. 41, cylinder
Example 1 and the conditions shown in Table 11 were prepared on a shaped Al substrate.
Similarly, by controlling the flow rate ratio of each gas, it is possible to form images for electrophotography.
Samples as component parts (Sample No. 61-1 to 610-13)
(Table 12). The distribution concentration of impurity atoms in each sample is
In Figure 42, the content distribution concentration of oxygen atoms is shown in Figure 43.
As shown in Figures A, 43B and 44, germanium
The content distribution concentration of nium atoms is shown in Figure 45.
Ru. For each of these samples, the same procedure as in Example 1 was carried out.
When we conducted an image evaluation test, all samples showed
It gave a high quality toner transfer image. Also, for each sample
Repeatedly 200,000 times in an environment of 38℃ and 80%RH.
When we conducted a usage test, all samples showed no image quality.
No deterioration in image quality was observed. Example 7 Articles showing the conditions for creating the second layer () in Table 13
Samples No. 11-1 and 12- of Example 1 were
1. Following the same conditions and procedures as 1, 13-1,
Each of the true image forming members (sample No. 11-1-1 to 11-
1-8, 12-1-1 ~ 12-1-8, 13-1-1 ~
13-1-8) were created. thus
Each of the obtained electrophotographic image forming members was individually
Installed in a copying machine and charged with corona for 0.2 seconds at 5kV
was performed and a light image was irradiated. The light source is tungsten la
A lamp was used, and the light intensity was 1.0 lux・sec. The latent image is
For electrically charged developers (including toner and carrier)
It was then developed and transferred to regular paper. transfer painting
The image was extremely good. not transcribed
Toner left on the electrophotographic imaging member during
Cleaned by Muplade. This way
Even if you repeat this process over 100,000 times, eventually
No image deterioration was observed in this case either. Comprehensive image quality evaluation and repeated series of transferred images of each sample.
Table 14 shows the results of durability evaluation after continuous use.
vinegar. Example 8 When forming the second layer (), Ar and NH₃mixed moth
silicon wafer and silicon nitride targets
By changing the surface area, the silico in the second layer ()
Except for changing the content ratio of nitrogen atoms and nitrogen atoms.
was carried out in exactly the same manner as Sample No. 11-2 in Example 1.
Thus, each of the imaging members was prepared. This is how you get it
For each of the imaging members described in Example 1,
The process of image creation, development, and cleaning takes about 5 minutes.
After repeating the image 10,000 times, we evaluated the image and found Table 15.
I got results like this. Example 9 When forming the second layer (), SiH_Fourgas and
M.H.₃By changing the gas flow ratio, the second layer ()
Change the content ratio of silicon atoms and nitrogen atoms in
Exactly the same as Sample No. 11-3 of Example 1 except for
Each of the imaging members was prepared by a method according to the following methods. child
For each imaging member thus obtained, the procedure in Example 1 was performed.
The process up to transfer was repeated approximately 50,000 times using the method described above.
After returning it, I performed an image evaluation and found that it was as shown in Table 16.
We obtained the following results. Example 10 When forming the second layer (), SiH_Fourgas,
SiF_Fourgas, NH₃By changing the gas flow rate ratio, the second
Inclusion of silicon and nitrogen atoms in the layer ()
Sample No. 11- of Example 1 except for changing the quantitative ratio.
4. Each of the image forming members is
Created. For each imaging member thus obtained
Imaging, development and cleaning as described in Example 1
After repeating the process approximately 50,000 times, image evaluation is performed.
The results shown in Table 17 were obtained. Example 11 Example except for changing the layer thickness of the second layer ()
The image was formed in exactly the same manner as Sample No. 11-5 in 1.
Each of the component parts was created. As described in Example 1
The process of image creation, development, and cleaning is repeated.
The results shown in Table 18 were obtained.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Evaluation criteria: ◎…Excellent
○…Good

[Table] ◎: Very good ○: Good △: Sufficient for practical use
×: Image defects occur.

[Table] ◎: Very good ○: Good △: Sufficient for practical use
×: Image defects occur.

[Table] ◎: Very good ○: Good △: Sufficient for practical use
×: Image defects occur.

[Table] Common layer forming conditions in the above embodiments of the present invention are shown below. Base temperature: Germanium atom (Ge) content...
Approximately 200℃ No germanium atom (Ge) content...Approx. 250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[Brief explanation of the drawing]

FIG. 1 is a schematic layer configuration diagram for explaining the layer configuration of the photoconductive member of the present invention, and FIGS. 2 to 10 are diagrams showing germanium atoms in the husband layer region (G). Figures 25 to 40 are explanatory diagrams for explaining the distribution state of oxygen atoms, respectively, and Figure 41 is an illustration of the device used in the present invention. FIGS. 42 to 45 are schematic explanatory diagrams showing the distribution state of each atom in the embodiment of the present invention. 100...Photoconductive member, 101...Support, 1
02...First layer (), 103...Layer region (G), 104...Layer region (S), 105...Second layer (), 107...Photoreceptive layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, and a layer having a thickness of 30 Å to 30 Å and made of an amorphous material containing germanium atoms in an amount of 1 to 10×10 ⁵ atomic ppm on the support.
A layer region (G) with a thickness of 50μ and a second layer region (S) with a layer thickness of 0.5 to 90μ made of an amorphous material containing silicon atoms (not containing germanium atoms) are provided in order from the support side. a first layer with a layer thickness of 1 to 100 .mu.m exhibiting photoconductivity in a layered structure; and a layer of 0.003 .mu.m thick consisting of an amorphous material containing silicon atoms and 1.times.10.sup. ^-3 to 60 atomic percent nitrogen atoms. and a second layer of ~30 μm, the first layer comprising:
Contains 0.001 to 50 atomic% oxygen atoms, and
A substance (C) for controlling conductivity is present in the second layer region (S) with a maximum distribution concentration in the layer thickness direction of 30 atomic ppm or more, and in the second layer region (S). A photoconductive member for electrophotography, characterized in that the above-described maximum value is contained on the side of the support. 2. The photoconductive member for electrophotography according to claim 1, wherein the first layer region (G) contains silicon atoms. 3. The photoconductive member for electrophotography 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. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is in a metal position in the layer thickness direction. 5 First layer region (G) and second layer region (S)
The photoconductive member for electrophotography according to claim 1, wherein at least one of the above contains a hydrogen atom. 6 First layer region (G) and second layer region (S)
The photoconductive member for electrophotography according to claim 1 or 5, wherein at least one of the photoconductive members contains a halogen atom. 7. The photoconductive member for electrophotography 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 for electrophotography according to claim 1, wherein the substance (C) that controls conductivity is an atom belonging to Group 3 of the periodic table. 9 Substances that control conductivity (C) are found in Periodic Table V
The photoconductive member for electrophotography according to claim 1, which is an atom belonging to the group A.