JPH0225176B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on light (here, light in a broad sense, ultraviolet light,
visible light, infrared light, X-rays, gamma rays, etc.)
For electrophotographic photoconductive materials that are sensitive to electromagnetic waves.
related. 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 electromagnetic waves emitted.
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 non-polluting 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. Especially for electronic devices used in offices as business machines.
An electrophotographic imaging member incorporated into a photographic device
In some cases, non-pollution during use is important.
This is a point. 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.
Application as material, German Publication No. 2933411
An application to a light guiding transducer and reader 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, it is necessary to improve the characteristics of the
The reality is that there are points that can be further improved.
be. For example, when applied to an electrophotographic imaging member
In order to simultaneously achieve high light sensitivity and high dark resistance,
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
The so-called "go" phenomenon occurs when fatigue accumulates due to
If the
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
absorption in a wavelength region longer than that on the long wavelength side.
Semiconductors with relatively small coefficients that are currently in practical use
Usually used in matching with body lasers.
Places where the light source is a halogen lamp or fluorescent lamp.
If the
There is still room for improvement in these areas.
Ru. In addition, if the irradiated light is in the photoconductive layer,
Therefore, the amount of light that reaches the support without being sufficiently absorbed is
If the amount increases, the support itself will pass through the photoconductive layer.
If the reflectance of light is high, the inside of the photoconductive layer
Interference due to multiple reflections occurs in the image, resulting in
This is one of the causes of "blur". 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 configuring the photoconductive layer with a-Si material,
to improve its electrical and photoconductive properties.
In addition, hydrogen atoms or halo atoms such as fluorine atoms and chlorine atoms
Gen atoms, and boron atoms for control of electrical conductivity type
particles, phosphorus atoms, etc., or for other property improvements.
Other atoms are included in the photoconductive layer as constituent atoms, respectively.
However, how are these constituent atoms contained?
Depending on the electrical or photoconductive
There may be problems with the characteristics. That is, for example, when a formed photoconductive layer is exposed to light,
Lifespan of photocarriers generated in this layer
If the support is insufficient or in the dark,
This may be due to insufficient prevention of charge injection from the side.
This occurs in many cases. Furthermore, when the layer thickness becomes more than 10 μm or more, it becomes necessary to
When left in air after being removed from the vacuum deposition chamber
Over time, the layer may lift or peel off from the surface of the support.
This may cause phenomena such as separation or cracks in the layers.
It was hot. This phenomenon occurs especially when the support is
Drum-shaped support used in the photographic field
In terms of stability over time, such as often occurring in the body,
There are some points that can be resolved. 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
−Si light guide used in electrophotographic imaging members
Is it from the perspective of applicability as an electrical component and its applicability?
As a result of comprehensive and intensive research studies, silicon
Atom is the host, hydrogen atom (H) or halogen atom
Containing at least one of the following (X)
Amorphous amorphous material, so-called hydrogenated amorphous silica
silicone, halogenated amorphous silicon, or
Halogen-containing hydrogenated amorphous silicon [hereinafter
“a-Si(H,X)” is used as a generic notation for these.
used] and has a layer that exhibits photoconductivity.
The layer structure of the photoconductive member is as explained below.
Photoconductive members that are specifically designed and manufactured are
Not only does it exhibit extremely superior properties in practical use, but it also
Compared to photoconductive materials, it is superior in all respects.
If the quality exceeds the
It has extremely excellent characteristics and long wavelength
It has excellent absorption spectrum characteristics on the long side.
It is based on the findings 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 the layer provided on the support.
and the support and between each laminated layer.
Excellent adhesion, dense and stable structure
We provide photoconductive materials for electrophotography with high layer quality.
Is Rukoto. Another object of the invention is to provide an imaging member for electrophotography.
When applied as a
for electrostatic imaging to the extent that it can be effectively applied.
Sufficient charge retention ability during charging process and high humidity
Almost no deterioration of its properties is observed even in the atmosphere.
Photoconductive material for electrophotography with excellent electrophotographic properties
It is to provide parts. Still another object of the present invention is to
High-quality images with clear tones and high resolution
Photoconductive part for electrophotography that makes it easy to obtain images
It is to provide materials. Yet another object of the present invention is high photosensitivity,
High signal-to-noise ratio characteristics and good electrical connection with the support
To provide a tactile photoconductive member for electrophotography.
That is. Photoconductive member for electrophotography of the present invention (hereinafter simply referred to as "photoconductive member")
(referred to as "conductive member") is a support for the photoconductive member.
and disposed on the support, silicon atoms and 1 to 1
9.5×10^FiveContains atomic ppm of germanium atoms.
The first layer is made of an amorphous material with a thickness of 30 Å to 50 μ.
layer region (G) containing silicon atoms (germani)
layer composed of amorphous material (does not contain umium atoms)
The second layer region (S) having a thickness of 0.5 to 90μ is the support.
Layer thickness of 1 to 100μ, layered in order from the side.
A first layer exhibiting photoconductivity, silicon atoms and 1×
Ten^-3Amorphous material containing ~90 atomic% carbon atoms
a second layer with a layer thickness of 0.003 to 30μ made of
The germanium in the first layer region (G) is
The distribution state of Ni atoms is non-uniform in the layer thickness direction.
Then, the fraction of germanium atoms on the support side is
Cloth concentration is 1000 atomic ppm to silicon atoms
The front part has a higher part than the support side.
The height is considerably lower on the interface side with the second layer region (S).
and 0.01 in the first layer region (G).
~5×10^FourSubstances that control the conductivity of atomic ppm
is contained in the first layer, and 0.001 to
Contains 50 atomic% nitrogen atoms.
be a sign. 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. In particular, it has been applied as an electrophotographic imaging member.
In some cases, the residual potential has no effect on image formation.
Its electrical characteristics are stable, high sensitivity, and high
It has a signal-to-noise ratio and is resistant to light fatigue and repeated use.
Good usage characteristics, high density, and vivid halftones.
Easily produce clear, high-resolution, high-quality images.
can be obtained repeatedly. Further, the photoconductive member of the present invention is formed on a support.
The first layer itself is strong and supportive.
It has excellent adhesion to the body and can be used at high speed for a long time.
Can be used repeatedly and continuously. 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 shows a photoconductive section of a first embodiment of the present invention.
Schematic diagram to explain the layer structure of the material
It is a configuration diagram. The photoconductive member 100 shown in FIG.
On top of the support 101 for use, a first layer ()
102 and a second layer () 103;
The layer () 103 has a free surface 106 on one end surface.
have. The first layer ( ) 102 is formed from the support 101 side.
a-Si (H,
X) (hereinafter abbreviated as "a-SiGe(H,X)")
The configured first layer region (G) 104 and a-Si
A second layer composed of (H,X) and having photoconductivity
The region (S) 105 has a layered structure in which the regions (S) 105 are laminated in order.
do. Gel contained in the first layer region (G) 104
The manium atoms are in the first layer region (G) 104.
The support 10 is continuous in the layer thickness direction and
The side opposite to the side where 1 is provided (the first layer
() 102 second layer () 103 side)
On the other hand, the shape is more distributed toward the support 101 side.
in the first layer region (G) 104 so that
Contains. In the photoconductive member 100 of the present invention, at least
Both control the conduction properties in the first layer region (G) 104.
The first layer region contains a substance (C) that
(G) 104 is given the desired conduction properties. In the present invention, the first layer region (G) 104
The substance (C) that controls the conduction properties contained in
Evenly distributed throughout the entire layer area of the first layer area (G) 104
It may be contained uniformly, and the first layer region (G) 1
Even if it is unevenly contained in some layer regions of 04
good. Substance (C) that controls conduction properties in the present invention
unevenly distributed in some layer regions of the first layer region (G)
When it is contained in the first layer region (G) as in
is the layer region (PN) containing the substance (C)
is provided as an end layer region of the first layer region (G).
It is desirable that the In particular, the first layer
The layer as the end layer region on the support side of region (G)
If a region (PN) is provided, the layer region
Type and type of the substance (C) contained in (PN)
By appropriately selecting the content of
specific polarity from the support into the first layer ()
This can effectively prevent charge injection. In the photoconductive member of the present invention, conductive properties can be controlled.
The substance (C) that can be controlled is the first layer.
In the first layer region (G) constituting a part of (),
As mentioned above, it is uniformly contained throughout the layer region (G).
It may be present, or it may be unevenly distributed in the layer thickness direction.
Furthermore, the first layer region
(G) Also in the second layer region (S) provided on
The substance (C) may also be included. Contains the substance (C) in the second layer region (S)
In the case where the content is contained in the first layer region (G),
The type and content of the substance (C) contained in the
Contained in the second layer region (S) depending on the manner of inclusion.
The type and content of the substance (C) to be contained, and its content.
The manner of inclusion of is determined as appropriate. In the present invention
contains the substance (C) in the second layer region (S).
If it has, preferably at least the first layer
The above substance is present in the layer region including the contact interface with region (G).
It is desirable to include quality. In the present invention
In this case, the substance (C) covers the entire layer of the second layer region (S).
It may be contained uniformly in the area, or it may be contained uniformly in the area.
It may be contained uniformly in a part of the layer area.
be. Both the first layer region (G) and the second layer region (S)
Contains a substance (C) that controls the conduction characteristics
In this case, the substance in the first layer region (G)
A layer region containing (C) and a second layer region
A layer region containing the substance (C) in
It is desirable to provide them so that they are in contact with each other.
Also, contained in the first layer region (G) and the second layer region
The substance (C) to be mixed with the first layer region (G)
The same type or different type in the second layer region (S)
The content may vary depending on each layer area.
They can be the same or different. However, in the present invention, each layer region
The substance (C) contained is the same in both.
In this case, the content in the first layer region (G)
or use species with different electrical characteristics.
Each of the above substances (C) is contained in each desired layer region.
It is preferable to In the present invention, at least the first layer ()
In the first layer region (G) constituting the
By containing the controlling substance (C),
Layer region containing the substance (C) [first layer region
(G) may be part or all of the layer area]
The conduction properties of can be arbitrarily controlled as desired.
However, as a substance like this, there are
The so-called impurities in the semiconductor field are listed below.
In the present invention, the first layer formed is
For a-SiGe(H,X) constituting (),
P-type impurities that give p-type conductivity and n-type conductivity
Examples include n-type impurities that impart properties. Ingredients
Physically, as an n-type impurity, it belongs to Group 3 of the periodic table.
Atoms belonging to the group (group atoms), for example, B (boron),
Al (aluminum), Ga (gallium), In (Tl)
(dium), Tl (thallium), etc., and particularly preferred
B and Ga are used. n-type impurity and
is an atom belonging to a group of the periodic table (a group element)
), for example, P (phosphorus), As (arsenic), Sb (antimony),
) Bi (bismuth), etc., and is particularly preferably used.
are P and As. In the present invention, a substance that controls conduction properties
(C) in the layer region (PN) containing
The content depends on the conduction characteristics required for the layer region (PN).
or the layer region (PN) is in direct contact with the support.
contact field with the support.
In organic relationships, such as relationships with characteristics on surfaces, etc.
You can select as appropriate. Moreover, the layer region
Other layer regions provided in direct contact with (PN),
Relationship with characteristics at the contact interface with other layer regions
The content of substances that control the conduction properties is also taken into account
is selected as appropriate. 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×
Ten³It is preferable to set it as atomic ppm. In the present invention, the substance that controls the conduction characteristics
The substance in the layer region (PN) containing (C)
Preferably the content of quality (C) is 30 atomic ppm or less.
above, more preferably 50 atomic ppm or more, optimally
By setting it to 100 atomic ppm or more,
If the substance (C) to be contained is the above-mentioned p-type impurity,
In case the free surface of the second layer () becomes polar
The first layer from the support side when subjected to charging treatment
() to effectively prevent the injection of electrons into
and the substance (C) to be contained is the above-mentioned substance (C).
In case of n-type impurities, the free table of the second layer ()
When the surface is polarized and charged, the support side
effectively block the injection of holes into the first layer ().
It can be stopped. In the above case, as mentioned above, the layer area
In the layer area (Z) excluding the area (PN), there is a layer
Substances that control the conduction properties contained in the region (PN)
The polarity of the conduction type is different from the polarity of the conduction type of quality (C).
It is also possible to contain a substance (C) that controls conduction characteristics.
or have conduction characteristics with conduction types of the same polarity.
The controlling substance (C) is contained in the layer region (PN).
Contained in a much smaller amount than the actual amount.
You can let it go. In such a case, in the layer area (Z)
Substance (C) that controls the conduction properties contained in
The content of the above substance contained in the layer region (PN) is
Adjust as desired depending on the polarity and content of quality (C).
It is determined according to the needs, but preferably 0.001~
1000atomic ppm, more preferably 0.05~
500atomic ppm, optimally 0.1-200atomic ppm
It is desirable that this is done. In the present invention, a layer region (PN) and a layer region
(Z) contains a substance (C) that controls the same kind of conductivity.
If it has, the content in the layer region (Z)
is preferably 30 atomic ppm or less.
Delicious. In the present invention, one layer is added in the first layer ().
Contains substances that control conductivity and have a polar conductivity type.
A conduction type having a layer region of one polarity and a conductivity type of the other polarity.
Directly contact the layer region containing the substance that controls conductivity.
A so-called depletion layer is formed in the contact area.
It is also possible to set one. Clogs, e.g. first layer
() The layer region containing the p-type impurity and the front
Direct contact with the layer region containing the n-type impurity described above.
A so-called p-n junction is formed by forming a depletion layer.
can be provided. In the photoconductive member of the present invention, the first layer region
(G) Distribution of germanium atoms contained in
In the layer thickness direction, the distribution state is as described above.
is uniform in the in-plane direction parallel to the surface of the support.
It is desirable that the distribution state is as follows. In the present invention, the
In the second layer region (S) where germanium is
Mu atoms are not contained in this layered structure.
By forming one layer (), it is possible to
The entire range from relatively short wavelengths to relatively long wavelengths, including
Photoconductive material with excellent photosensitivity to light with wavelengths in the range
It can be used as a member. In addition, germanium in the first layer region (G)
The distribution state of germanium atoms is such that germanium atoms are distributed throughout the entire layer.
The atoms are distributed continuously, and the layer thickness of germanium atoms is
The distribution concentration C in the direction is from the support side to the second layer region.
A decreasing change toward (S) is given.
The first layer region (G) and the second layer region (S)
It has excellent compatibility between
Distribution concentration of germanium atoms at the end of the support body
By making C extremely large, semiconductor laser
In the second layer region (S) when using
The light on the long wavelength side that cannot be completely absorbed is transferred to the first layer region.
In (G), substantially complete absorption is possible.
Prevents interference due to reflection from the support surface.
I can do it. Further, in the photoconductive member of the present invention, the first layer
The non-containing material forming the region (G) and the second layer region (S)
Each crystalline material has a common constituent element called silicon atoms.
Because it has a chemical element at the lamination interface,
Stability is sufficiently ensured. 2 to 10 show the photoconductive structure of the present invention.
Germa contained in the first layer region (G) of the member
A typical example of the distribution of Ni atoms in the layer thickness direction is shown.
be done. In Figures 2 to 10, the horizontal axis is germanium.
The vertical axis represents the distribution concentration C of nium atoms in the first layer region.
Indicates the layer thickness of the region (G), t_Bis the first layer on the support side
The position of the end face of region (G) is t_Tis opposite to the support side.
The position of the end face of the first layer region (G) on the opposite side is shown.
That is, the first layer region containing germanium atoms
Area (G) is t_BT from the side_Tlayer formation towards the side
Ru. 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
Support on which the first layer region (G) containing is formed
The surface of the body and the surface of the first layer region (G) are in contact with each other.
interface position t_BMoret₁Up to the position, germanium
The distribution concentration C of atoms is C₁while taking a certain value
The first layer region where germanium atoms are formed
Contained in (G), position t₁Rather than concentration C₂More interface
position t_Tis gradually and continuously reduced until
Ru. Interface position t_TIn this case, the fraction of germanium atoms is
Cloth density C is C₃It 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_Tup to the concentration C₈Than
Continuously gradually decreased position t_Tsubstantially in
It is said 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_TenIt is said that position t₃and position t_TThe distribution density is
The degree C is a linear function of the position t₃More position_Tup to
has been reduced. 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
After that, it decreased slowly and gradually.
position t₇At concentration C₁₉and position t₇and position t₈between
Then, the position t is gradually decreased very slowly.₈
, the concentration C₂₀leading to. position t₈and position t_TBetween
In this case, the concentration C₂₀Figure so that it becomes more substantially zero.
It is reduced according to a curve with a shape as shown in FIG. 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 side, the distribution concentration C is on the support side.
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.
It has a localized region A in which it is contained at a relatively high concentration.
It is desirable to do so. In the present invention, the localized region A is shown in FIGS.
To explain using the symbols shown in Figure 10, the interface position
t_BIt is preferable to set the distance within 5μ.
Ru. In the present invention, the localized region A is an interface position.
Placement_BFull layer area up to 5μ thick (L_T)
There is also a layer region (L_T)
There are also cases. Localized region A is defined as layer region (L_T) or as part of
is the entire first layer () to be formed.
It is determined as appropriate according to the required characteristics. Localized region A is germanium contained therein.
Germanium elementary as the distribution state of atoms in the layer thickness direction
Maximum value C of child distribution density_naxis for silicon atoms
preferably 1000 atomic ppm or more, more preferably
5000 atomic ppm or more, optimally 1×
Ten^FourThe distribution state is such that it is more than atomic ppm.
It is desirable that the layer be formed in such a way that it can be used as a layer. That is, in the present invention, germanium atoms
The first layer () contained is the layer from the support side
Thickness within 5μ (t_Bof the distributed concentration in the layer region of 5μ thickness from
maximum value C_naxIt is preferable that the structure be formed in such a way that there is
stomach. In the present invention, contained in the first layer region
The content of germanium atoms is determined so that the purpose of the present invention is effective.
be determined appropriately according to the desired results so as to achieve the desired results.
but preferably 1 to 9.5×10^Fiveatomic ppm, yo
Preferably 100 to 8×10^Fiveatomic ppm, optimally
is 500~7×10^FiveIt is preferable to use atomic ppm.
stomach. 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.
Formation is one of the important factors to achieve
The desired properties are sufficiently imparted to the photoconductive member to be used.
As such, due care must be taken when designing photoconductive materials.
need to be taught. In the present invention, the layer thickness of the first layer region (G)
T_Bis preferably 30Å to 50μ, more preferably
40Å to 40μ, optimally 50Å to 30μ.
Delicious. 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 desirable that the thickness 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 properties and requirements for the entire first layer ()
Based on the organic relationship between the properties, photoconductivity
It is determined as appropriate when designing the layer of the member according to the requirements.
Ru. In the photoconductive member of the present invention, the above (T_B
+T) preferably has a numerical range of 1 to 100μ, or more.
The preferred value is 1 to 80μ, and the optimal value is 2 to 50μ.
is desirable. In a more preferred embodiment of the present invention,
Above layer thickness T_Band layer thickness T is preferably T_B/T
Appropriate for each so as to satisfy the relationship ≦1.
It is desirable that an appropriate value be selected. 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_BIt is desirable that the values of the layer thickness T and the layer thickness T be determined.
stomach. In the present invention, contained in the first layer region (G)
The content of germanium atoms is 1×
Ten^FiveIn 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
The optimum thickness is preferably 20μ or less. In the present invention, if necessary, the first layer ()
A first layer region (G) and a second layer region constituting
As the halogen atom (X) contained in (S)
Specifically, fluorine, chlorine, bromine, and iodine are listed.
In particular, fluorine and chlorine are mentioned as suitable ones.
You can get it. In the present invention, a-SiGe(H,X)
For example, to form the first layer region (G)
Low discharge method, sputtering method, or ion beam
Vacuum deposition using discharge phenomena such as rating method
It is done according to the law. For example, using the glow discharge method
The first layer region composed of a-SiGe(H,X)
To form the region (G), basically silicon raw material is
Raw material gas and gel for Si supply that can supply Si (Si)
Ge supply source that can supply manium atoms (Ge)
supply gas and, if necessary, for introducing hydrogen atoms (H).
For introducing raw material gas or/and halogen atom (X)
The desired source gas is placed inside a deposition chamber where the internal pressure can be reduced.
Glow is released into the deposition chamber by introducing the gas at a pressure of
A place that generates electricity and is installed in a predetermined position in advance.
germanium atoms contained on a given support surface
The distribution concentration of
Form a layer consisting of a-SiGe(H,X).
Good. Also, when forming by sputtering method,
For example, inert gas such as Ar, He, etc.
Structured with Si in a gas-based mixed gas atmosphere.
the target that has been created, or
Using two targets composed of Ge,
Or use a mixed target of Si and Ge.
If necessary, dilute with diluent gas such as He or Ar.
The raw material gas for supplying Ge, if necessary, is
Hydrogen atom (H) or/and halogen atom (X) conduction
Introducing the required gas into the deposition chamber for sputtering
and form a plasma atmosphere of the desired gas.
, the desired gas flow rate of the raw material gas for the Ge supply is set.
while controlling according to the rate of change curve of
All you have to do is sputter the gettu. ion
In the plating method, for example, polycrystalline silicon
silicon or single crystal silicon and polycrystalline germanium or
and single-crystal germanium as evaporation sources.
A resistance heating method or
Alternatively, use the electron beam method (EB method), etc.
The flying evaporates are heated and evaporated into the desired gas plasma.
Sputtering except for passing through a
This can be done by doing the same thing as in the case of law. Raw material gas for supplying Si used in the present invention
SiH is a substance that can become_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 feed rate, etc._Four,Si₂H₆is preferable
It is mentioned as Raw material gas for Ge supply
Possible substances include GeH_Four,Ge₂H₆,Ge₃H₈，
Ge_FourH_Ten,Ge_FiveH₁₂,Ge₆H₁₄,Ge₇H₁₆,Ge₈H₁₈，
Ge₉H₂₀Gaseous or gasifiable hydrogenation, such as
Germanium is listed as an effective use.
In particular, ease of handling during layer creation work, Ge supply
GeH_Four,Ge₂H₆,Ge₃H₈
are listed as preferred. For introducing halogen atoms used in the present invention
Many halogen carbons are effective as raw material gas for
Examples include recon compounds, such as halogen gas,
Substituted with halides, interhalogen compounds, and halogens.
Gaseous state or gasification of converted silane derivatives etc.
Preferred examples include halogen compounds that can be used. Furthermore, silicon atoms and halogen atoms
Constituent halves in a gaseous state or capable of being gasified
Silicon hydride compounds containing rogen 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 1, basically,
For example, silicon halide, which is the raw material gas for supplying Si.
and germanium hydride, which is the raw material gas for supplying Ge.
Mu and Ar, H₂, He and other gases at a predetermined mixing ratio.
Form the first layer region (G) so that the flow rate becomes
This is introduced into a deposition chamber to generate a glow discharge.
By forming a plasma atmosphere of gases such as
to form a first layer region (G) on a desired support.
However, it is possible to control the harm caused by the introduction of hydrogen atoms.
to these gases to make it even easier to measure
Hydrogen gas or silicon compound gas containing hydrogen atoms
A layer may be formed by mixing a desired amount of these. In addition, each gas can be used not only as a single species but also in a predetermined mixing ratio.
It is safe to use a mixture of multiple types.
Ru. Sputtering method, ion plating method
In either case, halogen atoms are added to the layer formed.
To introduce the above-mentioned halogen compounds or the above-mentioned
A silicon compound gas containing halogen atoms is introduced into the deposition chamber.
to form a plasma atmosphere of the gas.
That's fine. In addition, when introducing hydrogen atoms, hydrogen atom guide
Necessary raw material gas, e.g. H₂, or the above-mentioned
or/and gases such as germanium hydride.
The gases are introduced into the deposition chamber for sputtering.
It is sufficient to form a plasma atmosphere. 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，
SiH₂I₂,SiH₂Cl₂,SiHCl₃,SiH₂Br₂,SiHBr₃etc
halogen-substituted silicon hydride, and GeHF₃，
GeH₂F₂, GeH₃F, GeHCl₃, GeH₂Cl₂，
GeH₃Cl, GeHBr₃, GeH₂Br₂, GeH₃Br,
GeHI₃, GeH₂I₂, GeH₃Hydrogenation and halogenation of I, etc.
germanium, etc., with hydrogen atoms as one of its constituent elements
halides, GeF_Four, GeCl_Four, GeBr_Four，
GeI_Four, GeF₂, GeCl₂, GeBr₂, GeI₂etc. halogen
Germanium oxide, etc., in a gaseous state or in a gasified state
The obtained material is also an effective source for forming the first layer region (G).
It can be cited as a source. Halogen compounds containing hydrogen atoms in these substances
When forming the first layer region (G), halogens are added to the layer.
Electrical or photoelectric properties upon introduction of gen atoms
Hydrogen atoms, which are extremely effective in controlling
Therefore, in the present invention, a suitable method for introducing halogen is
Used as raw material. Hydrogen atoms are structurally introduced into the first layer region (G).
In addition to the above, press H₂, or SiH_Four，
Si₂H₆,Si₃H₈,Si_FourH_TenGe is supplied with silicon hydride such as
germanium or germanium compounds for supplying
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~
30 atomic%, optimally 0.1 to 25 atomic%
is desirable. 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 power, etc. In the present invention, a-Si(H,X)
In order to form the second layer region (S) in which
In the starting material () for forming the first layer region (G)
The starting material, which becomes the raw material gas for Ge supply, is gradually
[Starting material for forming the second layer region (S)]
material ()] to form the first layer region (G).
It should be done in the same manner and under the same conditions as when forming.
I can do it. That is, in the present invention, a-Si(H,X)
For example, to form the second layer region (S)
Glow discharge method, sputtering method, or ion
Vacuum deposition using electrical discharge phenomena such as plating method
It is done by the product method. For example, in the glow discharge method
Therefore, the second layer composed of a-Si(H,X)
In order to form the region (S), basically the above-mentioned steps are performed.
Raw materials for supplying silicon that can supply silicon atoms (Si)
For introducing hydrogen atoms (H) as needed along with gas
or/and raw material gas for introducing halogen atoms (X)
the 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 position is
a-Si on a given support surface installed at
It is sufficient to form a layer consisting of (H,X). or,
When forming by sputtering method, for example, Ar,
Based on inert gas such as He or other gases
Target composed of Si in a mixed gas atmosphere
When sputtering, hydrogen atoms (H) or
/ and sparing gas for introducing halogen atoms (X)
It is sufficient to introduce it into the deposition chamber for vine ring. 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%
30 atomic%, optimally 5 to 25 atomic%.
is desirable. 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.
The starting material for the introduction of atoms or group atoms is in a gaseous state.
in the deposition chamber to form the first layer ()
It may be introduced together with the starting material. Like this
It can be used as a starting material for the introduction of group atoms.
is gaseous or at least layered at normal temperature and pressure.
Materials that can be easily gasified under conditions of formation are used.
is desirable. Starting point for the introduction of such group atoms
Specifically, as a material for introducing boron atoms,
B₂H₆,B_FourH_Ten,B_FiveH₉,B_FiveH₁₁,B_FiveH_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,PIr_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
Nitrogen atoms are contained in (). first layer
The nitrogen 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 nitrogen atoms is such that the distribution concentration C(N) is
The first layer () is uniform in the thickness direction.
However, the game explained using Figures 2 to 10 is
Similar to the distribution state of rumanium atoms, the distribution concentration C
(N) may be non-uniform in the layer thickness direction. Clogging, distribution concentration C(N) of nitrogen atoms is in the layer thickness direction
The distribution state of nitrogen atoms when the nitrogen atoms are non-uniform is
Germanium explained using Figures 2 to 10
It can be explained similarly to the case of atoms. In the present invention, provided in the first layer ()
The layer region (N) containing nitrogen 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 ().
This increases the adhesion strength between the support and the first layer ().
If the main purpose is to measure the
It is designed to occupy the end layer area on the support side of the layer ().
I get kicked. In the former case, nitrogen contained in the layer region (N)
The atomic content is relatively low to maintain high photosensitivity.
In the latter case, the adhesion with the support
It is desirable that it be relatively large in order to ensure the strengthening of
Delicious. Also, the purpose of achieving both the former and the latter at the same time.
In order to
On the second layer () side of the first layer ()
be distributed at a relatively low concentration or in the first layer.
In the region of the second layer () of (), nitrogen atoms
The distribution of nitrogen atoms such that they are not actively included in
What is necessary is to form the structure in the layer region (N). In the present invention, provided in the first layer ()
The content of nitrogen atoms contained in the layer region (N) is
Characteristics required for the layer region (N) itself or the layer
When the region (N) 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. Also, in direct contact with the layer region (N)
If another layer area is provided, the other layer area
characteristics of the area and the contact interface with other layer areas.
The relationship with properties is also considered, and the content of nitrogen atoms is
Selected appropriately. The amount of nitrogen atoms contained in the layer region (N) is
Depending on the characteristics required for the photoconductive member to be formed.
It can be determined appropriately according to the desire, but preferably
0.001~50atomic%, more preferably 0.002~
40atomic%, optimally 0.003~30atomic%
It is desirable to In the present invention, the layer region (N) is the first layer
() or the first layer ()
Even if it does not occupy the entire area, the layer thickness To of the layer region (N)
The proportion of the first layer () in the layer thickness T is sufficiently large.
If the nitrogen atoms contained in the layer region (N)
The upper limit of the content of
It is desirable to In the case of the present invention, the layer thickness To of the layer region (N) is
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 (N)
The upper limit of the amount of nitrogen atoms contained in is preferably
30 atomic% or less, more preferably 20 atomic% or less
Below, optimally it is desired to be less than 10 atomic%.
Yes. In the present invention, nitrogen constituting the first layer ()
The layer region (N) containing elementary atoms is as described above.
Nitrogen atoms are contained at a relatively high concentration on the support side.
It is designed as having a localized area (B) where
It is desirable that the support be
Further improves the adhesion between the first layer ()
It is possible to The above localized region (B) is shown in Figures 2 to 10.
To explain using symbols, the interface position t_B5μ or less
It is preferable that it be installed inside. In the present invention, the localized region (B) 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 (B) is transformed into a layered region (L_T) as part of
The first layer formed
It is determined as appropriate according to the characteristics required for (). The localized region (B) is the nitrogen atom contained therein.
The distribution concentration of nitrogen atoms as the distribution state in the layer thickness direction of
maximum value of C_naxis preferably 500 atomic ppm or more,
More preferably 800 atomic ppm or more, optimally
The distribution state is such that it is more than 1000 atomic ppm.
It is desirable that the layer be formed in such a way that it can be layered. That is, in the present invention, nitrogen atom-containing
The layer area (N) has a layer thickness of 5μ or more from the support side.
Inside (t_BThe maximum value of the distribution concentration in the layer region of 5μ thickness from
C_naxIt is desirable that the structure be formed in such a way that it exists. In the present invention, nitrogen atoms are added to the first layer ().
To provide a contained layer region (N), the first layer
The starting material for nitrogen atom introduction during the formation of ()
Together with the starting materials for forming the first layer () described above
while controlling its amount in the layer formed using
It is better to include it. Glow discharge method is used to form layer region (N)
If so, use the method described above for forming the first layer ()
selected starting materials as desired
Starting material for the introduction of nitrogen atoms is added. Like that
As a starting material for introducing nitrogen atoms, at least
is also a gaseous substance or gas whose constituent atoms are nitrogen atoms.
Most of the substances that can be gasified into gas
may be used. For example, a material whose constituent atoms are silicon atoms (Si).
Raw material gas and raw material containing nitrogen atoms (N) 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 nitrogen
The constituent atoms are elementary atoms (N) and hydrogen atoms (H).
and raw material gas at the desired mixing ratio.
It can be used by Also, separately, silicon atoms (Si) and hydrogen atoms
Nitrogen atoms in the raw material gas whose constituent atoms are (H)
Used by mixing raw material gases whose constituent atoms are (N)
You may do so. Nitrogen source used when forming layer region (N)
As a source gas for introducing nitrogen (N)
Effectively used starting materials include N as a constituent atom.
Or, for example, nitrogen whose constituent atoms are N and H
(N₂), ammonia (NH₃), hydrazine
(H₂NNH₂), hydrogen azide (HN₃), ammo azide
Nium (NH_FourN₃), etc., which are gaseous or capable of being gasified.
Nitrogen compounds such as nitrogen, nitrides and azides are listed.
You can get it. In addition, nitrogen atoms (N)
In addition to the introduction, halogen atoms (X) can also be introduced.
Nitrogen trifluoride (F₃N), Nitrogen tetrafluoride
element (F_FourN₂) and other halogenated nitrogen compounds.
I can do it. In the present invention, a nitrogen source is present in the layer region (N).
In order to further enhance the effect obtained with
In addition to oxygen atoms, it can also contain oxygen atoms.
Ru. Oxygen for introducing oxygen atoms into the layer region (N)
For example, oxygen is used as a raw material gas for introducing atoms.
(O₂), ozone (O₃), nitric oxide (NO), dioxide
Nitrogen (NO₂), nitrogen monoxide (N₂O), sesquioxide
Nitrogen (N₂O₃) trinitrogen tetraoxide (N₂O_Four), pentadic acid
Nitrogen (N₂O_Five), nitrogen trioxide (NO₃),silicon
Atom (Si), oxygen atom (O), hydrogen atom (H) and
For example, disiloxane whose constituent atoms are
(H₃SiOSiH₃), trisiloxane
(H₃SiOSiH₂OSiH₃) and other lower siloxanes.
You can get it. Contains nitrogen atoms by sputtering method
To form the layer region, monocrystalline or polycrystalline
Si wafer or Si₃N_FourWafer or Si
Si₃N_FourA 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
If so, the nitrogen atom and optionally the hydrogen atom 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.
Sputtering the Si wafer to form
Just do it. Also, separately, Si and Si₃N_Fourtarget different from
as or Si and Si₃N_FourA 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 nitrogen atom
As raw material gas for
The raw material gas for introducing nitrogen 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 (N) containing nitrogen atoms is provided in
In this case, the amount of nitrogen atoms contained in the layer region (N)
Create a desired layer by changing the cloth concentration C(N) in the layer thickness direction.
Layer with depth profile
To form the region (N), in the case of glow discharge
is the nitrogen atom whose distribution concentration C(N) should be changed.
Select the starting material gas for introduction and its desired gas flow rate.
Deposition while changing the rate of change appropriately according to the rate of change curve of
This can be done by introducing it indoors. For example, the hand
normally used motors such as motors or externally driven motors.
installed in the middle of the gas flow path system by some method that
The opening of a given needle valve is gradually changed.
All you have to do is to do the following. At this time, the rate of change in flow rate
does not have to be linear; for example, using a microcomputer, etc.
according to a pre-designed rate of change curve.
You can also control the flow rate and obtain the desired content curve.
Wear. Shape the layer region (N) by sputtering method
distribution concentration C of nitrogen atoms in the layer thickness direction
By changing (N) in the layer thickness direction, the nitrogen atom layer thickness direction
to form the desired depth profile of the direction.
The first step is to use the same method as with the glow discharge method.
Similarly, the starting material for introducing nitrogen atoms is used in a gaseous state.
gas flow rate when introducing the gas into the deposition chamber.
is achieved by appropriately changing the
It will be done. Second, the target for sputtering.
For example, Si and Si₃N_FourMixed target with
If you use Si and Si₃N_FourMixing ratio with
is changed in advance in the layer thickness direction of the target.
This is done by leaving it alone. 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%
30 atomic%, optimally 5 to 25 atomic%.
is desirable. In the photoconductive member 100 shown in FIG.
A second layer formed on the first layer ( ) 102
( ) 103 has a free surface and is mainly moisture resistant and connected.
Continuous repeated use characteristics, electrical voltage resistance, usage environment characteristics
In order to achieve the purpose of the present invention in terms of performance and durability,
provided. Further, in the present invention, the first layer ( ) 102
and the amorphous material constituting the second layer ( ) 103
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 a silicon raw material.
(Si), carbon atom (C), and hydrogen as necessary
Contains an atom (H) or/and a halogen atom (X)
amorphous material (hereinafter referred to as “a-(Si_xC_1-x)_y(H,X)
_1-y” However, it is written as 0<x, y<1).
It will be done. a-(Si_xC_1-x)_y(H,X)_1-yThe second consists of
The layer () is formed by glow discharge method, sputtering
method, ion plantation method, ion play
made by the Teing method, electron beam method, etc.
be done. These manufacturing methods depend on the manufacturing conditions and equipment capital.
Drop load level, manufacturing scale, photoconductive part to be manufactured
Selection is made as appropriate depending on factors such as the desired properties of the material.
photoconductive materials with the desired properties.
It is relatively easy to control the manufacturing conditions for manufacturing parts.
Along with silicon atoms, carbon atoms and halogen
Introducing atoms into the second layer to be prepared ()
Glow discharge method or
The sputtering 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_xC_1-x)_y(H,X)_1-yraw material for formation
Mix a predetermined amount of feed gas with diluent gas as needed
For vacuum deposition with mixed ratio and support installed
The gas is introduced into the deposition chamber of the
By generating electricity, the gas becomes plasma and the above-mentioned
on the first layer () already formed on the support
nia-(Si_xC_1-x)_y(H,X)_1-yAll you have to do is deposit
stomach. In the present invention, a-(Si_xC_1-x)_y(H,X)_1-y
As raw material gas for formation, silicon atoms (Si),
Carbon atom (C), hydrogen atom (H), halogen atom
A group whose constituent atoms are at least one of (X)
Gasified substances or substances that can be gasified
Most of them can be used. Si as one of the constituent atoms among Si, C, H, and X
When using a raw material gas that is
A raw material gas consisting of constituent atoms and a source gas containing C 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 C and H as constituent atoms.
raw material gas or/and raw material containing X as a constituent atom
and gas, also at the desired mixing ratio.
Or, a raw material gas containing Si as a constituent atom and Si,
A raw material gas containing three constituent atoms of C and H, or
A raw material gas containing three constituent atoms: Si, C, and X.
Can be used in combination. In addition, there is also a raw material gas whose constituent atoms are Si and H.
mixed with raw material gas containing C as a constituent atom.
It is also possible to use a raw material gas containing Si and X as constituent atoms.
mixed with raw material gas containing C as a constituent atom.
You may do so. In the present invention, contained in the second layer ()
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 must be in a gas state at room temperature and pressure, or it can be easily
There are substances that can be gasified. In the present invention, the raw material for forming the second layer ()
The gases that can be effectively used are Si and H.
SiH as a constituent atom_Four,Si₂H₆, Si₃H₈,Si_FourH_Tenetc.
Silicon hydride gas such as silane, C and H
and, for example, saturated carbon atoms with 1 to 4 carbon atoms.
Hydrocarbon, ethylene hydrocarbon having 2 to 4 carbon atoms,
Acetylenic hydrocarbons with 2 to 3 carbon atoms, halogens
Single substance, hydrogen halide, interhalogen compound, halo
silicon hydride, halogen-substituted silicon hydride, silicon hydride
I can list the basics. Specifically, methane is a saturated hydrocarbon.
(CH_Four) Ethane (C₂H₆), propane (C₃H₈), n
-butane (n-C_FourH_Ten), pentane (C_FiveH₁₂),workman
Ethylene (C₂H_Four),
Propylene (C₃H₆), butene-1 (C_FourH₈), Butte
N-2 (C_FourH₈), isobutylene (C_FourH₈), pente
(C_FiveH_Ten), as acetylenic hydrocarbons,
Acetylene (C₂H₂), methylacetylene
(C₃H_Four), butin (C_FourH₆), as a single halogen
is a halogen gas of fluorine, chlorine, bromine, and iodine.
Hydrogen halides include FH, HI, HCl,
HBr, interhalogen compounds include BrF, ClF,
ClF₃,ClF_Five,BrF_Five,BrF₃,IF₇,IF_Five, ICl, IBr,
BiF as silicon halide_Four,Si₂F₆,SiCl_Four，
SiCl₃Br, SiCl₂Br₂,SiClBr₃,SiCl₃I, SiBr_Four，
As halogen-substituted silicon hydride, SiH₂F₂，
SiH₂Cl₂,SiHCl₃,SiH₃Cl, SiH₃Br, SiH₂Br₂，
SiHBr₃As silicon hydride, SiH_Four,Si₂H₈，
Si_FourH_TenList of silanes, etc.
I can do it. In addition to these, CF_Four,CCl_Four, CBr_Four,CHF₃，
CH₂F₂,CH₃F, CH₃Cl, CH₃Br, CH₃I,
C₂H_FiveHalogen-substituted paraffinic hydrocarbons such as Cl,
science fiction_Four,SCIENCE FICTION₆Fluorinated sulfur compounds such as Si(CH₃)_Four，
Si(C₂H_Five)_FourAlkyl silicides such as SiCl(CH₃)₃，
SiCl₂(CH₃)₂,SiCl₃Silication containing halogens such as CH
Silane derivatives such as alkyl are also listed as effective.
You can get it. These second layer () forming substances are
silicon with a predetermined composition ratio in the second layer ()
atoms, carbon atoms and halogen atoms as appropriate
The second layer () contains hydrogen atoms.
Selected and used according to desired during formation.
Ru. For example, silicon atoms, carbon atoms, and hydrogen atoms
can be easily incorporated and a layer with desired properties can be formed.
Si(CH₃)_Fourand contains halogen atoms.
SiHCl as a material₃,SiH₂Cl₂,SiCl_FourOr
is SiH₃Cl, etc. are mixed in a predetermined mixing ratio in a gas state.
It is introduced into the device for forming the second layer () and released with glow.
By generating electricity, a-(Si_xC_1-x)_y(Cl
+H)_1-yforming a second layer () consisting of
I can do it. The second layer () by sputtering method
To form a single crystal or single crystal Si wafer
Or C wafer or a mixture of Si and C.
Targeting wafers that are
halogen atom or/and hydrogen atom as necessary
spa treatment in various gas atmospheres containing
This can be done by tuttering. For example, using a Si wafer as a target
Then, the raw materials for introducing C and H or/and X
Add the gas to the spa, diluting it with diluent gas if necessary.
These gases are introduced into the deposition chamber for
The Si wafer is sputtered by forming a sputtering plasma.
All you have to do is tarling. Additionally, Si and C are separate targets.
or using a single target with a mixture of Si and C.
By using hydrogen atoms or
is/and in a gas atmosphere containing halogen atoms.
It is done by sputtering.
As a material that becomes the raw material gas for introducing C, H and
This is the second layer shown in the glow discharge example mentioned above.
() When the forming material is sputtering method
It can also be used as an effective substance. In the present invention, the second layer () is glow discharged
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
carefully shaped to give the desired characteristics.
will be accomplished. That is, Si, C, 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 semiconductive to insulating.
properties ranging from photoconductive to non-photoconductive.
Since the properties up to the electrical properties are shown respectively, the present invention
has desired characteristics depending on the purpose. a-(Si_xC_1-x)_y(H,X)_1-yso that it is formed,
The selection of the production conditions is made strictly according to the desired
Ru. For example, the second layer () may be used to improve electrical resistance.
To provide the upper main purpose is a-(Si_xC_1-x)_y
(H,X)_1-yelectrically insulating behavior in the usage environment.
It is created as a highly dynamic amorphous 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.
It has a certain degree of sensitivity to the light that is exposed to it.
a-(Si_xC_1-x)_y(H,
X)_1-yis created. a-(Si) on the surface of the first layer ()_xC_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
This is an important factor that influences the characteristics, and is
In this case, a-(Si_xC_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 objective of the present invention is effectively achieved.
Depending on the method of forming the second layer () for
A suitable range is selected and the formation of the second layer () is carried out.
preferably at 20 to 400°C, more preferably
temperature is 50 to 350℃, optimally 100 to 300℃.
desirable. Formation of the second layer () constitutes the layer
Delicate control of the atomic composition ratio and layer thickness control
Because it is relatively easy compared to the method of
It is advantageous to use the low discharge method or sputtering method.
However, the second layer () can be formed using these layer forming methods.
In the case where the layer shape is
a-(Si_xC_1-x)_y
(H,X)_1-yOne of the important factors that influences the characteristics of
It is. Having the characteristics for achieving the object of the present invention
to a-(Si_xC_1-x)_y(H,X)_1-yis highly productive and effective.
The discharge power conditions for effectively creating
preferably 10-300W, more preferably 20-250W, optimally
It is desirable that the power is 50 to 200W. The gas pressure in the deposition chamber is preferably 0.01~
1 Torr, more preferably around 0.1 to 0.5 Torr
is desirable. In the present invention, in order to create the second layer ()
Support temperature, desired numerical range of discharge power and
The values in the range mentioned above can be mentioned, but these
Layer creation factors can be determined independently and separately
a-(Si_xC_1-x)_y(H,
X)_1-yso that a second layer () consisting of
Create factors for each layer based on mutual organic relationships
It is desirable to be able to determine the optimal value of -. The second layer () in the photoconductive member of the present invention
The amount of carbon 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
An important factor in the formation of the second layer ()
It is a child. Contained in the second layer () in the present invention
The amount of carbon atoms forming the second layer () is
as appropriate depending on the type of amorphous material and its characteristics.
It can be decided according to your wishes. That is, the general formula a-(Si_xC_1-x)_y(H,X)_1-y
Amorphous materials shown in can be roughly divided into silicon
Amorphous material (hereinafter referred to as
After that, “a-Si_aC_1-a”. However, 0<a<1),
Composed of silicon atoms, carbon atoms, and hydrogen atoms
amorphous material (hereinafter referred to as “a-(Si_bC_1-b)_cH_1-c"and
write down However, 0<b, 0<1), silicon atoms and
Carbon atoms, halogen atoms, and hydrogen atoms if necessary
(hereinafter referred to as a-(Si_d
C_1-d)_e(H,X)_1-e”. However, 0<d, e<
It is classified as 1). In the present invention, the second layer () is a-Si_a
C_1-acontained in the second layer ()
The amount of carbon atoms contained is preferably 1×10^-3~
90 atomic%, more preferably 1-80 atomic%, most
It is preferably 10 to 75 atomic%.
That is, the previous a-Si_aC_1-aIf we do this in the representation of a, then a
is preferably 0.1 to 0.99999, more preferably 0.2 to
0.99, optimally 0.25-0.9. In the present invention, the second layer () is a-(Si_b
C_1-b)_cH_1-cIf the second layer consists of ()
The amount of carbon atoms contained is preferably 1×10^-3
~90 atomic%, more preferably 1~
90 atomic%, optimally 10-80 atomic%
is desirable. The content of hydrogen atoms is preferably
1 to 40 atomic%, more preferably 2 to 35 atomic%
%, ideally 5 to 30 atomic%.
If the hydrogen content is within these ranges,
The photoconductive member formed has excellent practical properties.
It can be fully applied as such. That is, the previous a-(Si_bC_1-b)_cH_1-cDo it with the display
For example, b is preferably 0.1 to 0.99999, more preferably
0.1-0.99, optimally 0.15-0.9, preferably c
0.6-0.99, more preferably 0.65-0.98, optimally 0.7
~0.95 is desirable. The second layer is a-(Si_dC_1-d)_e(H,X)_1-eIt's okay
When formed, it is contained in the second layer ().
The content of carbon atoms is preferably 1×10^-3~
90 atomic%, more preferably 1-90 atomic%, most
It is preferably 10 to 80 atomic%.
The content of halogen atoms is preferably 1 to
20 atomic%, more preferably 1-18 atomic%, most
It is preferable that the content be between 2 and 15 atomic%.
If the halogen atom content is within these ranges,
The produced photoconductive member can be fully applied to the actual field.
It is something that Hydrogen atoms included as necessary
The content of is preferably less than or equal to 19 atomic%, and more
Preferably, it is 13 atomic % or less. That is, the previous a-(Si_dC_1-d)_e(H,X)_1-ed,
If expressed as e, d is preferably 0.1~
0.99999, more preferably 0.1-0.99, optimally 0.15
~0.9, e is preferably 0.8~0.99, more preferably
0.82 to 0.99, ideally 0.85 to 0.98
Yes. Layer thickness range of the second layer () in the present invention
are important for effectively achieving the purpose of the present invention.
This is one of the important factors to effectively achieve the purpose of the present invention.
Depending on the intended purpose, decide as appropriate to suit your needs.
It will be done. Also, the layer thickness of the second layer () is
The amount of carbon atoms contained and the thickness of the first layer ()
Also, in relation to
According to the desired organic relationship according to the characteristics
It needs to be decided accordingly. You can also add raw
Consideration is also given from the economic point of view, which takes into account productivity and mass production.
It is desirable that this be considered. The layer thickness of the second layer () in the present invention is preferably
preferably 0.003-30μ, more preferably 0.004-20μ, optimal
It is desirable that the value be 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, Pb, etc.
Or an alloy of these may be mentioned. electrically insulating support
The body is made of polyester, polyethylene, polyester.
carbonate, cellulose acetate, polypropylene
Pyrene, polyvinyl chloride, polyvinylidene chloride,
Synthetic resin films such as polystyrene and polyamide
Usually used as a film or sheet, glass, ceramic, paper, etc.
used. These electrically insulating supports are suitable
has at least one surface conductively treated,
Another layer is provided on the conductive treated surface side.
is desirable. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, t,
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 such that the photoconductive member is formed as desired.
The flexibility of the photoconductive member is determined as appropriate.
Sufficient support function if required
It is made as thin as possible within the range that can be achieved.
Ru. However, in such cases, the manufacturing of the support
It is preferable in terms of handling, mechanical strength, etc.
is considered to be 10μ or more. 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 11 shows an example of a manufacturing device for photoconductive members.
vinegar. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming the photoconductive member of the present invention is
For example, 110
2 is SiH diluted with He_FourGas (99.999% purity,
Below SiH_Four/He is abbreviated. ) cylinder, 1103 is He
GeH diluted with_FourGas (purity 99.999% or less)
GeH_Four/He is abbreviated. ) cylinder, 1104 is rare in He
interpreted B₂H₆Gas (purity 99.99%, below B₂H₆/
Abbreviated as He. ) cylinder, 1105 is NH₃gas (pure
99.999%) cylinder, 1106 is H₂Gas (purity
99.999%) cylinder. To allow those gases to flow into the reaction chamber 1101
is gas cylinder 1102~1106% valve 11
22-1126, leak valve 1135 is closed.
Check that the inlet valve 1112 is
~1116, outflow valves 1117~1121, supplementary
The auxiliary valves 1132 and 1133 are open.
After checking, first open the main valve 1134.
The reaction chamber 1101 and each gas pipe are evacuated.
Next, the continuation of vacuum gauge 1136 is about 5 × 10^-6torr
At the point when the auxiliary valves 1132 and 1133 leak
Close valves 1117-1121. Next, a first layer is placed on the cylindrical base 1137.
An example of forming () is a gas cylinder.
SiH from Nbe 1102_Four/He gas, gas cylinder 1
GeH from 103_Four/He gas, gas cylinder 1140
More B₂H₆/He gas, from gas cylinder 1105
N.H.₃Open gas valves 1122-1125
Pressure of outlet pressure gauge 1127-1130 is 1Kg/cm²
gradually adjust the inflow valves 1112 to 1115 to
Open it and install the mass flow controller 1107-1.
110 respectively. Continuing to spill out
valves 1117 to 1120, and auxiliary valve 1132.
The gas gradually opens and flows into each gas reaction chamber 1101.
let SiH at this time_Four/He gas flow rate and GeH_Four/
He gas flow rate and B₂H₆/He gas flow rate and NH₃gas flow
the outflow valve 11 so that the ratio with the amount is the desired value.
17 to 1120, and also inside the reaction chamber 1101.
the vacuum gauge 1136 so that the pressure is at the desired value.
Adjust the opening of main valve 1134 while checking the reading.
Arrange. Then, the temperature of the base 1137 becomes higher than that of the heater.
-1138 to set the temperature in the range of 50 to 400℃
After confirming that the power supply 1140 is
Set the desired power and emit glow into the reaction chamber 1101.
A pre-designed rate of change while generating electricity
GeH according to the curve_Four/He gas flow rate can be adjusted manually or
The valve 111 is driven by an external drive motor or the like.
It is formed by performing an operation to gradually change the opening of 8.
The distribution concentration of germanium atoms contained in the layer
Control the degree. In this way, boron atoms are placed on the base 1137.
(B) and a nitrogen atom (N),
The distribution state of germanium atoms according to the conversion rate curve is
It is formed. Composed of a-SiGe(H,X)
A layer region (B, N) with a desired layer thickness is formed.
At the stage when the layer region (B, N) is formed to the desired layer thickness
At the outflow valves 1118, 1119, 112
Completely close each of 0, and if necessary
Similar conditions and procedures except for changing discharge conditions
By maintaining the glow discharge for the desired time according to the
Boron atoms (B) and nitrogen atoms are placed on the recording region (B, N).
Contains atoms (N) and germanium atoms (Ge).
layer region composed of a-Si(H,X)
area (S) is formed, and the formation of the first layer () is
be terminated. When forming the above photoreceptive layer, start forming the layer.
After that, after the desired time has elapsed, transfer to the deposition chamber.
B₂H₆/He gas or NH₃Stopping the gas flow
Depending on the layer region containing boron atoms (B)
and each layer thickness of the layer region (N) containing nitrogen atoms
can be controlled arbitrarily. Also, the deposition chamber 110 can be adjusted according to a desired rate of change curve.
NH to 1₃By controlling the gas flow rate of the gas
Therefore, the amount of nitrogen atoms contained in the layer region (N)
The cloth state can be formed as desired. Including halogen atoms in the first layer ()
In case the above gases e.g. SiF_Fourmore gas
It is sufficient to add it to cause glow discharge. In addition, hydrogen atoms are not contained in the first layer ().
When containing a halogen atom, the above
SiH_Four/He gas and GeH_Four/Instead of He gas,
SiF_Four/He gas and GeF_Four/If you use He gas
good. First layer formed to desired layer 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, C₂H_Fourneed gas each
Dilute with diluent gas such as He to achieve desired conditions.
Therefore, by generating glow discharge,
be done. Including halogen atoms in the second layer ()
For example, SiF_Fourgas and C₂H_Fourgas or this
to SiH₂2nd 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 1101 and the outflow valve 1
Gases leading from 117 to 1121 into the reaction chamber 1101
To avoid any residue remaining in the piping,
Close the valves 1117 to 1121, and close the auxiliary valve 11.
Open main valve 1143 by opening 32, 1133.
It is necessary to fully open the system and evacuate the system to high vacuum.
This will be done as necessary. The amount of carbon atoms contained in the second layer () is
For example, in the case of glow discharge, SiH_Fourgas and
C₂H_FourFlow rate of gas introduced into reaction chamber 1101
Vary the ratio as desired or sputter
When layering with rings, form the target.
The silicon wafer and graphite wafer are
Either change the patch area ratio or use silicon powder.
Target by changing the mixing ratio of graphite powder
to control the molding as desired.
I can do it. Halogen contained in the second layer ()
The amount of halogen atoms (X) is the raw material for introducing halogen atoms.
gas, e.g. SiF_FourGas is introduced into the reaction chamber 1101
This is done by adjusting the flow rate when
Ru. Also, while forming layers, make sure that the layer formation is uniform.
For measurement, the base 1137 is rotated by a motor 1139.
It is desirable to rotate at a constant speed. Examples will be described below. Example 1 By the manufacturing equipment shown in Fig. 11, cylinder
Figure 12 was applied on the Al substrate of the shape shown in Table 1.
GeH according to the rate of change curve of gas flow ratio shown in_Four/
He gas and SiH_Four/He gas flow rate ratio after layer creation
Electrophotography is performed by forming layers by changing them over time.
An imaging member for use was obtained. The image forming member thus obtained was subjected to a charging exposure experiment.
Installed in the device and corona charged at 5.0kV for 0.3sec.
The light image was immediately irradiated. The light image is tungsten
Using a lamp light source, the light intensity of 2 lux・sec is transmitted through the transmission type.
It was irradiated through a test chart. Immediately thereafter, apply a chargeable phenomenon agent (toner and key).
(containing Yaria) on the surface of the imaging member.
By depositing good toner on the imaging member surface.
-I got an image. The toner image on the imaging member
When transferred onto transfer paper with 5.0kV corona charging, the solution was
Clear, high-density images with excellent image power and good gradation reproducibility
The image was obtained. Example 2 The manufacturing equipment shown in Figure 11 is shown in Table 2.
Under the conditions, the rate of change curve of gas flow rate ratio shown in Figure 13
Therefore, GeH_Four/He gas and SiH_Four/He gas gas
Change the flow rate ratio with the elapsed time of layer creation, etc.
The conditions for layer formation were the same as in Example 1, and the
An image forming member for child photography was obtained. Examples of the image forming member thus obtained
Form an image on the transfer paper using the same conditions and procedures as 1.
As a result, extremely clear image quality was obtained. Example 3 The manufacturing equipment shown in Figure 11 is shown in Table 3.
Under the conditions, the rate of change curve of gas flow rate ratio shown in Figure 14
Therefore, GeH_Four/He gas and SiH_Four/He gas gas
Change the flow rate ratio with the elapsed time of layer creation, etc.
The conditions for layer formation were the same as in Example 1, and the
An image forming member for child photography was obtained. Examples of the image forming member thus obtained
Form an image on the transfer paper using the same conditions and procedures as 1.
As a result, extremely clear image quality was obtained. Example 4 The results are shown in Table 4 using the manufacturing equipment shown in Figure 11.
Under the conditions, the rate of change curve of gas flow rate ratio shown in Figure 15
Therefore, GeH_Four/He gas and SiH_Four/He gas gas
Change the flow rate ratio with the elapsed time of layer creation, etc.
Layer formation was carried out under the same conditions as in Example 1.
An electrophotographic imaging member was obtained. Examples of the image forming member thus obtained
Form an image on the transfer paper using the same conditions and procedures as 1.
As a result, extremely clear image quality was obtained. Example 5 The manufacturing equipment shown in Figure 11 is shown in Table 5.
Under the conditions, the rate of change curve of gas flow rate ratio shown in Figure 16
Therefore, GeH_Four/He gas and SiH_Four/He gas gas
Change the flow rate ratio with the elapsed time of layer creation, etc.
Layer formation was carried out under the same conditions as in Example 1.
An electrophotographic imaging member was obtained. Examples of the image forming member thus obtained
Form an image on the transfer paper using the same conditions and procedures as 1.
As a result, extremely clear image quality was obtained. Example 6 The manufacturing equipment shown in Figure 11 produces the results shown in Table 6.
The rate of change curve of the gas flow rate ratio shown in Figure 17 under the conditions
According to GeH_Four/He gas and SiH_Four/He gas moth
By changing the gas flow rate ratio with the elapsed time of layer formation,
Other conditions were the same as in Example 1 to form layers.
An electrophotographic image forming member was obtained. Examples of the image forming member thus obtained
Form an image on the transfer paper using the same conditions and procedures as 1.
As a result, extremely clear image quality was obtained. Example 7 The manufacturing equipment shown in Figure 11 produces the results shown in Table 7.
The rate of change curve of the gas flow rate ratio shown in Figure 18 under the conditions of
According to GeH_Four/He gas and SiH_Four/He gas moth
By changing the gas flow rate ratio with the elapsed time of layer formation,
Other conditions were the same as in Example 1 to form layers.
An electrophotographic imaging member was obtained. Examples of the image forming member thus obtained
Form an image on the transfer paper using the same conditions and procedures as 1.
As a result, extremely clear image quality was obtained. Example 8 In Example 1, SiH_Four/Instead of He gas
Si₂H₆/He gas was used under the conditions shown in Table 8.
Layer formation was performed under the same conditions as in Example 1 except for this.
An electrophotographic image forming member was thus obtained. Examples of the image forming member thus obtained
Form an image on the transfer paper using the same conditions and procedures as 1.
As a result, extremely clear image quality was obtained. Example 9 In Example 1, SiH_Four/Instead of He gas
SiF_Four/He gas under the conditions shown in Table 9.
Layer formation was carried out under the same conditions as in Example 1, except for
An electrophotographic image forming member was obtained. Examples of the image forming member thus obtained
Form an image on the transfer paper using the same conditions and procedures as 1.
As a result, extremely clear image quality was obtained. Example 10 In Example 1, SiH_Four/Instead of He gas
(SiH_Four/He＋SiF_Four/He) using gas, Table 10
Same conditions as in Example 1 except for the conditions shown in
layer formation to obtain an electrophotographic imaging member.
Ta. Examples of the image forming member thus obtained
Form an image on the transfer paper using the same conditions and procedures as 1.
As a result, extremely clear image quality was obtained. Example 11 By the manufacturing equipment shown in Fig. 11, cylinder
Fig. 12 was applied on the Al substrate of the shape under the conditions shown in Table 11.
According to the rate of change curve of gas flow rate ratio shown in
GeH_Four/He gas and SiH_Four/He gas flow rate ratio
Layer formation The layer formation is performed by changing the elapsed time.
An electrophotographic imaging member was obtained. The image forming member thus obtained was subjected to a charging exposure experiment.
Installed in the device and corona charged at 5.0kV for 0.3sec.
The light image was immediately irradiated. The light image is tungsten
Using a lamp light source, the light intensity of 2 lux・sec is transmitted through the transmission type.
It was irradiated through a test chart. Immediately thereafter, the charged phenomenon agent (toner and carrier)
(including rear) across the imaging member surface.
In particular, good toner alignment on the imaging member surface is achieved.
Got the image. the toner image on the imaging member;
When transferred onto transfer paper with 5.0kV corona charging, the solution was
Clear, high-density images with excellent image power and good gradation reproducibility
The image was obtained. Example 12 In Example 11, when creating the first layer,
B₂H₆(SiH_Four+GeH_Four) for the second
B when creating layers₂H₆SiH_FourThe flow rate for
12 Same as Example 11 except for the changes shown in Table 12.
Each of the electrophotographic imaging members was prepared under the following conditions. Examples of the image forming member thus obtained
Form an image on transfer paper using the same conditions and procedures as 11.
As a result, the results shown in Table 12 were obtained. Example 13 In Examples 1 to 10, the conditions for creating the second layer were
Each implementation except for the conditions shown in Tables 13 and 14.
Electrophotographic imaging member under the same conditions as shown in the example.
(Sample Nos. 1301 to 1310, 1401 to
1401-1410) were created. For each of the image forming members thus obtained,
Images were transferred onto transfer paper under the same conditions and procedures as in Example 1.
The results shown in Table 13A and Table 14A are obtained when
was gotten. Example 14 In Example 1, the light source was a tungsten lamp.
810nm GaAs semiconductor laser instead of laser diode
(10mW) was used to form an electrostatic image.
The toner image forming conditions were the same as in Example 1.
For electrophotography, prepared under the same conditions as in Example 1.
Image quality evaluation of toner transfer images for image forming members
I found that it has excellent resolution and good gradation reproducibility.
Clear, high-quality images were obtained. Example 15 Set the creation conditions for layer () to each of the conditions shown in Table 15.
The same procedure as in Examples 1, 7, and 11 was performed except for the following.
Each of the electrophotographic imaging members according to the conditions and procedures
(Sample No. 12-101 to 12-108, 12-701 to 12-708,
24 samples (12-1101 to 12-1108) were created. The husband of each electrophotographic image forming member thus obtained
The husband was placed separately in the copying machine and described in each example.
Under the same conditions as above,
For each electrophotographic imaging member, the transferred image
Overall image quality evaluation and durability through repeated and continuous use.
I conducted an evaluation. Comprehensive image quality evaluation of transferred images of each sample and repeated series
Table 16 shows the results of durability evaluation after continuous use.
vinegar. Example 16 During layer () formation, silicon wafer and graph eye
By changing the target area ratio of
By changing the content ratio of silicon atoms and carbon atoms in
Images were obtained in exactly the same manner as in Example 1, except that
Each of the forming members was created. The image thus obtained
For each of the forming members, as described in Example 1,
Image creation, development, and cleaning processes are repeated approximately 50,000 times.
When I evaluated the image after returning it, I found the results as shown in Table 17.
I got the result. Example 17 During the formation of the layer (), SiH_Fourgas and C₂H_Fourgas
By changing the flow rate ratio of
Implemented except for changing the content ratio of carbon atoms and carbon atoms.
each of the imaging members in exactly the same manner as in Example 1.
It was created. For each image forming member thus obtained, Examples
The process up to transfer was repeated approximately 50,000 times using the method described in 1.
After repeating the image evaluation, Table 18
I got results like this. Example 18 During the formation of the layer (), SiH_Fourgas, SiF_Fourgas,
C₂H_FourAmorphous material () by changing the gas flow rate ratio
By changing the content ratio of silicon atoms and carbon atoms in
The same method as in Example 1 was used except that
Then, each of the image forming members was prepared. obtained in this way
For each imaging member prepared as described in Example 1.
Image, development, and cleaning processes are repeated approximately 50,000 times.
After that, we performed image evaluation and found the results shown in Table 19.
I got the result. Example 19 Example 1 and all except for changing the layer thickness of layer ().
Each of the image forming members was made in a similar manner.
Ta. Imaging, development, and cleaning as described in Example 1
The washing process was repeated and the results shown in Table 20 were obtained.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] ◎: Excellent ○: Good

【table】

[Table] ◎: Excellent ○: Good

【table】

[Table] ◎: Excellent ○: Good

【table】

【table】

【table】

[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
× = Causes image defects

[Table] Common layer forming conditions in the above embodiments of the present invention are shown below. Substrate temperature: germanium atom (Ge) containing layer
...About 200℃ Germanium atom (Ge)-free layer
…Approx. 250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 each show the distribution state of germanium atoms in the first layer region (G). FIG. 11 is a schematic explanatory diagram of the device used in the present invention, and FIG.
18 are explanatory diagrams showing rate of change curves of the gas flow rate ratio in the embodiments of the present invention, respectively. 100...Photothin electric member, 101...Support, 1
02...First layer (), 103...Second layer (), 104...First layer region (G), 105...
...Second layer region (S).

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography;
A first layer region (G) with a layer thickness of 30 Å to 50 μ made of an amorphous material containing 10 ⁵ atomic ppm of germanium atoms and an amorphous material containing silicon atoms (but not germanium atoms) layer thickness
A first layer exhibiting photoconductivity having a layer thickness of 1 to 100 μ and a second layer region (S) having a thickness of 0.5 to 90 μ are provided in order from the support side, a silicon atom and a 1×
and a second layer with a layer thickness of 0.003 to 30 μ made of an amorphous material containing 10 ^-3 to 90 atomic% of carbon atoms, and the distribution state of germanium atoms in the first layer region (G). is nonuniform in the layer thickness direction, and the distribution concentration of germanium atoms on the support side is 1000 atomic ppm relative to silicon atoms.
The interface side with the second layer region (S) is considerably lower than the support side, and the first layer region (G) has a high part of 0.01
A substance controlling conductivity of ~5×10 ⁴ atomic ppm is contained in the first layer, and a conductivity of ~5×10 4 atomic ppm is contained in the first layer.
A photoconductive member for electrophotography characterized by containing 50 atomic% of nitrogen atoms. 2. The photoconductive member for electrophotography according to claim 1, wherein at least one of the first layer region (G) and the second layer region (S) contains hydrogen atoms. 3. The photoconductive member for electrophotography according to claim 1 or 2, wherein at least one of the first layer region and the second layer region (S) contains a halogen atom. . 4. The photoconductive member for electrophotography according to claim 1, wherein germanium atoms in the first layer region (G) are distributed more toward the support side. 5. The photoconductive member for electrophotography according to claim 1, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table. 6. The photoconductive member for electrophotography according to claim 1, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table.