JPH0215868B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical field] The present invention is based on light (here, light in a broad sense, ultraviolet light).
rays, visible rays, infrared rays, X-rays, gamma rays, etc.)
Regarding photoconductive materials sensitive to electromagnetic waves such as
Ru. [Prior art] Solid-state imaging devices or electronics in the image forming field
Light guide in image forming members for photographic images and document reading devices
As a photoconductive material that forms a conductive 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 must be non-polluting to the human body and solid-state photography.
In imaging devices, afterimages can be easily removed within a predetermined time.
Characteristics such as being able to manage
In particular, electronic photocopying machines used in offices as business machines
In the case of an electrophotographic imaging member incorporated into a real device.
In some cases, non-polluting during the above use is important.
It is a point. Based on this perspective, there has been a lot of attention recently on
Amorphous silicon (hereinafter a-
Si), for example, the German publication No.
Publications No. 2746967 and No. 2855718 contain electronic photographs.
The application to image forming members for
Publication No. 2933411 describes its application to photoelectric conversion/reading devices.
Each is listed. However, the conventional light guide made of a-Si
A photoconductive member having a conductive layer has a dark resistance value, photosensitivity,
Electrical, optical, photoconductive properties such as photoresponsiveness,
In terms of usage environment characteristics such as moisture resistance and moisture resistance, and
In terms of stability, it is necessary to improve overall characteristics.
There are issues that need to be further improved.
That is the reality. For example, when applied to an electrophotographic imaging member
Attempts were made to achieve high light sensitivity and high dark resistance at the same time.
Conventionally, when using the product, there is no residual
Cases where a potential remains are often observed, indicating that this type of photoconductivity
If parts are used repeatedly for a long time, they may
Places where afterimages occur due to accumulation of fatigue due to use.
The so-called ghost phenomenon has started to occur, or
When used repeatedly at high speeds, responsiveness gradually decreases.
There were many inconveniences, such as having to do something. Furthermore, compared to the short wavelength side of the visible light region, a-Si
Therefore, the absorption in the wavelength region longer than the wavelength region on the long wavelength side is
It has a relatively small absorption coefficient and is currently in practical use.
When mating with a conductor laser, it is also possible to
The light source is a commonly used halogen lamp or fluorescent lamp.
In this case, the long wavelength side light cannot be used effectively.
In this respect, there is room for improvement in each
It remains. Alternatively, the irradiated light may be applied to the photoconductive layer.
Light that reaches the support without being sufficiently absorbed within it
When the amount of
If the reflectance of the incoming light is high, the light guide
Interference due to multiple reflections occurs within the electrical layer, resulting in an image
This is one of the causes of "blurring" of images. This influence
makes the irradiation spot smaller to increase resolution.
In particular, semiconductor lasers are used as light sources.
If so, it becomes a big problem. Furthermore, when configuring the photoconductive layer with a-Si material,
in order to improve its electrical and photoconductive properties.
In addition, hydrogen atoms, fluorine atoms, chlorine atoms, etc.
For control of halogen atoms and electrical conductivity
Boron atoms, phosphorus atoms, etc., or other special
In order to improve the properties, other atoms are added as constituent atoms.
Although these constituent atoms are contained in the photoconductive layer,
Depending on the content, the electricity of the formed layer may vary.
This may cause problems with optical or photoconductive properties.
Ru. That is, for example, when light is irradiated into the formed photoconductive layer,
The lifespan of photocarriers generated by
It is possible to obtain sufficient image density based on the fact that the life is not sufficient.
If the support is not exposed or in the dark,
This is based on insufficient prevention of charge injection from the side.
In many cases, problems may occur. Therefore, it is important to improve the properties of the a-Si material itself.
However, when designing photoconductive members, the above
The desired electrical and optical properties such as
It is necessary to devise ways to The present invention has been made in view of the above points, and includes a
- Regarding Si, electrophotographic image forming members and solid-state imaging devices
As a photoconductive member used in equipment, reading devices, etc.
Comprehensive and thorough from the perspective of applicability and applicability
As a result of continued research and consideration, we found that silicon (Si) is the base material.
Amorphous materials, especially silicon atoms (Si),
and hydrogen atom (H) or halogen atom (X)
Amorphous material containing at least one of the two
material, so-called hydrogenated amorphous silicon,
Halogenated amorphous silicon or halogen
Hydrogenated amorphous silicon containing
is generically expressed as a-Si(H,X)] and Si
Licon atom (Si) and germanium atom (Ge)
Amorphous materials based on these atoms, especially
hydrogen atom (H) or halogen atom (X)
Amorphous amorphous containing at least one of the above
material, so-called hydrogenated amorphous silicon
Germanium, halogenated amorphous silicon
Germanium or halogen-containing hydrogenated amol
FAS silicon germanium (hereinafter referred to as generic name)
(denoted as a-SiGe(H,X))
The photoconductive member to be used is treated as described below.
Photoconductive members made with a specified layer structure 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.
Superiority, especially in photoconductive materials for electrophotography
It has extremely excellent properties as
Excellent absorption spectrum characteristics on the long wavelength side
This is based on the findings that [Purpose of the invention] The present invention is characterized in that electrical, optical, and photoconductive properties are
The entire ring is stable over time and is almost unaffected by the usage environment.
It is said to have excellent photosensitive characteristics on the long wavelength side.
It also has excellent light fatigue resistance and can be used repeatedly.
No deterioration phenomenon occurs even when the residual potential is
aims to provide photoconductive materials that are rarely observed.
Make it the main purpose. Another object of the present invention is to provide light sensitivity in the entire visible light range.
High degree of accuracy, especially suitable for matching with semiconductor lasers
To provide a photoconductive member with excellent and fast photoresponse.
That is. 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.
It has sufficient charge retention ability during charging processing, and has excellent chargeability.
By providing a photoconductive member with photographic properties,
be. Still another object of the present invention is to
Clear tones, high resolution, and no image defects
It is possible to obtain high-quality images without defects or image blurring.
To provide a photoconductive member for electrophotography that can be easily produced.
That's true. Yet another object of the present invention is to provide sufficient dark resistance.
We offer a photoconductive member that provides a high and sufficient acceptance potential.
It also improves the adhesion between each layer.
The goal is to improve productivity. Yet another object of the present invention is high photosensitivity,
To provide a photoconductive member having high SN ratio characteristics
There is also. [Structure of the invention] That is, the photoconductive member of the present invention can be used as an electrophotographic light source.
A support for the conductive member and a support provided on the support.
and a photoreceptive layer having photoconductivity.
In the true photoconductive member, the photoreceptive layer is
From the support side, we start from the side containing silicon atoms (germanium
Layer thickness composed of amorphous material (does not contain atoms)
The first layer () with a thickness of 1 to 100 μm and silicon atoms and
Availability 1~9.5×10^Fiveatomic ppm germanium raw material
Layer thickness of 1000 Å ~ composed of amorphous material including
50 μm second layer () containing silicon atoms and
Amount 1×10^-3~90 atomic% carbon atoms and non-containing
A third layer with a thickness of 0.003 to 30 μm composed of crystalline material
layer (), and the second layer
The germanium atoms contained in ( ) are
The distribution concentration of germanium atoms is
near the interface with the first layer () and/or
is 1000 atomic near the interface with the third layer ()
has a maximum value of ppm or more, and has a second layer
At the center of (), the distribution concentration is the first
Near the interface with the layer () and with the third layer ()
It has a much lower part than near the boundary surface of
It is unevenly distributed in the sea urchin, and the first layer ()
and at least one of the second layer (), oxygen
It is characterized by containing atoms. in the first layer () and in the second layer
At least one of the parentheses has a hydrogen atom or
and/or halogen atoms.
Also, in the first layer () and in the second layer (),
conductivity in at least one of the layers ()
It is preferable that a substance that controls the
stomach. So that the photoreceptive layer has a layer structure as described above.
The photoconductive member of the present invention configured as follows
It can solve all problems and is extremely excellent.
Electrical, optical, photoconductive properties, 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.
It has stable electrical characteristics, high sensitivity,
It has a high signal-to-noise ratio and is resistant to light fatigue and repetition.
Excellent reversal characteristics, high image density, and half-tone
High-quality images with clear images and high resolution.
Images can be stably and repeatedly obtained. Furthermore, the photoconductive member of the present invention is transparent in the entire visible light range.
It has high photosensitivity, especially when used with semiconductor lasers.
Excellent photo-resistance and fast photoresponse. [Best mode for carrying out the invention] Hereinafter, the photoconductive member of the present invention will be explained according to the drawings.
This will be explained in detail. FIG. 1 illustrates the layer structure of the photoconductive member of the present invention.
FIG. A photoconductive member 100 of the present invention is shown in FIG.
On the support 101 for the photoconductive member, there is sufficient
It has a photoreceptive layer 102 having volume resistivity and photoconductivity.
do. The light-receiving layer 102 is formed from the support side. First layer () 10 made of a-Si(H,X)
3, Second layer ()1 made of a-SiGe(H,X)
04, Third layer ()1 made of a-SiC(H,X)
05 It is composed of: Photoconductivity is the first layer
() and the second layer ().
However, in any case, the incident light may reach
It is necessary to design the layers so that they have photoconductivity.
be. Also, in this case, the first layer () and the first layer
Both layers () each have a desired wavelength spectrum.
photoconductive and in sufficient amount to
Designed as a layer that can generate photocarriers.
It is desirable to In the photoconductive member of the present invention, high photosensitivity and
High dark resistance or between support and light-receiving layer
Or improving the adhesion between the layers that make up the photoreceptive layer.
In order to measure the first layer () and the second layer ()
At least one of them contains an oxygen atom. At least the first layer () and the second layer ()
Oxygen atoms contained in one layer cover all of these layers.
It may be contained evenly in the layer area, or it may be contained evenly in the layer area.
Alternatively, it may be contained in a partially unevenly distributed manner. The distribution state of oxygen atoms is determined by the distribution concentration C(O).
Even if the layer is uniform in the thickness direction, it may be uneven.
It may be uniform. In the present invention, the first layer () and
and the second layer ().
The region containing oxygen atoms (O) has high photosensitivity.
and where the main purpose is to measure the improvement of dark resistance.
If the
I get kicked. Also, the tightness between the support and the first layer ()
Inside the adhesive surface and the adhesion surface between each layer that constitutes the light-receiving layer
The purpose is to strengthen the adhesion of the desired adhesion surface.
In this case, for example, the support and the first layer
If you want to strengthen the adhesion with (), use the first
The ( ) support side end layer region of the layer is also
Strengthened the adhesion between layer () and second layer ()
If the first layer () and the second layer ()
The layer interface and the area near the layer interface are covered with the second layer ().
The purpose is to strengthen the adhesion between the
In this case, the side edge of the third layer () of the second layer ()
Strengthen adhesion by placing it so that it occupies the lower part area.
Occupies the layer interface and the area near the layer interface where the
It is set up so that it can be used. To achieve these objectives even more effectively
The oxygen atoms are added to the first layer () and the second layer.
It is preferable to include both of (). If you are trying to achieve the former purpose,
The content of oxygen atoms contained in the region (O) is high.
The latter is relatively less to maintain light sensitivity
In case of comparison, to strengthen the adhesion between the layers
It is desirable to be targeted. Also, the former and the latter
In order to achieve the objectives at the same time, it is necessary to
The free surface side of the photoreceptive layer is
The layer area is distributed at a relatively low concentration in the layer area.
What is necessary is to form a region (O). Furthermore, the charge from the support or the first layer ()
injection and increase the apparent dark resistance.
If the purpose is to
Distribute oxygen atoms on the side or first layer () and
At the interface and/or near the interface of the second layer ()
It is desirable to distribute it at a high concentration. In addition, in the present invention, the above-mentioned layer region
(O) is not limited to only one, but the above
Multiple layer regions (O) in the photoreceptive layer depending on the purpose of
may be provided. In the present invention, the first layer () and
and the second layer ().
The content of oxygen atoms contained in the layer region (O)
The amount should be determined in such a way that the above objectives can be achieved.
Characteristics required for the area (O) itself, as well as the layer area
When (O) is provided in direct contact with the support
has the required characteristics at the contact interface with the support.
or layer area (O) is directly connected to another layer area.
If the other layer areas are provided in contact with each other,
characteristics and contact field between layer region (O) and other layer regions
In organic relationships such as the characteristics required on the surface
and can be selected as appropriate. The amount of oxygen atoms contained in the layer region (O) is
Depending on the characteristics required for the photoconductive member to be formed.
Although it can be determined appropriately according to desire, preferably,
0.001~50atomic%, more preferably 0.002~
40atomic% Optimally 0.003~30atomic%
is preferable. In the photoconductive member of the present invention, the first layer
() and the second layer ().
By containing a substance (C) that controls conductivity,
to control the conductivity of the included layers as desired.
can be done. The substance (C) is in the first layer () and
and the second layer (),
Either uniform or non-uniform distribution in the layer thickness direction
It is contained so that it may be in a state. Also, the substance
In the layer region (PN) containing (C), that layer
In the thickness direction, the material (C) is continuously uniform or uneven.
It is contained in a uniform distribution state. For example, the layer thickness of the second layer () is the same as that of the first layer ().
The second layer () is made thicker than the layer thickness of
To function as a biological layer and a charge transport layer
When used as a substance that controls conductivity (C)
In the first layer (), it seems to increase on the support side.
It is desirable to have a uniform distribution state.
The substance (C) that controls the conductivity is the second layer ().
is the interface between the first layer () and the second layer ().
Or, it is possible to create a distribution state in which the amount increases near the interface.
is desirable. The substance (C) that controls such conductivity is
Name the so-called impurities in the semiconductor field.
In the present invention, for Si or Ge,
p-type impurities and n-type conductivity that give p-type conduction characteristics.
We can list n-type impurities that give conductive properties.
Ru. Specifically, as a p-type impurity, the periodic table
Atoms belonging to the group (step group atoms), such as B,
Al, Ga, In, Tl, etc. are used particularly preferably.
It is B and Ga. As an n-type impurity,
Atoms belonging to group of the periodic table (group atoms), examples
Examples include P, As, Sb, Bi, etc., and these are particularly preferably used.
It is P and As that are shown. In the present invention, the conductive layer provided in the photoreceptive layer
Layer region containing the substance that controls sex (C)
Substance controlling conductivity contained in (PN) (C)
The content of is the conductivity required for the layer region (PN).
properties, or the layer area (PN) is directly attached to the support.
When provided in contact with the support, the contact field with the support
In organic relationships, such as relationships with characteristics on surfaces, etc.
can be selected as appropriate. In addition, the layer region
(PN)
properties and the properties at the contact interface with other layer regions.
Inclusion of the substance (C) that controls conductivity, taking into account the relationship between
The amount is selected accordingly. In the present invention, contained in the layer region (PN)
The content of the substance (C) that governs the conductivity is preferably
Preferably 0.001~5×10^Fouratomic ppm, more preferred
Or 0.5 to 1×10^FourAtomic ppm, optimally 1~
5×10³It is preferable to set it as atomic ppm. In the present invention, transmission in the layer region (PN) is
Preferably, the content of the substance (C) that controls conductivity is
30atomic ppm or more, more preferably 50atomic
ppm or more, optimally 100 atomic ppm or more
For example, the substance (C) may contain the p-type impurity.
In the case of , the free surface of the photoreceptor layer becomes polar charged.
When processed, it enters the light-receiving layer from the support side.
can effectively prevent the injection of electrons, and one
On the other hand, when the substance (C) is the n-type impurity,
When the free surface of the receptor layer is subjected to polar charging treatment
In this method, holes are injected from the support side into the photoreceptive layer.
can be effectively prevented. In the above case, the layer area (PN)
The removed layer area (Z) has a layer area (PN)
What is the polarity of the substance (C) that controls conductivity contained in
Contains a substance (C) that controls conductivity of another polarity
or a substance that controls conductivity of the same polarity.
The quality (C) is more uniform than the quantity contained in the layer area (PN).
It may be contained in a much smaller amount. In such a case, contained in the layer region (Z)
As the content of the substance (C) that controls the conductivity,
is the polarity of the substance (C) contained in the layer region (PN).
The properties are determined appropriately according to the content.
but preferably 0.001 to 1000 atomic ppm, more preferably
Preferably 0.05~500atomic ppm, optimally 0.1~
It is desirable to set it to 200 atomic ppm. In the present invention, a layer region (PN) and a layer region
(Z) contains the same kind of substance (C) that controls conductivity.
If the content is in the layer area (Z),
Therefore, it is preferable to keep it below 30 atomic ppm.
desirable. In addition to the above cases, in the present invention
supports conductivity with one polarity in the photoreceptor layer.
The polarity of the layer region containing the substance (C) and the other
A layer containing a substance (C) that controls conductivity with
area in direct contact with the contact area, and
A so-called depletion layer can also be provided. i.e. e.g.
For example, a layer containing the above p-type impurity in the photoreceptive layer
The layer region containing the n-type impurity is directly connected to the layer region containing the n-type impurity.
A so-called p-n junction is formed by providing the
Thus, a depletion layer can be provided. In the present invention, if necessary, the first layer ()
The halogen atom (X) contained in
Physically, fluorine, chlorine, bromine, and iodine are listed.
However, fluorine and chlorine are particularly preferred.
can be done. In the present invention, it is composed of a-Si(H,X).
To form the first layer (), e.g.
Discharge method, sputtering method, or ion pretreatment method
Vacuum deposition method that utilizes discharge phenomena such as taing method
applies. For example, by glow discharge method, a-Si(H,X)
To form the first layer () consisting of
Basically, Si supply that can supply silicon atoms (Si)
Along with the raw material gas for hydrogen atom (H) introduction,
Raw material gas for introducing gas and/or halogen atoms (X)
The gas is placed in a predetermined deposition chamber in which the internal pressure can be reduced.
Introduce the mixture to match the mixing ratio and gas flow rate, and then
A glow discharge is generated in the deposition chamber to remove these gases.
By forming a plasma atmosphere,
a-Si on the surface of the support installed in a fixed position.
Form the first layer () consisting of (H,X)
do. In addition, when forming by sputtering method,
For example, inert gas such as Ar, He, etc.
Si or Si in a mixed gas atmosphere based on
SiO₂, or a mixture of these.
When sputtering a target, hydrogen atoms (H) and
and/or a gas for introducing halogen atoms (X).
It can be introduced into a deposition chamber for vine ring. In the present invention, forming the first layer ()
As a starting material for the raw material gas used in
The following are listed as valid: First, as a starting material that becomes the raw material gas for supplying Si,
Well, SiH_Four,Si₂H₆,Si₃H₈,Si_FourH_Tengaseous such as
silicon hydride (silane)
) are mentioned as those that can be effectively used, and
In addition, it is easy to handle the layer creation work, and has good Si supply efficiency.
SiH in terms of_Four,Si₂H₆are listed as preferable.
It will be done. It can be used as an effective starting material as raw material gas for supplying Si.
In addition to the silicon hydride mentioned above, halogen atoms
Silicon compounds containing (X), so-called halogen atoms
Substituted silane derivatives, specifically e.g.
SiF_Four,Si₂F₆, SiCl_Four, SiBr_Foursilicon halides such as
can be mentioned as preferable, and furthermore
is SiH₂F₂,SiH₂I₂,SiH₂Cl₂, SiHCl₃,
SiH₂Br₂,SiHBr₃halogen-substituted hydrogenated silicon such as
water in a gaseous state or capable of being gasified, such as
There are also halides that have elementary atoms as one of their constituent elements.
listed as a starting material for the formation of an effective first layer ().
can be done. Silicon compounds containing these halogen atoms (X)
As mentioned above, when using
The first layer formed by appropriate selection of
Introducing a halogen atom (X) together with Si in ()
can be done. In the present invention, forming the first layer ()
Raw material gas for introducing halogen atoms (X) used in
Valid starting materials for this process include those listed above.
In addition, halogens such as fluorine, chlorine, bromine, and iodine are also available.
Logen gas, ClF, ClF₃, BrF, BrF₃,BrF_Five,
IF₃,IF₇, interhalogen compounds such as ICl, IBr, HF,
Hydrogen halides such as HCl, HBr, HI, etc.
I can do it. In the present invention, the layer region constituting the first layer ()
a layer region containing oxygen atoms in the desired layer region of the region;
When providing (O), use the above starting materials.
For introducing oxygen atoms when forming the first layer ()
The starting materials are used together in controlled amounts,
It may be contained in the layer to be formed. The oxygen atoms contained in the first layer () are
It is evenly contained in the entire area of layer 1 ().
It is also good that it is contained only in some areas.
Also good. Moreover, the distribution state C(O) of oxygen atoms is the first
Even if the layer () is uniform in the thickness direction,
It may be uniform. In the present invention, provided in the first layer ()
The layer region containing oxygen atoms (OI) is
When the purpose is to improve sensitivity and dark resistance, the first
The layer () is provided so as to occupy the entire layer area, and the base
Strengthening the adhesion with the board and even with the second layer ()
When measuring the substrate or second layer () or
or occupy the edge layer area on both sides.
It will be done. In this way, the layer area provided in the first layer ()
The content of oxygen atoms contained in the region (OI) is
A layer area that can achieve the objectives mentioned above.
Characteristics required for (OI) itself, contact field with support
Required properties on the surface or layer area
of other layer areas provided in direct contact with the (OI).
characteristics and the relationship between the layer region (OI) and other layer regions
Organic relationships such as properties required at the contact interface
The gender can be selected as appropriate. The amount of oxygen atoms contained in the layer region (OI) is
Depending on the characteristics required for the photoconductive member to be formed.
Although it can be determined appropriately according to desire, preferably,
0.001~50atomic%, more preferably 0.002~
40atomic% Optimally 0.003~30atomic%
is preferable. Glow discharge method is used to form layer region (OI)
When applied, for forming the above first layer ()
selected as desired from among the starting materials of
In addition, a starting material for introducing oxygen atoms is added.
As starting materials for introducing oxygen atoms,
Gas containing at least oxygen atoms as constituent atoms
gaseous substances or substances that can be gasified.
You can use most of the things that have been standardized.
can. The combination of raw material gases used is as follows: (a) Raw material gas whose constituent atoms are silicon atoms (Si)
and raw material gas containing oxygen atoms (O) as constituent atoms.
hydrogen atom (H) and/or halo as necessary.
A raw material gas containing Gen atoms (X) as constituent atoms.
Mix and use at the desired mixing ratio, (b) Silicon atoms (Si) and hydrogen atoms (H) are the constituent elements.
The raw material gas and the halogen atom (X) are
The raw material gas as constituent atoms and the oxygen atoms (O) as constituent atoms
Mix the raw material gas with the constituent atoms at the desired mixing ratio.
and use it, (c) Raw material gas whose constituent atoms are silicon atoms (Si)
and the constituent elements oxygen atom (O) and hydrogen atom (H)
and raw material gas at the desired mixing ratio.
Ru, (d) Raw material gas whose constituent atoms are silicon atoms (Si)
with silicon atoms (Si) and oxygen atoms (O)
An element whose constituent atoms are hydrogen atom (H) and three atoms.
It is used by mixing with the raw material gas at a desired mixing ratio. Combinations of the following can be mentioned. Acid used to form layer region (OI)
Effectively used as raw material gas for supplying elementary atoms (O)
The starting materials include O as a constituent atom,
Or O and N are constituent atoms, for example oxygen
(O₂), ozone (O₃), nitric oxide (NO), dioxide
Nitrogen (NO₂), nitrogen monoxide (N₂O), sesquioxide
Nitrogen (N₂O₃), nitrogen tetroxide (N₂O_Four), pentoxide
Nitrogen (N₂O_Five), nitrogen trioxide (NO₃), silicon raw material
Consists of a child (Si), an oxygen atom (O), and a hydrogen atom (H)
atomic, e.g. disiloxane
(H₃SiOSiH₃), trisiloxane
(H₃SiOSiH₂OSiH₃) and other lower siloxanes.
can be given. Oxygen-containing oxygen atoms are produced by sputtering.
When forming the first layer (), single crystal or
or polycrystalline Si wafer or SiO₂wafer
– or Si and SiO₂Contains a mixture of
The target is a variety of wafers.
By sputtering in a gas atmosphere of
Just do it. For example, using a Si wafer as a target
When using oxygen atoms and optionally hydrogen atoms and
and/or raw material gas for introducing halogen atoms.
Dilute the solution with diluent gas as necessary to make a sputtering
These gases are introduced into a deposition chamber for
The Si wafer is sputtered by forming a smattering.
All you have to do is run. Also, Si and SiO₂As a separate target from
Or Si and SiO₂A single target mixed with
When using it as a sputter, use the sputter guide.
in an atmosphere of diluent gas as a gas or at least
also hydrogen atom (H) and/or halogen atom (X)
Sputtering in a gas atmosphere containing constituent atoms
Oxygen source in the desired layer area by
a first layer provided with an layer region (OI) containing children;
layer () can be formed. Note that the gas for introducing oxygen atoms is as described above.
In the glow discharge method, the gas for introducing oxygen atoms and
The gases listed above are suitable for sputtering.
can also be used. conductivity in the layer region constituting the first layer ()
Dominating substance (C), e.g. group atom or group
In order to introduce atoms structurally, the first step is required during layer formation.
Starting materials for group atom introduction or group atom introduction
The starting materials for the first layer are placed in a gaseous state in the deposition chamber.
Introduced with other starting materials to form ()
Just do it. For such group atom introduction
Possible starting materials include:
readily under gaseous or at least layer-forming conditions
It is desirable to use something that can be gasified. child
Starting materials for introducing group atoms such as
Specifically, for introducing boron atoms, B₂H₆,
B_FourH_Ten, B_FiveH₉, B_FiveH₁₁, B₆H_Ten, B₆H₁₂, B₆H₁₄
Boron hydride, BF etc.₃, BCl₃,BBr₃etc. halo
Examples include boron genide. In addition, other
For the introduction of group atoms, AlCl₃, GaCl₃,Ga
(CH₃)₃,InCl₃, TlCl₃etc. can be mentioned. As a starting material for the introduction of group atoms,
What is effectively used is for introducing phosphorus atoms.
Then, PH₃,P₂H_FourPhosphorus hydride, PH_FourI,
P.F.₃, P.F._Five, PCl₃, PCl_Five, PBr₃, PBr_Five, P.I.₃etc.
Examples include phosphorus halide. In addition,
AsH₃,AsF₃,AsCl₃, AsBr₃,AsF_Five, SbH₃,
SbF₃, SbF_Five, SbCl₃, SbCl_Five, BiH₃, BiCl₃,
BiBr₃etc. are also effective starting materials for the introduction of group atoms.
It can be mentioned as a thing. In the present invention, contained in the first layer ()
The content of the substance (C) that controls conductivity is
Conductive properties required for () or the layer ()
The characteristics of other layers provided in direct contact with the
The relationship between the properties of the contact interface with the organic
Appropriate selection will be made based on the relevance. In the present invention, contained in the first layer ()
The content of the substance that controls the conductivity is preferably
Or 0.001~5×10^Fouratomic ppm, more preferred
is 0.5~1×10^Fouratomic ppm, optimally 1-5
×10³It is preferable to set it as atomic ppm. In the present invention, contained in the first layer ()
The amount of hydrogen atoms (H) that may be present, the amount of halogen atoms (X)
amount or the sum of the amounts of hydrogen atoms and halogen atoms (H
+X) is preferably 1 to 40 atomic%, more preferably
It is preferably 5 to 30 atomic%. Hydrogen atoms that may be contained in the first layer ()
Controlling the amount of (H) and/or halogen atoms (X)
For example, support temperature, hydrogen atom (H) and halogen
Starting material used to contain atom (X)
The amount of quality introduced into the deposition system or the discharge voltage
All you have to do is control the force. The layer thickness of the first layer () of the present invention is as follows:
() is mainly the adhesion layer between the support and the second layer ()
When acting as a charge transport layer, preferably 1
~100μm, more preferably 1-80μm, optimally
The thickness is preferably 2 to 50 μm. In the photoconductive member of the present invention, the first layer
A second layer ( ) 104 is formed on ( ) 103 .
It will be done. The first layer () and the second layer () are
each has a common constituent atom, the silicon atom.
The main component is an amorphous material made of
Sufficient chemical stability is ensured at the laminated interface.
has been done. In the photoconductive member of the present invention, the second layer
Distribution of germanium atoms contained in ()
The distribution state is non-uniform in the layer thickness direction.
However, regarding the in-plane direction parallel to the surface of the support
It is desirable that the distribution is uniform. Forming a second layer () in such a layered structure
Relatively short wavelengths, possibly including the visible light range
For light in the entire wavelength range from to relatively long wavelengths
A photoconductive member having excellent photosensitivity is formed. In addition, germanium in the second layer ()
The distribution of atoms is such that germanium atoms are present in the entire region.
Continuously distributed, with germanium atoms in the layer thickness direction
The distribution concentration C is from the boundary with the first layer () to the third layer
The distribution decreases towards the boundary with the layer ().
from the boundary with the first layer () to the third layer
The distribution increases towards the boundary with the layer ().
or have characteristics of both
Layered structures, etc., are permitted. FIG. 2 to FIG. 13 show the light guide in the present invention.
Germanium contained in the second layer () of the electrical member
A typical example of the distribution state of umium atoms in the layer thickness direction is shown.
has been done. In Figures 2 to 13, the horizontal axis is germanium.
The vertical axis represents the distribution concentration C of um atoms in the second layer.
() indicates the layer thickness, t_Bis the first layer () and the second
Let the position of the interface with the layer () be t_Tis the second layer
The position of the interface between () and the third layer () is shown.
That is, the second one containing germanium atoms
layer() is t_Bt from the side_Tlayer formation towards the side
Ru. Figure 2 shows the gel contained in the second layer ().
The first source of the distribution state of rumanium atoms in the layer thickness direction
A type example is shown. In the example shown in Figure 2, the germanium atom
a first layer on which a second layer () containing is formed;
Interface position t with ()_BMoret₁Until the position of
The distribution concentration C of rumanium atoms is C₁a certain value
is contained in the second layer () while taking the position
t₁From is the concentration C₂The interface with the third layer ()_T
has been gradually and continuously reduced until . boundary
face t_TIn , the distribution concentration C of germanium atoms 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_FiveShape the distribution state such that
has been completed. 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_TIn , 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 C₁₄linearly so as to more effectively reach zero
is decreasing. 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 Figure 10, germanium
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 t₆near the position of
is sharply decreased at position t₆Then the concentration C₁₈considered to be
Ru. position t₆and position t₇At first, the gap between
decreased, and then slowly decreased gradually
position t₇At concentration C₁₉and position t₇and position t₈between
is very slowly and gradually reduced to position t.₈to
At the concentration C₂₀leading to. position t₈and position t_Tin between
Then, the concentration C₂₀Figure so that it becomes more substantially zero
is reduced according to a curve with the shape shown in
Ru. In the example shown in FIG. 11, the position t_BMore position
t₉Germanium concentration up to C_{twenty two}constant at position t₉Kara position
Placement_BThe germanium concentration C remains constant until C_{twenty one}made to be
ing. In the example shown in FIG. 12, the position t_BSo gel
The manium concentration is essentially zero at position t_Tgermanium
concentration of C_{twenty three}It increases according to the curve shown in the figure so that
ing. In Figure 13, position t_BSo germanium
The concentration is essentially zero at position t_Bfrom position t_Tenconcentration at
C_{twenty four}The germanium concentration increases with the curve shown in the figure until
addition, position t_Tenfrom position t_Tgermanium concentration up to
C_{twenty four}is constant. In addition, germanium shown in Figures 2 to 13
From Figure 2 to Figure 10, the concentration distribution of
The germanium concentration near the interface with the layer () is
From Figures 11 to 13, it shows a large distribution.
Germanium concentration near the interface with the third layer ()
However, a game that combines these
It may also be a rumanium concentration distribution. As described above, according to FIGS. 2 to 13, the second layer
Layer thickness of germanium atoms contained in ()
As I have explained some typical examples of distribution states of
In the present invention, the boundary with the first layer ()
Near the surface and/or near the interface with the third layer ()
, the distribution concentration C of germanium atoms is high
In the middle of the second layer (),
The distribution concentration C is near the interface with the first layer ()
and the area near the interface with the third layer ().
of a germanium atom with a lowered portion
A distribution state is provided in the second layer (). Photoreceptive layer constituting the photoconductive member in the present invention
The second layer () constituting preferably the above-mentioned
Near the interface with the first layer () and/or
There is a germanium source near the interface with the third layer ().
The localized region (A) containing a relatively high concentration of children is
It is desirable to have one. In the present invention, the localized region (A) is
To explain using the symbols shown in Figure 13, the boundary surface position
Placement_Bor t_TProvided in an area within 5μm from
is desirable. In the present invention, the localized region (A) is located at an interface position.
Placement_Bor t_TFull layer area up to 5 μm thick (L_T)and
In some cases, the layer area (L_T) one
Sometimes it is referred to as a department. The localized region (A) is transformed into a layered region (L_T) as part of the pot
or all, depending on the layer being formed.
It can be determined appropriately according to the characteristics. The localized region (A) is the germanium contained therein.
Germanium elementary as the distribution state of atoms in the layer thickness direction
The maximum value Cmax of the distribution concentration of children is
and preferably 1000 atomic ppm or more, more preferably 1000 atomic ppm or more.
Suitably 5000 atomic ppm or more, optimally 1×
Ten^FourThe distribution state is such that it is atomic ppm or more.
It is desirable that the layer be formed in such a way that it can be formed into layers. That is, in the present invention, germanium raw material
The second layer () containing the child is the first layer
() side or from the free surface of the second layer ()
layer thickness within 5 μm (t_Bfrom 5 μm thick layer area) to
The fabric is formed so that there is a maximum value Cmax of concentration.
It is preferable to In the present invention, contained in the second layer ()
The content of germanium atoms in the present invention is as follows:
adapted as desired so that the purpose is effectively achieved.
It can be determined according to your needs, but preferably 1 to 9.5×10^Fiveatomic
ppm, more preferably 100-8×10^Fiveatomic
ppm, optimally 500 to 7×10^Fiveconsidered to be atomic ppm
It is desirable to In the photoconductive member of the present invention, high photosensitivity and
High dark resistance, and even the first layer () and second layer
() or the second layer () and the third layer () and
adhesion between the first layer () and the second layer
To improve the adhesion between () and the third layer ()
For the purpose, the second layer () contains oxygen atoms.
It is desirable that the The oxygen atoms contained in the second layer () are
It is evenly contained in the entire area of layer 2 ().
It is also good that it is contained only in some areas.
Also good. Moreover, the distribution state C(O) of oxygen atoms is the second
Even if the layer is uniform in the thickness direction, it is not uniform.
It's okay if it's hot. In the present invention, provided in the second layer ()
The layer region (O) containing oxygen atoms is
When the purpose is to improve sensitivity and dark resistance, the second
The layer () is provided so as to occupy the entire layer area, and the
with the first layer () and/or with the third layer ()
When aiming to strengthen the adhesion with
() and/or end layer area on the third layer () side
It is set up so that it occupies the area. In this way, the layer area provided in the second layer ()
The content of oxygen atoms contained in the region (O) is
The layer area (O
) itself, the characteristics required for the first layer () and the
The characteristics required at the contact interface with layer 3 ()
gender, or the first layer () or the third layer () layer
In the organic relationship with the characteristics etc. of
You can choose. Amount of oxygen atoms contained in layer region (O)
corresponds to the characteristics required for the photoconductive member to be formed.
Although it can be determined appropriately according to the user's needs, it is preferable that
is 0.001~50atomic%, more preferably 0.002~
40atomic%, optimally 0.003~30atomic%
It is preferable to In the photoconductive member of the present invention, the first layer
When the layer thickness of () is thin, germanium atoms
The second layer () contains a material that controls conductivity.
The layer region (PN) containing the substance (C) is the first layer.
By providing localized information on the () side, the layer area
(PN) functions as a so-called charge injection blocking layer
be able to. In other words, it contains a substance (C) that controls conductivity.
The content of the substance in the layer region (PN)
Preferably 30 atomic ppm or more, more preferably
50 atomic ppm or more, optimally 100 atomic ppm or more
By placing the contained substance on, e.g.
When (C) is the above p-type impurity, the photoreceptive layer is
When the support surface is polarized and charged,
effectively prevents electron injection from into the photoreceptor layer.
and the contained substance (C) is
In the case of the n-type impurity shown below, the free surface of the photoreceptive layer
When subjected to polar charging treatment, light is emitted from the support side.
Effectively prevent hole injection into the receptor layer
Can be done. In the above case, in the second layer ()
The layer area (Z) excluding the layer area (PN)
) is the conductivity contained in the layer region (PN).
Governing conductivity that is different from the polarity of the governing substance (C)
Substance (C) may be included, or substances of the same polarity may be included.
Contains substance (C) that controls conductivity in layer region (PN)
Contain it in a much smaller amount than the amount you want to use.
Good too. In such a case, the content contained in the layer region (Z)
As the content of the substance (C) that controls the conductivity,
is the polarity of the substance (C) contained in the layer region (PN).
The properties are determined appropriately according to the content.
but preferably 0.001 to 1000 atomic ppm, more preferably
Preferably 0.05~500atomic ppm, optimally 0.1~
It is desirable to set it to 200 atomic ppm. In the present invention, provided in the second layer ()
The same type of transmission exists in layer area (PN) and layer area (Z).
When containing a substance (C) that controls conductivity,
Controls the conductivity contained in the recording region (Z)
The content of the substance (C) is preferably
It is desirable to set it to 30 atomic ppm or less. above
In addition to the case where the second layer is
In (), there is a dominant conductivity with one polarity.
The layer region containing the polarity substance (C) and the other polarity
A layer region containing a substance (C) that controls conductivity
are placed in direct contact with each other, and a so-called
A depletion layer can also be provided. That is, for example
Contains the above p-type impurity in the second layer ()
layer region and the layer region containing the n-type impurity,
They are placed in direct contact to form a so-called p-n junction.
Thus, a depletion layer can be provided. In the present invention, the second layer () may be added as necessary.
The halogen atom (X) contained in
Physically, fluorine, chlorine, bromine, and iodine are listed.
However, fluorine and chlorine are particularly preferred.
can be done. In the present invention, a-SiGe (H,
To form the second layer (), e.g.
– Discharge method, sputtering method, or ion beam method
Vacuum deposition using discharge phenomena such as rating method
The law applies. For example, a-SiGe (H,
To form the second layer () consisting of
can basically supply silicon atoms (Si)
Raw material gas for Si supply and germanium atoms (Ge)
raw material gas for Ge supply that can supply
The raw material gas and/or halo for introducing hydrogen atoms (H)
The raw material gas for introducing Gen atoms (X) is
Introduce the desired gas pressure into the deposition chamber that can be reduced in pressure.
to generate a glow discharge in the deposition chamber, and
The first layer () in place
The gel contained on the support formed on the surface
The distribution curve of Ni atoms becomes the desired rate of change curve.
composed of a-SiGe (H,
A second layer () is formed. In addition, when forming by sputtering method,
For example, inert gas such as Ar, He, etc.
composed of Si in a mixed gas atmosphere based on
The selected target is composed of the target and Ge.
two targets with the same target, or
Using a mixed target of Si and Ge,
Ge supply source diluted with diluent gas such as Ar, He, etc.
Raw material gas and raw material gas for introducing hydrogen atoms (H) as necessary.
Raw material gas for introducing gas and/or halogen atoms (X)
Introduce the sputtering material into the deposition chamber for sputtering, and
While forming a gas plasma atmosphere,
Change the gas flow rate of the source gas for Ge supply to the desired rate of change.
The said target is controlled according to the curve.
All you have to do is sputtering. In the case of ion plating, for example,
Crystalline silicon or single crystal silicon and polycrystalline germanium
evaporation of aluminum or single crystal germanium, respectively.
The evaporation source is housed in a evaporation boat and this evaporation source is resisted.
Heating method or electron beam method (EB method)
etc. to heat and evaporate the flying evaporates into a specified gas.
Sputtery except for passing through plasma atmosphere
This can be done in the same way as in the case of In the present invention, forming the second layer ()
The starting materials that become the raw material gas used in
The following are valid: First, as a starting material that becomes the raw material gas for supplying Si,
Well, SiH_Four,Si₂H₆,Si₃H₈,Si_FourH_Tengaseous such as
silicon hydride (silane)
) are mentioned as those that can be effectively used, and
In addition, it is easy to handle the layer creation work, and has good Si supply efficiency.
SiH in terms of_Four,Si₂H₆are listed as preferable.
It will be done. As a starting material that becomes the raw material gas for supplying Ge.
So, GeH_Four, Ge₂H₆, Ge₃H₈, Ge_FourH_Ten,
Ge_FiveH₁₂, Ge₆H₁₄, Ge₇H₁₆, Ge₈H₁₈, Ge₉H₂₀etc
Hydrogenated germanium in a gaseous state or capable of being gasified
Umum is mentioned as one that can be effectively used, and especially
In addition, it is easy to handle the layer creation work and has good Ge supply efficiency.
GeH in terms of etc._Four, Ge₂H₆, Ge₃H₈is preferable
It is mentioned as. In the present invention, forming the second layer ()
Raw material gas for introducing halogen atoms (X) used in
Many halogens are useful starting materials.
Examples include halogen gas and halogen compounds.
Substituted with genides, interhalogens, halogens
Gaseous or gasified silane derivatives etc.
The halogen compounds obtained are preferably mentioned. Ma
Furthermore, silicon atoms and halogen atoms may be
Constituent gaseous or gasifiable halo
Silicon hydrides containing gen atoms are also effectively used.
It is mentioned as a thing. In the present invention, forming the second layer ()
Examples of halogen compounds suitably used for
Physically, halogens such as fluorine, chlorine, bromine, and iodine
Gengas, ClF, ClF₃, BrF, BrF₃,BrF_Five,
IF₃,IF₇, ICl, IBr and other interhalogen compounds
be able to. Silicon compounds containing halogen atoms (X), so-called
As a silane derivative substituted with a halogen atom
Specifically, SiF_Four,Si₂F₆, SiCl_Four, SiBr_Fouretc
Silicon halides are listed as preferred.
be able to. Silication containing such halogen atoms (X)
of the present invention by a glow discharge method using a compound of the present invention.
When forming the second layer () of the photoconductive member
can supply Si along with the raw material gas for Ge supply.
Eliminates the use of silicon hydride gas as a raw material gas
In both cases, the first layer () is a support formed on its surface.
On the support, a second layer composed of a-SiGe (H,
2 layers () can be formed. According to the glow discharge method, halogen atoms (X) are
When forming a second layer () containing basically
For example, halogenated gas is used as a raw material gas for supplying Si.
Silicon and hydrogenated gas, which is the raw material gas for Ge supply.
Mix rumanium with a gas such as Ar or He in a specified manner.
Introduce the gas to match the combined ratio and gas flow rate, and then
is introduced into the deposition chamber to form a layer of
generate electricity and form a plasma atmosphere of these gases.
by forming the first layer () on its surface.
Forming a second layer () on the support formed in
can be done. In addition, it is possible to control the introduction ratio of hydrogen atoms.
These gases are further added to make them easier to control.
Gas of hydrogen gas or silicon compounds containing hydrogen atoms
The second layer () can also be formed by mixing the desired amount of
good. In addition, each gas is not only a single species, but also a specified
It is okay to use more than one at a mixing ratio of Sputtering method, ion plating method
In either case, halogen sources are present in the layer formed.
In order to introduce the child (X), the above-mentioned halide or
or deposit a silicon compound gas containing halogen atoms.
Introduced into the storage chamber to form a plasma atmosphere of the gas
Just do it. In addition, when introducing hydrogen atoms, hydrogen atoms
Introductory gas, e.g. H₂, or the above
gases such as carbons and/or germanium hydride.
The gas is introduced into the deposition chamber for sputtering, and
All you have to do is create a Zuma atmosphere. In the present invention, when forming the second layer ()
The above-mentioned halogen gas is used as a raw material gas for introducing halogen atoms.
Silicon compounds containing halides or halogen atoms
Things are used as valid things, but in addition,
Hydrogen halides such as HF, HCl, HBr, HI,
SiH₂F₂,SiH₂I₂,SiH₂Cl₂, SiHCl₃,SiH₂Br₂,
SiH₂Br, SiHBr₃halogen-substituted hydrogenated silicon such as
and GeHF₃, GeH₂F₂, GeH₃F, GeHCl₃,
GeH₂Cl₂, GeH₃Cl, GeHBr₃, GeH₂Br₂,
GeH₃Br, GeHI₃, GeH₂I₂, GeH₃Hydrogenation of I etc.
Hydrogen atoms are the constituent elements of germanium rogenide, etc.
One of the halides, GeF_Four,,GeCl_Four,
GeBr_Four, GeI_Four, GeF₂, GeCl₂, GeBr₂, GeI₂etc.
Germanium halides, etc. in gaseous state
Hydrogen atoms are one of the constituent elements, and can be gasified.
Halides are also effective for forming the second layer ().
can be mentioned as a starting material. Among these substances, halogens containing hydrogen atoms
The compound is added into the second layer () during formation of the layer.
At the same time as the introduction of halogen atoms, electrical or photoconductive
Introducing hydrogen atoms, which are extremely effective in controlling electrical properties.
Therefore, in the present invention, a suitable halogen atom
Used as raw material for introduction. Introducing hydrogen atoms structurally into the second layer ()
In addition to the above,₂Or SiH_Four,Si₂H₆,
Si₃H₈,Si_FourH_TenSupply Ge with silicon hydride etc.
germanium or germanium compounds for
or GeH_Four, Ge₂H₆, Ge₃H₈, Ge_FourH_Ten,
Ge_FiveH₁₂, Ge₆H₁₄, Ge₇H₁₆, Ge₈H₁₈, Ge₉H₂₀etc
Si to supply germanium hydride to Si
coexistence with silicon or silicon compound in the deposition chamber.
It can also be carried out by causing an electric discharge.
Wear. In a preferred embodiment of the invention, the light guide formed
Water that may be contained in the second layer () of the electrical member
Amount of elementary atoms (H), amount of halogen atoms (X) or water
The sum of the amounts of elementary atoms and halogen atoms (H+X) is
Preferably 0.01-40 atomic%, more preferably 0.05
~30atomic%, optimally 0.1~25atomic%
It is desirable to Hydrogen atoms that may be contained in the second layer ()
Controlling the amount of (H) and/or halogen atoms (X)
For example, support temperature, hydrogen atom (H) and halogen
Starting material used to contain atom (X)
The amount of quality introduced into the deposition system or the discharge voltage
You can also control the force. A substance that controls conductivity in the second layer ()
(C), e.g. group atoms or group atoms structurally
Introducing the method of forming the first layer ()
In the same way as when forming the layer, the above-mentioned group
Starting material for atom introduction or group atom introduction
A second layer of starting material is introduced into the deposition chamber in gaseous state.
Introduced with other starting materials to form ()
Just do it. The second layer () in the photoconductive member of the present invention
The layer thickness is such that the second layer () is mainly a photo carrier.
When used as a generation layer, photo carrier
The absorption coefficient of the second layer () for the excitation light source is
Determined as appropriate in consideration, preferably 1000 Å ~
50μm, more preferably 1000Å to 30μm, optimally
The thickness is preferably 1000 Å to 20 μm. In the present invention, the second layer () contains oxygen atoms.
To provide the contained layer region (O), the above-mentioned
During the formation of the second layer (), oxygen atoms
In combination with the starting material for introduction, in the layer formed.
It is sufficient if it is contained while controlling its amount. The glow discharge method is used to form the layer region (O).
When used, for forming the second layer () described above.
selected as desired from among the starting materials of
In addition, a starting material for introducing oxygen atoms is added.
As starting materials for introducing oxygen atoms,
Gas containing at least oxygen atoms as constituent atoms
gaseous substances or substances that can be gasified.
You can use most of the things that have been standardized.
can. Examples of raw material gas combinations are: (a) Raw material gas whose constituent atoms are silicon atoms (Si)
and germanium atoms (Ge) as constituent atoms.
raw material gas and oxygen atoms (O) as constituent atoms.
raw material gas and hydrogen atoms (H) as necessary.
and/or halogen atom (X) as a constituent atom.
and raw material gas at the desired mixing ratio.
Ru, (b) Silicon atoms (Si) and hydrogen atoms (H) are the constituent elements.
The raw material gas and the halogen atom (X) are
Raw material gas and germanium atoms
Raw material gas containing (Ge) as a constituent atom and oxygen atom
(O) is mixed with the raw material gas as a constituent atom as desired.
Mix and use at the same ratio, (c) Silicon atom (Si) and halogen atom (X)
A raw material gas consisting of constituent atoms and a germanium source
(Ge) and halogen atom (X) are constituent atoms
The raw material gas and the constituent atoms of oxygen atoms (O)
A raw material gas with hydrogen atoms (H) as constituent atoms.
and raw material gas at the desired mixing ratio.
Ru, (d) Raw material gas whose constituent atoms are silicon atoms (Si)
and germanium atoms (Ge) as constituent atoms.
raw material gas, silicon atoms (Si) and oxygen source
The three atoms of hydrogen atom (O) and hydrogen atom (H) are constituent atoms.
The raw material gas is mixed with the raw material gas at the desired mixing ratio.
use. Combinations of the following can be mentioned. acid used to form layer region (O)
Effectively used as raw material gas for supplying elementary atoms (O)
The starting materials include O as a constituent atom,
Or O and N are constituent atoms, for example oxygen
(O₂), ozone (O₃), nitric oxide (NO), dioxide
Nitrogen (NO₂), nitrogen monoxide (N₂O), sesquioxide
Nitrogen (N₂O₃), nitrogen tetroxide (N₂O_Four), pentoxide
Nitrogen (N₂O_Five), nitrogen trioxide (NO₃), silicon raw material
Consists of a child (Si), an oxygen atom (O), and a hydrogen atom (H)
atoms, e.g. disiloxane (and
₃SiOSiH₃), trisiloxane
(H₃SiOSiH₂OSiH₃) and other lower siloxanes.
can be given. Oxygen-containing oxygen atoms are produced by sputtering.
When forming the second layer (), single crystal or
or polycrystalline Si wafer or SiO₂wafer
- or Si and SiO₂Contains a mixture of
The target is a variety of wafers.
By sputtering in a gas atmosphere of
Just do it. For example, using a Si wafer as a target
If you want, oxygen atoms and germanium atoms and
Introducing hydrogen atoms and/or halogen atoms as required
Dilute the raw material gas with diluent gas as necessary.
This is then introduced into a deposition chamber for sputtering.
The Si wafer is formed by forming a gas plasma of gas from the
All you have to do is sputter the hair. Also, Si and SiO₂As a separate target from
Or Si and SiO₂A single target mixed with
When using it as a sputter, use the sputter guide.
Germanium atoms (Ge) as constituent atoms
In an atmosphere of diluent gas containing the raw material gas to be
or at least consists of germanium atoms (Ge)
Raw material gas as atoms and hydrogen atoms (H) as constituent atoms
Containing gas and/or halogen atom (X)
Spacing in an atmosphere with gases containing constituent atoms
Add acid into the desired layer area by trickling
The first layer is provided with a layer region (O) containing elementary atoms.
2 layers () can be formed. Note that the gas for introducing oxygen atoms is as described above.
In the glow discharge method, the gas for introducing oxygen atoms and
The gases listed above are suitable for sputtering.
can also be used. In the present invention, the first layer () and the second layer
When forming (), a layer containing oxygen atoms
A region (O) is provided in at least one of these layers.
When the oxygen atoms contained in the layer region (O)
By changing the distribution concentration C(O) in the layer thickness direction, the desired
Obtain the distribution state (depth profile) in the layer thickness direction.
In order to achieve this, in the case of glow discharge, the distribution concentration C
Starting material for introducing oxygen atoms to change (O)
The quality of the gas is determined by the desired rate of change curve of its flow rate.
Introduce it into the deposition chamber while changing it accordingly.
can be applied to form these layers.
Wear. If caused by sputtering, sputtering
For example, Si and SiO₂with
When using mixed targets, Si and
SiO₂The mixing ratio with
By changing the layer thickness in advance, the desired layer thickness can be achieved.
Distribution state of oxygen atoms in the direction (depth profile)
can be obtained. On the second layer ( ) 104 of the photoconductive member of the present invention
The third layer ( ) 105 formed on the free surface
Mainly moisture resistance, continuous repeated use characteristics,
Superior in terms of air pressure resistance, operating environment characteristics, and durability.
established to achieve the stated purpose of second layer
() and the third layer () are each made of silicone.
An amorphous substance that has a common constituent atom called
Because the main component is material, the laminated interface
Chemical stability is sufficiently ensured. The third layer () in the present invention is made of silicon raw material.
(Si), carbon atom (C), and hydrogen atom if necessary
Amorphous containing (H) and/or halogen atom (X)
Materials whose main component is a-(Si)_xC_1-x)_y,
(H,X)_1-yHowever, 0<x, y<1) is sufficient.
will be accomplished. a-(Si_xC_1-x)_y(H,X)_1-y, however, 0
<x, y<1). a-(Si_xC_1-x)_y(H,X)_1-yThe third consisting of
The layer () is formed by glow discharge method, spatter
ion implantation method, ion implantation method,
by plating method, electron beam method, etc.
It will be implemented. These manufacturing methods are based on manufacturing conditions,
The degree of equipment capital investment, manufacturing scale, and the amount produced
Depending on factors such as the desired properties of the photoconductive member,
It is selected and adopted as appropriate, but it has the desired characteristics.
Comparative control of conditions for manufacturing photoconductive materials
carbon atoms as well as silicon atoms.
and halogen atoms in the third layer () to be prepared.
Due to its advantages such as easy introduction,
Discharge method or sputtering method is preferably adopted.
It will be done. In addition, glow discharge method and sputtering method
are used together in the same equipment system to form the third layer ().
You may. Forming the third layer () by glow discharge method
To do this, a-(Si_xC_1-x)_y(H,X)_1-yraw material for formation
The feed gas is mixed with the diluent gas as required at a predetermined mixing ratio.
of the support on which the second layer () is formed.
Introduce it into the vacuum deposition chamber that has been installed.
By causing a glow discharge in the gas
A second layer on the support is formed into a gas plasma.
() on a-(Si_xC_1-x)_y(H,X)_1-ydeposited
All you have to do is do it. 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) and halogen atom (X)
Contains at least one of the following as its constituent atoms
Gasification of gaseous 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, for example, Si
A raw material gas with C as a constituent atom and C as a constituent atom.
raw material gas and H as constituent atoms as necessary.
Raw material gas and/or raw material gas containing X as a constituent atom
and mixed at the desired ratio, or
is a raw material gas containing Si as a constituent atom, and C and H.
Constituent raw material gas and/or C and
Mix the raw material gas with the constituent atoms at the desired mixing ratio.
Alternatively, Si can be used as a constituent atom.
raw material gas and three constituent atoms of Si, C and H
The raw material gas or three components of Si, C and X
By mixing the raw material gas as atoms at the desired mixing ratio.
can be used. Alternatively, Si and H can be used as constituent atoms.
and a source gas containing C as a constituent atom.
It may be used in combination, or Si and X may be used in combination.
Raw material gas as constituent atoms and C as constituent atoms
It may be used in combination with raw material gas. In the present invention, contained in the third layer ()
Suitable halogen atom (X)
are F, Cl, Br, and I, with F and Cl being particularly desirable.
It's something new. In the present invention, raw materials for forming the third 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; C and H are constituent atoms,
For example, saturated hydrocarbons having 1 to 4 carbon atoms, carbon atoms
Ethylene hydrocarbon with 2 to 4 children, 2 carbon atoms
~4 acetylenic hydrocarbon; simple halogen; ha
hydrogen halides; interhalogen compounds;
Iron; include halogen-substituted silicon hydrides, etc.
Can be done. Specifically, saturated hydrocarbons include methane,
Ethane, propane, n-butane, pentane; ethyl
Examples of ethylene hydrocarbons include ethylene and propylene.
Butene-1, Butene-2, i-butylene, Pen
As an acetylenic hydrocarbon, acetylene
Ren, methylacetylene, butyne; simple halogen
Examples include halogens of fluorine, chlorine, bromine, and iodine.
Hydrogen gas: Hydrogen halides include HF, HI,
HCl, HBr; Interhalogen compounds include ClF,
ClF₃,ClF_Five, BrF, BrF₃,BrF_Five,IF_Five,IF₇,
ICl, IBr; As silicon halide, SiF_Four,
Si₂F₆, SiCl_Four, SiCl₃Br, SiCl₂Br₂, SiClBr₃,
SiCl₃I, SiBr_Four;Halogen-substituted silicon hydride
Well, SiH₂F₂,SiH₂Cl₂, SiHCl₃,SiH₃Cl,
SiH₂Br, SiH₂Br₂,SiHBr₃etc. can be mentioned.
Wear. In addition to these, CF_Four,CCl_Four, CBr_Four,CHF₃,
CH₂F₂,C.H.₃F, 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)_Four, etc.; SiCl(CH₃)₃,
SiCl₂(CH₃)₂, SiCl₃CH₃Halogen-containing silicification such as
Silane derivatives such as alkyl are also listed as effective.
can be given. These third layer () forming substances are formed
The third layer () contains silicon at a predetermined composition ratio.
atoms, carbon atoms and, if necessary, halogen atoms and
and/or a third layer containing hydrogen atoms.
Selected and used according to the desire when forming ()
be done. For example, silicon atoms, carbon atoms, and hydrogen atoms
can be easily contained and a layer with desired properties can be formed.
Si(CH₃)_Fourand contains halogen atoms
SiHCl as a₃,SiH₂Cl₂, SiCl_FourMa
Or SiH₃Cl, etc. are mixed in a specified ratio in a gas state.
Glow by introducing into the device for forming the third layer ()
By generating a discharge, a-(Si_xC_1-x)_y
(H,X)_1-yform a third layer () consisting of
be able to. Form the third layer () by sputtering method
To achieve this, single crystal or polycrystalline Si wafers are used.
– and/or C wafer or a mixture of Si and C
Target the wafer containing the
and add halogen atoms and/or these as necessary.
or various gas atmospheres containing hydrogen atoms as constituents.
If done by sputtering in an atmosphere
good. For example, using a Si wafer as a target
Then, for introducing C, H and/or
Dilute the raw material gas with diluent gas as necessary,
These gases are introduced into the deposition chamber for sputtering.
The Si wafer is sputtered by forming a gas plasma.
All you have to do is tumble. Another method is to use separate targets for Si and C.
One target with Tsuto or a mixture of Si and C
hydrogen as needed by using
Gas atmosphere containing atoms and/or halogen atoms
done by sputtering in the air
Ru. Substances that serve as raw material gas for introduction of C, H and X
As for the third example shown in the glow discharge example mentioned above,
The material for forming the layer () is used in the sputtering method.
It can also be used as an effective substance in various cases. In the present invention, the third layer () is subjected to glow discharge.
Used when forming by sputtering method or sputtering method.
As the diluent gas, so-called rare gases such as He,
Ne, Ar, etc. can be mentioned as suitable ones.
Ru. The third layer () in the present invention satisfies its requirements.
carefully to ensure that the desired characteristics are given as desired.
It is formed. That is, Si, C, H and/or 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.
The electrical properties range from conductivity to semiconductivity.
Properties ranging from insulating properties to photoconductive properties
Each shows properties up to non-photoconductive properties, so
In the present invention, the
Do a-(Si_xC_1-x)_y(H,X)_1-ywill be formed
However, the selection of the production conditions is strictly according to the desired
will be accomplished. For example, the third layer () is
If the main purpose is to improve sexual performance, a-
(Si_xC_1-x)_y(H,X)_1-yis the electrical environment in which it is used.
Created as an amorphous material with remarkable insulating behavior
Ru. We also aim to improve the characteristics of continuous repeated use and the usage environment.
A third layer () is provided with the main purpose of
If the electrical insulation is
It has a certain degree of sensitivity to the light that is applied to it.
As an amorphous material having a-(Si_xC_1-x)_y(H,
X)_1-yis created. a-(Si_xC_1-x)_y
(H,X)_1-yform a third layer () consisting of
In this case, the temperature of the support during layer forming depends on the structure of the formed layer.
It is one of the important factors that influences the structure and characteristics.
Therefore, in the present invention,
a-(Si_xC_1-x)_y(H,X)_1-yis created as desired
The support temperature during layer creation is strictly controlled to ensure
It is desirable that The desired objectives of the present invention are effectively achieved.
suitable for the formation method of the third layer () to
The optimal range is selected to form the third layer ().
is carried out, preferably between 20 and 400°C, and above.
The preferred temperature is 50 to 350℃, and the optimal temperature is 100 to 300℃.
It is desirable to For the formation of the third layer (), the layer
Another method is to delicately control the composition ratio of the atoms that make up the
Because it is relatively easy compared to
- It is advantageous to use the discharge method or sputtering method.
However, when forming the third layer () using these layer forming methods,
In the same way as the support temperature described above, the layer formation temperature
When the discharge power is created a-(Si_xC_1-x)_y
(H,X)_1-yOne of the important factors that influences the characteristics of
It can be mentioned as follows. In order for the purpose of the present invention to be effectively achieved
a-(Si_xC_1-x)_y(H,X)_1-yis raw
Discharge power conditions to be effectively created with good productivity
Preferably 10~300W, more preferably
It is desirable that the power output is 20 to 250W, optimally 50 to 200W.
It's a beautiful thing. The gas pressure in the deposition chamber is preferably 0.01~
1 Torr, preferably about 0.1 to 0.5 Torr
is desirable. In the present invention, in order to create the third layer (),
Desired numerical ranges for support temperature and discharge power
The values in the range mentioned above are listed as
The layer creation factors for are determined independently and separately.
a-(Si_xC_1-x)_y(H,
X)_1-yso that a third layer () consisting of
Create each layer based on mutual organic relationships.
It is desirable to be able to determine the optimal value of the parameter. The third layer () in the photoconductive member of the present invention
The amount of carbon atoms contained depends on the composition of the third layer ().
The desired conditions for accomplishing the objectives of the present invention as well as the
Because a third layer () is formed that provides the properties
is one of the important factors. Third in the present invention
The amount of carbon atoms contained in the layer () is the third
Appropriate depending on the characteristics of the amorphous material that makes up the layer ().
It can be determined 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, a-Si_aC_1~aIt is written as However, 0<a<1),
Composed of Licon atoms, carbon atoms, and hydrogen atoms
Amorphous material (hereinafter referred to as a-(Si_bC_1-b)_cH_1-cIt is written as
However, 0<b, c<1), silicon atoms and carbon atoms
Consisting of a child, a halogen atom, and a hydrogen atom if necessary.
The amorphous material (hereinafter referred to as a-(Si_dC_1-d)_e
(H,X)_1-eIt is written as However, if 0<d, e<1)
being classified. In the present invention, the third layer () is a-Si_a
C_1-aWhen composed of
The amount of carbon atoms included is preferably 1×10^-3~
90 atomic%, more preferably 1-80 atomic%, most
Suitably, it is desirable to set it to 10 to 75 atomic%.
It is. That is, the previous a-Si_aC_1-aIn the display of a of
If carried out, a is preferably 0.1 to 0.99999, more preferably
0.2 to 0.99, optimally 0.25 to 0.9. On the other hand, in the present invention, the third layer () is a-
(Si_bC_1-b)_cH_1-cIf the third layer consists of
The amount of carbon atoms contained in () is preferably
1×10^-3~90 atomic%, more preferably
1 to 90 atomic%, optimally 10 to 80 atomic%.
It is desirable that the Hydrogen atom content
is preferably 1 to 40 atomic%, more preferably 1 to 40 atomic%.
Preferably 2-35 atomic%, optimally 5-35 atomic%
It is desirable to set it to 30 atomic%, and these ranges
Photoconductor formed when there is hydrogen content in the surrounding area
The material is well applied as being excellent in practical terms.
It is possible to do so. 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 third layer () is a-(Si_dC_1-d)_e(H,X)
_1-eIn the third layer ()
The content of carbon atoms is preferably
is 1×10^-3~90 atomic%, more preferably 1~
90 atomic%, optimally 10-80 atomic%
is desirable. Content of halogen atoms
is preferably 1 to 20 atomic%, or more.
Preferably 1 to 18 atomic%, optimally 2 to 18 atomic%
It is desirable to set it to 15 atomic%, and these ranges
Created when there is a halogen atom content in
The photoconductive member can be fully applied to practical applications.
Ru. The content of hydrogen atoms and
preferably less than 19 atomic%, more preferably
It is desirable that the value be less than 13 atomic%.
It is. That is, the previous a-(Si_dC_1-d)_e(H,X)_1-ed,
If expressed as e, d is preferably from 0.1 to
More suitable than 0.99999 is 0.1~0.99, optimally 0.15~
0.9, e is preferably 0.8 to 0.99, more preferably
0.82 to 0.99, ideally 0.85 to 0.98
Yes. Numerical range of layer thickness of third layer () in the present invention
The following are important elements for effectively achieving the purpose of the present invention.
This is one of the important factors. effectively accomplishing the purpose of the invention
as appropriate depending on the intended purpose so as to achieve it.
It is determined accordingly. Further, the layer thickness of the third layer () is as follows:
The amount of carbon atoms contained in () and the first layer
() and the relationship with the layer thickness of the second layer ().
Even if the organic layer is
need to be determined as appropriate based on the
Ru. In addition, it is possible to add productivity and mass production.
It is desirable to consider economic efficiency as well. As the layer thickness of the third layer () in the present invention
is preferably 0.003 to 30 μm, more preferably 0.004
~20μm, optimally 0.005~10μm.
It's a beautiful thing. As the support 101 used in the present invention
may be electrically conductive or electrically insulating. conductive
Examples of the support include NiCr, stainless steel,
Al, Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pd
Metals such as these or alloys thereof can be mentioned. As the electrically insulating support, polyester, polyester, etc.
Liethylene, polycarbonate, cellulose acetate
Tate, polypropylene, polyvinyl chloride, poly
Vinylidene chloride, polystyrene, polyamide, etc.
Synthetic resin film or sheet, glass, ceramic
Tsuku, paper, etc. are usually used. electrical insulation of these
The sexual support preferably has at least one surface thereof.
is conductive treated and the other is on the inductively treated surface side.
Preferably, layers are provided. In other words, for example, if it is glass, its surface
, NiCr, Al, Cr, Mo, Au, Ir, Nd, Ta,
V, Ti, Pt, In₂O₃, SnO₂, ITO (In₂O₃+SnO₂)
Conductivity can be increased by providing a thin film consisting of
or synthetic resin such as polyester film.
For fat films, NiCr, Al, Ag, Pb, Zn,
Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt
thin films of metals such as vacuum evaporation, electron beam evaporation,
Place it on the surface by sputtering or the like, or
Laminate the surface with
Provides electrical conductivity. The shape of the support may vary as desired.
Although the shape is determined, for example, the photoconductive member 1 in FIG.
Since 00 is used as an electrophotographic image forming member,
If available, use an endless belt for continuous high-speed copying.
Alternatively, it is desirable to have a cylindrical shape. Support thickness
are adjusted appropriately so that the desired photoconductive member is formed.
However, flexibility is required as a photoconductive member.
If the support is
It is made as thin as possible within the range. deer
However, in such cases, the manufacturing and handling of the support
In terms of handling and mechanical strength, it is usually
It is considered to be 10μm or more. Next, an example of the method for manufacturing the photoconductive member of the present invention will be described.
The outline will be explained. Figure 20 shows a photoconductive member produced by glow discharge decomposition method.
This shows the manufacturing equipment. Gas cylinders 1102 to 1106 in the diagram include
For forming the photoconductive layer of the photoconductive member of the present invention
The raw material gas is sealed, for example:
For example, 1102 is SiH diluted with He._FourGas (purity
99.999%, below SiH_Four/He gas) cylinder,
1103 is GeF diluted with He_FourGas (purity
99.999%, below GeF_Four/He gas) cylinder,
1104 is B diluted with He₂H₆Gas (purity
99.999%, below B₂H₆/He gas) cylinder,
1105 is NO gas (99.99% purity) cylinder, 11
06 is C₂H_FourIt is a gas cylinder (99.99% purity). In addition to these not shown, as necessary.
It is possible to add cylinders of the desired gas type.
be. To allow these gases to flow into the reaction chamber 1101
is each valve 1 of gas cylinders 1102 to 1106
122 to 1126 and leak valve 1135 are closed.
Check that the inflow valve 1 is
112-1116, outflow valve 1117-112
1 and auxiliary valves 1132 and 1133 are opened.
Check that the main valve 1134 is
Open the reaction chamber 1101 and exhaust the inside of each gas pipe.
do. Next, the reading of vacuum gauge 1136 is about 5×
Ten^-6When it becomes torr, auxiliary valve 1132,1
133 and outflow valves 1117 to 1121 are closed.
Ru. First, a first layer is formed on the cylindrical substrate 1137.
An example of forming () is a gas cylinder.
SiH from Be1102_Four/He gas, gas cylinder 11
B from 04₂H₆/He gas, gas cylinder 1105.
valves 1122, 1124, 112 for NO gas
5 and outlet pressure gauges 1127 and 11 respectively.
29,1130 pressure 1Kg/cm²Adjust the inflow bar to
Gradually open Lubes 1112, 1114, 1115.
, mass flow controllers 1107, 1109,
1110 respectively. continues to flow
Outlet valves 1117, 1119, 1120 and auxiliary
Gradually open the valve 1132 to release each gas.
It is made to flow into the reaction chamber 1101. At this time, SiH_Four/
He gas flow rate, NO gas flow rate and B₂H₆/He gas flow rate
the outflow valve 111 so that the ratio of
7, 1119, 1120 and also reaction chamber
Vacuum gauge 1136 so that the pressure inside reaches the desired value.
While checking the reading, open the main valve 1134.
adjust. and the temperature of the base cylinder 1137
is heated to a predetermined temperature of 50 to 400℃ by heating heater 1138.
After making sure the temperature is set to
1140 to the desired power and the reaction chamber 1101
A glow discharge is generated within the base cylinder 1.
A first layer () is formed on 137. Also, the layer
During the formation, to ensure uniform layer formation,
For this purpose, connect the base cylinder 1137 to the motor 1139.
Rotate at a more constant speed. all last used
Close the gas operation system valve of the reaction chamber 1101.
Evacuate to high vacuum. Next, the first layer formed in this way ()
An example of forming the second layer () on top of
Then, the reading of vacuum gauge 1136 is about 5×10^-6torr
When it gets old, repeat the same operation as above.
cormorant. In other words, SiH from the gas cylinder 1102_Four/
He gas, GeF from gas cylinder 1103_Four/Hega
B from gas cylinder 1104₂H₆/He gas, gas
NO gas is supplied from the cylinder 1105 to the valve 112.
Open 2, 1123, 1124, 1125 respectively.
Outlet pressure gauge 1127, 1128, 1129, 1
1Kg/cm of pressure of 130²Adjust the inflow valve 11 to
Gradually open 12, 1113, 1114, 1115.
and mass flow controllers 1107, 110.
8, 1109, 1110 respectively.
Ru. Subsequently, the outflow valves 1117, 1118,
1119, 1120 and auxiliary valve 1132
Gradually open each gas to the reaction chamber 1101
Let it flow. At this time, SiH_Four/He gas flow rate and
GeF_Four/He gas flow rate and B₂H₆/He gas flow rate and NO
Outlet valve 1 so that the ratio of gas to
Adjust 117, 1118, 1119, 1120
Also, make sure that the pressure inside the reaction chamber reaches the desired value.
While checking the reading of vacuum gauge 1136, check the main valve.
Adjust the aperture of 1134. and the base cylinder
-1137 temperature is changed by heating heater 1138
Make sure the temperature is set at a predetermined temperature between 50 and 400℃.
After checking, set the power supply 1140 to the desired power.
to generate a glow discharge in the reaction chamber 1101,
Forming the first layer () on the base cylinder 1137
Form the second layer () in the same way as in the case of
Ru. Next, the second layer formed in this way ()
When forming the third layer () on top of
All gas-operated valves used, as well as
Close the chamber and evacuate the reaction chamber 1101 to high vacuum.
Then, the reading of vacuum gauge 1136 is about 5×10^-6torr
In the same way as above, for example,
SiH from Nbe 1102_Four/He gas, gas cylinder 1
C from 106₂H_FourSupply gas to generate glow discharge
A third layer () is formed. third layer
The amount of carbon atoms in () is C₂H_FourGas supply flow rate
controlled by adjusting. Examples will be described below. Example 1 Using the photoconductive member manufacturing equipment shown in Figure 20,
Al was made by the glow discharge decomposition method described in detail earlier.
on the cylinder according to the manufacturing conditions shown in Table 1.
Forming a light-receiving layer, each of electrophotographic imaging members
Samples (sample No. 1-1-1 to 16-10-6 total 960
) was created. The first layer () in the photoreceptive layer in each sample and
Boron contained in the layer region consisting of the second layer ()
The distribution state of atoms is shown in Figures 14A and 14B,
The distribution state of oxygen atoms is shown in Figure 15, and the second layer
Distribution state of germanium atoms contained in ()
is shown in FIG. Boron atoms, oxygen atoms, and
The distribution state of germanium atoms and
It is expressed by the sample number (No.). In other words, the distribution state of boron atoms and oxygen atoms is
They are numbered 1-1 to 16-10 as shown in the table.
Furthermore, the distribution state of germanium atoms is
Accordingly, the distribution state of the six species shown in Figure 16 (50
Numbers 1 to 6 corresponding to the last numbers of 1 to 506)
The end of the numbers 1-1 to 16-10 shown in Table 3
granted to. Such boron atoms, oxygen atoms, and germanium atoms
The distribution of U atoms is determined by changing the predetermined gas flow rate.
Automatically changes the open/close status of the corresponding valve according to the curve
By manipulating B₂H₆/He, NO and
GeF_Four/By adjusting the gas flow rate of He
Formed. For each sample of the imaging member thus obtained,
Each was set individually in the charging exposure experiment equipment.
Corona charging is performed at 5.0KV for 0.3 seconds and immediately exposed to light.
The image was illuminated. The light image is a tungsten lamp light source
using a transmission type test chip with a light intensity of 0.2 lux・sec.
The light was irradiated through the yarn. Immediately thereafter, use a charged developer (toner and
cascading the photoconductive member surface
A good toner is formed on the surface of the photoconductive member by
-I got the image. The toner image on the surface of the photoconductive member
Transferred onto transfer paper using 5.0KV corona charging
Clear, high-density images with excellent resolution and good gradation reproducibility
images were obtained. Next, replace the light source with a tungsten lamp,
Uses 810nm GaAs semiconductor laser (10mW)
Same as above except that the electrostatic image was formed using
Under the toner image forming conditions, the toner transfer image is
When we evaluated the image quality, we found that the gradation reproducibility was good and clear.
A high-quality image was obtained. Example 2 Using the manufacturing equipment shown in Figure 20, a cylindrical
The manufacturing conditions shown in Table 2 were applied on an Al substrate.
Except for this, the image form for electrophotography was prepared in the same manner as in Example 1.
Each sample of component parts (Samples 21-1-1 to 28-9-6)
A total of 432 pieces) were produced. The first layer in the photoreceptive layer of each sample obtained in this example
contained in the layer region consisting of the layer () and the second layer ().
Figure 17 shows the distribution of boron atoms in oxygen.
The distribution state of atoms is shown in Figure 18, and the second layer
Distribution state of germanium atoms contained in ()
is shown in FIG. Boron atoms, oxygen atoms, and
and the distribution state of germanium atoms are the same as in Example 1.
By the sample number (No.) assigned to each sample
expressed. That is, the distribution state of boron atoms and oxygen atoms is
They are indicated by numbers 21-1 to 28-9 as shown in the table.
Furthermore, the distribution state of germanium atoms is
The distribution status of the six species shown in Figure 19 (601
~606) Numbers 1 to 6 corresponding to the last number
Added to the end of the numbers 1-1 to 16-10 shown in Table 4.
gave. For each sample of the imaging member thus obtained,
Toner was prepared in the same manner as in Example 1 using each separately.
When we evaluated the image quality of the transferred image, we found that it had excellent resolution.
This allows you to obtain clear, high-quality images with good gradation reproducibility.
It was. Example 3 Using the manufacturing apparatus shown in Fig. 20, the third layer () is
Except for the creation conditions shown in Table 5,
Sample No. 5-5-2 and 14-10 of Example 1, respectively
-5 and sample No. 25-3-4 of Example 2 were prepared.
xerographic images following the same conditions and procedures as
Each forming member (sample No. 5-5-2-1 to 5
-5-2-8, 14-10-5-1 to 14-10-5-
8. Total of 24 pieces from 25-3-4-1 to 25-3-4-8
sample) was prepared. Each of the imaging members thus obtained
image quality evaluation under the same conditions as in Example 1 using
Durability was evaluated through repeated and continuous use.
The evaluation results for each of these samples are shown in Table 6. Example 4 The third layer () was produced by sputtering method.
A silicon wafer and a graphite are used during the formation.
By changing the target area ratio of the fiite,
Containment of silicon atoms and carbon atoms in layer 3 ()
Sample No. 8-9 of Example 1 except that the quantitative ratio was changed.
- On a cylindrical Al substrate in the same way as in 4.
Forming a light-receiving layer to form an electrophotographic image forming member (trial)
Fee No. 8-9-4-1 to 8-9-4-7, 7 in total)
was created. Each of the imaging members thus obtained
Image formation, development, and cream were carried out in the same manner as in Example 1.
After repeating the printing process approximately 50,000 times, the image quality was evaluated.
As a result, the evaluation results shown in Table 7 were obtained. Example 5 When forming the third layer (), SiH_Fourgas and C₂H_Four
By changing the gas flow rate ratio, the silicon in the third layer () is
Except for changing the content ratio of carbon atoms and carbon atoms
was carried out in exactly the same manner as Sample No. 8-9-4 of Example 1.
A light-receiving layer is formed on a cylindrical Al substrate.
Image forming member for electrophotography (Sample No. 8-9-4-
11 to 8-9-4-18) were made respectively.
Ta. Each of the imaging members thus obtained
Image formation, development, and cream were carried out in the same manner as in Example 1.
After repeating the printing process approximately 50,000 times, the image quality was evaluated.
As a result, the evaluation results shown in Table 8 were obtained. Example 6 When forming the third layer (), SiH_FourGas and SiF_Four
gas and C₂H_FourThe third layer is formed by changing the gas flow rate ratio.
The content ratio of silicon atoms and carbon atoms in () is
Sample No. 8-9-4 of Example 1 except for the changes.
In exactly the same way, light was applied onto a cylindrical Al substrate.
Forming a receptive layer to form an electrophotographic image forming member (sample
No. 8-9-4-21 to 8-9-4-28 (8 pieces in total)
Each was produced. Each of the imaging members thus obtained
Image formation, development, and cream were carried out in the same manner as in Example 1.
After repeating the printing process approximately 50,000 times, the image quality was evaluated.
As a result, the evaluation results shown in Table 9 were obtained. Example 7 The actual results are the same except for changing the thickness of the third layer ().
The series was prepared in exactly the same manner as Sample No. 8-9-4 of Example 1.
A photoreceptive layer is formed on a powder-like Al substrate to generate electricity.
Image forming member for child photographs (sample No. 8-9-4-31 ~
A total of 4 pieces (8-9-4-34) were produced. Each of the imaging members thus obtained
Image formation, development, and cream were carried out in the same manner as in Example 1.
After repeating the printing process approximately 50,000 times, the image quality was evaluated.
As a result, the evaluation results shown in Table 10 were obtained. The common layer creation conditions in this example above are as follows.
Shown below. Support temperature When forming the first layer and third layer: approximately 250°C When forming the second layer: approximately 200℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use.
× = Causes image defects

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use. × = Causes image defects

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use.
× = Causes image defects

【table】 [Brief explanation of drawings]

FIG. 1 is a diagram schematically showing the layer structure for explaining the structure of the photoconductive member of the present invention, and FIGS.
Figure 3 is a schematic diagram showing the distribution state of germanium atoms in the second layer (2) of the present invention, and Figures 14A and 14B are photoconductive diagrams prepared in Example 1 of the present invention. Figure 15 shows the distribution of boron atoms in the photoreceptive layer of the member, and Figure 15 shows the distribution of oxygen atoms in the photoreceptor layer of the photoconductive member prepared in Example 1 of the present invention. The diagrams shown in FIG. 16 are schematic diagrams showing the distribution state of germanium atoms in the second layer ( ) of the photoconductive member prepared in Example 1 of the present invention, and FIG. FIG. 18 is a diagram showing the distribution state of boron atoms in the photoreceptive layer of the photoconductive member prepared in Example 2 of the present invention. FIG. 19 is a diagram showing the distribution state of oxygen atoms in the photoreceptive layer of the member. FIG. 20, a schematic diagram for showing the distribution state, is a diagram showing an apparatus for manufacturing a photoconductive member using a glow discharge decomposition method. 100: Photoconductive member, 101: Support, 10
2: Photoreceptive layer, 103: First layer, 104: Second
layer, 105: third layer, 1101: reaction chamber, 1
102-1106: Gas cylinder, 1107-11
11: Mass flow controller, 1112-111
6: Inflow valve, 1117-1121: Outflow valve, 1122-1126: Valve, 1127-1
131: Pressure regulator, 1132: Auxiliary valve, 1
133: Auxiliary valve, 1134: Main valve,
1135: Leak valve, 1136: Vacuum gauge, 1
137: Base cylinder, 1138: Heater, 1139: Motor, 1140: High frequency power source (matching box).

Claims (1)

[Scope of Claims] 1. A photoconductive member for electrophotography comprising a support for a photoconductive member for electrophotography and a photoreceptive layer provided on the support and having photoconductivity, The receptor layer includes, from the support side, a first layer ( ) having a thickness of 1 to 100 μm and made of an amorphous material containing silicon atoms (but not containing germanium atoms), and a first layer ( ) having a thickness of 1 to 100 μm and a silicon atom content of 1 to 9.5×. A second layer () with a layer thickness of 1000 Å to 50 μm composed of an amorphous material containing 10 ⁵ atomic ppm of germanium atoms, and silicon atoms and carbon atoms with a content of 1 × 10 ^-3 to 90 atomic%. Layer thickness composed of amorphous material containing 0.003
The germanium atoms contained in the second layer () are composed of a third layer () with a thickness of ~30 μm, and the germanium atoms have a distribution concentration of the first layer in the thickness direction of the layer. Near the interface with the layer () and/or near the interface with the third layer ()
The distribution concentration has a maximum value of 1000 atomic ppm or more, and in the center of the second layer (), the distribution concentration is near the interface with the first layer () and near the interface with the third layer (). The electrons are distributed non-uniformly so as to have a considerably lower portion than the electrons, and furthermore, at least one of the first layer () and the second layer () contains oxygen atoms. Photoconductive material for photography. 2. The photoconductive member for electrophotography according to claim 1, wherein at least one of the first layer () and the second layer () contains hydrogen atoms and/or halogen atoms. 3. The photoconductive member for electrophotography according to claim 1 or 2, wherein at least one of the first layer () and the second layer () contains a substance that controls conductivity. 4. The photoconductive member for electrophotography according to claim 3, wherein the substance that controls conductivity is an atom belonging to Group 3 of the periodic table. 5. The photoconductive member for electrophotography according to claim 3, wherein the substance that controls conductivity is an atom belonging to Group 3 of the periodic table.