JPH0551909B2 - - Google Patents

Description

[Detailed description of the invention]

[Description of the field to which the invention pertains] The present invention is directed to light (here, light in a broad sense, ultraviolet light).
rays, visible light, infrared rays, x-rays, gamma rays, etc.
Ru. ) that are sensitive to electromagnetic waves such as
The present invention relates to a photographic light-receiving member. [Description of conventional technology] In the image forming field, for electrophotographic light receiving members.
The photoconductive material forming the photoreceptive layer in
High sensitivity and SN ratio [photocurrent (Ip)/dark current (Id)]
Highly compatible with the spectral characteristics of the electromagnetic waves being emitted
have absorption spectrum characteristics, photoresponsiveness
is fast and has the desired dark resistance value when in use.
Characteristics such as being non-polluting to the human body
is required. Especially for office use as a business machine.
For electrophotography built into electrophotographic equipment used
In the case of light-receiving members, the above-mentioned
Pollution is an important point. Based on these points, light has recently been attracting attention.
Amorphous silicon (hereinafter referred to as A-Si) is used as a conductive material.
For example, German Publication No. 2746967
Publication No. 2855718 describes a photoreceptor for electrophotography.
Application as a member is described. However, the conventional photoreceptor made of A-Si
An electrophotographic light-receiving member having a dark resistance layer has a dark resistance.
Electrical, optical, optical values, photosensitivity, photoresponsiveness, etc.
In terms of conductive properties and use environment characteristics, as well as aging
In terms of physical stability and durability, each
Although the characteristics have been improved, the overall characteristics
There is room for further improvement in measuring improvement.
This is the reality. For example, when applied to light-receiving members for electrophotography,
In this case, we are trying to achieve high light sensitivity and high dark resistance at the same time.
Therefore, in the past, the residual voltage was
This type of photoreceptor material
If the product is used repeatedly for a long period of time, it may become damaged due to repeated use.
This is the so-called gore that accumulates due to fatigue and causes afterimages.
There are fewer inconveniences such as the occurrence of
It was gone. In addition, when configuring the photoreceptive layer with A-Si material,
to improve its electrical and photoconductive properties.
In addition, hydrogen atoms, fluorine atoms, chlorine atoms, etc.
For control of halogen atoms and electrical conductivity type
contains boron atoms, phosphorus atoms, etc., or has other property modifications.
For good reason, other atoms each serve as a light guide.
Contained in the electric layer, but the content of these constituent atoms
Depending on the method used, the electrical properties of the formed layer may be
Otherwise, problems may occur with photoconductive properties or voltage resistance.
It was hot. That is, for example, when a formed photoconductive layer is exposed to light,
Lifespan of photocarriers generated in this layer
There may be insufficient information, or the image may not be transferred to the transfer paper.
Localized radiation, commonly called “white spots”, appears in the image.
Image defects or creases that may be caused by electrical breakdown
When a blade is used for cleaning, due to its abrasion,
There is no image of what is commonly referred to as "white stripes."
There were some pitfalls. Also, it may not be used in a humid atmosphere.
or, for example, by applying a surface layer of a certain thickness to the surface.
so that it is substantially transparent to the light used.
In such cases, the damage may appear due to wear caused by long-term rubbing.
Changes occur in the reflection spectrum of the surface layer, especially sensitivity etc.
Unfavorable changes may occur over time regarding
There was no shortage of them. Also, if used in a humid atmosphere,
or immediately after being left in a humid atmosphere for a long time.
When used, it is rare that the so-called blurring of the image occurs.
It was gone. Therefore, efforts were made to improve the properties of the A-Si material itself.
On the other hand, when designing photoreceptive materials, the above-mentioned
The layer structure and each layer are designed to solve all of these problems.
It is necessary to devise the chemical composition and preparation method of
Ru. [Purpose of the invention] The present invention provides a secondary structure made of A-Si as described above.
For electrophotographic light-receiving members with conventional light-receiving layers.
The aim is to solve various problems that
Ru. That is, the main purpose of the present invention is to
The photoconductive properties mostly depend on the usage environment.
It is virtually always stable and has excellent resistance to light fatigue.
It is durable even after repeated use without causing any deterioration phenomenon.
Excellent durability and moisture resistance, with no or almost no residual potential.
In A-Si and polycrystalline silicon, which is rarely observed.
Electrophotographic light-receiving unit having a light-receiving layer configured
The aim is to provide materials. Another object of the invention is the layer provided on the support.
and the support and between each laminated layer.
Excellent adhesion, dense and stable structure
A-Si and polycrystalline silicon with high layer quality.
Electrophotographic light-receiving unit having a light-receiving layer configured
The aim is to provide materials. Still another object of the present invention is to provide a photoreceptor for electrophotography.
When applied as a material, it can be used as a strip for electrostatic imaging.
It has sufficient charge retention ability during electrical processing, and is
Excellent electrophotography to which electrophotography can be applied very effectively
In A-Si and polycrystalline silicon, which exhibits photographic properties.
Electrophotographic light-receiving unit having a light-receiving layer configured
The aim is to provide materials. Another object of the invention is to improve the image quality in long-term use.
There are no defects or blurred images, high density, and hard
High quality with clear contrast and high resolution
A for electrophotography that allows you to easily obtain images
-A photoreceptive layer composed of Si and polycrystalline silicon
An object of the present invention is to provide a light-receiving member having the following. Still another object of the present invention is to provide high photosensitivity and high SN.
A-Si and
A cell with a photoreceptive layer made of polycrystalline silicon.
An object of the present invention is to provide a light-receiving member for child photography. [Structure of the invention] The electrophotographic light-receiving member of the present invention comprises a support and a light-receiving member for electrophotography.
On the support, silicon atoms and germanium atoms
Contains, is composed of inorganic materials and is sensitive to long wavelength light.
A long-wavelength photosensitive layer with a silicon atom matrix
and atoms belonging to group or groups of the periodic table.
Charge injection blocking layer composed of polycrystalline material containing
, with silicon atoms as the base material, hydrogen atoms and halo atoms
At least one of the Gen atoms is a constituent element.
It is composed of an amorphous material that exhibits photoconductivity.
Photoconductive layer, silicon atoms, carbon atoms, and hydrogen atoms
It is composed of an amorphous material containing as a constituent element
and a light-receiving layer having the above-mentioned
In the surface layer, the surface layer and the photoconductive layer
The concentration of carbon atoms decreases towards the interface of
The concentration distribution of the constituent elements in the layer thickness direction is changed as follows.
and the surface layer in the layer thickness direction of hydrogen atoms.
characterized by a maximum concentration of 41 to 70 at%
Ru. The surface layer contains halogen atoms.
The charge injection blocking layer has a uniform thickness in the layer thickness direction.
Constituent elements are distributed in large amounts on the support side or on the side of the support.
As a child, an atom belonging to a group or a group of the periodic law.
However, it may contain substances that control conductivity.
stomach. In addition, it is distributed uniformly in the layer thickness direction or in large part on the support side.
Oxygen atoms or/
and may contain a nitrogen atom. The charge injection barrier
Oxygen atoms and/or nitrogen atoms in the stop layer are on the support side
may be inherent in Further, the photoconductive layer has oxygen atoms as constituent atoms,
At least a nitrogen atom and a substance that controls conductivity
It may contain one type. In the present invention, the long wavelength photosensitive layer is composed of
Required with silicon atoms and germanium atoms as children
At least one hydrogen atom and a halogen atom depending on
Amorphous materials containing seeds, so-called hydrogen
amorphous silicon germanium, halogen
amorphous silicon germanium, or
Halogen-containing hydrogenated amorphous silicon germanium
(Hereinafter, these generic notations will be referred to as “A-
It is composed of SiGe (H,
Ru. In addition, the long wavelength photosensitive layer contains a substance that controls conductivity.
(atom belonging to group or groups of the periodic table), acid
Contains at least one of elementary atoms and nitrogen atoms
It's okay. It was designed to have the layer structure described above.
The light-receiving member for electrophotography of the present invention has the above-mentioned problems.
Extremely superior electrical and optical technology that can solve all problems
Indicates optical properties, photoconductive properties, pressure resistance, and usage environment characteristics.
vinegar. In other words, it is applied as a light-receiving member for electrophotography.
In this case, the influence of residual potential on image formation is completely
It has stable electrical characteristics and high sensitivity.
It has a high signal-to-noise ratio, light fatigue resistance,
Has excellent repeatability, high concentration, and half-tone
High-quality images with clear images and high resolution.
Images can be stably and repeatedly obtained. Furthermore, the electrophotographic light-receiving member of the present invention can be
Semiconductor lasers have high photosensitivity in the visual range, especially
It has excellent matching with other materials and fast photoresponse. Hereinafter, according to the drawings, the photoreceptor for electrophotography of the present invention will be described.
The members will be explained in detail. 1-1 and 1-2 are electrophotographs of the present invention.
A schematic diagram to explain the light-receiving member for use
It is a configuration diagram. The electrophotographic light-receiving member shown in FIG.
The receptor layer 100 is a support 10 for a light-receiving member.
1, and the photoreceptive layer 100 is provided on
long wavelength photosensitive layer 102, charge injection blocking layer 103,
A-Si(H,X) light with photoconductivity
conductive layer 104, silicon atoms, carbon atoms and water
It is composed of an amorphous material whose constituent elements are elementary atoms.
and the concentration of these components is at least as high as the photoconductor.
Optical bandgap alignment at interfaces with layers
It has changed into a shape that gives it a hydrogen atom.
surface layer 104 with a maximum concentration of 41 to 70 atomic percent
It has a layered structure consisting of. Below, the components constituting the electrophotographic light receiving member of the present invention are as follows.
Describe each layer. The support used in the present invention includes conductive
Conductive support that can be electrically conductive or electrically insulating
For example, NiCr, stainless steel, Al,
Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pb, etc.
Examples include metals and alloys thereof. As the electrically insulating support, polyester, polyester, etc.
Liethylene, polycarbonate, cellulose acetate
Tate, polypropylene, polyvinyl chloride, poly
Vinylidene chloride, polystyrene, polyamide, etc.
Alloy resin film or sheet, glass, ceramic
Tsuku, paper, etc. are usually used. These electric shock
The edge support preferably has at least one surface.
The surface is electrically conductive treated, and the other surface is electrically conductive.
It is desirable that a layer of . For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Pd, In₂O₃, SnO₂, ITO (In₂O₃+SnO₂) etc.
Conductivity is imparted by providing a thin film of
or synthetic resin film such as polyester film.
For ilms, NiCr, Al, Ag, Pb, Zn, Ni,
Gold such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc.
Vacuum evaporation, electron beam evaporation, sputtering
Provided on the surface with a ring etc., or attached with the metal mentioned above.
The surface is laminated to make it conductive.
Granted. The shape of the support body may be cylindrical or base.
It can be of any shape such as a bolt shape or a plate shape, and can be shaped as desired.
For example, the shape is determined by
In the case of copying, it should be in the form of an endless belt or a cylinder.
is desirable. The thickness of the support can be adjusted to
determined as appropriate to form a photographic light-receiving member.
However, flexibility is required as a light-receiving member for electrophotography.
If the material is
It is made as thin as possible within the specified range. death
However, in such cases, the manufacturing and
In terms of handling and mechanical strength, it is usually 10μ or more.
considered to be above. In particular, image recording using coherent light such as laser light
When recording, it is important to
Eliminates image defects caused by so-called interference fringes.
For this reason, the surface of the support may be provided with irregularities. The unevenness provided on the surface of the support is a V-shaped cut.
Cutting tools with blades using milling machines, lathes, etc.
Fixed in place on the machine tool, e.g. cylindrical support
A program designed in advance according to your wishes
Move regularly in a specified direction while rotating according to
The support surface can be precisely cut by
By doing this, the desired uneven shape, pitch, and depth can be formed.
be done. Formed by this cutting method
The inverted V-shaped linear protrusion created by the unevenness is a cylindrical support.
It has a spiral structure centered on the central axis of the holder. reverse
The spiral structure of the V-shaped protrusion has double and triple spirals.
It may be a linear structure or a crossed spiral structure.
stomach. Alternatively, in addition to the spiral structure, parallel along the central axis
A line structure may also be introduced. Vertical cross-sectional shape of the uneven convex portion provided on the support surface
The shape is the layer thickness within the microcolumn of each layer formed.
controlled heterogeneity of the support and the support
Good adhesion between the directly applied layer and the desired
It is shaped like an inverted V to ensure electrical connection, but
Preferably substantially second order as shown in FIG.
It is considered a side triangle, right triangle, or scalene triangle.
It is desirable to In the middle of these shapes, isosceles three
Preferably a square or right triangle. In the present invention, the surface of the support is controlled in a controlled manner.
Each dimension of unevenness provided in the
Taking these points into consideration, the purpose of the present invention can be achieved as a result.
It is set up so that it can be done. That is, the first is A-Si(H,
X) The layer is structurally sensitive to the conditions of the surface on which it is formed.
The layer quality varies greatly depending on the surface condition.
Ru. Therefore, the deterioration of the layer quality of the A-Si(H,X) layer is
An uneven design is provided on the surface of the support to prevent
It is necessary to set up an image. Second, the free surface of the photoreceptor layer has extreme irregularities.
When cleaning after image formation,
You will not be able to perform the process completely. Also, when cleaning the blade,
There is a problem in that the board becomes damaged more quickly. The above-mentioned layer deposition problems and the electrophotographic process
problems with access and conditions to prevent interference fringes.
As a result of the study, the pitch of the recesses on the surface of the support was found to be suitable.
Preferably 500 μm to 0.3 μm, more preferably 200 μm
~1μm, optimally 50μm ~ 5μm is desirable.
stomach. Furthermore, the maximum depth of the recess is preferably 0.1 μm.
~5μm, more preferably 0.3-3μm, optimally
It is desirable that the thickness be 0.6 μm to 2 μm. Support surface
If the pitch and maximum depth of the recess are within the above range,
In this case, the slope of the slope of the recess (or linear protrusion) is
Preferably 1 degree to 20 degrees, more preferably 3 degrees to 15 degrees
degree, optimally 4 degrees to 10 degrees. Also, the layer pressure of each layer deposited on such a support
The maximum difference in layer thickness due to the non-uniformity of
Preferably 0.1 μm to 2 μm, more preferably 0.1 μm
~1.5μm, optimally 0.2μm ~ 1μm.
Delicious. Also, when using coherent light such as laser light
Another method to eliminate image defects caused by interference fringe patterns
As a result of multiple spherical trace depressions on the surface of the support.
An uneven shape may be provided. That is, the surface of the support is required for electrophotographic light receiving members.
It has finer irregularities than the required resolution, and
The unevenness is due to a plurality of spherical trace depressions.
Ru. The electrophotographic light receiving member of the present invention will be described below.
The shape of the surface of the support and its preferred manufacturing example,
As will be explained with reference to FIGS. 21 and 22, the present invention
Shape of support in light-receiving member and manufacture thereof
The law is not limited thereby. FIG. 21 shows the electrophotographic light receiving member of the present invention.
A typical example of the surface shape of the support is shown below.
A partially enlarged and schematic diagram of the uneven shape of
It is something. In FIG. 21, 1601 is a support, 1602
is the support surface, 1603 is a rigid true sphere, and 1604 is
It shows a spherical trace depression. Furthermore, FIG. 21 shows how to obtain the surface shape of the support.
An example of a preferred manufacturing method is also shown.
That is, the rigid true sphere 1603 is connected to the support surface 1602.
Let it fall naturally from a predetermined height to the support surface.
By colliding with the surface 1602, the spherical depression 1
604 can be formed. and,
Using a plurality of rigid true spheres 1603 with approximately the same diameter R',
from the same height h, simultaneously or sequentially.
By dropping, onto the support surface 1602,
A plurality of curves having approximately the same curve radius R and the same width D
A spherical vestigial depression 1604 can be formed. As mentioned above, there are multiple spherical trace depressions on the surface.
The following is a typical example of a support with an uneven shape formed by
It is shown in Figure 22. In the same figure, 1701 is the support
The dotted line at 1702 indicates the position of the uneven part, 1703
1704 indicates a rigid true sphere, and 1704 indicates a concave surface. By the way, the support for the electrophotographic light receiving member of the present invention
The curvature half of the uneven shape due to the spherical trace depression on the surface of the holding body
The diameter R and width D of the light receiving member of the present invention are
Effectively prevents interference fringes in
This is an important factor in achieving this goal. Inventor
As a result of various experiments, they discovered the following:
did. That is, the radius of curvature R and the width D are as follows: D/R≧0.035 If it satisfies the
0.5 or more Newton rings due to ring interference
It will exist. Furthermore, the following formula: D/R≧0.055 If it satisfies the
There is one or more Newton rings due to ring interference.
There will be. Because of these things, it occurs throughout the photoreceptor member.
Interference fringes are dispersed within each trace depression, allowing light reception.
In order to prevent interference fringes from occurring in the member,
The D/R is 0.035, preferably 0.055 or more. is desirable. In addition, the width D of the unevenness due to the trace depression is at most
About 500 μm, preferably 200 μm or less, more preferably
More preferably, the thickness is 100 μm or less. Figure 23 shows the unevenness formed by the above method.
The slope of the unevenness on the support body 2301 having the shape
A photoreceptor with a photoreceptor layer 2300 along the surface.
It shows the material. At this time, the free surface 2306 is arranged
At the interface formed in the photoreceptive layer 2300
Since the degree of inclination is different, the free surface 2306 is aligned
Reflection at the interface formed in the light-receiving layer 2300
Each has a different angle of light reflection. Therefore, it corresponds to the so-called Newton ring phenomenon.
Shearing interference occurs, and the interference fringes are inside the depression.
This is where it will be dispersed. This results in
The image that appears through the photoreceptor is microscopic.
Even if interference fringes appear, they are
is something that cannot be grasped visually.
That is, the support body 2301 having such a surface shape
The use of a multilayer photoreceptive layer 2300 on top of the photoreceptive layer 2300
In the light-receiving member formed by forming the light-receiving layer, the light-receiving layer
2300, the light passes through the layer interface and the support surface.
formed by reflection and their interference.
This method effectively prevents striped images from appearing in the image.
Ru. In Figure 23, 2302 is long wavelength photosensitive
2303 is a charge injection blocking layer, 2304 is a light guide layer.
The electric layer 2305 is a surface layer. Long wavelength photosensitive layer The long wavelength photosensitive layer in the present invention is a silicon raw material.
Inorganic materials containing atoms and germanium atoms (polycrystalline)
(crystalline material or amorphous material) and is contained in the layer.
The germanium atoms are uniform throughout the layer.
Alternatively, it may be distributed throughout the layer thickness direction.
It is contained evenly, but the distribution concentration is uneven.
It's good to wear. However, in any case, the support
In the in-plane direction parallel to the surface, the distribution is uniform.
Being evenly contained is a special feature in the in-plane direction.
This is also necessary from the perspective of equalizing gender. Sunawa
It is uniformly contained in the layer thickness direction of the long wavelength photosensitive layer.
and the side on which the support is provided;
is for the opposite side (free surface side of the photoreceptor layer)
It seems that more of the particles are distributed on the support side.
or the opposite distribution state.
It is contained in the long wavelength photosensitive layer. In the light receiving member of the present invention, as described above,
Germanium atoms contained in the long wavelength photosensitive layer
In the layer thickness direction, the distribution state of
The distribution state is taken in the in-plane direction parallel to the surface of the support.
It is desirable to have a uniform distribution state. Also, in one of the preferred embodiments, a long
Distribution of germanium atoms in the wavelength photosensitive layer
The state is such that germanium atoms are continuously distributed throughout the entire layer.
Evenly distributed, germanium atoms are distributed in the layer thickness direction.
The cloth density C is from the support side toward the charge injection blocking layer.
Given the decreasing change, long wavelength light sensitivity
Excellent affinity between the optical layer and the charge injection blocking layer
In addition, as will be described later, there is a gap at the end of the support.
Extremely increase the distribution concentration C of rumanium atoms
Therefore, when using a conductor laser etc.,
The photoconductive layer absorbs almost no light at long wavelengths.
In the long wavelength photosensitive layer, virtually complete absorption is achieved.
interference caused by reflection from the support surface.
It can be prevented. FIG. 2 to FIG. 7 show the photoreceptor in the present invention.
Germanium contained in the long wavelength photosensitive layer of the member
Typical case where the distribution state of the layer thickness direction is non-uniform
An example is shown. In Figures 2 to 7, the horizontal axis is germanium.
The vertical axis represents the distribution concentration C of atoms in the long wavelength photosensitive layer.
indicates the layer thickness of t_Bis the long wavelength photosensitive layer on the support side.
The position of the end face is t_Tis the long wavelength on the side opposite to the support side
The position of the end face of the photosensitive layer is shown. That is, germanium
The long wavelength photosensitive layer containing mu atoms is t_BT from the side_T
Layering takes place towards the sides. Figure 2 shows the gel contained in the long wavelength photosensitive 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
The surface on which the contained long-wavelength photosensitive layer is formed and the corresponding
Interface position t in contact with the surface of the long wavelength photosensitive layer_BThan
t₁Up to the position, the distribution concentration of germanium atoms C
is C₁germanium atoms while taking a certain value
A long wavelength photosensitive layer is formed, and the position t₁
Rather than concentration C₂The interface position t_Tgradually until it reaches
It is being continuously reduced. Interface position t_TIn the game
The distribution concentration C of rumanium 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_FiveForm a distribution state such that
are doing. In the case of Figure 4, position t_BMore position₂until then
The distribution concentration C of rumanium atoms is the concentration C₆and a constant value
and position t₂and position t_Tgradually between
Continuously decreased position t_T, the distribution concentration C
is substantially zero (here, substantially zero and
is below the detection limit). In the case of Figure 5, the distribution concentration of germanium atoms is
Degree C is position t_BMore position_Tup to the concentration C₈Than
Continuously gradually decreased position t_Tsubstantially in
It is said to be zero. In the example shown in Figure 6, germanium atoms
The distribution concentration C of is given by the position t_Band t₃In between, the concentration
C₉is a constant value, and the position t_TThe concentration C_Tenand
be done. position t₃and position t_Tbetween, the distribution concentration C
is the position t linearly₃More position_Tdecreased up to
has been done. In the example shown in FIG. 7, the position t_Bposition from the side
t_TUntil , the distribution concentration C of germanium atoms is
Concentration C₁₁linearly so that it more effectively reaches zero
is decreasing. As described above, from Fig. 2 to Fig. 7, long wavelength photosensitive
germanium atoms contained in the layer in the layer thickness direction
As we have explained some typical examples of distribution states, the present invention
In the light, germanium is added on the support side.
It has a part with a high distribution concentration C of atoms, and the interface t_Tto the side
In this case, the distribution concentration C is smaller than that on the support side.
germanium atom with a reduced portion
When the distribution state is provided in the long wavelength photosensitive layer
is cited as one of the preferred examples. Germani
Germanium atoms are distributed in the layer thickness direction.
The maximum value Cmax of the distribution concentration of silicon atoms is
preferably 1000 atomic ppm or more relative to the sum of
More preferably 5000 atomic ppm or more, optimally 1×
Ten^FourThe distribution state can be such that it is considered to be more than atomic ppm.
It is desirable that the layer be constructed in such a way that the In the present invention, the long wavelength photosensitive layer contains
The content of germanium atoms in the present invention is as follows:
Appropriately as desired so that the purpose is effectively achieved
However, it is preferable for the sum with silicon atoms.
Preferably 1~10×10^FiveAtomic ppm, preferably 100~
9.5×10^FiveAtomic ppm, optimally 500 to 8×10^Fiveatom
Preferably in ppm. The above-mentioned long wavelength photosensitive layer further controls the conductivity.
At least one of the substances, oxygen atoms, and nitrogen atoms
It may contain one. In addition, as the substance that controls the conductivity,
List of so-called impurities in the semiconductor field.
In the present invention, it is possible to provide p-type conduction characteristics.
Atoms belonging to groups of the periodic table (hereinafter referred to as "group atoms")
"Child". ), or the period that gives N-type conduction characteristics
Atoms belonging to the Ritual Table Group (hereinafter referred to as "Group atoms")
cormorant. ) is used. As a group atom, specifically
are B (boron), Al (aluminum), Ga (gallium).
In (indium), Tl (thallium), etc.
Particularly suitable are B and Ga. As group atoms,
Specifically, P (phosphorus), As (arsenic), Sb (antimony)
), Bi (bismuth), etc. P and As are particularly preferred.
suitable. In the present invention, the long wavelength photosensitive layer contains
The content of the substance that controls the conduction properties is preferably
Preferably 0.01~5×10^FiveAtomic ppm, more preferably
is 0.5~1×10^FourAtomic ppm, optimally 1-5×10³
Preferably, it is expressed in atomic ppm. Nitrogen atoms (N) contained in the long wavelength photosensitive layer
amount, or amount of oxygen atoms (O), or nitrogen atoms and oxygen atoms
The sum of the amounts (N+O) is preferably 0.01 to 40 atoms
%, more preferably 0.05 to 30 atomic %, optimally
The content is preferably 0.1 to 25 at%. In the present invention, the layer thickness of the long wavelength photosensitive layer is preferably
preferably 30 Å to 50 μm, more preferably 40 Å to 40 μm
m, preferably 50 Å to 30 μm.
stomach. In the electrophotographic light receiving member of the present invention, the support
Improved adhesion between the carrier and the long wavelength photosensitive layer.
For the purpose of measuring the top, for example, Si₃N_Four, SiO₂, SiC,
Sio, at least one of a hydrogen atom and a halogen atom
and at least nitrogen, oxygen, and carbon atoms.
On the other hand, amorphous materials containing silicon atoms and
An adhesion layer made of a crystalline material or the like may be provided. Charge injection blocking layer The charge injection blocking layer in the present invention is made of polycrystalline silicon.
The conductivity is controlled in the entire layer area of the layer.
Apply the substance uniformly or preferably in large quantities on the support side.
Contains in a non-uniform distribution. Furthermore, it is necessary
If necessary, add acid to the entire layer area or a part of the layer area.
elementary atoms and/or nitrogen atoms uniformly or preferably
is contained in a non-uniform state so that it is mostly distributed on the support side.
By having the layer between the layer and the long wavelength photosensitive layer,
Improve adhesion and adjust band gap.
I can do that. In the present invention, the charge injection layer is made of polycrystalline silicon.
The conductivity of the contained material can be controlled.
to a substance (group group or group atom of the periodic table)
conduction properties can be controlled more effectively.
and over a long period of time, the amount of charge during charging
This makes it possible to more effectively prevent
The flow of charge is not interrupted. Therefore, high quality
High quality images can be obtained over a long period of time. The above-mentioned conductive properties contained in the charge injection blocking layer are
As substances to be controlled, there are
In the present invention, so-called impurities can be mentioned.
belongs to group of the periodic table which gives p-type conductivity characteristics.
(hereinafter referred to as "group atoms"), or
Elements belonging to group V of the periodic table that give N-type conduction characteristics
(hereinafter referred to as "Group V atoms"). No.
Specifically, the group atoms include B (boron), Al
(aluminum), Ga (gallium), In (indium)
), Tl (thallium), etc. B and Ga are particularly preferred.
suitable. Specifically, the Group V atoms include P
(phosphorus), As (arsenic), Sb (antimony), Bi (bisma)
Among them, P and As are particularly suitable. In FIGS. 8 to 12, the charge injection blocking layer contains
group atoms or the portion of group atoms in the layer thickness direction
Typical examples of cloth conditions are shown. In the examples in Figures 3 to 12, the horizontal axis is the group.
The distribution concentration C of atoms or group atoms is shown, and the vertical axis is the charge.
Indicates the layer thickness t of the injection blocking layer, t_Bis the interface on the support side
position, t_Tis the position of the interface on the opposite side from the support side.
show. That is, the charge injection blocking layer is t_BT from the side_Ttowards the side
Layer formation is then carried out. FIG. 8 shows the charge injection blocking layer containing
The distribution state of group atoms or group atoms in the layer thickness direction
One typical example is shown. In the example shown in Figure 8, the interface position t_Bthan t₁of
Up to the position, the group atom or the concentration of group atom
Degree C is C₁It is contained while taking a certain value, and the position
Placement₁Therefore, the distribution concentration C is the interface position t_TC up to₂Yo
has been gradually and continuously reduced. Interface position t_Tto
The distribution concentration C is C₃It is said that In the example shown in FIG.
The distribution concentration C of group atoms or group atoms is at position t_B~ side
More position_TC up to_Fourgradually and continuously decreasing from
and position t_TC in_FiveForm a distribution state such that
are doing. In the example shown in Figure 10, the group atoms or
The distribution concentration C of group atoms is given by the position t_Band position t₂Between
In other words, C₆is a constant value, and the position t_TIn
C₇It is said that position t₂and position t_TThe distribution density is
The degree C is a linear function of the position t₂More position_Tup to
has been reduced. In the example shown in FIG. 11, the distribution concentration C
is position t_BMore position₃Until C₈Take a constant value of
Placement₃More position_TUntil C₉More C_Tenlinear function up to
It is said that the distribution state decreases to . In the example shown in FIG. 12, the distribution concentration C
is position t_BMore position_Tup to C₁₁takes a constant value. In the present invention, the charge injection blocking layer is composed of group atoms or
is the proportion of group atoms distributed more on the support side.
When contained in a cloth state, group atoms or group elements
The maximum value of the child distribution concentration value is preferably 50 atoms.
ppm or higher, more preferably 80 atomic ppm or higher, optimally
The distribution state is such that the amount is more than 100 atomic ppm.
It is desirable that the layer be formed in such a way that it can be used as a layer. Contained in the charge injection blocking layer in the present invention
The content of group atoms or group atoms is
Follow the wishes so that the purpose of the invention is effectively achieved
It can be determined as appropriate, but preferably 30 to 5 x 10^Fouroriginal
ppm, more preferably 50 to 1×10^Fouratomic ppm,
Optimally 1×10²~5×10³The atomic ppm is
It is desirable. As mentioned above, the charge injection blocking layer is made of oxygen atoms or
Due to the inclusion of nitrogen atoms,
Improving the adhesion between the long-photosensitive layer and the charge injection blocking layer
Adhesion between top and charge injection blocking layer and photoconductive layer
improvement or adjustment of the handgap of the layer.
It will be done. FIG. 13 to FIG. 19 show the charge injection blocking layer.
Layer thickness direction of oxygen atoms and/or nitrogen atoms
A typical example of the distribution state of is shown. In the examples in Figures 13 to 19, the horizontal axis is oxygen.
The vertical axis represents the distribution concentration C of atoms and/or nitrogen atoms.
Indicates the layer thickness t of the charge injection blocking layer, t_Bis on the support side
The interface position is t_Tis the position of the interface on the opposite side from the support side.
Indicates the location. That is, the charge injection blocking layer is t_BMoret_Tto the side
Layer formation is carried out in this direction. Figure 13 shows the acid contained in the charge injection blocking layer.
Distribution state of elementary atoms and/or nitrogen atoms in the layer thickness direction
The first typical example is shown below. In the example shown in Fig. 13, the interface position t_Bthan t_Four
Up to the position, the content of oxygen atoms and/or nitrogen atoms is
The concentration C is C₁₂It is contained while taking a certain value.
position t_FourTherefore, the distribution concentration C is the interface position t_TC up to₁₃
It has been gradually and continuously reduced. Interface position t_T
In , the distribution concentration C is C₁₄It is said that In the example shown in Figure 14, it contains
The degree of distribution C of oxygen atoms and/or nitrogen atoms is at position t_B
More position_TC up to₁₅gradually and continuously decreases from
a little position t_TIn C₁₆The distribution state becomes
is forming. In the case of Figure 15, position t_BMore position_FiveUntil
The distribution concentration C of oxygen atoms and/or nitrogen atoms is C₁₇
is assumed to be a constant value, and the position t_Fiveand position t_TThe smell between
is gradually and continuously decreased, and the position t_TIn,
It is essentially zero. In the case of Figure 16, oxygen atoms or/and nitrogen
Atom is at position t_BMore position_Tuntil the distribution concentration C
is C₁₉The position t is gradually decreased more continuously_TNii
It is said that it is essentially zero. In the example shown in FIG. 17, oxygen atoms or /
and the distribution concentration C of nitrogen atoms is at the position t_BMore position₇Ma
Then C_{twenty two}Take a constant value of and position t₇More position_TUntil
C_{twenty three}More C_{twenty four}It is assumed that the distribution state is a linear function until
ing. In the example shown in FIG. 18, oxygen atoms or /
and the distribution concentration C of nitrogen atoms is at the position t_Band position t₆while
In C₂₀is a constant value and the position t_Tin
is C_{twenty one}It is said that position t₆and position t_TThe distribution is between
The concentration C is linearly proportional to the position t₆More position_Tuntil
has been reduced. In the example shown in FIG. 19, the distribution concentration C
is position t_BMore position_TUntil C_{twenty five}takes a constant value. In the present invention, the charge injection blocking layer 103 is composed of oxygen atoms.
or/and more nitrogen atoms on the support 101 side.
When contained in a distributed state, oxygen atoms or
is/and the distribution concentration value of nitrogen atoms or the sum of both atoms
The maximum value is preferably 500 atomic ppm or more, preferably
is above 800 atomic ppm, optimally above 1000 atomic ppm
The layers are formed in such a way that a distribution state can be obtained.
It is desirable to Contained in the charge injection blocking layer in the present invention
Content of oxygen atoms and/or nitrogen atoms or both
Overall, the objectives of the present invention are effectively achieved.
Although it can be determined appropriately according to the desired condition, it is preferable that
0.001-50 atomic%, more preferably 0.002-40 atomic%
%, ideally 0.003 to 30 at%.
Yes. In the present invention, the layer thickness of the charge injection blocking layer is determined as desired.
Obtaining electrophotographic properties and economical effects, etc.
From the point, preferably 0.01 to 10μ, more preferably
The desired value is 0.05 to 8μ, optimally 0.1 to 5μ.
stomach. photoconductive layer The photoconductive layer in the present invention is A-Si(H,X)
A photoconductive material that satisfies the desired electrophotographic properties.
have characteristics. In addition, a substance that controls conductivity is applied to the entire layer area.
within the range that does not impair the properties required for the layer.
May be contained. In addition, the characteristics required for the layer are provided in the entire layer area.
Carbon atoms, oxygen atoms and
It may contain at least one of nitrogen atoms. As the substance that controls the conductivity, the above-mentioned electrical
Similar to the charge injection blocking layer, group atoms and
can be used. In the present invention, group elements are present in the entire layer region of the photoconductive layer.
If it contains children or group atoms, it is mainly conductive.
It has the effect of controlling type and/or conductivity, and
Relatively small content of group atoms or group atoms
and preferably 1×10^-3~3×10²atomic ppm,
More preferably 5×10^-3~Ten²Atomic ppm, optimally
1×10^-2It is desirable that it be ~50 atomic ppm. Furthermore, oxygen is present in the entire layer region of the photoconductive layer in the present invention.
If it contains atoms or carbon atoms, it is mainly
dark resistance and the difference between the charge injection blocking layer and the photoconductive layer.
It has the effect of improving adhesion, but especially the layer 10
In order not to deteriorate the photoconductive properties of 4, oxygen atoms or
Although the content of carbon atoms is considered to be relatively small, it is desired that
Delicious. In the case of nitrogen atoms, in addition to the above points, e.g.
Increased photosensitivity in coexistence with group atoms, especially B.
You can measure the top. Contained in photoconductive layer 104
content of oxygen atoms or nitrogen atoms, or both
The sum of the numbers is preferably 1×10^-3~Ten³Atomic ppm, yo
Preferably 5×10^-2~5×10²Atomic ppm, optimally
is 1×10^-1~2×10²Preferably in atomic ppm
Yes. In the present invention, the purpose is effectively achieved.
It is formed on the support and constitutes a part of the photoreceptive layer.
The photoconductive layer formed has the semiconductor properties shown below,
A-Si(H,
X). p-type A-Si (H,X)...acceptor only
including. Or between donor and acceptor
Contains both and has a high relative concentration of acceptor
thing. In the type of p-type A-Si(H,X)...
If the acceptor concentration (Na) is low or
has a low relative concentration of acceptor. n-type A-Si(H,X)...contains only donor
thing. or include both donor and acceptor.
and those with a high relative concentration of donor. In the type of n-type A-Si(H,X)...
If the donor concentration (Nd) is low or the donor
The relative concentration of - is low. i-type A-Si(H,X)……NaNdO also
or NaNd. In the present invention, the long wavelength photosensitive layer or/and the electrode
Contained in charge injection blocking layer and/or photoconductive layer
Preferred halogen atoms (X) are F, Cl, Br,
I, particularly F and Cl are preferred. In the present invention, the long wavelength photosensitive layer or/and the electrode
Forming charge injection blocking layer 103 and/or photoconductive layer
For example, glow discharge method, microwave discharge method
method, sputtering method, or ion platey method.
By using a vacuum deposition method that utilizes discharge phenomena such as
It will be done. For example, by using the glow discharge method,
A charge injection blocking layer made of crystalline silicon or/
and A-Si(H,X).
Basically, silicon atoms (Si) are provided to
Along with the raw material gas for Si supply that can be supplied, hydrogen atoms (H)
Raw material for introduction and/or introduction of halogen atom (X)
A gas is introduced into a deposition chamber whose interior can be reduced in pressure.
A glow discharge is generated in the deposition chamber, and a predetermined
on a given support surface in place.
From crystalline silicon or/and A-Si(H,X)
It is sufficient to form a layer. Also, sputtering
When forming by the method, for example, an inert material such as Ar or He
atmospheric gases or mixed atmospheres based on these gases
Sputtering a target composed of Si in air
When grouping hydrogen atoms (H) or/and halogen atoms (X)
Introducing the introduction gas into the deposition chamber for sputtering
Just do it. In addition, silicon atoms and gel can be separated by glow discharge method.
Polycrystalline or amorphous material containing manium atoms
To form a long wavelength photosensitive layer composed of
Basically, it is a Si donor that can supply silicon atoms (Si).
Along with the feedstock gas, germanium atoms (Ge)
Raw material gas for Ge supply that can supply
and/or halogen atom for hydrogen atom (H) introduction
(X) Deposition where the internal pressure can be reduced for the raw material gas for introduction.
Introduced into the chamber to generate a glow discharge within the deposition chamber.
and a predetermined support that has been installed in a predetermined position.
It is sufficient to form a layer on the body surface. Also, spatuta
When forming by the ring method, for example, Ar, He, etc.
inert gases or mixtures based on these gases.
A target composed of Si in a gas atmosphere,
Alternatively, a target composed of the target and Ge
Using two pieces of Tuto, or a mixture of Si and Ge.
He, if necessary, using the target
Raw material gas for Ge supply diluted with diluent gas such as Ar
hydrogen atoms (H) or/and halo atoms as necessary.
The gas for introducing Gen atoms (X) is added to the sputtering deposit.
Introduced into the storage chamber to form a plasma atmosphere of the desired gas.
It is accomplished by doing. Raw material gas for supplying Si used in the present invention
As, SiH4, Si₂H₆,Si₃H₈,Si_FourH_Tenmoths such as
Silicon hydride (silane) in gaseous or gasifiable form
class) are listed as those that are effectively used and are especially
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. Substances that can be used as raw material gas for Ge supply include:
GeH_Four,Ge₂H₆,Ge₃H₈,Ge_FourH_Ten,Ge_FiveH₁₂，
Ge_FiveH₁₄,Ge₇H₁₅,Ge₈H₁₈,Ge₉H₂₀gaseous such as
germanium hydride is effective
It is used for layer creation, especially for layer creation.
Ease of handling during work, good Ge supply efficiency, etc.
So, GeH_Four,Ge₂H₆,Ge₃H₈is preferred.
can be mentioned. For introducing halogen atoms used in the present invention
Many halogenated gases are effective as raw material gases for
For example, halogen gas, halogen
compounds, interhalogens, halogen-substituted
Gaseous or gasifiable materials such as silane derivatives
Preferred examples include rogogen compounds. Furthermore, silicon atoms and halogen atoms
Constituent halves in a gaseous state or capable of being gasified
Silicon compounds containing rogen atoms are also considered effective.
In the present invention, the following can be mentioned. Halogen compounds that can be suitably used in the present invention
Specifically, the substances include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF₃，
BrF_Five,BrF₃,IF₃,IF₇, ICl, IBr, etc.
Intermediate compounds can be mentioned. Silicon compounds containing halogen atoms, so-called halogens
Examples of silane derivatives substituted with carbon atoms include
For example, SiF_Four,Si₂F₆,SiCl_Four, SiBr_Fouretc.
Silicon rogenide is preferred.
I can do it. Adopts silicon compounds containing such halogen atoms
The characteristic light guide of the present invention is produced by the glow discharge method.
When forming electrical parts, raw materials that can supply Si
Even without using silicon hydride gas as a gas,
Halogen atoms as constituents on a given support
It is possible to form a layer consisting of A-Si:H containing
Ru. A layer containing halogen atoms according to the glow discharge method
When producing Si, basically the raw material gas for supplying Si is
Silicon halide gas and Ar, H₂, He et al.
Place the gas at the specified mixing ratio and gas flow rate.
Glow discharge is introduced into the deposition chamber to form the desired layer.
to form a plasma atmosphere of these gases.
The desired layer is deposited on a given support by
Although it can be formed, in order to introduce hydrogen atoms
In addition, silicon compounds containing hydrogen atoms in these gases
A layer may be formed by mixing a predetermined amount of gases. In addition, when forming a long wavelength photosensitive layer, halogen
The halo gas mentioned above as a raw material gas for introducing gen atoms
Contains hydrogen compounds or silicon compounds containing halogens.
It is used as an effective thing, but other
In, GeHF₃, GeH₂F₂, GeH₃F, GeHCl₃，
GeH₂Cl₂, GeH₃Cl, GeHBr₃, GeH₂Br₂，
GeH₂Br, GeHI₂, 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., or
is a long-wavelength photosensitive layer formation that is effective even for substances that can be gasified.
can be mentioned as a starting material for In addition, each gas can be used not only as a single species but also in a predetermined mixing ratio.
It is safe to use a mixture of multiple types.
Ru. Reactive sputtering method or ion platey
A layer consisting of A-Si(H,X) is formed using the
For example, in the case of sputtering method,
Using a target consisting of Si, this is
Sputtering in a gas plasma atmosphere to generate iodine
In the case of the plating method, polycrystalline silicon
Or use monocrystalline silicon as an evaporation source in a deposition boat.
This silicon evaporation source is heated using resistance heating method or
is added by electron beam method (EB method) etc.
Thermal evaporation and flying evaporates are placed in a specified gas plasma atmosphere.
This can be done by passing air through it. At this time, sputtering method, ion plate
In both cases, halogen is present in the layer formed.
In order to introduce a ion atom, the above-mentioned halogen compound or
is the silicon compound gas containing the above halogen atom.
The gas is introduced into the deposition chamber to form a plasma atmosphere.
It is good if you can do it. In addition, when introducing hydrogen atoms, hydrogen atom guide
Necessary raw material gas, e.g. H₂, or the above
In a deposition chamber for sputtering gases such as silanes.
to form a plasma atmosphere of the gas.
That's fine. In the present invention, the raw material for introducing halogen atoms
The halogen compounds or halogens listed above as gases
silicon compound containing gen or gel containing halogen
Although manium compounds are used as effective
In addition, HF, HCl, HBr, HI, etc.
Hydrogen halide, SiH₂F₂,SiH₂I₂,SiH₂Cl₂，
SiHCl₃,SiH₂Br₂,SiHBr₃halogen-substituted water such as
In the gaseous state or capable of being gasified, such as silicon nitride, etc.
, halogenation with hydrogen atom as one of the constituent elements
Also effective long wavelength photosensitive layer, charge injection blocking layer and
It can be mentioned as a starting material for forming a photoconductive layer.
Ru. These halides containing hydrogen atoms are layered.
The introduction of halogen atoms into the layer formed during
At the same time, it is extremely useful for controlling electrical or photoelectric characteristics.
Since effective hydrogen atoms are also introduced, in the present invention,
is used as a suitable raw material for introducing halogen atoms.
It will be done. Hydrogen atoms are introduced structurally into the formed layer.
In addition to the above,₂, or SiH_Four,Si₂H₆，
Si₃H₈,Si_FourH_TenSupply Si with silicon hydride gas such as
coexist with a silicon compound in the deposition chamber to
This can be done by causing electrical discharge. For example, in the case of the reactive sputtering method, Si
Gas for introducing halogen atoms using a target
and H₂If necessary, use an inert gas such as He or Ar.
A plasma atmosphere is created by introducing the
forming and sputtering the Si target.
In some cases, polycrystalline silicon or A-Si may be deposited on the substrate.
A layer consisting of (H,X) is formed. Furthermore, B also serves as impurity doping.₂H₆etc
It is also possible to introduce gas. In the present invention, the electrophotographic light receptor formed
Long wavelength photosensitive layer, charge injection blocking layer and light guiding layer
Amount of hydrogen atoms (H) or halogen contained in the electrical layer
Amount of atom (X) or sum of amounts of hydrogen and halogen atoms
is preferably 1 to 40 at%, more preferably 5 to 30
It is preferable to express it in atomic percent. Hydrogen atoms (H) or/
and to control the amount of halogen atoms (X), e.g.
Support temperature or/and hydrogen atom (H) or halo
Starting material used to contain the Gen atom (X)
Controls the amount introduced into the volumetric device system, discharge power, etc.
Just do it. Long wavelength photosensitive layer, charge injection blocking layer and photoconductive layer
a group atom or a group atom, and a carbon atom,
In order to contain oxygen atoms or nitrogen atoms,
-Charge injection by discharge method, reactive sputtering method, etc.
When forming an entry blocking layer or a photoconductive layer, group atoms or
is the starting material for the introduction of group atoms, and the oxygen atom conductor.
The starting materials for nitrogen introduction, nitrogen introduction, and carbon introduction, respectively, were
Starting material for forming the charge injection blocking layer and photoconductive layer described above
used with a substance to deposit its amount into the layer formed.
This is achieved by controlling the content. In this way, for introducing carbon atoms and for introducing oxygen atoms.
is/and the starting material for the introduction of nitrogen atoms, or group
As starting materials for introducing atoms or group atoms,
At least carbon atoms, oxygen atoms and nitrogen atoms
or a group atom or a group atom
A gaseous substance or a substance that can be gasified into atoms
Most of the gasified materials can be used.
Ru. For example, if it contains oxygen atoms, silicon
A raw material gas containing silicon atoms (Si) and an acid
Raw material gas containing elemental atoms (O) and, if necessary,
hydrogen atom (H) or halogen atom (X) as a constituent element.
Mix the raw material gas at the desired mixing ratio and use it.
or silicon atoms (Si)
A raw material gas with oxygen atoms (O) and hydrogen atoms (H)
The raw material gas, which is the constituent atoms, is also mixed in the desired manner.
Mix in a composite ratio or silicon atoms (Si)
Raw material gas with constituent atoms and silicon atoms
(Si), oxygen atom (O) and hydrogen atom (H).
It is possible to use it by mixing it with raw material gas.
come. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
Oxygen atoms (O) are formed in the raw material gas whose constituent atoms are
A mixture of raw material gases containing atoms may be used. Departures for the introduction of oxygen atoms and for the introduction of nitrogen atoms
Specifically, as a substance, 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), nitrogen (N₂),
Ammonia (NH₃), hydrogen azide (HN₃), Hido
Radin (NH₂N.H.₂), silicon atoms (Si) and oxygen
For example, the constituent atoms are an atom (O) and a hydrogen atom (H).
Dicycloxane (H₃SiOSiH₃), trisiloxane
(H₃SiOSiH₂OSiH₃) and other lower siloxanes.
You can get it. Carbon atom-containing compounds that serve as raw materials for introducing carbon atoms
For example, saturated hydrocarbons having 1 to 4 carbon atoms
Ethylene hydrocarbon with 2 to 4 carbon atoms, carbon number
Examples include 2 to 3 acetylene hydrocarbons. Specifically, methane is a saturated hydrocarbon.
(CH_Four), ethane (C₂H₆), propane (C₃H₈), n
-butane (n-C_FourH_Ten), pentane (C_FiveH₁₂),workman
Ethylene (C₂H_Four),
Propylene (C₃H₆), butene-1 (C_FourH₈), Butte
N-2 (C_FourH₈), isobutylene (C_FourH₈), pente
(C_FiveH_Ten), as acetylenic hydrocarbons,
Acetylene (C₂H₂), methylacetylene
(C₃H_Four), butin (C_FourH₆) etc. As a raw material gas containing Si, C, and H as constituent atoms
is Si(CH₃)4,Si(C₂H_Four)_Fouralkyl silicide such as
I can list the following. Group atoms or long wavelengths contained in group atoms
Forming a photosensitive layer, a charge injection blocking layer and a photoconductive layer
When using the glow discharge method to form the layer,
The starting material that becomes the raw material gas is
Starting material for forming optical layer, charge injection blocking layer and photoconductive layer
A suitable selection of substances may contain group atoms or
is added with starting material for introduction of group atoms
It is. Such a group atom or group atom conductor
Group atoms or group atom(s) are used as starting materials.
A gaseous substance or gasified substance whose constituent atoms are
Any gasified substance that can be used
It may be so. In the present invention, the starting material for introducing group atoms
Specifically, what can be effectively used as
B for introducing boron atoms₂H₆,B_FourH_Ten,B_FiveH₉，
B_FiveH₁₁,B₆H_Ten,B₆H₁₂,B₆H₁₄Boron hydride, such as
BF₃, BCl₃,BBr₃Boron halides such as
In addition, AlCl₃,GaCl₃,InCl₃，
TlCl₃etc. can also be mentioned. In the present invention, the starting material for introducing group atoms
Specifically, phosphorus atom conductors are effectively used as
For use, PH₃,P₂H_FourPhosphorus hydride, etc.
PH_FourI, P.F.₃,PF_Five, PCl₃, PCl_Five, PBr₃, PBr_Five，
P.I.₃Examples include halogenated phosphorus such as. In addition,
AsH₃,AsF₃,AsCl₃, AsBr₃,AsF_Five,SbH₃，
SbF₃,SbF_Five,SbCl₃,SbCl_Five, BiH₃, BiCl₃，
BiBr₃etc. can also be mentioned. Group atoms or long wavelength light containing group atoms
Photosensitive layer, charge injection blocking layer and photoconductive layer are introduced.
The content of group atoms or group atoms in the deposition chamber
for the introduction of group atoms or group atoms into
Starting material gas flow rate, gas flow rate ratio, discharge power,
Controlling support temperature, pressure inside the deposition chamber, etc.
Therefore, it can be controlled arbitrarily. In order to effectively achieve the purpose of the present invention,
The support temperature should be selected within the optimum range, but polycrystalline
A long-wavelength photosensitive layer and a charge injection layer composed of
When forming an entry blocking layer, preferably 200°C to 700°C
°C, more preferably 250 °C to 600 °C, constructed of amorphous material.
forming a long wavelength photosensitive layer and a photoconductive layer
preferably from 50℃ to 350℃, more preferably 100℃
It is desirable to set it as ℃~300℃. Long wavelength photosensitive layer in the present invention, charge injection prevention
The formation of layers and photoconductive layers involves
Fine control of composition ratio and layer thickness compared to other methods
Glow discharge method and spa
It is desirable to adopt the vine ring method, but these layered
Long wavelength photosensitive layer, charge injection blocking layer and light guiding layer
When forming a conductive layer, the temperature of the support is the same as above.
Similarly, during the formation of the layer, the discharge power and gas pressure created
Long wavelength photosensitive layer, charge injection blocking layer and photoconductive layer
It is an important factor that influences the properties of the layer. Long wavelength having characteristics that can achieve the purpose of the present invention
Productivity of photosensitive layer, charge injection blocking layer and photoconductive layer
In order to create a good and efficient discharge power
- Regarding the conditions, long-wavelength
When forming a long photosensitive layer and a charge injection blocking layer,
Preferably 100~5000W, more preferably 200~
It is desirable to set it to 2000W, and it is made of amorphous material.
When forming a long wavelength photosensitive layer and a photoconductive layer,
preferably 10~1000W, more preferably 20~
It is desirable to set it to 500W. Also, the gas in the deposition chamber
Regarding pressure, long wavelength light composed of polycrystalline materials
When forming a photosensitive layer and a charge injection blocking layer, preferred
Or 10^-3~0.8Torr, more preferably 5×10^-3~
It is desirable to set it to about 0.5 Torr, and it is made of amorphous material.
forming a long wavelength photosensitive layer and a photoconductive layer
If so, preferably 0.01 to 1 Torr, more preferably 0.1
It is desirable to set it to about 0.5 Torr. In the present invention, a long wavelength photosensitive layer, a charge injection
support temperature for creating the blocking layer and photoconductive layer;
The range described above as the desirable numerical range of discharge power
However, these layer formation factors
are not normally determined independently and separately.
A long-wavelength photosensitive layer with desired properties, a charge injection layer, etc.
mutually and
of each layer creation factor based on organic relevance.
It is desirable to determine the optimal value. In the present invention, contained in the photoconductive layer formed
The amount of carbon, oxygen or nitrogen formed is
It greatly influences the characteristics of light-receiving materials for electrophotography.
Therefore, it must be determined appropriately according to the desired
However, preferably 0.005 to 30 atom%, more preferably
is 0.001 to 20 at%, optimally 0.002 to 15 at%.
It is desirable that The layer thickness of the photoconductive layer has the desired spectral characteristics.
Photocarrier generated by irradiation with light
Decide as appropriate to ensure efficient transport of
usually 1 to 100μ, more preferably 2 to 50μ.
It is desirable that surface layer The surface layer formed on the photoconductive layer covers the free surface.
Mainly moisture resistance, continuous repeated use characteristics, electrical
The focus of the present invention is on pressure resistance, use environment characteristics, and durability.
It is established to achieve a goal. In the light-receiving member of the present invention, the surface layer and
At the interface with the photoconductive layer, the optical band of the quantum layer
If the gap is aligned or the surface layer and photoconductive layer
Can substantially prevent reflection of incident light at the interface
be configured to at least match the degree of
This is an extremely important point. At the same time, this
This has a very unique correlation with the hydrogen content.
It is also an important point to bring about favorable conditions.
It is. Furthermore, in the present invention, the surface of the surface layer
Hydrogen contained in the region close to, at least on the outermost surface
It is necessary to set the amount to a predetermined concentration. In order to satisfy the above conditions, the structural elements in the surface layer
The distribution state of the elements is determined under strict control of conditions.
I need to be kicked. Furthermore, in addition to the above conditions, the free surface side of the surface layer
At the edge of the
Ensuring sufficient amount of incident light reaches the photoconductive layer
The free surface edge of the surface layer
In some parts, the optical band gear that the surface layer has
Constructed to make Eopt sufficiently large
This is also something to consider. And the surface layer and light
Optical band gap at the interface with the conductive layer
Configure the Eopt to match and
Optical band gear at the free surface end of the layer
If you configure Eopt to be large enough,
In this case, the optical bandgap of the surface layer is
The area that changes continuously in the thickness direction of the surface layer
Constructed to include at least Optical bandgap Eopt layer thickness of surface layer
To control the value in the direction as described above, the representative
In other words, it is the main tuning atom of the optical bandgap.
The amount of carbon atoms (C) contained in the surface layer of
This can be done by controlling the
Other parts of the surface layer change in response to changes in dogpup.
Water that has the function of matching properties to optimal conditions
The content of the elements is also adjusted to achieve a specific distribution state.
Control. Below, the carbon and hydrogen atoms in the surface layer are
Some typical examples of distribution states are shown in Figures 25 to 25.
As will be explained with reference to FIG. 28, the present invention
The examples are not intended to be limiting. In Figures 25 to 28, the horizontal axis is the atom
Distribution concentration C of (C, Si) and atoms (H), vertical axis is surface
The layer thickness t of the layer is shown, and in the figure, t_Tis the photosensitive layer and the surface
Interface position with surface layer, t_Fis the free surface position, the solid line is the charcoal
Changes in the distribution concentration of elementary atoms (C), the chain double-dashed line is silicon
Changes in the distribution concentration of atoms (Si), and the dashed line indicates hydrogen
Each figure shows changes in the distribution concentration of atoms (H). Figure 25 shows carbon atoms (C) contained in the surface layer.
and layer thickness direction of silicon atoms (Si) and hydrogen atoms (H)
The first typical example of the distribution state is shown. In this example
is the interface position t_TMore position₁up to, the number of carbon atoms (C)
Cloth density C is less than zero₁linear function until
On the other hand, the distribution concentration of silicon atoms is
Concentration C₂From concentration C₃decreases linearly until
Also, the distribution concentration of hydrogen atoms is C_Fouror C_FiveTonaruma
increases linearly at position t₁from position t_Fwas in
Until carbon atoms (C), silicon atoms and hydrogen
The distribution concentration C of atoms is each concentration C₁and concentration C₃as well as
Concentration C_FiveFor convenience of explanation, we keep a constant value of
For convenience, let the inflection point of the distribution state of each component be t₁But
Even if they are shifted from each other, there is virtually no problem. In the example shown in FIG. 26, the position t_Tfrom position t_FMa
So, carbon atom (C) increases from zero to concentration C₆Until then, Siri
Con atom (Si) is C₇from C₈until, also, hydrogen atom
(H) is C₉from C_Tenup to
ing. In this example, the formation occurs over the entire surface layer.
The negative effects caused by the discontinuity of the components as the components change.
It is possible to further improve this. Also, for example, as shown in FIGS. 27 to 28, the components
A pattern in which the rate of change of
Combinations of the typical examples described in Figures 5 to 28 are also possible.
Depending on the desired film properties or manufacturing equipment conditions, etc.
can be selected as appropriate. Furthermore, the bandgi at the interface
As mentioned above, Yatsupu's consistency is practically sufficient.
In that sense, it is fine._Tamount of carbon in
is not necessarily 0, but may have a certain finite value,
In addition, the changes in the components stagnate over a certain period in the distribution region.
From this point of view, it is also permissible to do so. The surface layer is formed using glow discharge method or microwave discharge.
method, sputtering method, ion implantation method
Yon method, ion plating method, electron
This is done by the beam method, etc. How to make these
depends on manufacturing conditions, the level of capital investment, and manufacturing regulations.
It is desired for the electrophotographic light-receiving member to be produced.
be selected and adopted as appropriate depending on factors such as the characteristics
However, the electrophotographic light receiving part has the desired characteristics.
It is relatively easy to control the production conditions for manufacturing materials.
Ru. Carbon and hydrogen atoms along with silicon atoms
Easily introduced into the surface layer to be prepared, etc.
Glow discharge method or sputtering method is preferred due to the advantages of
Suitably adopted. Furthermore, in the present invention, glow discharge method and spatula
The surface layer is
It may be formed. To form the surface layer by glow discharge method,
Even in the distribution area of the constituent elements, in a certain area
are also basically the same A-(Si_XC_1-X)_y:H_1-yfor forming
Mix a predetermined amount of raw material gas with dilution gas as needed
For vacuum deposition with mixed ratio and support installed
is introduced into the deposition chamber, and the introduced gas is glow discharged.
The support is converted into gas plasma by generating
A-(Si_X
C_1-X)_y:H_1-yAll you have to do is deposit it. distribution area
The formation is carried out by modifying the components, e.g. carbon-containing gases.
gas, silicon atom-containing gas, hydrogen atoms, etc.
The desired distribution pattern is achieved from the starting flow rate.
increase or decrease according to a specific sequence set to
If you let it, it will be prepared. In the present invention, A-(Si_XC_1-X)_y:H_1-yraw material for formation
At least one of Si, C, and H is used as the source gas.
A gaseous substance or gasifying substance whose constituent atoms are
Most of the gasified substances used are
can be done. Si is one of the constituent atoms among Si, C, and H.
For example, when using raw material gas containing Si as a component gas,
A raw material gas containing C as a constituent atom and a raw material gas containing C as a constituent atom.
A desired mixture of gas and raw material gas containing H as a constituent atom is formed.
Use by mixing in a composite ratio, or use Si as a constituent atom.
A raw material gas containing C and H as its constituent atoms
and the feed gas at the desired mixing ratio.
Or, a raw material gas containing Si as a constituent atom,
A raw material gas containing three constituent atoms: Si, C, and H.
Can be used in combination. In addition, there is also a raw material gas whose constituent atoms are Si and H.
mixed with raw material gas containing C as a constituent atom.
You may do so. In addition, in the division area, the above mixture
It is only necessary to change the rate according to a predetermined sequence.
stomach. In the present invention, the raw material gas for forming the surface layer is
What is effectively used is Si and H as constituent atoms.
SiH_Four,Si₂H₆,Si₃H₃,Si_FourH_TenSilane etc.
Silicon hydride gas such as (Silane), which consists of C and H.
For example, saturated hydrocarbons having 1 to 4 carbon atoms
Ethylene hydrocarbon with 2 to 4 carbon atoms, carbon number
Examples include 2 to 3 acetylene hydrocarbons. Specifically, methane is a saturated hydrocarbon.
(CH_Four), ethane (C₂H₆), propane (C₃H₈), n
-butane (n-C_FourH_Ten), pentane (C_FiveH₁₂),workman
Ethylene (C₂H_Four),
Propylene (C₃H₆), butene-1 (C_FourH₈), Butte
N-2 (C_FourH₈), isobutylene (C_FourH₈), pente
(C_FiveH_Ten), as acetylenic hydrocarbons,
Acetylene (C₂H₂), methylacetylene
(C₃H_Four), butin (C_FourH₆) etc. As a raw material gas containing Si, C, and H as constituent atoms
is Si(CH₃)_Four,Si(C₂H_Five)_FourAlkyl silicide such as
I can list them. In addition to these raw material gases, H
Of course, H is used as the raw material gas for introduction.₂is also valid
used as. To form a surface layer by sputtering method
is a single crystal or polycrystalline Si wafer or C wafer.
-Har or curing containing a mixture of Si and C
These can be used as targets for various types of gas.
This can be done by sputtering in a gas atmosphere.
Good. For example, using a Si wafer as a target
Then, the raw material gas for introducing C and H is required.
Deposit for sputtering by diluting with diluent gas according to
These gases are introduced into the chamber to form a gas plasma.
If the above-mentioned Si wafer is sputtered with
good. In this case, the distribution area is, for example, a C-containing area.
The raw material gas concentration is changed according to a certain sequence.
Just let it happen. Additionally, Si and C are separate targets.
or using a single target with a mixture of Si and C.
containing at least a hydrogen atom.
by sputtering in a gas atmosphere that
It will be done. In this case, the distribution area is C or Si
Combined with a gas containing at least one of the following:
and the concentrations of these gases follow a certain sequence.
It is necessary to make changes. As the raw material gas for introducing C or H, the above-mentioned
The raw material gas shown in the glow discharge example is
It can also be used as an effective gas in the case of
In the present invention, the surface layer is formed using a glow discharge method or a sputtering method.
Diluent gas used when forming by the tuttering method
So-called rare gases, such as He, Ne, Ar
etc. can be mentioned as suitable ones. The surface layer in the present invention is as described above.
It has a distribution area according to the principle of
The required characteristics are as desired from the perspective of all layers.
It is carefully formed so that it can be given to the child. That is, a substance whose constituent atoms are Si, C, and H is
Depending on its creation conditions, the structure varies from crystal to amorphous.
It takes the form of up to FAS, and is electrically conductive in terms of electrical properties.
properties ranging from conductivity to insulation, and photoconductivity.
properties ranging from photoconductive properties to non-photoconductive properties.
Therefore, in the present invention, the desired
A-Si with the characteristics of_XC_1-Xso that it is formed,
The selection of the production conditions is made strictly according to the desired
Ru. For example, the main purpose of the surface layer is to improve pressure resistance.
A-(Si_XC_1-X)_y:H_1-yis the usage environment
Amorphous materials with remarkable electrically insulating behavior in
and arranged. In addition, improvements in continuous repeated use characteristics and usage environment characteristics
When the surface layer is provided primarily for the purpose of
The above degree of electrical insulation is relaxed to some extent, and
Amorphous that has a certain degree of sensitivity to the light that is emitted
A-Si as a quality material_XC_1-Xwill be arranged. A-(Si_XC_1-X)_yH_1-yconsists of
When forming the surface layer, the support temperature during layer formation is
Important factors that influence the structure and properties of the formed layer
In the present invention, the desired characteristics
(A-Si_XC_1-X)_yH_1-ycreated as desired
The support temperature during layer creation is strictly controlled so that
It is desirable that In order to effectively achieve the purpose of the present invention,
The support temperature when forming the surface layer is
The optimal range is selected according to the layer formation method,
Formation of the surface layer is carried out, preferably at 50°C
~350℃, more preferably 100℃~300℃
is desirable. To form the surface layer, layer
Subtle control of the composition ratio of constituent atoms and control of layer thickness
This is because it is relatively easy compared to other methods.
Advantages of using glow discharge method and sputtering method
However, the surface layer is formed using these layer formation methods.
In this case, the temperature of the support may be changed during layer formation as well as
A-(Si_X
C_1-X)_y:H_1-yOne of the important factors that influences the characteristics of
It is one. Having the characteristics to achieve the purpose of the present invention
A-(Si_XC_1-X)_y:H_1-ybe productive and effective
The preferable discharge power conditions for creating
preferably 10-1000W, more preferably 20-500W.
It is desirable that The gas pressure in the deposition chamber is favorable
is about 0.01 to 1 Torr, more preferably about 0.1 to 0.5 Torr
It is desirable that this is done. In the present invention, the support for creating the surface layer is
The desired numerical ranges for body temperature and discharge power are
The values in the range shown are listed, but these layers cannot be created.
Factors can be determined independently and separately.
A-Si with desired characteristics_XC_1-Xsurface layer consisting of
based on mutual organic relationships so that
Therefore, the optimal value of each layer formation factor can be determined.
is desirable. Surface layer in the electrophotographic light-receiving member of the present invention
The amount of carbon atoms and hydrogen atoms contained in
As described above, the objective of the present invention is as well as the preparation conditions of the surface layer.
A surface layer is formed that achieves the desired properties.
This is an important factor. Carbon contained in the surface layer 105 in the present invention
The amount of atoms is similar to that of silicon atoms in the distribution region.
Usually 0 to 90 atom% based on the total amount of carbon atoms,
Preferably 0 to 85 atom%, optimally 0 to 80 atom%
It is desirable to vary within a certain range.
Usually 1×10^-3~90 atom%, preferably
It is considered to be 1 to 90 at%, optimally 10 to 80 at%.
is desirable. As the content of hydrogen atoms
is relative to the total amount of constituent atoms in the distribution region.
It is constant or variable within the range of 1 to 70 atomic%.
It is desirable that the
Usually 41 to 70 atom% on the outermost surface, suitable
It is desirable that the content be 45 to 60 atom%. The amount range and the distribution state as described above as well as the above
Light with a surface layer created under the stated manufacturing conditions
The receiving member is actually much superior to conventional ones.
It can be fully applied as a standard. below
The effect will be explained using a few examples. First, we will discuss the consistency aspect of the band gap.
For example, the conventional surface layer and photoconductive layer
If there is a clear optical interface between
Reflection of the incident light occurs at the interface, but this and the free
to the photoconductive layer due to interference of reflections on the surface.
There is a phenomenon in which the amount of incident light is affected to some extent.
It will be done. In particular, coherent light, e.g. a laser, is used as a light source.
This tendency is noticeable when using laser light, etc.
Ru. On the other hand, for example, using the blade cleaning method
In the case of copiers, the surface layer may deteriorate due to long-term use.
Although some wear is inevitable, this
The change in the thickness of the surface layer that results in wear is due to the interference state mentioned above.
effect change; i.e. light by abrasion
The fact that the amount of light incident on the conductive layer is influenced to some extent.
This means that you can see an elephant. Control of bandgap integrity in the present invention
One is that the reflection at the interface is a plane of continuity of the components.
One aspect is that it has the effect of minimizing the
Also, the band gap is changed.
By doing so, the light absorption property itself has continuity.
This produces two favorable effects: accordingly
Among the preferable electrophotographic properties already mentioned,
Outstanding effectiveness in maintaining properties during long-term use.
The noteworthy effect in this case is to show
It can be said. Next, we will discuss the role of hydrogen in the surface layer. Defects present in the surface layer (mainly silicon atoms and
Dangling bonds of carbon atoms) are used as light for electrophotography.
Known to have an adverse effect on properties as a receiving member.
For example, bands due to charge injection from the free surface
Deterioration of electrical characteristics, use environment, such as high humidity
Fluctuations in charging characteristics due to changes in surface structure;
Furthermore, during corona charging or light irradiation, the surface of the photoconductive layer
Charge is injected into the layer and defects in the surface layer are charged.
Afterimage during repeated use due to being trapped
Examples include phenomena. However, if the hydrogen content in the surface layer is reduced,
can be controlled to 41 atomic% or more in the outermost surface area.
All of the above problems are solved, especially the conventional one.
In terms of electrical characteristics and high-speed continuous use compared to
It is possible to measure dramatic improvements. On the other hand, the hydrogen content in the surface layer is 71 atomic% or more.
As the hardness of the surface layer decreases,
Cannot withstand repeated use. Therefore, water in the surface layer
It is much easier to control the elemental content within the above range.
Very important in obtaining excellent desired electrophotographic properties
This is one of the important factors. The hydrogen content in the surface layer is
H₂Gas flow rate, support temperature, discharge power, gas
It can be controlled by pressure, etc. In addition, the consistency of the band gap and the hydrogen content
There is also a unique correlation between
Carbon atom (C), which is a typical variable component of Yatsupu
In the fabric area, the hydrogen content is
So as to optimize the structure of or dung
Its content is designed to minimize ring bonds.
and the role of hydrogen in the surface layer.
so that it has the value necessary to achieve the effect described in
In other words, at least towards the free surface side, hydrogen
The most unreasonable way to create a tendency toward increasing volume is to
It is set to no shape. Therefore, the hydrogen-containing state of the surface layer in the present invention
is the effect of bandgap integrity and hydrogen content.
The effects of itself will be maximized together.
Another goal is to match the sea urchins and sea urchins.
It can be said that it also has an effect. Halogen atoms may be included in the surface layer.
stomach. A method of containing halogen atoms in the surface layer and
For example, SiF is added to the raw material gas._Four,SiFH₃,Si₂F₆，
SiF₃SiH₃,SiCl_Foursilicon halide gas such as
Mix or/and CF_Four,CCl_Four,CH₃C.F.₃
Glow discharge by mixing halogenated carbon dioxide gas such as
It may be formed by a decomposition method or a sputtering method. The numerical range of the layer thickness in the present invention is
It is one of the important factors to effectively achieve the target.
Ru. The numerical range of the layer thickness of the surface layer in the present invention is
To the intended purpose so as to effectively achieve the purpose of the invention
It can be determined as appropriate and desired. Also, the thickness of the surface layer is related to the thickness of the photoconductive layer.
Even in
Determined as appropriate based on the organic relationship between
need to be done. In addition, productivity and
Economic efficiency including productivity is also taken into consideration.
is desirable. The thickness of the surface layer in the present invention is preferably
preferably 0.003 to 30μ, more preferably 0.004 to 20μ, optimal
It is desirable that the value be 0.005 to 10μ.
Ru. The light receiving member 100 for electrophotography according to the present invention
The thickness of the photoreceptive layer can be adjusted as desired depending on the purpose.
To be determined accordingly. In the present invention, the layer thickness of the photoreceptive layer is as follows:
It is added to the photoconductive layer and surface layer that make up the photoreceptive layer.
The objectives of the present invention can be achieved by effectively utilizing each of the characteristics
The layer thickness relationship between the photoconductive layer and the surface layer is
It shall be decided as appropriate and according to the wishes of the concerned parties.
and preferably the thickness of the photoconductive layer relative to the layer thickness of the surface layer.
It is preferable that the layer thickness is several hundred to several thousand times or more.
It's a beautiful thing. In the electrophotographic light receiving member of the present invention, the support
Improved adhesion between the support 101 and the photoconductive layer
For the purpose of measuring the upper₃N_Four, SiO₂,SiO,water
At least one of elementary atoms and halogen atoms and nitrogen
At least one of elementary atoms, oxygen atoms, and silicon
An adhesion layer made of an amorphous material containing atoms, etc.
It may be provided. Next, the light guide formed by glow discharge decomposition method
A method of manufacturing an electric member will be explained. Figure 24 shows electrophotography using glow discharge decomposition method.
1 shows an apparatus for manufacturing a light-receiving member. 1102, 1103, 1104, 110 in the diagram
No. 5,1106 gas cylinders have each of the present invention.
The raw material gas for forming the layer is sealed,
As an example, 1102 is SiH_Four(purity
99.999%) cylinder, 1103 is H₂diluted with
B₂H₆Gas (purity 99.999%, below B₂H₆/H₂Abbreviation
vinegar. ), 1104 is H₂Gas (99.99999% purity) bottle
1105 is NO gas (99.999% purity) cylinder
Be, 1106 is CH_FourGas (99.99% purity) cylinder
It is. To allow these gases to flow into the reaction chamber 1101
is the valve 112 of the gas cylinders 1102 to 1106
2-1126, leak valve 1135 is closed
Also, check that the inflow valves 1112~
1116, outflow valve 1117-1121, auxiliary
Check that valves 1132 and 1133 are open.
After checking, first open the main valve 1134 and react.
The chamber 1101 and the gas piping are evacuated. Next, the vacuum gauge
The reading of 1136 is approximately 5×10^-6As soon as it becomes torr
Auxiliary valves 1132, 1133, outflow valve 11
Close 17-1121. Next, on the cylindrical base 1137, as shown in FIG.
When forming an electrophotographic light-receiving member with a layer structure
For example, from gas cylinder 1102
SiH_FourGas, H from gas cylinder 1104₂gas
B from Sbonbe 1103₂H₆/H₂gas, gas bottle
NO gas is supplied from valve 1105 to valve 1122.
~1125 open and outlet pressure gauge 1127~11
30 pressures each 1Kg/cm²Adjust the inflow valve 1 to
Gradually open each of 112 to 1115, and
into the controllers 1107 to 1110, respectively.
let Subsequently, the outflow valves 1117-1120
Gradually open the auxiliary valve 1132 to supply each gas.
It is made to flow into the reaction chamber 1101. SiH at this time_Four
Gas flow rate and B₂H₆/H₂Gas flow rate, NO gas flow rate and
Outflow pulse 1117 such that the ratio of
~1120 and also the desired pressure in the reaction chamber.
Check the reading on the vacuum gauge 1136 so that the value is
Then adjust the opening of the main valve 1134. stop
The temperature of the base cylinder 1137 is increased by the heating heater.
1138 to a temperature range of 50 to 350℃.
After confirming that the power supply 1140 is
Glow discharge is generated in the reaction chamber 1101 by setting the power to
and at the same time a pre-designed rate of change.
B according to the curve₂H₆/H₂Gas or/and NO gas
Flow rate can be adjusted manually or by external drive motor, etc.
Therefore, valves 1118 and/or 1120 are gradually
Contained in a layer formed by performing an operation to change
of boron atoms and/or oxygen atoms in the layer thickness direction
Control distribution concentration. As described above, boron atoms and oxygen atoms are added to the desired layer thickness.
When the charge injection blocking layer containing the particles is formed
Then close the outflow valves 1120 and 1118 and
B to reception room 1101₂H₆/He gas and NO gas
At the same time, the outflow valves 1117 and 1
SiH by adjusting 119_Fourgas and H₂gas flow rate
By controlled and subsequent layer formation, acid
Charge a photoconductive layer that does not contain elementary atoms or boron atoms.
A desired layer thickness is formed on the injection blocking layer. Also, light containing oxygen atoms and/or boron atoms
When forming a conductive layer, the outflow valve 1118 or
to the desired flow rate instead of closing 1120.
Just adjust it. Halogen atoms in charge injection blocking layer and photoconductive layer
If the above gas contains SiF, for example,_FourGa
Further add gas and send it into the reaction chamber 1101.
nothing. Depending on the gas type selected when forming each layer, the layer
The formation rate can be further increased. for example
SiH_FourSi instead of gas₂H₆Layer formation using gas
If you do this, you can increase it several times and improve productivity.
do. A surface layer is placed on the photoconductive layer created as described above.
To form the photoconductive layer, a barrier similar to that used in forming the photoconductive layer is used.
For example, SiH_Fourgas, CH_Fourgas
And H as necessary₂etc. to the desired dilution gas.
Flow into the reaction chamber 1101 at a flow rate ratio to achieve desired conditions.
Therefore, by generating glow discharge,
be done. The amount of carbon atoms contained in the surface layer is, for example,
SiH_FourGas and CH_FourGas is introduced into the reaction chamber 1101.
Arbitrarily changing the input flow rate ratio as desired
can be controlled as desired. Also, the amount of hydrogen atoms contained in the surface layer is
Ba, H₂A flow of gas introduced into the reaction chamber 1101
by arbitrarily varying the amount as desired.
It can be controlled as desired. Outflow of gases other than those required to form each layer
It goes without saying that all valves are closed, and
When forming each layer, remove the gas used to form the previous layer.
inside the reaction chamber 1101, outflow valves 1117-1
Remains in the piping from 121 to reaction chamber 1101
In order to avoid the outflow valve 1117~
1121 and open the auxiliary valve 1132 to
Fully open the in-valve 1134 to create a high vacuum inside the system.
Perform the operation to exhaust the air as necessary. Also, while forming layers, make sure that the layer formation is uniform.
For this purpose, the base cylinder 1137 is connected to the motor 11.
Rotate constantly at the desired speed by 39
Ru. Example 1 Using the manufacturing equipment shown in Figure 24, the manufacturing conditions shown in Table 1
on an aluminum cylinder with a mirror finish according to
A light receiving member for electrophotography was formed. Also, Figure 24
using the same type of equipment and on a cylinder with the same specifications.
Those with only a charge injection blocking layer and long wavelength light
Samples with only the photosensitive layer formed are used for analysis.
Prepared separately as a pull. Light-receiving member (hereinafter referred to as
(expressed as ram) has a wavelength of 780 nm.
A digital exposure function using a conductor laser as a light source.
Set it on the secondary photographic device and take pictures under various conditions.
Electrophotography of initial chargeability, residual potential, ghost, etc.
We checked the characteristics and also tested the belt after 1.5 million sheets of actual machine durability.
We investigated the decrease in power, sensitivity deterioration, and increase in image defects.
In addition, the driver can be operated in a high temperature and high humidity atmosphere of 35℃ and 85%.
We also evaluated the image flow in the images. And evaluation
The completed drum corresponds to the top, middle, and bottom of the image area.
Cut out the part and use SIMS to measure the inside of the surface layer.
The sample was subjected to quantitative analysis of hydrogen contained in the sample. Also, electric charge Note
Sample with only entry blocking layer and only long wavelength photosensitive layer
The sample was cut out in the same manner and then subjected to X-ray treatment.
Using a diffraction device, we focused on Si111 with a diffraction angle of around 27°.
Obtain the corresponding diffraction pattern and examine the presence or absence of crystallinity.
Ta. The above evaluation results and the hydrogen content in the surface layer
Maximum value, plus charge injection blocking layer and long wavelength photosensitive layer
The presence or absence of crystallinity is summarized in Table 2. Table 2
As seen in Figure 2, the initial charging ability, image blur, and residual
Increase in storage potential, ghost, image defects and generatrix direction
Significant problems such as uneven light sensitivity and deterioration of sensitivity
superiority was recognized. Comparative example 1 Implemented except that the manufacturing conditions were changed as shown in Table 3.
Drum and analytical sample were prepared using the same equipment and method as in Example 1.
A pull was created and subjected to similar evaluation and analysis. the
The results are shown in Table 4. As seen in Table 4, there are various differences compared to Example 1.
It was recognized that the performance was inferior in the following items. Example 2 Using the manufacturing equipment shown in Figure 24, the manufacturing conditions shown in Table 5
on an aluminum cylinder with a mirror finish according to
A light-receiving member for electrophotography was formed. Also, Figure 24
using the same type of equipment and on a cylinder with the same specifications.
Forming only a charge injection blocking layer and a long wavelength photosensitive layer
The results obtained can be used separately as samples.
I meant it. For the light-receiving member (hereinafter referred to as drum)
is a semiconductor laser with a wavelength of 780 nm.
It is set in an electrophotographic device with digital exposure function as a source.
The initial charging capacity and residual
Check electrophotographic characteristics such as retention potential and ghost
However, the charging ability and sensitivity decrease after 1.5 million sheets of actual machine durability.
Deterioration and increase in image defects were investigated. Furthermore, 35℃, 85
% of image drift on the drum in a high temperature and high humidity atmosphere.
I also evaluated it. Then, the driver whose evaluation has been completed
The image is cut off at the top, middle, and bottom of the image.
hydrogen contained in the surface layer using SIMS.
It is also used for quantitative analysis of silico in the surface layer.
Layer thickness of carbon atoms (Si), carbon atoms (C), and hydrogen atoms (H)
We investigated the component profile in the direction of Furthermore, the charge Note
Boron (B) and oxygen (O) in the layer thickness direction in the entry blocking layer
component profile and long wavelength photosensitive layer of
Germanium (Ge) composition profile in the layer thickness direction
I looked into the aisle. On the other hand, the charge injection blocking layer alone is
Samples and samples with only long wavelength photosensitive layer
was cut out in the same manner and diffracted using an X-ray diffraction device.
The diffraction pattern corresponding to Si111 around the 27° angle is
The presence or absence of crystallinity was investigated. The above evaluation results and
Maximum value of hydrogen content in surface layer and charge injection
Comprehend the presence or absence of crystallinity of the blocking layer and the long wavelength photosensitive layer.
are shown in Table 6. Furthermore, the element in the above surface layer
The component profile is shown in Figure 31.
Component profile of the element in the stop layer and the above long wavelength
The component profile of the element in the long-photosensitive layer is determined first.
Shown in Figure 32. As shown in Table 6, especially initial chargeability and residual
Potential, ghost, image deletion, image defect, image defect
increase, uneven light sensitivity in the generatrix direction, sensitivity deterioration and interference
Remarkable superiority has been recognized across many types and items of stripes.
It was done. Example 3 (Comparative example 2) The surface layer was prepared under several conditions shown in Table 7.
other than that, under the same conditions as Example 1.
A drum was formed and subjected to the same evaluation. stop
After the evaluation was completed, the drum was placed in the same manner as in Example 1.
cut out and use it as a sample for similar analysis.
I got it. The above results are shown in Table 8. Example 4 Several conditions for producing the photoconductive layer are shown in Table 9.
, and the other conditions were the same as in Example 1.
I prepared several drums. Examples of these drums
The results of the same evaluation as in 1 are shown in Table 10.
I got good results. Example 5 Several conditions for preparing the charge injection blocking layer are shown in Table 11.
The conditions were changed to , and the other conditions were the same as in Example 1.
Forming only multiple drums and charge injection blocking layer
A sample was prepared. These drums and
The sample for analysis was evaluated and analyzed in the same manner as in Example 1.
As a result, the results shown in Table 12 were obtained. Example 6 Table 13 shows several conditions for preparing the charge injection blocking layer.
The conditions were changed to , and the other conditions were the same as in Example 1.
Forming only multiple drums and charge injection blocking layer
A sample was prepared. These drums and
The sample for analysis was evaluated and analyzed in the same manner as in Example 1.
As a result, the results shown in Table 14 were obtained. Example 7 Several conditions for producing the long wavelength photosensitive layer are shown in Table 15.
The conditions were changed to , and the other conditions were the same as in Example 1.
Forms only multiple drums and long wavelength photosensitive layer
A sample for analysis was prepared. drum person
was subjected to the same evaluation as in Example 1, and the sample
If so, cut out a part and diffract it using an X-ray diffraction device.
The diffraction pattern corresponding to Si111 around the 27° angle is
The presence or absence of crystallinity was investigated. Table 16 shows the above results.
Shown below. Example 8 Several conditions for producing the long wavelength photosensitive layer are shown in Table 17.
The conditions were changed to , and the other conditions were the same as in Example 1.
Forms only multiple drums and long wavelength photosensitive layer
A sample for analysis was prepared. As for the drums
The sample was subjected to the same evaluation as in Example 1.
Cut out a part and measure the diffraction angle using an X-ray diffraction device.
Find the diffraction pattern corresponding to Si111 around 27°.
The presence or absence of crystallinity was investigated. The above results are shown in Table 18.
show. Example 9 Several conditions for producing the long wavelength photosensitive layer are shown in Table 19.
The conditions were changed to , and the other conditions were the same as in Example 1.
Forms only multiple drums and long wavelength photosensitive layer
A sample for analysis was prepared. As for the drums
The sample was subjected to the same evaluation as in Example 1.
Cut out a part and measure the diffraction angle using an X-ray diffraction device.
Find the diffraction pattern corresponding to Si111 around 27°.
The presence or absence of crystallinity was investigated. The above results are shown in Table 20.
show. Example 10 Several conditions for producing the long wavelength photosensitive layer are shown in Table 21.
The conditions were changed to , and the other conditions were the same as in Example 1.
Forms only multiple drums and long wavelength photosensitive layer
A sample for analysis was prepared. As for the drums
The sample was subjected to the same evaluation as in Example 1.
Cut out a part and measure the diffraction angle using an X-ray diffraction device.
Find the diffraction pattern corresponding to Si111 around 27°.
The presence or absence of crystallinity was investigated. The above results are shown in Table 22.
show. Example 11 Several types of fabrication strips shown in Table 23 are formed on the base cylinder.
Under certain conditions, an adhesion layer is formed and further applied on top of it.
Forming a light-receiving member under the same manufacturing conditions as Example 1
did. A sample with only an adhesion layer formed
I prepared a file. The light receiving member is the same as in Example 1.
In addition, some of the samples were cut out.
Si1 with a diffraction angle of around 27° was taken out using an X-ray diffraction device.
Obtain the diffraction pattern corresponding to 11 and determine the presence or absence of crystallinity.
I looked into it. The above results are shown in Table 24. Example 12 Several types of fabrication strips shown in Table 25 are formed on the base cylinder.
Under certain conditions, an adhesion layer is formed and further applied on top of it.
Forming a light-receiving member under the same manufacturing conditions as Example 1
did. A sample with only an adhesion layer formed
I prepared a file. The light receiving member is the same as in Example 1.
In addition, some of the samples were cut out.
Si1 with a diffraction angle of around 27° was taken out using an X-ray diffraction device.
Obtain the diffraction pattern corresponding to 11 and determine the presence or absence of crystallinity.
I looked into it. The above results are shown in Table 24. Example 13 The mirror-finished cylinder can be viewed from various angles.
Figure 29.
With the cross-sectional shape as shown in Table 27, various cross-sectional patterns are available.
Multiple cylinders with turns were prepared. The
Set the cylinders one after another in the manufacturing equipment shown in Figure 24,
A drum was manufactured under the same manufacturing conditions as in Example 1.
Ta. The created drum has a wavelength of 780nm
Digital exposure function using a semiconductor laser as a light source
Various evaluations were conducted using the electrophotographic equipment, and the 28th
Obtained the results in the table. Example 14 Continue to polish the mirror-finished surface of the cylinder.
The series is exposed to the dropping of many bearing balls.
This causes countless dents on the surface of the so-called
The surface is dimpled, as shown in Figure 30.
Various cross-sectional patterns as shown in Table 29 can be created by cross-sectional shape.
I prepared multiple cylinders to hold. the cylinder
were sequentially set in the manufacturing equipment shown in Fig. 24, and Example 1
A drum was fabricated under the same fabrication conditions. created
The drum is equipped with a semiconductor laser with a wavelength of 780 nm.
Electronic photography with digital exposure function using a laser as a light source
Various evaluations were performed using the equipment, and the results in Table 30 were
Obtained.

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[Summary of effects of the invention]

The light-receiving member of the present invention has a photoconductive layer composed of A-Si (H, It can solve all the problems with conventional electrophotographic light-receiving members composed of (H, It is something that has gender, etc. In addition, there is no influence of residual potential and its electrical characteristics are stable, and the images obtained using it have high density and
The results are excellent, with clear halftones and other features. In particular, in the electrophotographic light-receiving member of the present invention, by providing a charge injection blocking layer, it has become possible to use a relatively low-resistance photoconductive layer that is sensitive to light in a relatively wide range of wavelengths. . Furthermore, due to the specific layer structure described above, a large number of charges that are irradiated with light and thermally excited are swept out sufficiently quickly not only in the photoconductive layer but also in the charge injection blocking layer and the surface layer. No residual potential or ghosting occurs even under exposure conditions.
Moreover, high-resolution, high-quality images can be stably and repeatedly obtained.

[Brief explanation of the drawing]

1-1 and 1-2 are schematic layer configuration diagrams for explaining the layer configuration of the electrophotographic light-receiving member of the present invention, and FIGS. 2 to 7 are long-wavelength photosensitive layers, respectively. FIGS. 8 to 12 are explanatory diagrams for explaining the distribution state of germanium atoms constituting the charge injection blocking layer, respectively. , FIG. 13 to FIG. 19 are explanatory diagrams for explaining the distribution state of oxygen atoms or nitrogen atoms constituting the charge injection blocking layer, respectively, and FIG. 20 to FIG. 22 are explanatory diagrams for explaining the uneven shape of the support surface and the FIG. 23 is an explanatory diagram of another electrophotographic light-receiving member of the present invention, and FIG. 24 is a light-receiving layer of the electrophotographic light-receiving member of the present invention. FIG. 2 is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method, which is an example of an apparatus for forming a . Figures 25 to 28 are distribution charts showing the distribution of carbon atoms and hydrogen atoms; Figure 29;
FIG. 30 is a schematic diagram showing the shape of the support, and FIGS. 31 and 32 are distribution diagrams showing the distribution of each atom in the layer. Regarding Figures 1-1 and 1-2, 100...
...Photoreceptive layer, 101...Support, 102...Long wavelength photosensitive layer, 103...Charge injection blocking layer, 104
... photoconductive layer, 105 ... surface layer, 106 ... free surface, 107 ... adhesion layer, regarding Fig. 23,
2300...Photoreceptive layer, 2301...Support, 2
302... Long wavelength photosensitive layer, 2303... Charge injection blocking layer, 2304... Photoconductive layer, 2305...
Surface layer, 2306...free surface, FIG. 21, 2
Regarding Figure 2, 1601, 1701...Support,
1602, 1702...Support surface, 1603,
1703... Rigid true sphere, 1604, 1704...
Regarding the spherical trace depression, Fig. 24, 1101...
Reaction chamber, 1102-1106...Gas cylinder, 1
107-1111...Mass flow controller, 1
112-1116...Inflow valve, 1117-1
121...Inflow valve, 1122-1126...
Valve, 1127-1131...Pressure regulator, 1
132, 1133...Auxiliary valve, 1134...
Main valve, 1135...Leak valve, 11
36... Vacuum gauge, 1137... Base cylinder,
1138... Heater, 1139... Motor, 1140... High frequency power supply.

Claims (1)

[Claims] 1. A support, which contains silicon atoms and germanium atoms on the support, and is made of an inorganic material,
A long-wavelength photosensitive layer sensitive to long-wavelength light; a charge injection blocking layer made of a polycrystalline material containing silicon atoms as a matrix and containing atoms belonging to Group 1 or Group 3 of the periodic table; The base material is an amorphous material containing at least one of a hydrogen atom and a halogen atom as a constituent element,
a photoreceptive layer having a photoconductive layer exhibiting photoconductivity and a surface layer made of an amorphous material containing silicon atoms, carbon atoms, and hydrogen atoms as constituent elements; The concentration distribution of the constituent elements in the layer thickness direction is changed such that the concentration of the carbon atoms decreases toward the interface between the surface layer and the photoconductive layer, and the concentration distribution of the hydrogen atoms in the layer thickness direction is changed. A light-receiving member for electrophotography, characterized in that the maximum concentration in the surface layer of is 41 to 70 atomic %. 2. The light-receiving member for electrophotography according to claim 1, wherein the distribution region of the constituent elements of the surface layer is present on the support side of the surface layer. 3. The light-receiving member for electrophotography according to claim 1, wherein the distribution area of the constituent elements of the surface layer extends over the entire surface layer. 4. Claims 2 and 3, wherein the surface layer contains carbon atoms in a distribution state in which carbon atoms are distributed more toward the surface side in the distribution region of the constituent elements.
2. The electrophotographic light-receiving member described in 1. 5. The light-receiving member for electrophotography according to claims 1 to 4, wherein the surface layer contains hydrogen atoms in a distribution state in which hydrogen atoms are distributed more toward the surface side in the distribution region of the constituent elements. . 6. The electrophotographic light-receiving member according to claim 1, wherein the surface layer contains halogen atoms. 7. The electrophotographic light-receiving member according to claim 1, wherein the photoconductive layer contains at least one of carbon atoms, oxygen atoms, and nitrogen atoms. 8. The electrophotographic light-receiving member according to claim 1, wherein the charge injection blocking layer contains at least one of oxygen atoms and nitrogen atoms. 9. The electrophotographic light according to Claims 1 and 8, wherein the charge injection blocking layer contains atoms belonging to Group 1 or Group 3 of the periodic table in a distribution state in which the charge injection blocking layer is distributed more toward the support side. Receptive member. 10. The electrophotographic light-receiving member according to claims 8 and 9, wherein the charge injection blocking layer contains at least one of oxygen atoms and nitrogen atoms in a distribution state in which the charge injection blocking layer is distributed in large quantities on the support side. 11. The electrophotographic light-receiving member according to claims 8 to 10, wherein at least one of oxygen atoms and nitrogen atoms contained in the charge injection blocking layer is present on the support side. 12. The electron according to claims 1 to 11, wherein the long wavelength photosensitive layer contains at least one of an atom belonging to Group 1 or Group 3 of the periodic table, an oxygen atom, and a nitrogen atom. Photographic light-receiving member.