JPS59129858A - Photoconductive material - Google Patents

Abstract

PURPOSE:To obtain a long-lived a-Si insusceptible of an effect of the material of a substrate and good in photosensitivity characteristics in the side of long wavelengths by forming a specified photoconductive amorphous layer consisting of a 3-layer structure on the substrate. CONSTITUTION:An amorphous layer 102 is formed on a substrate 101 to prepare a photoconductive material 100. The layer 102 is composed of Ge or Ge and Si as a base material optionally contg. H or halogen when needed, and it consists of the first layer 106 at least a part of which crystallizes, the second layer 103 of amorphous Si (a-Si) contg. Ge, and the third photoconductive layer 104 of a-Si. Moreover, a conductivity governing substance, such as B or Ga for p type impurity, P or As for n type impurity, is added to at last one of the first and second layers 106, 103. A mark 105 stands for a free surface.

Description

Detailed Description of the Invention The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (herein, light in a broad sense refers to ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, etc.). As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it has high sensitivity and a high signal-to-noise ratio [photocurrent (Ip)].
/dark current (■d)], has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has the desired dark resistance value, and has low resistance to the human body during use. Solid-state imaging devices are required to have characteristics such as being non-polluting and being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member that is installed in an electrophotographic apparatus used in an office, the above-mentioned non-polluting property during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as a-8i) is a photoconductive material that has recently attracted attention.
Publication No. 855718 describes an image forming member for electrophotography,
DE 2933411 describes an application to a photoelectric conversion reader.

On the other hand, photoconductive members having conventional photoconductive layers composed of a-Si have excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics such as, and furthermore, stability over time, which requires comprehensive improvement of characteristics.

For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use. When a photoconductive member is used repeatedly for a long time, fatigue accumulates due to repeated use, and a so-called ghost phenomenon occurs in which an afterimage occurs, or
When used at high speeds, there are many cases where inconveniences such as a gradual decrease in button responsiveness occur.

Furthermore, ast has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match it with semiconductor lasers currently in practical use. However, when using a commonly used halogen lamp or fluorescent lamp as a light source, there is still room for improvement in that the light on the longer wavelength side cannot be used effectively.

In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases,
If the support itself has a high reflectance for the light that passes through the photoconductive layer, multiple reflections occur within the photoconductive layer, which is one of the factors that causes "blurring" in the image. Become.

This effect becomes more serious as the irradiation spot becomes smaller in order to increase the resolution, and it becomes a serious problem especially when a semiconductor laser is used as the light source.

Furthermore, when forming a photoconductive layer using an a-St material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties, but depending on how these constituent atoms are contained, , problems may arise in the electrical or photoconductive properties of the formed layer. That is, for example, the lifetime of photocarriers generated in the formed photoconductive layer by light irradiation in the core layer is not sufficient; Alternatively, in dark areas, there are many cases where the injection of charge from the support side is not sufficiently prevented.

On the other hand, in consideration of matching with a semiconductor laser, it has been proposed to provide an amorphous layer made of an amorphous material containing at least germanium atoms on a support9.
In this case, there may be problems with the adhesion between the support and the amorphous layer and the diffusion of impurities from the support into the amorphous layer.

Therefore, while efforts are being made to improve the properties of the A-8T material itself, it is necessary to take measures to solve all of the above-mentioned light-like problems when designing photoconductive members.

The present invention has been made in view of the above points, and has applicability and applicability to A-8T as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of continuing comprehensive research studies from the viewpoint of
si, especially silicon atoms as a host, hydrogen atoms (6)
or an amorphous material containing at least one of the halogen atoms (3), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as these generically [a5t(H+X)] 1. A photoconductive member designed and produced with the layer structure of a photoconductive member having an amorphous layer exhibiting photoconductivity specified as explained below is a photoconductive member that exhibits extremely excellent properties in practical use. Moreover, when compared with conventional photoconductive materials, it is superior in every respect, and in particular, it has extremely excellent properties as a photoconductive material for electrophotography, and it has excellent absorption on the long wavelength side. This is based on the discovery that it has excellent spectral characteristics.

The present invention is not easily affected by the material of the support, has always stable electrical, optical, and photoconductive properties, and is applicable to all environments with almost no restrictions on the usage environment. The main object of the present invention is to provide a photoconductive part M which has excellent photosensitivity characteristics and good resistance to light fatigue, does not cause deterioration even after repeated use, and has no or almost no residual potential observed.

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

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

Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution.

Yet another object of the present invention is high photosensitivity, high SN
It is also an object to provide a photoconductive member having specific properties.

The photoconductive member of the present invention includes a support for the photoconductive member, a first layer region made of a material containing at least germanium atoms and at least partially crystallized, and at least silicon atoms and germanium atoms. and a third layer region containing an amorphous material containing at least silicon atoms and exhibiting photoconductivity are provided in order from the support side. an amorphous layer, and at least one of the first layer region and the second layer region contains a substance that controls conductivity.

The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, and photoconductive properties, as well as high voltage resistance. characteristics and use environment characteristics.

In particular, when applied as an image forming member for electrophotography, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it has high sensitivity and a high signal-to-noise ratio. Therefore, it has good resistance to light fatigue and repeated use, and can produce high-quality images with high density, clear halftones, and high resolution at a low cost.

Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast photoresponse.

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

FIG. 1 is a schematic configuration diagram schematically showing a button for explaining the layer configuration of a photoconductive member according to a first embodiment of the present invention.

A photoconductive member 100 shown in FIG. 1 has an amorphous layer 102 on a support 101 for the photoconductive member, and the amorphous layer 102 has a free surface 105 on one end surface. There is. The amorphous layer 102, on the support body 101 side, has only sigermanium atoms or germanium atoms and silicon atoms as a matrix, and contains either hydrogen atoms or halogen atoms as necessary. A material composed of at least a part of crystallized material (゛hereinafter [/J(! Ge (S iHHH
The first layer region (C) is composed of ai (H+X) (hereinafter abbreviated as "a-3t Ge(H, second layer region (G) 103 and a −S i(H+
A third layer region (
S) 1 (J-4) has a layered structure stacked in order.

When the first layer region (C) 106 is composed of a material containing germanium atoms and silicon atoms, the germanium atoms and silicone atoms are the first layer region (C) 1
It is contained so as to be continuous and uniformly distributed in the layer thickness direction of 06 and in the in-plane direction parallel to the surface of the support.

The germanium atoms contained in the second layer region (G) 103 are continuously and uniformly distributed in the layer thickness direction of the second layer region (G) 103 and in the in-plane direction parallel to the surface of the support 101. It is contained in the second layer region (G) 103 so as to form a state.

In the photoconductive member 100 of the present invention, the first layer region (
C) At least one of the layer region (G) 103 and the second layer region (G) 103 contains a substance (c) that controls the conduction properties, and in particular, the second layer region (G) 103 contains a substance that imparts the desired conduction properties. It is preferable to include it.

In the present invention, the substance (c) that controls the conductive properties contained in the first layer region (C) 106 or the second layer region (G) 103 is 106 or the second layer region (G) 103 may be evenly and uniformly contained in the entire layer region of the first layer 6. Area (C) 106
Alternatively, it may be contained unevenly in a part of the layer region of the second layer region (G) 103.

In the present invention, when the substance (c) that controls conduction characteristics is contained in the second layer region (G) so as to be unevenly distributed in a part of the second layer region (G), , the substance (c)
It is desirable that the layer region (PN) containing PN is provided as an end layer region of the 20th layer region. In particular, when the layer region (PN) is provided as an end layer region on the support side of the second layer region (G), the substance (D) contained in the layer region (PN) ) and its content as desired, it is possible to effectively prevent charge injection of a specific polarity from the support into the amorphous layer.

In the photoconductive member of the present invention, the substance (c) capable of controlling the conduction properties is contained in the second layer region G) constituting a part of the amorphous layer as described above. It is contained in the entire area of the layer region (G), or evenly distributed in the layer thickness direction. The substance (1) may also be contained in the third layer region (S).
When the substance (D) is contained in the second layer region (G), the third layer region (S) The type of substance (D) to be contained therein, its content, and the manner in which it is contained are determined as appropriate.

In the present invention, the substance (
When D) is contained, it is preferable that the substance is contained in at least the layer region including the contact interface with the second layer region (G).

In the present invention, the substance (D) may be contained uniformly in the entire layer area of the third J-layer area S), or may be contained uniformly in a part of the layer area. It's a good thing.

When both the second layer region (G) and the third layer region (S) contain a substance (D) that controls conduction characteristics, the substance i (D) in the second layer region (G) ) in the second layer region (8) and the substance (D) in the second layer region (8).
(desirable) Also, the first layer region (0), the second layer region (G), and the third layer region (S) When the substance (D) is contained in the first layer region (0), the substance (D) is contained in the first layer region (0).
may be the same or different types in the second layer region (G) and third layer region (S), and the content may be the same or different in each layer region. It's okay.

However, in the present invention, when the substance (D) contained in each layer region is the same in the three regions, the second
It is preferable that the content in the layer region (G) is sufficiently increased, or that substances (D) of different electrical characteristics are contained in each desired layer region.

In the present invention, at least the second layer constituting the amorphous layer
By containing a substance (D) that controls the conductive properties in the layer region (G), the layer region containing the substance (D) [a part of the second layer region (G) or It is possible to arbitrarily control the conduction properties of any of the layer regions as desired, and examples of such substances include so-called impurities in the semiconductor field.
In the present invention, a constituting the amorphous layer to be formed is
For -8iGe (H,

Specifically, P-type impurities include atoms belonging to Group ■ of the periodic table (Group ■ atoms), such as B (boron), A/'(
Aluminum), Ga, (Gallium).

Examples include In (indium) and Tl (merium), and B and Ga are particularly preferably used.

As nm impurities, atoms belonging to Group Ⅰ of the periodic table (Group Ⅰ atoms), such as P (phosphorus), As (arsenic), 8b'
(antimony), Bi (bismuth), etc., but sPrAs is particularly preferably used. In the present invention, a layer region (PN) containing a substance that controls conduction properties is Its content in the layer area (PN
) or, if the layer region (PN) is provided in direct contact with the support, the relationship with the characteristics at the contact interface with the support, etc. It can be selected as appropriate depending on the relationship.

In addition, the relationship with other layer regions provided in direct contact with the layer region (PN) and the characteristics at the contact interface with the other layer regions is also considered, and the material that controls the conduction characteristics is determined. The content is selected appropriately.

In the present invention, there is a substance contained in the layer region (PN) that controls the conduction properties! j CD> content is preferably O, O1~5 X 10 atomic p
pm, more preferably 0.5 to I x 10 atoms
ic ppm, optimally 1-5 x 10 atoms
ic 11p + 1 + 7) 7% desired'J 4 (7
) There is.

In the present invention, the content of the substance (D) in the layer region (PN) containing the substance (D) that controls conduction properties is preferably 30 atomic 1+p111 or more, preferably 1 or more. By setting so atomic p- or more, optimally 100 atoms or more, for example, when the substance (D) to be contained is the above-mentioned P-type impurity, the free surface of the amorphous layer can be charged to polarity. At least the second layer region (U
) into the third layer region (S), and the substance to be contained (D
) is the above-mentioned n-type impurity, when the free surface of the amorphous layer is charged to e polarity, it passes through at least the second layer region CG) from the support side to the third layer region. (8) Injection of holes into the structure can be effectively prevented.

In the above case, as mentioned above, the layer region (PN
) in the layer region (Z) excluding the layer region (PN) contains a substance that controls the conduction characteristics of a conduction type polarity different from the conduction type polarity of the substance that governs the conduction characteristics contained in the layer region (PN). Alternatively, a substance having the same polar conductivity type and controlling the conduction characteristics may be contained in a much smaller amount than the actual amount contained in the layer region (PN). be.

In such a case, the content of the substance controlling the conductive properties contained in the layer region (Z) is set to 1 set region (P
It is suitably determined as desired depending on the polarity and content of the substance contained in N), but preferably 0.
001-1000 atomic fermentation, preferably 0.001-1000.
05-500 atomic PPm, optimally 0.1
~200 atomic PIXI is desirable.

In the present invention, when the layer region (1'N) and the layer region (Z) contain a substance (D) that controls the conductivity of the layer, the content in the layer region (Z) is preferably 30 atomic 11 m or less.

In the present invention, a layer region containing a substance controlling conductivity having a conductivity type of %-force polarity in an amorphous layer;
A so-called depletion layer can also be provided in the contact region by containing a substance controlling conductivity having the conductivity type of the other polarity and providing it in direct contact with the fCNII@ region.

For example, the layer region containing the P-type impurity and the layer region containing the N-type impurity are uniformly provided in direct contact with each other in the amorphous layer to form a so-called P-n junction. form,
In the invention in which a depletion layer is provided, germanium atoms are not contained in the third layer region (8) provided on the second layer region (G); By forming an amorphous layer in the structure, a photoconductive member can be made that has excellent photosensitivity to light in the entire wavelength range from short wavelengths to relatively long wavelengths, including the relatively visible light region. It is.

In addition, the distribution state of germanium atoms in the first layer region (0) is such that germanium atoms are continuously distributed in the entire layer region, so that the distribution state of germanium atoms in the first layer region (0) and the second layer region is different. region(
When a semiconductor laser or the like is used, the first layer region (0) K In this case, substantially complete absorption can be achieved, and interference due to reflection from the support surface can be prevented.

Further, in the photoconductive member of the present invention, the first layer region (G
) and the second layer region (8) each have the common constituent elements of silicon atoms and germanium atoms, ensuring chemical stability in terms of lamination. has been sufficiently accomplished.

In the present invention, the content of germanium atoms contained in the first layer region ((J) is appropriately determined as desired so that the object of the present invention is effectively achieved.
Preferably 1 to i x i o' atom ic pi
ll, more preferably 100 to I x 10 ato
mic solution, optimally 500 ~ I x 10 atoms,
It is desirable to be designated as Lord +c.

The content of germanium atoms contained in the second layer region (G) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 9.
It is desirable that the amount is 5 x 10' atomic ppl, more preferably 100 to 8 x 10 atom x c ppl, and most suitably 500 to 7 x 10 atom x c ppl.

In the present invention, the first layer region (0) and the second layer region (
The layer thickness of G) is one of the important factors for effectively achieving the object of the present invention. In the present invention, the layer thickness of the first layer region (0) is preferably 30λ to 50μ, more preferably 40λ to 40μ.
, the optimum value is preferably 50λ to 30μ.

Further, the layer thickness TB of the second layer region (G) is preferably 30
It is desirable that the depth be λ to 50μ, preferably 40λ to 40μ, most preferably 50λ to 30μ.

Further, the layer thickness T of the third layer region (S) is preferably 0.5
~90μ, preferably 1-80μ, optimally 2-5
It is desirable that it be 0μ. The sum of the layer thickness 'rB of the second layer region (G) and the layer thickness T of the third layer region (S) (TB+T)
The characteristics are appropriately determined as desired when designing the layers of the photoconductive member, based on the mutual organic relationship between the characteristics required for both layer regions and the characteristics required for the entire amorphous layer. Ru.

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

In a highly preferred embodiment example yc of the present invention, the above layer thickness 'rB and layer thickness T are preferably 'l'B/
When satisfying the relationship T≦1, it is desirable that appropriate numerical values be selected for each.

In selecting the numerical values of layer thickness TB and layer thickness T in the above case, preferably TB/T≦0.9, optimally T
The layer thickness TB is adjusted so that the relationship B/'l'≦0.8 is satisfied.
It is desirable that the values of and the layer thickness T be determined.

In the present invention, the content of germanium atoms contained in the first layer region (0) is I x 105105ato
In this case, it is desirable that the layer thickness of the first layer region (0) be made considerably thinner, preferably 30 μm.
Hereinafter, the thickness is preferably 25μ or less, most preferably 20μ or less.

In the present invention, the halogen atoms (X) contained in the first layer region (0), second layer region (G), and third layer region (S) as necessary include specific examples. Examples include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred.

In the present invention, pc-(je(Si, H, X')
The first layer region (0) having the above structure is formed by, for example, a vacuum deposition method using a discharge phenomenon such as a claw discharge method, a sputtering method, or an ion blating method, and a vacuum evaporation method.

For example, ttc-Ge (Si,
In order to form the first layer region (0) composed of H, A raw material gas for supplying 8i that can supply Si ).

When there is a shortage of raw material gas for introducing hydrogen atoms (H), the raw material gas for introducing halogen atoms (X) is introduced at the desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber. It is preferable to cause a layer of μc-Ge (Si, H, In addition, when forming by sputtering, one target made of Ge and one made of Si are formed in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases. or by using two targets consisting of the target and Ge, or by using SN and G.
H as needed using a mixed target of e.
e, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) is introduced into a deposition chamber for sputtering, as necessary, a raw material gas for supplying a pile diluted with a diluent gas such as Ar, It is preferable to sputter the target by forming a desired gas plasma atmosphere.

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

In addition, when forming the first layer region (C), the support temperature is 50°C to 20°C higher than the support temperature when forming the second layer region (G).
It is necessary to raise the temperature by 0°C.

The second layer region (
G) is formed by, for example, a glow discharge method, a sputtering method, or a vacuum deposition method that utilizes a discharge phenomenon such as an ion plating method. For example, in order to form the second layer region (G) composed of a-8iGe (H, A source gas for Ge supply that can supply source gas and germanium atoms (Ge), and a source gas for introducing hydrogen atoms (H) and/or a source gas for introducing halogen atoms (X) as necessary, are is introduced at a desired gas pressure into a deposition chamber that can be evacuated to cause a glow discharge in the deposition chamber, and a SiGe is deposited on a predetermined support surface that has been placed in a predetermined position in advance.
(H9X) may be formed. In addition, when forming by sputtering method, for example, Ar, H
One of the targets made of Ge and the target made of St, or the target and the target made of Ge in an atmosphere of an inert gas such as E or a mixed gas based on these gases. Using two pieces or using a mixed target of St and Ge,
G diluted with diluent gas such as He or Ar as necessary
eThe raw material gas for supply is converted into hydrogen atoms (H) as necessary.
Alternatively, a gas for introducing halogen atoms (X) may be introduced into a deposition chamber for sputtering, a desired gas plasma atmosphere may be formed, and the target may be sputtered.

In the case of the ion blating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in one evaporation boat as evaporation sources, and this evaporation source is heated by resistance heating or electron beam. This can be carried out in the same manner as in the case of sputtering, except that the flying evaporates are heated and evaporated by a method such as the EB method and passed through a desired gas plasma atmosphere.

Substances that can be used as the raw material gas for supplying Si used in the present invention include SiH, SiJ, St, and Mt.

Silicon hydride (silanes) in a gaseous state or that can be gasified, such as 3i4H, etc., can be used effectively, especially in terms of ease of handling during layer creation work and good St supply efficiency. SiH4+ 5itHa is preferred.

As a material that can be a source gas for supplying Ge, GeH
,,GetHs,Ge+Ha 4H,. , Ge
,H, ,Ge5H14,Ge,H, .

Ge5H14s Ge+H*. Germanium hydride in a gaseous state or which can be gasified, such as
GeH4, Ge, Ha, etc. in terms of supply efficiency.

Preferable examples include Ge and H.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halogen compounds, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds in the form of scum or which can be gasified.

In addition, in the present invention, silicon hydride compounds containing halogen atoms, which are in a gaseous state or can be gasified and have silicon atoms and halogen atoms as constituent elements, can also be mentioned as effective compounds in the present invention. Examples of suitable halogen compounds include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, and CI! F, CeFB.

BrF, , BrF5. IF3. IFy, I
/% (intergen compounds such as ce, IBr, etc.) can be mentioned.

Examples of silicon compounds containing halogen atoms (so-called) silane derivatives substituted with 10 gen atoms include, for example, SiF4. Si, F, , SiC/4. SiBr
Preferred examples include silicon halides such as No. 4.

When a silicon compound containing such a halogen atom is employed to form the characteristic photoconductive part of the present invention by a glow discharge method, a raw material gas capable of supplying St together with raw material waste for supplying Ge may be used. The first layer region containing halogen atoms (
C) and a second layer region (G) can be formed.

When creating a first layer region (C) and a second layer region (G) containing nitrogen atoms according to the glow discharge method,
Basically, for example, silicon halide, which will be the raw material gas for Si supply, germanium hydride, which will be the raw material gas for Ge supply, and gases such as Ar, H2, He, etc., are mixed at a predetermined mixing ratio and gas flow rate. 79f into a deposition chamber forming a first layer region (C) and a second layer region (G) and generating a glow discharge to form a plasma atmosphere of these gases. A first layer region (
C)" and the second layer region (G), but in order to more easily control the introduction ratio of hydrogen atoms, hydrogen gas or hydrogen atoms may be added to these gases. A desired amount of silicon compound gas may also be mixed to form a layer.

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

Furthermore, when forming the first layer region (C), the support temperature is set to 50 to 50°C lower than the support temperature for forming the second layer region (G).
It is necessary to raise the temperature to 200°C.

In order to introduce halogen atoms into the layer formed by either the sputtering method or the ion blating method,
What is necessary is to introduce a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms into the deposition chamber to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H or the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a gaseous plasma atmosphere.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCe, etc.

Hydrogen halides such as HBr, HI, SiH, F2
,・SiH,I,.

SiH,C/2.5iHC/3. SiH, Br, ,
Halogen-substituted silicon hydride such as 5iHBr8, and Ge
HF5lGeH,F, , GeHsF.

GeHCe, +'GeH,C/, , GeHsC
e, GeHBr8. GeH, Br2, GeH, Br2
r.

GeHIs, GeH, I, , GeH, I, etc. are hydrogenated germanium halides, etc., as one of all hydrogen atom constituents...Rogge/Cide, GeF, , GeCe
4. GeBr4, GeI4.

GeF2, GeClt, 'GeBr, , Ge
Gaseous or gasifiable substances such as germanium halides such as 11, etc. may also be mentioned as useful starting materials for the formation of the first layer region (C) and the second layer region (G).

Among these substances, halides containing hydrogen atoms are sometimes introduced electrically or Since hydrogen atoms, which are extremely effective in controlling photoelectric properties, are also introduced, they are used as a suitable raw material for introducing halogen in the present invention.

Hydrogen atoms are added to the first layer region (C) and the second layer region (G
) In addition to the above, Peng or S
With germanium or a germanium compound for supplying Ge to silicon hydride such as iH,, St, H,, St, H,, 5i4H, or GeH,, Ge, H,.

GeBH@, Ge4H46, Ge,,H,,Ge4
H46Ge@Mountain. This can also be carried out by causing germanium hydride such as the like and silicon or a silicon compound for supplying Si to coexist in the deposition chamber to generate a discharge.

In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the amount of hydrogen atoms and halogen atoms contained in the first layer region (C) of the photoconductive member to be formed The sum (H x ) is preferably 0.000 t4
0 at'omic%, more preferably 0.005-3
0 atomic%, optimally 0.01-25 atoms
It is desirable to set it as ic%.

In order to control the amount of hydrogen atoms (I) and/or halogen atoms (X) contained in the first layer region (C), for example, the support temperature and/or hydrogen atoms (H) or halogen atoms The amount of the starting material used to contain (X) introduced into the deposition system, the discharge force, etc. may be controlled.

In a preferred example of the present invention, the amount of hydrogen atoms (I) or the amount of halogen atoms (X) or the amount of hydrogen atoms and halogen atoms contained in the second layer region (G) of the photoconductive member to be formed is The sum of the amounts (H+X) is preferably 0.01 to 40
atomic%, more preferably 0.05-30 at
omic%, most preferably O11 to 25 atomic%.

In order to control the amount of hydrogen atoms () or/and halogen atoms (X) contained in the second layer region (G), for example, the support temperature or/and the hydrogen atoms (H) or - - The amount of the starting material used to contain the rogen atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled.

In the present invention, the third
[ The starting material (■) for forming the third layer region (S) can be used to form the second layer region (G) using the same method and conditions.

That is, in the present invention, to form the third layer region (S) composed of a-8t (H, It is made by a vacuum deposition method. For example, by glow discharge method, a-8t(H,X)
In order to form the third layer region (S) consisting of
Along with the raw material gas for supply, hydrogen atoms (I(
) A raw material gas for introduction and/or for introduction of halogen atoms (X) is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber. a 5i(H+X) on a given support surface
What is necessary is to form a layer consisting of.

In addition, when forming by sputtering method, for example, Ar
, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) when sputtering a target composed of St in an atmosphere of an inert gas such as He or a mixed gas based on these gases. may be introduced into the deposition chamber for sputtering.

In the present invention, the amount of hydrogen atoms (H) or the amount of hydrogen atoms (X) or hydrogen atoms contained in the third layer region (S) constituting the amorphous layer to be formed is The sum of the amount of halogen atoms (H+X) is preferably 1 to 40 ato
The mic ratio is preferably 5 to 30 atomic%, most preferably 5 to 25 atomic%.

A layer containing the substance (D) by structurally introducing a substance (D) that controls conduction characteristics, for example, a group II atom or a group V atom, into the layer region constituting the amorphous layer. Area (PN
), in order to form an amorphous layer, a starting material for introducing group I atoms or a starting material for introducing group V atoms is placed in a deposition chamber in a dregs state during layer formation. It may be introduced together with other starting materials. As a starting material for such introduction of Group 1 II atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, as a starting material for introducing a group Ⅰ atom, for introducing a boron atom, BtHa -B4HIO BIIIB+Hu
IB! Examples include boron hydride such as IHIOνBsH+z tBllHI4, and /% boron hydride such as BF, Be/1, BBrs, etc. In addition, AeCIB
, GaCIB +Ga(CH,), , InC/
3. TeCIB and the like can also be mentioned.

In the present invention, as a starting material for introducing a group V atom, Pus is effectively used for introducing a phosphorus atom.
, hydrogen north neighbors such as PtHa, PH,I, PF, .

PFs + PCI! s + PC1* r PBrl
Examples include 10genated phosphorus such as lPBrs and PIS. In addition, A3H8, AsFl.

A8(l!, , A3Br, , A8F, l S
bH,, SbF3.8bF, , SbC/, .

SbC/, , SiH,, SiC/4, B1Br
, etc. can also be mentioned as effective starting materials for the introduction of Group I atoms.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr and stainless steel.

At, Cr, Mo, Au, Nb,
Examples include metals such as Ta, V, Ti, Pt, and Pd, and alloys thereof.

Polyester is used as an electrically insulating support.

Polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, etc., and glass.

Ceramic, paper, etc. are commonly used. These electrically insulating supports preferably have at least one surface conductively treated, and it is desirable that another layer is provided on the conductively treated surface side.For example, if the support is made of glass, the surface and NiCr.

Ae, Cr, Mo, Au, Ir, Nb,
Ta, V, Ti, Pt, Pd.

In, O,, SnO,, ITO (In, 0.+SnO,
), etc., or a synthetic resin film such as a polyester film, NiCr1A7? , Ag, Pb, Zn, Ni
, Au.

Cr, Mo, Ir, Nb, Ta, V, Ti
, vacuum evaporation of metal thin films such as Pt, electron beam evaporation,
Conductivity is imparted to the surface by sputtering or the like, or by laminating the surface with the metal. The shape of the support is cylindrical.

The photoconductive member 1 shown in FIG.
If 00 is used as an electrophotographic image forming member, it is determined as appropriate so that it can be formed in the case of continuous high-speed copying, but if flexibility is required as a photoconductive member, it may be used as a support. It is made as thin as possible within the range that allows the function to be fully demonstrated. However, in such cases, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is usually 10μ.
This is considered to be the above.

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

FIG. 2 shows an example of a photoconductive member manufacturing apparatus.

Gas cylinders 202 to 206 in the figure are sealed with raw material gas for forming the photoconductive member of the present invention.
H, gas (purity 99.999%.

Hereinafter, 5iI (abbreviated as 4/He) cylinder, 203 is He
GeH, gas (purity 99.999%, hereinafter referred to as GeI (4/He)) cylinder, 2o4 is SiF4 gas (purity 99.99%, hereinafter referred to as SiF4) diluted with
/1 (abbreviated as e) cylinder, 205 is B, H, gas diluted with He (purity 99.999X, hereinafter referred to as B, H
Abbreviated as 6/He. ) cylinder, 206 is H, gas (purity 9
9.999%) cylinder.

In order to allow these gases to flow into the reaction chamber 201, make sure that the pulps 222-226 and leak pulp 235 of the gas cylinders 202-206 are closed. Pulp 232. After confirming that the main pulp 233 is opened, the main pulp 234 is first opened to exhaust the inside of the reaction chamber 201 and each waste pipe. Next, when the reading on the vacuum gauge 236 reaches approximately 5 x 10 torr K, the auxiliary pulp 2
32, 233, close the outflow pulps 217-221.

Next, to give an example of forming the first layer region on the cylindrical substrate 237, SiH
4/He gas, 203 to GeH to the gas cylinder.

/He gas, B2H from gas cylinder 205, /He i
Pulp 222. 223, 225 respectively to check the pressure of the outlet pressure gauges 227, 228, 230.
Adjusted to Kg/ca, inflow pulp 212, 213
, 215 gradually open, and the mass flow controller 207
, 208 and 210, respectively. Subsequently, outflow pulp 217.218.220, auxiliary pulp 2
32 is gradually opened to allow each gas to flow into the reaction chamber 201. At this time, 5L1 (4/He gas flow rate and GeH,
/He gas flow rate and B2H6/He gas flow rate to the desired value.
0 of the main valve 2 while checking the reading of the vacuum gauge 236 so that the pressure inside the reaction chamber 201 reaches the desired value.
Adjust the aperture of 34. After confirming that the temperature of the substrate 237 is set to a temperature in the range of 400°C to 600°C by the heater 238, the power source 240 is set to the desired power to generate glow discharge in the reaction chamber 201. In this way, a first layer region (C) is formed on the base body 237.

At the time when the first layer region (C) is formed to a desired layer thickness, the temperature of the base body 237 is increased to 50% by the heating heater 238.
The glow discharge is maintained on the first layer region (C) for a desired time under the same conditions and procedures except for setting the temperature at 0 to 400°C and changing the discharge conditions as necessary. Two layer regions (G) can be formed.

Similar conditions were applied, except that at the time when the second layer region (G) was formed to the desired layer thickness, the outflow pulp 21'8 was completely closed and the discharge conditions were changed as necessary. By following the steps and maintaining the glow discharge for the desired time,
A third layer region (S) containing no germanium atoms can be formed on the second layer region CG).

In the third layer region (8), a substance (D) that controls conductivity
When forming the third layer region (S), in order to contain
For example, gases such as 82H, PH, etc. may be added to other gases introduced into the deposition chamber 201.

In this way, the first layer region (C) and the second layer region (G)
and a third layer region (S) are formed on the base 2.
37.

During layer formation, it is desirable that the substrate 237 be rotated at a constant speed by a motor 239 in order to ensure uniform layer formation.

Examples will be described below.

Example 1 Using the manufacturing apparatus shown in FIG. 2, layers were formed on a cylindrical M substrate under the conditions shown in Table 1 to obtain an electrophotographic image forming member.

The image forming member obtained in this way is installed in the Tei-1 exposure experiment apparatus; 5. Corona charging was performed for 0.3 f1 with OKV, and the butt image was immediately irradiated with a light image using a tungsten lamp light source and a light amount of 21 uX was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading an O-charged developer (including toner and carrier) over the imaging member surface. The toner image on the image forming member is processed by 5. When transferred to Transfer Paper-H using OKV corona charging, a clear, high-density image with excellent resolution and good 8M4 reproducibility was obtained.

Example 2 An electrophotographic image forming member was obtained by forming layers in the same manner as in Example 1 using the manufacturing apparatus shown in FIG. 2, except that the conditions shown in Table 2 were used.

An image was formed on a transfer paper using the thus obtained one-layer forming member under the same conditions and procedures as in Example 1, except that the charging polarity and the charging polarity of the developer were respectively opposite to those in Example 1. Clear image quality was obtained.

Example 3 Using the manufacturing apparatus shown in FIG. 2, layer formation was carried out in the same manner as in Example 1 except that the conditions shown in Table 3 were used to obtain an electrophotographic image forming member.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 4 In Example 1, GeH4/He gas and 5il (4/
Electrophotographic image forming members were prepared in the same manner as in Example 1, except that the content of germanium atoms contained in the first layer was changed as shown in Table 4 by changing the gas flow rate ratio of He gas. Created.

Regarding the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1.
The results shown in the table were obtained.

Example 5 Electrophotographic image forming members were prepared in the same manner as in Example 1 except that the thickness of the first layer was changed as shown in Table 5.

Images were formed on transfer paper for each of the thus-obtained image-forming members under the same conditions and procedures as in Example 1, and the results shown in Table 5 were obtained.

Example 6 Using the manufacturing apparatus shown in FIG. 2, layers were formed on a cylindrical M substrate under the conditions shown in Table 6 to obtain an electrophotographic image forming member.

The image-forming member thus obtained was used as band 1! Install it in the exposure experiment equipment ■5. Corona charging was performed using OKV for Q, 3 seconds, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light amount of 2/ux was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading an e-chargeable developer (including toner and carrier) over the imaging member surface. The toner image on the image forming member is processed by 5. When transferred onto transfer paper using OKV's corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Example 7 Using the manufacturing apparatus shown in FIG. 2, layers were formed on a cylindrical M substrate under the conditions shown in Table 7 to obtain an electrophotographic image forming member.

The image forming member thus obtained was placed in a charging exposure experiment device.5. Corona charging was performed for 0.3 Sec at OKv, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light intensity of 2/ux-x was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the image forming member by cascading a charged developer (including toner and carrier) over the surface of the image forming member. When the toner image on the image forming member was transferred onto a transfer paper by corona charging at EO, 5 KV, a clear, high density image with excellent resolution and good gradation reproducibility was obtained.

Example 8 Using the manufacturing apparatus shown in FIG. 2, layers were formed on a cylindrical M substrate under the conditions shown in Table 8 to obtain a layer-forming member for electrophotography.

The image forming member thus obtained was placed in a charging exposure experiment device.5. Corona charging was performed for Q and 3 see with OKV, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light intensity of 2/ux-(8) was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the image forming member by cascading a charged developer (containing toner and carrier) over the surface of the image forming member. When transferred onto transfer paper using e5.OKV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Example 9 A J@ layer was formed using the manufacturing apparatus shown in FIG. 2 in the same manner as in Example 1 except that the conditions shown in Table 9 were used to obtain an electrophotographic image forming member.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 1O Layer formation was performed using the manufacturing apparatus shown in FIG. 2 in the same manner as in Example 1 except that the conditions shown in Table 10 were used to obtain an electrophotographic image forming member.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 11 In Example 1, the light source was a tungsten lamp.

Instead of 810 nm GaAs semiconductor laser (10 m
Example 1 except that the electrostatic image was formed using W)
When the image quality of the toner transfer image was evaluated on an electrophotographic image forming member prepared under the same toner image forming conditions as in Example 1, it was found that it had excellent resolution and good gradation reproducibility. Clear, high-quality images were obtained.

Common j-creation conditions in the above embodiments of the present invention are shown below.

Discharge frequency: 13.56M) lz Reaction and reaction chamber pressure 0.3’J’orr”

[Brief explanation of the drawing]

′? Figure Jj1 is a schematic layer configuration diagram for explaining the 14 configurations of the photoconductive member of the present invention, and Figure 2 is a diagram of the apparatus used to produce the photoconductive member of the present invention in Examples. It is a Chinese-style explanatory diagram. 100...Photoconductive member 101...Support 102...Amorphous layer Applicant: Canon Inc.

Claims (5)

[Claims] (1) A support for a photoconductive member, a first layer region on the support that contains at least gel and manium atoms and is at least partially crystallized, and at least silicon atoms and germanium atoms. and a third layer region containing an amorphous material containing at least silicon atoms and exhibiting photoconductivity are provided in order from the support side. and an amorphous layer having a layered structure, and at least one of the first layer region and the second layer region contains a substance that controls conductivity. Photoconductive member. (2) The photoconductive member according to claim 1, wherein hydrogen atoms are contained in any one of the first layer region, the second layer region, and the third layer region. (3) The photoconductive member according to claims 1 and 2, wherein any of the first layer region, the second layer region, and the third layer region contains halogen atoms. (4) The photoconductive member according to claim 1, wherein the substance that controls conductivity is an atom belonging to Group 1 of the periodic table. (5) The photoconductive member according to claim 1, wherein the substance that controls conductivity is an atom belonging to Group Ⅰ of the periodic table.