JPS5984252A - Photoconductive material - Google Patents

Abstract

PURPOSE:To obtain a photoreceptor superior in sensitivity to wide wavelength light, etc. by laminating the first amorphous material layer region contg. Gex Si1-x and the second photoconductive amorphous material layer region contg. Si on a substrate, and incorporating oxygen in each layer region. CONSTITUTION:The first amorphous material layer region 103 contg. GexSi1-x is formed on a conductive substrate 101, where 0.95<x<=1, to obtain a photoconductive layer high in sensitivity to the IR region. Then, the second amorphous material layer region 104 contg. Si not but photoconductive Ge is formed on the region 103 to form the laminated amorphous photoconductive layer 102 serviceable as a photoconductive material 100. Oxygen atoms are incorporated in each of the regions 103, 104, and H or halogen is added to either or both of the regions, too. The electrophotographic photosensitive body, etc. thus obtained have high sensitivity to throughout the visible and IR regions and all-environmental type durability, etc.

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.). Regarding.

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 (Id)), has absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, has the desired dark resistance value, and does not cause any pollution to the human body during use. In addition, solid-state imaging devices are required to have characteristics such as being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, 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.
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

According to Hyakunen et al., a conventional photoconductive member having a photoconductive layer composed of a-St has excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and furthermore, stability over time, which requires a comprehensive improvement in characteristics.

For example, in the case of applying it to an image forming member for photographic use, when trying to achieve high light sensitivity 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
Repeated use at high speeds often causes disadvantages such as a gradual decrease in responsiveness.

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 light that passes through the photoconductive layer, interference due to multiple reflections will occur within the photoconductive layer, which is one of the causes of "blurring" in the image. .

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

Furthermore, when the photoconductive layer is composed of a-Si material,
In order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and boron atoms and phosphorus atoms to control the electrical conductivity type, or other property improving properties. Therefore, other atoms are contained in the photoconductive layer as constituent atoms, but depending on how these constituent atoms are contained, problems may arise in the electrical or photoconductive properties of the formed layer. There is.

That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer may not be sufficient, or the injection of charge from the support side may not be sufficiently prevented in dark areas. There are many cases.

Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved in terms of stability over time. .

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

The present invention has been made in view of the above points, and is characterized by its applicability and applicability to A-8I as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive research and consideration from this point of view, we have discovered an amorphous material that has a silicon atom as its base material and contains at least either a hydrogen atom I or a halogen atom (■).
So-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to generically as [a-8i]
(H, The photoconductive material not only exhibits extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in every respect, especially as a photoconductive material for electronic photography. This is based on the discovery that it has excellent absorption spectrum characteristics on the long wavelength side.

The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member that is durable, 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 optical response to the eye.

Another object of the present invention is to have excellent adhesion between a layer provided on a support and the support and between each layer of laminated layers,
It is an object of the present invention to provide a photoconductive member that is dense and stable in terms of structural arrangement and has high layer weight.

Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. An object of the present invention is to provide a photoconductive member having sufficient electrophotographic properties.

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.

It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics and good electrical contact with the support.

The photoconductive member of the present invention includes a support for the photoconductive member and a Ge
A first layer region made of an amorphous material containing zSil-X (0,95 (x≦1)) and a second layer made of an amorphous material containing silicon atoms and exhibiting photoconductivity. and an amorphous layer having a light layer configuration, the regions being provided in the order of the support side, and the amorphous layer containing oxygen atoms.

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 and optical properties.

Indicates photoconductive properties, pressure resistance, and usage environment characteristics.

In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, it is highly sensitive, and it has a high signal-to-noise ratio. As a result, high-quality images with high density, clear halftones, and high resolution can be stably and repeatedly obtained with excellent light fatigue resistance and repeated use characteristics.

In addition, the photoconductive member of the present invention has a strong layer structure and excellent adhesion to the support, and can be used continuously at high speed for a long time. Can be used repeatedly.

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 shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention.

A photoconductive member 100 shown in Figure 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 is formed of GezS iI from the support 101 side.
-X (0,95<x≦1) containing amorphous [hereinafter a
The first layer region (G) 103 is composed of a-5t (H, )104
It has a layered structure in which these are laminated in order.

The germanium atoms contained in the first layer region (G) 103 are continuous in the layer thickness direction of the first layer region (G) 103 and in the in-plane direction parallel to the surface of the support 101. It is contained in the first layer region (G) 103 so as to be uniformly distributed.

In the present invention, germanium atoms are not contained in the second layer region (S) provided on the first layer region (G), and an amorphous layer is not included in such a layer structure. By forming this, it is possible to obtain a photoconductive member that has excellent photosensitivity to light in the entire wavelength range from relatively short wavelengths to relatively short wavelengths, including the visible light region.

In addition, the distribution state of germanium atoms in the first layer region (G) is such that germanium atoms are continuously distributed in the entire layer region, so the distribution state of germanium atoms in the first layer region (G) and the second layer region is different. (S
) has an excellent affinity between In (G),
Substantially complete absorption can be achieved, and interference due to reflection from the support surface can be prevented.

In the present invention, the content of silicon atoms contained in the first layer region (NSI / (NSi + NGe)
: NA (total number of A atoms in the layer) is determined as desired so as to effectively achieve the purpose of the present invention, but is usually 5 x 10' atonic ppm.
Hereinafter, preferably I x 10” atomic ppm
Hereinafter, it is desirable that the I
The value of X in Si, ->((', H, X > is usually 0.95, 'x each 1.

Preferably 0.99<x≦1. Optimally 0.999
It is desirable that <x≦1.

In the present invention, the first layer region (G) and the second layer region (S)
The layered film is one of the important factors for effectively achieving the object of the present invention, so it is necessary to sufficiently impart the desired characteristics to the formed light guide member. Due attention must be paid to the ψ in the design of the photoconductive member.

In the present invention, the layer thickness TB of the first layer region is usually 30λ to 50μ, preferably 40μ to 40μ, and in the case of a kiko commercial, it is preferably 50λ to 30μ.

In addition, the layer thickness T of the second layer region (S) is 0.
5-90μ, preferably -80μ, optimally 2-50
It is preferable that it be μ.

The layer thickness ゛rB of the first layer region (G) and the second layer region (S'
), the sum of the layer thicknesses 'r' (TB + T) is determined based on the organic relationship between the characteristics required for both layer regions and the characteristics required for the entire amorphous layer. It is determined as desired when designing the layers of the member.

In the photoconductive member of the present invention, it is desirable that the numerical range of (TB+T) and 1- is normally 1 to 100μ, preferably 1 to 80μ, and optimally 2 to 50μ. Yes.

In a more preferred embodiment of the present invention, the above-mentioned layer thickness TB and layer thickness T usually satisfy the relationship Tn/T≦1, and are set to appropriate values for each. is preferably selected.

In selecting the values of layer thickness TB and layer/@T in the above case, it is more preferable that Tn/T≦0.9. Optimally, the layer thickness TB is adjusted so that the relationship TB/T≦0.8 is satisfied.
It is desirable that the values of and the layer thickness T be determined.

In the present invention, the first layer region 00 layer thickness TB is as follows:
It is desirable that the thickness be as thin as possible, preferably 30μ or less, more preferably 25μ or less, and optimally 20μ or less.

In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the amorphous 1'iML, the amorphous layer contains , contains an oxygen atom. The oxygen atoms contained in the amorphous layer may be uniformly contained in the entire layer region of the amorphous layer, or may be contained in only some layer regions of the amorphous layer so that they are unevenly distributed. You can let me.

In addition, even if the distribution state of oxygen atoms is uniform in the thickness direction of the amorphous layer, the distribution concentration C(0) is uniform in the thickness direction of the amorphous layer.
0) may be non-uniform in the layer thickness direction.

In the present invention, the layer region 0) containing oxygen atoms provided in the amorphous layer is the entire layer region of the amorphous layer when the main purpose is to improve photosensitivity and dark resistance. If the main purpose is to strengthen the adhesion between the support and the amorphous layer, it is provided so as to occupy the end layer area of the amorphous layer on the side of the support. It will be done.

In the former case, the content of oxygen atoms contained in the layer region (0) is kept relatively low in order to maintain high photosensitivity, and in the latter case to ensure enhanced adhesion with the support. It is desirable to have a relatively large amount for measurement purposes.

Also, for the purpose of achieving both the former and the latter at the same time,
Oxygen atoms may be distributed at a relatively high concentration on the support side and at a relatively low concentration on the free surface side of the amorphous layer, or oxygen atoms may be distributed in the surface layer region on the free surface side of the amorphous layer. What is necessary is to form a distribution state of oxygen atoms in the layer region (O) such that oxygen atoms are not actively contained.

In the present invention, the content of oxygen atoms contained in the layer region 0) provided in the amorphous layer depends on the characteristics required for the layer region (0) itself, or when the layer region (0) is a support. When provided in direct contact with the support, it can be appropriately selected depending on the organic relationship, such as the relationship with the properties of the contact interface with the support.

In addition, when another layer region is provided in direct contact with the layer region (0), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The content of oxygen atoms is appropriately selected taking into account the following. The 1- content of oxygen atoms contained in the layer region (0) is determined as desired depending on the properties required of the photoconductive member to be formed, but is usually 0.001 to 50 atomic%. , preferably 0.002-40 atomic%, optimally 0
．． It is desirable that it be assigned to 003-30 atomic c.

In the present invention, whether the layer region (0) occupies the entire area of the amorphous layer or not, the layer thickness T of the layer region (0). When the proportion of the amorphous layer in the layer thickness T is sufficiently large, it is desirable that the upper limit of the content of oxygen atoms contained in the layer region (0) is sufficiently smaller than the above value.

In the case of the invention, the layer thickness T of the layer region (0). When the ratio of oxygen atoms to the layer thickness T of the amorphous layer is two-fifths or more, the upper limit of the amount of oxygen atoms contained in the layer region 0) is usually 30 atomic % or less, preferably 20 atomic % or less, optimally 10 atomic % or less
It is desirable that it be atomic% or less.

2 to 10 show typical examples of the distribution state of oxygen atoms contained in the layer region (0) of the photoconductive member in the present invention in the layer thickness direction.

In FIGS. 2 to 10, the horizontal axis represents the distribution concentration C of oxygen atoms, the vertical axis represents the layer thickness of the layer region (0), and tB represents the position of the end surface of the layer region (0) on the support side. , tT indicates the position of the end surface of the layer region (0) on the side opposite to the support side. That is,
The layer region (0) containing oxygen atoms is formed as a layer from the tB side toward the tT side.

The second section shows a first typical example of the distribution state of oxygen atoms contained in the layer region (0) in the layer thickness direction.

In the example shown in FIG. 2, from the interface position tB where the surface where the layer region (0) containing oxygen atoms is formed and the surface of the layer region (O) contact, the oxygen atoms are The distribution concentration C takes a constant value of C1 and is contained in the layer region 0) where oxygen atoms are formed, and the position tlJ: is the concentration C2.
It is gradually and continuously decreased until the interface position tTlc is reached. At the interface position tT, the distribution concentration of oxygen atoms C
is assumed to be C3.

In the example shown in FIG.
The concentration C6 decreases gradually and continuously from [tT]
The distribution state is formed as follows.

In the case of FIG. 4, the distribution concentration C of oxygen atoms is kept at a constant value C6 from position tB to position t2, and gradually and continuously decreases between position t2 and position tT until position 1ttT. In the above, the distribution concentration C is substantially zero (here, substantially [zero means the case where the amount is less than the detection limit).

In the case of FIG. 5, the distribution concentration C of oxygen atoms is continuously and gradually reduced from the concentration C8 from the very position tB to the position tT, and becomes substantially zero at the position #tT. In the example shown in FIG. 6, the distribution concentration C of oxygen atoms is
Between position tB and position t5, the density C9 is a constant value, and at position [ttT, it is # degrees CIO. Between the position t3 and the position tT, the distribution density C is linearly decreased until it reaches the position t and then reaches the position tT.

In the example shown in FIG. 7, the distribution concentration C is of order 1it.
From u to position t4, the concentration C11 takes a constant value, and from position t4 to position tT, the distribution state is such that the concentration decreases linearly from Cl11 to concentration CI3.

In the example shown in FIG. 8, from position tB to position tT, the distribution concentration C of oxygen atoms decreases linearly from the concentration CI4 to substantially zero.

In FIG. 9, from position tB to position t, the distribution concentration C of oxygen atoms decreases linearly from concentration Cta to concentration 016, and between position t and position tT, the concentration An example in which CI6 is set to a constant value is shown.

In the example shown in FIG. 10, the distribution concentration C of oxygen atoms is the concentration CI? at position tB? At first, the concentration CI7 is gradually decreased until reaching the position t, and around the position t6, it is rapidly decreased until the concentration CI7 reaches the position t.
6 is considered to be 4 degrees CI8.

Between position t6 and position t7, the concentration is decreased rapidly at first, then slowly and gradually decreased to C19 at position t7, and between position t7 and position t8, it gradually decreases very slowly. If it is reduced to! At its, concentration C20 is reached. Between position t8 and position tT, the concentration is reduced from C20 to substantially zero according to the curve shown in the figure.

As described above from FIGS. 2 to 10 Kosan, some typical examples of the distribution state of oxygen atoms contained in the layer region (0) in the layer thickness direction, in the present invention, Id, on the support side , has a portion with a high distribution concentration C of oxygen atoms, and has an interface t
On the T side, a layer region (0) K is provided with a distribution state of oxygen atoms having a portion where the distribution concentration CI''i is considerably lower than that on the support side.

In the present invention, the layer region 0) containing oxygen atoms constituting the amorphous layer is the localized region (B) containing oxygen atoms in a relatively planar concentration toward the support side, as described above. It is desirable that the amorphous layer be provided as having the following properties, and in this case, the adhesion between the support and the amorphous layer can be further improved.

The localized region (B) is desirably provided within 5 μm from the interface position tB, if explained using the symbols shown in FIGS. 2 to 10.

In the present invention, the localized region (B) may be the entire 1-region (LT) up to 5μ thick from the r, t, interface position tdttB, or may be a part of the j-region (LT). In some cases, it is said that

Whether the localized region is a part or all of the layer region (LT) is determined as appropriate depending on the characteristics required of the amorphous layer to be formed.

The localized region (B) is In of the oxygen atoms contained therein.
, the maximum value Cmax of the distribution concentration of oxygen atoms in the distribution state in the 1!1 direction is usually 500 atomic ppm.
As mentioned above, it is desirable to form a layer so that a distribution state can be obtained, preferably 800 atomic ppm or more, optimally 1001000 atomic ppm or more.

That is, in the present invention, the layer region 0) containing oxygen atoms is within 15 μm in layer thickness from the support side (5 μm from tn).
It is desirable that the pupil maximum value Cmax of distribution m1 degrees exists in a layer region of μ thickness.

In the present invention, the first layer constituting the amorphous layer as necessary
Specific examples of the halogen atoms (3) which are introduced into the layer region (G) and the 1-region C8) of 2J2 include fluorine, chlorine, bromine, and iodine, particularly fluorine, j' A
Preferable examples include:

In the present invention, a GezSt, -X(H,X)
(first layer region G composed of (0,95<X≦1))
For example, a vacuum deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blating method can be used to form the film.

For example, a -GezSil-
In order to form the first layer region (G'l) consisting of 1 (T(,, Raw material gas and raw material gas for St supply that can supply silicon atoms (Si), and raw material gas for introducing hydrogen atoms (F-1) or/and raw material for introducing hydrogen atoms (oO) as necessary. Introducing gas at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure [7
A glow discharge is generated in the deposition chamber, and a GexS
It is sufficient to form a layer consisting of i+-x (H, X).

When x=1, it is sufficient to exclude the Sl supplying gas from among the aforementioned source gases.

In addition, when forming by sputtering method, it, for example, A
In an atmosphere of inert gas such as , r, He or a mixed gas based on these gases, one target made of Ge or two targets made of Ge and one made of St are used. I(e
, A raw material gas for supplying Ge diluted with a diluent gas such as Ar is introduced into a deposition chamber for sputtering, as necessary, and a gas for introducing hydrogen atoms (I) and/or (2) and (2) chloride atoms is introduced into the deposition chamber for sputtering. The target may be sputtered by forming a gas plasma atmosphere.

In the case of ion-blating methods, for example polycrystalline germanium or single-crystal germanium.

If necessary, polycrystalline silicon or single crystal silicon is used as an evaporation source and placed in a deposition boat 1~, and this evaporation source is heated and evaporated by a resistance heating method, an electron beam method (EB method), etc. to obtain flying evaporates as desired. This can be carried out in the same manner as in the case of sputtering, except for passing through the gas plasma atmosphere.

Substances that can be used as the raw material gas for supplying St used in the present invention include SiH, 5i2H, Si, T(
,.

Gaseous or gasifiable silicon hydride (silanes) such as 5i4H, +1 can be used effectively, especially in terms of ease of handling during layer creation work and good St supply efficiency. Preferred examples include SiH+ and 5iJ4e.

As a material that can be a source gas for supplying Ge, GeH
,,Ge,H,+Ge3Ha,Ge4Hto,
Ge1H,2,Ge,F(,.

Ge7H16, Ge5H1B, GeoHza and other gaseous or gasifiable germanium hydrides are effectively used, especially in terms of ease of handling during layer creation work, good Ge supply efficiency, etc. GeH,.

Preferred examples include Ge2H, . . . Ge5Hs.

Effective raw material gases for introducing 10-gen atoms (used in the present invention) include many non-rogen compounds, such as no-rogen gas, no-logenides, interhalogen compounds, and no-rogen-substituted compounds. Preferred examples include halogen compounds that can be gasified in a gaseous state, such as silane derivatives.

Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or obtained by gasification, and which has a silicon atom and a halogen atom as its constituent elements, can also be mentioned as an effective compound in the present invention.

Specifically, the norogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF + CIF, ClF5°BrF
, , BrF5 , IF51 IF7. IC,/
Examples include intergen compounds such as IBr.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF, , 5i2FI, + 5iClt + 5iB
Preferred examples include silicon halides such as r.

When a photoconductive member characteristic of the present invention is formed by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen is used as a raw material gas capable of supplying St together with a raw material gas for supplying Ge. aGe)(containing halogen atoms) on a desired support without using silicon oxide gas.
A first layer region (G) consisting of S i, -z can be formed.

When creating the first layer region (G) containing halogen atoms according to the glow discharge method, basically, for example, silicon halide is used as a raw material gas for supplying St, and hydrogenation is used as a raw material gas for supplying Ge. Germanium and Ar, H2+ He
Gases such as these are introduced into the deposition chamber forming the first layer region (G) at a predetermined mixing ratio and gas flow liquid, and a glow discharge is generated to form a plasma atmosphere of these gases. By doing this, the first layer region (G) can be formed on the desired support, but in order to more easily control the ratio of hydrogen atoms introduced, these gases may be further added. A desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may also be mixed to form a layer.

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

In order to introduce norogen atoms into the layer formed by either the sputtering method or the ion blasting method, a gas of the above-mentioned no-rogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere of the gas.

In the case of introducing hydrogen atoms, the raw material gas for hydrogen atom introduction, for example, F2, or the above-mentioned silane or /
Gases such as germanium hydride and the like may be introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gases.

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 HF, HC/.

Hydrogen halides such as HT3r, HI, SiH2F2.
5iH2I2+SiT■2CIh) 5iHC/3
, 5iH2Br2, 5iHBr3, etc., and Ge) IF, , GeF2 F
2 +GeH3F, GeCl4+, GeH2C1
2, GeHsCll, GeHBr5 +GeH2B
r2. GeH3Br, GeF(I3, GeF
2 I 2 , GeH,, hydrogenated germanium halide such as T, etc., in which hydrogen atoms are one of the constituent elements).
Logenide, GeF4.

GeCl4+ GeBr4, Ge14, GeF
2, GeC12,GeBr2.

In the first layer region 0, gaseous or gasifiable substances such as germanium halides such as Ge I 2 are also effective.
) can be mentioned as a starting material for the formation.

Among these substances, 10-genides containing hydrogen atoms are
When forming the first layer region (G), hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced into the layer at the same time as halogen atoms are introduced into the layer. used as raw material.

In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, F2 or 5HI415t2H6+5
tsL, silicon hydride such as S+4H1o with germanium or a germanium compound for supplying Ge, or GeH+ + Ge2H,, + Ge5Ha l G
e7H16+ Ge5Hu +Ge, HI4. Ge
This can also be done by causing germanium hydride such as 7H16, Ge61 (181Ge7H16, etc.) 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 I or the amount of hydrogen atoms (3) contained in the first layer region (G) constituting the amorphous layer to be formed, or the amount of hydrogen atoms and halogen atoms The sum of the amounts of atoms (H+X) is usually 0.01 to 4
0 atomic%, preferably 0.05-30 atomic%
It is desirable that the amount is mic%, most preferably 0.1 to 25 atomic%.

To control the amount of hydrogen atoms α and/or halogen atoms contained in the first layer region (first layer region), for example, the support temperature and/or hydrogen atoms (F, I) or halogen What is necessary is to control the ψ, concentration, power, etc. of the starting material used to incorporate the atoms into the deposition system.

In the present invention, in order to form the second layer region (S) composed of a-8t (FT,, X), the starting material (I) for forming the first layer region O) described above is used. From inside, Ge
Using the starting material excluding the starting material that becomes the raw material gas for supply [starting material for forming the second layer region (S) (■)], proceed as in the case of forming the first layer region (Q). It can be carried out according to the method and conditions of.

That is, in the present invention, to form the second layer region (S) composed of a-8t (H, It is made by a vacuum deposition method.

For example, by glow discharge method, a-8i (H,X)
In order to form the second layer region (S) made up of the A source gas for introduction of 0 () and a raw material gas for introduction of halogen atom flash is introduced into a deposition chamber whose interior is under reduced pressure (7) to generate a glow discharge in the deposition chamber, and the source gas for introduction of halogen atom flash is What is necessary is to form a layer consisting of a-8i (TI, S in a mixed gas atmosphere based on
When sputtering a target composed of i, a gas for introducing hydrogen atoms σ■ and/or halogen atoms (3) may be introduced into the deposition chamber for sputtering.

In the photoconductive member of the present invention, the second layer region (S) provided on the first region (0) containing germanium atoms and not containing germanium atoms has conductive properties. By containing a controlling substance, the conductive properties of the layer region (S) can be controlled as desired.

Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-8t(H,X) constituting the second layer region (S) to be formed In contrast, examples include a P-type impurity that provides P-type conduction characteristics, and an n-type impurity that provides N-type conduction characteristics.

Specifically, P-type impurities include atoms belonging to Group Ⅰ of the periodic table (Group Ⅰ atoms), such as B (boron), Al (
Aluminum), Ga (gallium), In (indium), Tl (thallium), etc., and 8% Ga is particularly preferably used. Examples of n-type impurities include atoms belonging to Group V of the periodic table (Group II atoms), such as P (phosphorus).

As (arsenic), sb (antimony), Bi (bismuth), etc., and P is particularly preferably used.

It is Aa.

In the present invention, the content of the substance controlling the conduction properties contained in the second layer region (S) is determined based on the conduction properties required for the layer region (S) or the content of the substance controlling the conduction properties contained in the second layer region (S). In terms of organic relationships, such as the characteristics of other layer regions provided in direct contact and the relationship with the characteristics at the contact interface with the other layer region,
It can be selected as appropriate.

In the present invention, the content of the substance controlling conduction properties contained in the second layer region (S) is 0.001 to 1000 atomic ppm in the case of 31f1,
Preferably 0.05 to 500 atomjc ppm,
The optimum content is preferably 0.1 to 200 atomic ppm.

In order to structurally introduce a substance that controls the conduction properties into the second layer region (S), such as a group Ⅰ atom or a group V atom, a starting material for introducing a group Ⅰ atom is required during layer formation. The substance or the starting material for introducing Group I atoms may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the second layer region. As the starting material for such introduction of Group (I) atoms, it is desirable to employ materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, B2H is used as a starting material for introducing boron atoms.
6, B4H+n.

B6Ho, B51'(11, B6'F(10, BeH
+2, B61 (+4 etc. hydrogenated fdllll element, BF
3. BC/8. BBr3. Examples include boron halides such as. In addition, AsCl3. GaC/R,Ga
(C1f,'),.

InC/3. 'LVCI! s etc. can also be mentioned.

-C1 as a starting material for introducing a group (III) atom In the present invention, PH3 is effectively used as a starting material for introducing a phosphorus atom.
, hydrogen north neighbor of P28.4, PH4I, PF3゜P
F5, PCl5 + PCI5, PBr3 +
Examples include halogen atoms such as PBra l PI3.

In addition, AsH3, AsF”3.

AsCl3. AsBr, + Ash', , Sb
H3, SbF, , SbF, , SbC#, .

SbC/s, B:Hs, BiCl3, B1B
r3 and the like can also be mentioned as effective starting materials for introducing Group I atoms.

In the present invention, in order to provide the layer region 0) containing oxygen atoms in the amorphous layer, a starting material for introducing oxygen atoms is added to the amorphous layer during formation of the amorphous layer. It may be used together with the starting materials for controlling the amount in the formed layer. When the glow discharge method is used to form layer region 0), a starting material for introducing oxygen atoms is added to one selected as desired from among the starting materials for forming the amorphous layer described above. As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used.

A raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing oxygen atoms (0), and hydrogen atoms (I) or (2) as necessary. A raw material gas containing silicon atoms (Si) may be mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and silicon may be mixed at a desired mixing ratio. It is possible to use a mixture of a raw material gas having three constituent atoms: atoms (Si) + oxygen atoms (0) and hydrogen atoms I.

Also, separately, silicon atoms (Si) and hydrogen atoms (14
) may be mixed with a raw material gas containing oxygen atoms (0) as constituent atoms.

Specifically, for example, oxygen (02), ozone (03),
-Nitrogen oxide (NO), nitrogen dioxide (NO2), -nitrogen dioxide (N20), nitrogen sesquioxide (N203), trinitrogen tetraoxide (N204).

Nitrogen sesquioxide (N205), nitrogen trioxide (NOl),
For example, disiloxane (H, Si
ts iH,).

Trisiloxane (N3 S t,'s lH2O5iH
Examples include lower siloxanes such as 3).

To form the first amorphous layer (I) containing oxygen atoms by sputtering, single crystal or polycrystalline S
i wafer or 5if2 wafer, or Si and 5i
This can be carried out by sputtering a wafer containing a mixture of n2 as a target in various gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gas for introducing oxygen atoms and optionally hydrogen atoms or halogen atoms can be diluted with a diluent gas as necessary for sputtering. The Si wafer may be sputtered by introducing the Si wafer into a deposition chamber to form a gas plasma of these gases.

Alternatively, by using Sl and 5in2 as separate targets, or by using a single mixed target of Si and Si02, in an atmosphere of dilution gas as a sputtering gas, or at least hydrogen atoms I or/and by sputtering in a gas atmosphere containing halogen atoms (a) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the example of glow discharge described above can be used as an effective gas also in the case of sputtering.

In the present invention, when forming a layer region (0) containing oxygen atoms when forming an amorphous layer, the distribution concentration C(0) of oxygen atoms contained in the layer region (0) is By changing the distribution state in the thickness direction (depth prof.
In order to form a layer region (0) having an area (Ile ), in the case of a glow discharge, a starting material gas for introducing oxygen atoms whose distribution concentration C(0) is to be changed is introduced, and the gas flow rate is adjusted to a desired rate of change. This is accomplished by introducing it into the deposition chamber while changing it appropriately according to the curve. For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manually or using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear, and a desired content rate curve can also be obtained by controlling the flow rate according to a pre-designed rate-of-change curve using, for example, a microcomputer.

When forming the layer region (0) by a sputtering method, the distribution concentration C(0) of oxygen atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state (d) of oxygen atoms in the layer thickness direction.
epth profile), firstly, as in the case of the glow discharge method, the starting material for introducing oxygen atoms is used in a gaseous state, and the gas flow when introducing the gas into the deposition chamber is This is accomplished by appropriately changing the scenery as desired.

Second, the target for sputtering, e.g.
If a target containing a mixture of Sj and 5if2 is used, this can be done by changing the mixing ratio of St and 5i02 in advance in the layer thickness direction of the target.

In the present invention, the amount of hydrogen atoms (6) or the amount of halogen atoms contained in the second layer region (S) constituting the amorphous layer to be formed, or the amount of hydrogen atoms and halogen atoms The sum of the amounts (H x ) is usually 1 to 40 atomic
q6. Preferably 5-30 atomic %+optimally 5-25 atomic %.

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

kl +Cr, Mo, All +Nb +Ta,
Examples include metals such as V + Ti + Pt and Pd, and alloys thereof.

Polyester is used as an electrically insulating support.

Polyethylene, polycarbonate, cellulose acetate, polypropylene, polycarbonate vinyl.

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

Ceramic, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, NiCr is applied to its surface.

Af, Cr, MO, Au, Ir, Nb, T
a eV, Tt, Pt, PcLIn20s l 5
If a thin film made of n02, ITO (In20. +5nO2), etc. is provided, conductivity will be imparted by K, or if it is a synthetic resin film such as a polyester film, NiCr, kl +Ag +Pb, Zn, Ni
, A11 *Cr+Mo+Ir+Nb,Ta
Conductivity is imparted to the surface by providing a thin film of metal such as +V + T+ + Pt on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal. The shape of the support may be any shape such as cylindrical, belt-like, or plate-like, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. In the case of continuous high-speed copying, it is desirable to use an endless belt or a cylindrical shape.

The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. Hyakunen et al. In such cases, the thickness is usually 10 μμ or more from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.

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

FIG. 11 shows an example of a photoconductive member manufacturing apparatus.

Gas cylinders 1102 to 1106 in the figure are sealed with raw material gases for forming the photoconductive member of the present invention. As an example, 1102 is a SiH gas diluted with He (purity 99. 999%.

Hereinafter, it will be abbreviated as S i H4/He. ) cylinder, 1103
is GeH4 gas diluted with He (99.999% purity)
, hereinafter abbreviated as GeH4/He. ) cylinder, 1104 is a SiF4 gas diluted with He (purity 99.99%, hereinafter abbreviated as 5ift/He) cylinder, 1105 is NO
Gas cylinder (purity 99.999%) 1106 is a H2 gas cylinder (purity 99.999%).

In order to cause these gases to flow into the reaction chamber 1101, pulps 1122-1126 of gas cylinders 1102-1106.
Confirm that the leak pulp 1135 is closed, and also check the inflow pulps 1112 to 1116 and the outflow valve 11.
After confirming that 17 to 1121, auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe.

Next, the reading on the vacuum gauge 1136 is approximately 5 x 10″6tor
When the time reaches r, the auxiliary valves 1132 and 1133 and the outflow pulp 1117 to 1121 are closed.

Next, to give an example of forming an amorphous layer on the cylindrical substrate 1137, SiH
4/He gas, GeH from gas cylinder 1103.

/ He gas, M gas from gas cylinder 1105, open halves 1122, 1123, 1124 and set the pressure on outlet pressure gauges 1127, 1128, 1129 to 11 Cg/t.
i K adjust, inflow valve 1112, month 13, 11
14 gradually open, and the mass flow controller 1107
, 1108 and 1109, respectively. Subsequently, the outflow valves 1117, 1118, and 1119, and the auxiliary valve 1132 are gradually opened to supply each gas to the reaction chamber 1.
101. At this time, S i T(4/H
The outflow valves 1117, 1 are adjusted so that the ratio between the e gas flow rate and the Gem/He gas flow rate and the non-gas flow rate becomes a desired value.
118 and 1119, and the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure in the reaction chamber 1101 reaches the desired value. Then, the temperature of the base 1137 is raised to 50°C by the heating heater 1138.
After confirming that the temperature is set in the range of ~400°C, the power source 114° is set to the desired power to generate glow discharge in the reaction chamber 1101 and maintain the glow discharge for a desired time. A first layer region 0) is formed on the substrate 1137 to a desired layer thickness. At the stage where the first layer region 0) has been formed to the desired layer thickness, the glow is performed for the desired time according to the same conditions and procedure, except for completely closing the outflow valve 1118 and changing the discharge conditions as necessary. By maintaining the discharge, a second layer region (S) substantially free of germanium atoms can be formed on the first layer region (G).

Second layer region [F]) In order to contain a substance that controls the medium conductivity, when forming the second layer region (S), for example,
Gases such as B, H, PH3, etc. may be added to the gas introduced into the deposition chamber 1101.

During layer formation, it is desirable that the substrate 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation.

Examples will be described below.

Example 1 A cylinder-shaped Al
Layers were formed on the substrate under the conditions shown in Table 1 to obtain an electrophotographic image forming member.

ζThe thus obtained image forming member was placed in a charging exposure experiment apparatus and the temperature was set at θ5. Corona charging was performed for 0.3 sec using OKV, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light amount of 2 lux, see 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. The toner image on the imaging member is set at θ5. When the image was transferred onto transfer paper using OKV's corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Example 2 Layer formation was performed using the manufacturing apparatus shown in FIG. 11 in the same manner as in Example 1 except that the conditions shown in Table 2 were used to obtain an electrophotographic image forming member.

An image was formed on a transfer paper using the obtained image forming member under the same conditions and procedures as in Example 1, except that the charge polarity and the charge polarity of the developer were each reversed from Example 1. Extremely clear image quality was obtained.

Example 3 Layer formation was performed using the manufacturing apparatus shown in FIG. 11 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 SiH,/
Electrophotographic image forming members were prepared in the same manner as in Example 1, except that the gas flow rate ratio of He gas was changed and the content of germanium atoms contained in No. 11 was changed as shown in Table 4. 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 using the image forming members obtained in Example 1 under the same conditions and procedures as in Example 1, and the results shown in Table 5 were obtained.

Example 6 A cylindrical kl was manufactured using the manufacturing apparatus shown in FIG.
A layer was formed on the substrate under the conditions shown in Table 6 to obtain an electrophotographic image forming member.

The image forming member thus obtained was placed in a charging exposure experiment apparatus, corona charging was performed at θ5 and OKV for 0.3 sec, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light intensity of 2 lux, sec 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. The toner image on the imaging member is set at θ5. When the image was 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 In Example 1, the light source was replaced with a tungsten lamp.
Toner image formation conditions were the same as in Example 1, except that an electrostatic image was formed using a 10 nm GaAs-based semiconductor laser (10 mW). When evaluating the image quality of toner transfer images for electrophotographic image forming members, it was found that the resolution was excellent and the gradation level was 11.
A clear, high-quality image with good visibility was obtained.

Table 4 Table 5 0: Excellent O: Good or better Common layer-forming discharge frequency in the examples of the present invention: 13.56 MIIz Reaction chamber pressure during reaction: 0.3 Torr

[Brief explanation of the drawing]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are illustrations for explaining the distribution state of oxygen atoms in the amorphous material, respectively. 11A and 11B are schematic explanatory diagrams of an apparatus used for producing the photoconductive member of the present invention in Examples. 100... Photoconductive member 101... Support body 102... Amorphous 1fi

Claims (3)

[Claims] (1) A support for a photoconductive member, and on the support, Ge)
A first layer region made of an amorphous material containing (Sit-X(0,95(x≦1)) and a second layer region made of an amorphous material containing silicon atoms and exhibiting photoconductivity. 1. A photoconductive member comprising: an amorphous layer having a layered structure in which layer regions are provided in order from the support side, and the amorphous layer contains oxygen atoms. (2) The photoconductive member according to claim 1, wherein at least one of the first layer region and the second layer region contains hydrogen atoms. (3) The photoconductive member according to claims 1 and 2, wherein at least one of the first layer region and the second layer region contains a norogen atom.