JPS6048048A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain an all-environment type photosensitive body superior in photoconductive characteristics, etc., by forming photoreceptive layer composed of the first layer region G contg. Ge nonuniformly distributed in the film thickness direction and the second layer region S contg. Si and a conduction controller C in a specified distribution. CONSTITUTION:An amorphous layer G103 contg. Ge in a distribution nonuniform in the film thickness direction but uniform in a plane in parallel to the layer surface and high in concn. on the side of a conductive substrate 101 and low on the other side of the layer, and also contg. Si and H or halogen, such as F, is formed on the conductive substrate 101, including the electrically insulating material layer having the surface made conductive by proper treatment. Next, a layer S104 contg. Si as a principal component, and a conductive controller C of an element of group III or V, such as B or P, in a distribution high in concn. on the side of the substrate 101 and low on the opposite side and uniform in a plane parallel to the layer surface is formed on the layer 103 to obtain a photoconductive member 100, such as electrophotographic sensitive body, having a photoreceptive layer 102. As a result, the obtained member is high in photosensitivity in all the visible light region, especially high in sensitivity to a semiconductor laser beam, and an image high in density, sharp in halftone, and high in resolution can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to light that is sensitive to electromagnetic waves such as light (herein referred to as "light", which refers to ultraviolet light, visible light, infrared light, X-rays, gamma rays, etc.). It relates to a conductive member.

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 a high l value, has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has a desired dark resistance value, and has low resistance to the human body during use. It is pollution-free,
Furthermore, 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 S, 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.

A photoconductive member having a conventional photoconductive layer composed of a-8i has excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are areas that can be further improved in terms of usage environment characteristics and 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, and this type of If a conductive member is used repeatedly for a long period of time, fatigue may accumulate due to repeated use, resulting in the so-called ghost phenomenon that causes afterimages, or when used repeatedly at high speeds, responsiveness gradually decreases. There were many cases where spots appeared.

Furthermore, a-8i has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, making it suitable for matching with semiconductor lasers currently in practical use. In this case, when a commonly used halogen lamp or fluorescent lamp is used as a light source, there is still room for improvement in that the light on the long wavelength side cannot be used effectively. ``Also, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases,
When the support itself has a high reflectance for light transmitted through the photoconductive layer, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images.

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 forming a photoconductive layer using a-8i material, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms for control purposes, or other atoms for the purpose of improving other properties. This may cause problems with the electrical or photoconductive properties of the formed layer. In other words, for example, if the lifetime of the short-lived carriers generated in the formed photoconductive layer by light irradiation is insufficient, In many cases, this may not be the case, or the injection of charges from the side of the support may not be sufficiently prevented in dark areas.

Therefore, while efforts are being made to improve the properties of the a-8i 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-mentioned 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 perspective, we have discovered that an amorphous material that uses silicon atoms as its base material and contains at least either a hydrogen atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon, or a halogen amorphous material, has been developed. hydrogenated amorphous silicon, or hydrogenated amorphous silicon containing ``'d-'' (hereinafter a-8i (H, A photoconductive member designed and produced with the layer structure of a photoconductive member having a photoreceptive layer specified as explained below not only exhibits extremely superior properties in practical use, but also exhibits superior properties to conventional photoconductive members. It is superior in all respects when compared to other materials, and has particularly excellent properties as a photoconductive material for electrophotography.It also has excellent absorption spectrum characteristics on the long wavelength side. It is based on what was discovered.

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, is particularly good in matching with semiconductor lasers, and has a fast photoresponse. The purpose is to provide light that has sufficient charge retention ability during charging processing for electrostatic image formation to the 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 conductive member.

Still another object of the present invention is to provide a photoconductive material for electrophotography that can easily obtain high-quality images with high density, high density, high resolution, and clear image contrast. It is to provide parts.

Yet another object of the invention is light sensitivity.

It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics.

The photoconductive member of the present invention includes a support using a photoconductive portion, a first layer region (G) made of an amorphous material containing germanium atoms, and a non-crystalline material containing silicon atoms on the support. A second layer region (S
) and a light-receiving layer having a layered structure provided in order from the support side, and the light-receiving layer comprises a conductivity controlling substance (C
), in the photoreceptive layer, the maximum value of the distribution density 1 degree in the layer thickness direction is in the second layer region (S), and
The layer region (8) is characterized in that it is contained in a larger amount on the support side.

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, electrical pressure resistance, and usage environment characteristics.

In particular, when applied as an image forming member for electrophotography, it is possible to sufficiently prevent interference even when using coherent light, and there is no influence of residual potential on image formation, and the electrical It has stable optical characteristics, high sensitivity, and a high signal-to-noise ratio, and is excellent in light fatigue resistance and repeated use characteristics, has high density, clearly extends nof tones, and has high resolution and high resolution. Quality images can be stably and repeatedly obtained. 4 Furthermore, 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 optical response.

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

FIG. 1 is a schematic diagram schematically showing the layer structure of the photoconductive member of the present invention. The photoconductive member 100 shown in FIG. Above the 1 inch is a photoreceptive layer 102 having a free surface 105 on one end.

The photoreceptive layer 102 is made of germanium atoms and, if necessary, silicon atoms (Si 2 ) from the support ioi side.

An amorphous material containing at least one of a hydrogen atom (H) and a halogen atom (X) (hereinafter referred to as j''a-Ge(Si, f
-1°X) J and abbreviated as iC)
Area (G) 103 and a-8i ()1. X) consists of
It has a layer structure in which a second layer region (S) 104 exhibiting photoisoelectricity is laminated in order.

Photoreceptor 1iB102 is a substance that controls conduction properties (C)
The substance (C) has a maximum distribution concentration in the layer thickness direction in the second layer region (S) in the photoreception j·Δ102, and the second layer region (S) S') is contained in a state where it is distributed in large quantities toward the support 101 side.

The germanium atoms in the first layer region (G) are contained uniformly in the in-plane direction parallel to the surface 1ni of the support, but are not uniformly contained in the layer thickness direction. There is no problem even if it is uneven.

In addition, if the distribution state of germanium atoms in the first layer region (G) is non-uniform in the layer thickness direction, the distribution concentration C in the layer thickness direction may be changed to the support side or the second layer region. (S
) side, it is desirable to change it gradually, stepwise, or linearly.

In particular, 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, and the distribution concentration of germanium atoms in the layer thickness direction C(O
) decreases from the support side toward the second layer region (S), the difference between the cooling layer region (G) and the second layer region (S) In addition, as will be described later, by making the distribution concentration C of germanium atoms extremely large at the edge of the support, the second layer region (S) when using a semiconductor laser, etc. In the first layer region (G), it is possible to substantially completely absorb light on the long wavelength side, which is almost completely absorbed, and interference due to reflection from the support surface can be prevented. In both cases, reflection at the interface between the layer region (G) and the layer region (S) can be sufficiently suppressed.

Further, in the photoconductive member of the present invention, the first layer region (G
) and the second layer region (S) each have a common constituent element of silicon atoms, so chemical stability can be ensured at the laminated interface with sufficient acidity. has been done.

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

In FIGS. 2 to 1O, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer region (G), and s'B represents the first layer region (G) on the support side. The position of the end face of G
) indicates the position of the end face.

That is, the first layer region containing germanium atoms (G
), layers are formed from the tB side toward the 1T side.

FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the first layer region (G) in the layer thickness direction.

In the example shown in FIG. 2, the distance t from the interface position tB where the surface where the first layer region (G) containing germanium atoms is formed and the surface of the first layer region (G) is in contact with each other. Up to the position t, the distribution concentration C (G) of germanium atoms takes a constant value C1 and is contained in the first layer region (G) where germanium atoms are formed, and from the position t, the concentration C2
It is gradually and continuously decreased until the interface position tTrrc is reached.

At the interface position tT, the distribution concentration C of germanium atoms is
is assumed to be C3.

In the example shown in FIG. 3, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration C4 from the position tB to the position 1T, and reaches the concentration C11 at the position tT. is formed.

In the case of FIG. 4, position 1. The distribution concentration C of germanium atoms is kept constant at the concentration C6 up to position t2, and gradually and continuously decreases between position t and position 1T, and at position 1T, the distribution concentration C becomes substantially It is assumed that the amount is zero (substantially zero here means the amount is less than the detection limit).

In the case of FIG. 5, the distribution concentration C of germanium atoms is gradually decreased continuously from position 1B to position 1, and becomes substantially zero at position t.

In the example shown in FIG. 6, the distribution concentration C of germanium atoms is a constant value of concentration C0 between the position 1B and the position 1s, and the concentration C at the position tT. be done.

Between the positions t and tl''T, the distribution concentration C is linearly decreased from the position ts to the position tT.

In the example shown in FIG. 7, the distribution concentration C is at the position tB.
From position t, a constant value of concentration C8 is taken, and from position t
From 4 to position 1T, the concentration is CIl! The distribution state decreases in a linear function up to the concentration C+s.

In the example shown in FIG. 8, from positions irt and tB, position 1
Up to T, the distribution concentration C of germanium atoms is the concentration C
It decreases linearly from I4 to substantially zero.

In FIG. 9, from position tB to position t, the distribution concentration C of germanium atoms decreases numerically from concentration C15 to concentration C1, and from position t to position tT.
An example is shown in which the density is set to a constant value C, 11 between the two.

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is the concentration CI? at position tB? Until reaching position t6, the concentration C17 is slowly decreased at first, and around the position '6, it is rapidly decreased to the concentration C2A at position t6.

Between position t6 and position t7, the concentration is decreased rapidly at first, and then gradually decreased to reach C1 at position t7, and between position t and position t8, the concentration is decreased extremely slowly. It is gradually reduced to a concentration of C7° at 1 itta. Between position t and position 1T, the concentration is reduced by C7° to substantially zero according to a curve shaped as shown in the figure.

As described above, from FIGS. 2 to 10, the first layer region (G)
As described above, some typical examples of the distribution state of germanium atoms contained in the layer thickness direction, in the present invention,
On the support side, there is a part where the distribution concentration C of germanium atoms is increased, and on the interface 1T side, the distribution concentration C is increased.
The first layer region It (G) is provided with a distribution state of germanium atoms having a portion that is considerably lower than that on the support side.

The first layer region (G) constituting the photoreceptive layer constituting the photoconductive member of the present invention is preferably a layer region (G) containing germanium atoms at a relatively high concentration on the support side, as described above. It is desirable to have a location area (A).

In the present invention, the localized region (A) is
To explain using the symbols shown in the figure, the interface position is t8.
It is desirable that it be provided within 5p.

In the present invention, the localized region (A) is located at the interface position t
It may be the entire layer region (LT) with a thickness of up to 5 μm across B, or it may be a part of the layer region (LT).

Whether the localized region (A) 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 (A) has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration of germanium atoms is preferably 1000 atomic blue or more with respect to the sum with silicon atoms, More preferably 5000 atomic 4 or more, optimally I x 1.
It is desirable that the layer be formed in such a way that a distribution state such as 0' atomic rIpa or higher can be achieved. That is, in the present invention, the layer region (G) containing germanium atoms is formed from the side of the support. It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists within a layer thickness of 5 μm (preferably in a layer region with a thickness of 5 μm).

In the present invention, the content of germanium atoms contained in the first layer region (G) is determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 1. 1oX10' atomic flIa,
More preferably 100 to 9.5 x 106ato10
6ato optimally 500~8 x 105105ato
It is desirable to set it as Pin.

In the present invention, the first layer region (G) and the second layer region (S
) is one of the important factors for effectively achieving the object of the present invention, so the photoconductive member should be designed so that the formed photoconductive member has sufficient desired properties. Sufficient care needs to be taken when

In the present invention, the layer thickness TB of the first layer region (G) is preferably 30λ to 50μ, more preferably 40λ to
It is desirable that the thickness be 40μ, most preferably 50λ to 30μ.

Further, the layer thickness T of the second layer region (8) is preferably 0.5
~90μ, more preferably 1-80μ, optimally 2-80μ
It is desirable that the thickness be 50μ.

The sum (TB+T) of the layer thickness TB of the first layer region (G) and the layer thickness T of the second layer region (S) is determined by the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. It is appropriately determined as desired when designing the layers of the photoconductive member based on the organic relationship between the properties.

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 more preferred embodiment of the present invention, the above layer thickness TB and layer thickness T are preferably T, / T
When satisfying the relationship ≦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
It is desirable that the values of the layer thickness TB and the layer thickness T be determined so that the relationship B/T≦0.8 is satisfied. The content of germanium atoms is I x 105 atomic
In the case where the layer thickness TB of the first layer region CG> is as thin as possible, it is desirable that the layer thickness TB of the first layer region CG> be as thin as possible, preferably 30
It is desirable that the thickness be less than μ, more preferably less than 25 μ, optimally less than 20 μ.

In the present invention, the first layer region (G
) and/or the second layer region <S> as necessary, specific examples of the halogen atom (X) include fluorine, chlorine, bromine, and iodine. It can be mentioned as a suitable one.

In the present invention, a-Ge (S i + My X )
The first layer region (G) consisting of h is formed by, 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. For example, by glow discharge method, @Ge
First layer region (G) composed of (81# He
Basically germanium atoms (Ge) are used to form
A raw material gas for Ge supply that can supply Ge, and if necessary,
A raw material gas for supplying Si that can supply silicon atoms (St), a raw material gas for introducing hydrogen atoms (H), and/or a raw material gas for introducing halogen atoms (X) are placed in a desired deposition chamber where the internal pressure can be reduced. The material may be introduced under gas pressure to generate a glow discharge within the deposition chamber, thereby forming a layer on the surface of a predetermined support that has been placed at a predetermined position in advance. To make the germanium atoms non-uniformly distributed, the distribution concentration C of the contained germanium atoms is controlled according to the desired rate of change curve, and a −Qm (R!'IJ v) −A, l mol L
II! fz T & l brutal'r J) J'l kF
White 14-Also, when forming by a sputtering method, a target made of Si or a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases is used. Using two targets composed of Ge or a mixed target of Si and Go, if necessary, He,
The raw material gas for Ge supply or the raw material gas for 8i supply diluted with a diluting gas such as Ar is converted into hydrogen atoms (
A gas for introducing H) or/and halogen atoms (X) is introduced into a deposition chamber for sputtering to form a plasma atmosphere of the desired gas, and at the same time, The target may be sputtered while controlling the flow rate of the raw material gas according to a desired rate of change curve.

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 the evaporation sources are heated using a resistance heating method or an electron beam. This can be carried out in the same manner as in the sputtering method, except that the evaporated material is heated and evaporated by a method such as the EB method, and the flying evaporated material is passed through a desired gas plasma atmosphere.

Substances that can be used as the raw material gas for supplying s1 used in the present invention include 5l) Ta t 5itHe *
5t3Hs tSt, H, etc., ice/silanes (silanes) in a gaseous state or that can be gasified are listed as effective, especially for ease of handling during layer creation work,
5iH4t 512H6 is preferred in terms of 8i supply efficiency and the like.

As a material that can be a source gas for supplying Ge, GeH
,, Ge2Ha , Ge5L l ceJ (10, G
e, H,, GeaH14.

GeyHla, Ge@H,g, Ge,H,. Germanium hydride in a gaseous state or that can be gasified is mentioned as one that can be effectively used. In particular, Ge
H.

Ge2L t Ge5Hs is preferred.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halides, interhalogen compounds, and gases such as halogen-substituted silane derivatives. Preferable mention may be made of halogen compounds in the state or which can be gasified.

Furthermore, 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. Specifically, halogen compounds that can be suitably used include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CIF, and CIF.

BrF5 l BrF, , IF, , IF, ,
Examples include interhalogen compounds such as ICJ and IBr.

Specifically, silicon compounds containing halogen atoms, so-called silano derivatives substituted with halogen atoms, include, for example, 8
1F, , Si, F, , 5iC1,, 5iBra
.

Preferred examples include silicon halides such as the following.

When forming the characteristic photoconductive member of the present invention by a glow discharge method by employing a silicon compound containing such a)-logen atom, a raw material gas capable of supplying Si together with a raw material gas for supplying Ge may be used. a-8iG containing nitrogen atoms on a desired support without using silicon hydride gas.
It is possible to form a first layer region (G) consisting of e.

When creating the first layer region (G) containing NO 2 atoms according to the glow discharge method, basically, for example, NO 2 silicon which will be the raw material gas for supplying 8i and the raw material gas for Ge supply will be used. Germanium hydride and Ar >'5
, He and other gases are introduced into the deposition seat forming the first layer region (G) at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to create a plasma atmosphere of these gases. By forming the first layer region (G) on the desired support, it is possible to form the first layer region (G) on the desired support, but in order to more easily control the introduction ratio of hydrogen atoms, these gases Furthermore, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed to form a layer.

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

In order to introduce VC halogen atoms into the layer formed by either the sputtering method or the ion blasting method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halide is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for hydrogen atom introduction, such as H2, or the above-mentioned silanes 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 silicon compounds containing halogen are effective and used as the raw material gas for introducing halogen atoms.
In addition, Hfi', HC/.

liquid, hydrogen halide such as HI, 5iH2F, ,
St x, l5iH, C12, 5iHC1! s, 8
Halogen-substituted silicon hydrides such as iH, Br, , 5iHBr, - and GeHF5 p GeH,F, , G
eF1pGeHC1g, GeH,Clz, Ge
H, (J, GeF output rm, GeH, Br, .

GeH, Br, GeHI3. GeH,I, ,G
Halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides such as eHsI, GeF,
, GeCl, .

GeBr4, GeI4, GeF, , GaC
l2. Gaseous or gasifiable substances such as germanium halides such as GeBr, GeI, etc. can also be mentioned as useful starting materials for forming the first layer region (G).

Halides containing hydrogen atoms in these substances are the first
When forming the 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.

In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, or 8iH, St, H, etc.

The germanium compound for supplying Ge to silicon hydride such as st, H,, st4''10, etc. is a germanium compound or GeH,, Gem)'Ia y Ge5Hs t
Ge, H, o s Ge1H1! IGe,H,,G
e,H,,,Go,H,,,Ge,H,. This can also be done by coexisting germanium hydride such as the like and silicon or a silicon compound for supplying Si 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 (G) of the photoconductive member to be formed The sum (H+X) is preferably 0.01 to 40
atomic%, preferably 0.05 to 30 atomic%
mic%, optimally o, i~25 atomic%.

In order to control the amount of hydrogen atoms (6) and/or halogen atoms (X) contained in the first layer region (G), for example, the support temperature or/and the hydrogen atoms (H) or halogen atoms The amount of the starting material used to contain (X) introduced into the base of the deposition apparatus, the discharge force, etc. may be controlled.

In the photoconductive member of the present invention, the second layer region (S) that does not contain germanium atoms and, if necessary, the first layer region (G) that contains germanium atoms, have conductive properties that can be controlled. By containing the substance (C), the conductive properties of the layer region (S) and the layer region CG') can be arbitrarily controlled as desired.

At this time, the substance (C) contained in the second layer region (S)
) may be contained in the entire layer region (G) or in a part of the layer region, but in either case, it needs to be contained in a state where it is distributed more toward the support side.

That is, the layer region (SPN) containing the substance (0) provided in the second layer region (S) is provided as the entire layer region of the second layer region (S), or is provided as the entire layer region of the second layer region (S). (S) is provided as a support side end layer region (SE).When provided as a full layer region of the former, the distribution concentration C(S) is linearly distributed toward the support side. It is provided so that it increases in a stepwise manner, or in a curved manner.

When the distribution concentration C(S) increases in a curved manner, it is desirable to provide a substance (C) that controls the conductivity in the layer region (S) so that the conductivity increases monotonically toward the support side. .

When the layer region (SPN) is provided as a part of the second layer region (S), the distribution state of the substance (C) in the layer region (SPN) is parallel to the surface of the support. Although it is assumed to be uniform in the in-plane direction, it may be uniform or non-uniform in the layer thickness direction.

In this case, in order to provide the substance (C) so as to be distributed non-uniformly in the layer thickness direction in the layer region (SPN), the first
It is desirable to provide the same distributed concentration line as in the case of providing in the entire layer region (S).

When the first layer region (G) contains a substance (Q) that controls conductivity and a layer region (GPN) containing the substance (C) is provided, a layer region (GPN) containing the substance (C) is provided in the second layer region (S). In the present invention, a substance (C) that controls conduction properties is added to both the first layer region (G) and the twentieth layer region (S). When containing, the substances (C) contained in both layer regions may be the same type or different types.

Hyakunen et al., Substance that controls the same kind of conductivity in both layer regions (C)
When containing substance (C), the maximum distribution concentration in the layer thickness direction is in the second layer region (S), that is, inside the second layer region (S) or inside the first layer region (S). It is preferable to provide it at the interface with the layer region (G).

In particular, it is desirable that the maximum distribution concentration is provided in the first layer region (at the contact interface with Q or in the vicinity of the interface).

In the present invention, as described above, the substance (C) that controls conduction properties is contained in the photoreceptive layer, and the layer region (PN) containing the substance (C) is replaced by the second layer region (PN). It is preferably provided as the support side end layer region (SE) of the second layer region (S) so as to occupy at least a part of the layer region of the second layer region (S).

In the case where the layer region (PN) is generally spread over both the first layer region (S) and the second layer region (G), the layer region (PN) of the substance (C) controlling the conduction properties is used. There is a difference between the maximum distribution concentration C(G)max in the layer region (GPN) and the maximum distribution concentration C(slmax) in the layer region (SPN).
The substance (C) is contained in the photoreceptive layer so that the relational expression x < C(S)max is established.

A substance (C) that controls conductivity contained in the layer region (PN)
) can include so-called impurities outside of semiconductors and in the field, and in the present invention, P-type impurities that give P-type conductivity to Si or Examples include n-type impurities that provide properties.

Specifically, as P-type impurities, atoms belonging to group Ⅰ of the periodic table (group Ⅰ atoms), such as B (boron), At(
(aluminum), Ga (gallium), In (indium), 'rt (thallium), etc., and 8% Ga is particularly preferably used. Atoms (group Ⅰ atoms), such as P (phosphorus), As (arsenic), sb (antimony), Bi (bismuth), etc., and particularly preferably used are P, As
It is.

In the present invention, a layer region (PN
) The content of the substance (C) that controls the conductive properties contained in the layer region (PN) depends on the conductive properties required for the layer region (PN), or the support body or material with which the layer region (PN) is provided in direct contact. Relationship with properties at the contact interface with other layer regions, etc.
Depending on the organic relationship, it can be selected as appropriate. In addition, the characteristics of the other layer regions provided in direct contact with the layer region and the relationship with the characteristics at the contact interface with the other layer regions are also taken into consideration to determine the conduction characteristics of the substance (C). The content is selected appropriately.

In the present invention, the content of the substance (C) that controls conduction properties contained in the layer region (PN) is preferably 0.01 to 5 x 10' atomic ppm,
More preferably 0.5 to I x 10' atomic
ppm% optimally 1-5 X 10” atomic
It is desirable to be p.

In the present invention, a layer region (P'N) containing a substance (Q) that controls conduction properties is placed in contact with the contact interface between the first layer region (S) and the second layer region (G), or Area (PN)
occupies at least a part of the first layer region (G), and the content of the substance (C) in the layer region (PN) is preferably 30 atomic I)I)m or more, More preferably, the amount is 50 atomic ppm or more, optimally 100 atomic ppm or more, so that, for example, when the substance to be contained is the above-mentioned P-type impurity, the free surface of the photoreceptive layer is subjected to polar charging treatment. When the substance to be contained is the n-type impurity, the movement of electrons injected from the support side into the second layer region (G) can be effectively blocked. When the free surface of the layer is charged to ○ polarity, the movement of holes injected from the support side into the second layer region (G) can be effectively prevented. In this case, in the layer region (Z) of the above-mentioned Reimoto structure of the present invention except for the layer region (PN),
It is also possible to contain a substance that controls the conduction properties of a polarity different from the polarity of the substance that controls the conduction properties contained in the layer region (PN), or a substance that controls the conduction properties of the same subject. However, the actual amount contained in the layer region (PN) may be much smaller.

In such a case, the content of the substance controlling the conductive properties contained in the layer region (Z) is
) is determined as desired depending on the polarity and content of the substance contained in the substance, but preferably 0.
001-1000 atoms (1) I) m%, preferably 0.05-500 atomic ppm.

The optimum range is 0.1 to 200 atomic ppm.

In the present invention, when the layer region (PN) and the layer region (2) contain the same type of substance governing conductivity, the content in the layer region (Z) is preferably 30
It is desirable to set it to atomic ppm or less.

In addition to the above-mentioned cases, in the present invention, the photoreceptive layer contains a layer region containing a substance controlling conductivity having one polarity and a substance controlling conductivity having the other polarity. It is also possible to provide a so-called depletion layer in the contact region by providing the contact region directly with the contact region. Tsumashi,
For example, in the photoreceptive layer, the layer region containing the P-type impurity and the layer region containing the N-type impurity are provided so as to be in direct contact with each other to form a so-called P-n junction, thereby forming a depletion layer. can be provided.

FIGS. 11 to 24 show typical examples of the distribution state of the substance (C) in the layer thickness direction, which is contained in the photoreceptive layer and controls the conduction characteristics.

In these figures, the horizontal axis shows the distribution concentration C (PN) of the substance (C) in the layer thickness direction, and the vertical axis shows the layer thickness t from the support side of the photoreceptive layer. to is the layer area (G) and the layer area (
The position of the contact interface of S) is shown.

Further, the symbols used on the horizontal and vertical axes have the same meanings as those used in FIGS. 2 to 10 unless otherwise specified.

FIG. 11 shows a first typical example of the distribution state of the substance (C) that controls the conduction characteristics contained in the photoreceptive layer in the layer thickness direction.

In the example shown in FIG.
), and the concentration CI is only in the layer region (S).
Contained in a uniformly distributed concentration.

Clogging, layer area (S) is t. The end layer region between and 27 contains the substance (C) at a constant distribution concentration of C1.

In the example of FIG. 12, the layer region (G) contains the substance (C) evenly, but the layer region (S') contains the substance (C).
C) is not contained.

The substance (C) has a distribution concentration of C! in the layer region between to and t2. In the open layer regions between t and tT, C2 and C2 are contained at a constant concentration of C3, which is a much lower concentration.

By containing the substance (C) with such a distributed concentration C(1)Nl in the layer region (S) constituting the photoreceptive layer, the layer region (
G) It is possible to effectively prevent the charge injected into the layer region (S) from moving toward the surface, and at the same time, it is possible to improve photosensitivity and dark resistance.

In the example shown in FIG. 13, the layer region (G) contains the substance (C) evenly, but the concentration C4 at 7 monotonically decreases toward the upper surface and at tT. The substance (
C) is contained. In the case of the layer region shown in FIGS. 14 and 15, the substance (Q) is unevenly contained in the lower end layer region of the layer region (S). In the case of the example shown in the figure, layer ′#k(S) is the substance (
It has the hj layer region containing Q, the layer region not containing the substance ((,'), and the layer structure in which the layer is layered from the support side in this ll11,1.

The difference between the examples in FIG. 14 and FIG. 15 is that in case 14-, the distribution storm C(pN) is t.

Between and 18, VC decreases monotonically with the concentration 0-1 at the t3 position from Δ1 degree C3 at the chi position, whereas in the case of the 15th meat, at to, t, j14j t, t
This means that the concentration decreases linearly and continuously from the concentration C0 at the position o to the concentration 0 at the position t4.

Also in the examples shown in FIGS. 14 and 151, layer region 0 does not contain substance 0.

In the examples of FIGS. 17 to 24, layer regions 0 and N
It is shown whether the substance 0 that controls conductivity is contained in both regions (8).

In the case of the examples from factor 17 to FIG. In the examples shown in FIGS. 17 to 21, the layer area 0 is
The distribution state of the substance (Q) in the layer region (S) is determined by the interface position t with the second layer region (S).

Distribution concentration C (PN) decreasing towards the support side
It has a state of change.

In the examples shown in FIGS. 23 and 24, the substance 0 is contained in the entire layer region of the photoreceptive layer in the layer thickness direction.

In addition, in the case of FIG. 23, in layer region 0, t is lower than the concentration C23 at tB. tB up to the concentration C22 at
It increases linearly toward io, and in the layer region (S), the concentration 0 at tT is lower than the concentration C12 at to.
Until t. It decreases monotonically and continuously toward tT.

In the case of FIG. 24, in the layer region between j13 and tlll, the substance (Q) is contained with a constant distribution of concentration C24, and in the layer region between t13 and tT, the concentration C2 !
It decreases more linearly and reaches 0 at tT.

As explained above in Figures 11 to 24 of typical examples of changes in the distribution concentration C (PN) of the substance (Q) that controls conductivity in the photoreceptive layer, which In the example as well, the substance (Q) is contained in the photoreceptive layer such that the maximum distribution concentration of the substance ◎ exists in the second layer region (S).

In the present invention, the second
To form the layer region (8), the first layer region 0 described above is
From the starting materials (I) for katakai, excluding the starting materials that will become the raw material gas for G supply [second layer region (S)]
It can be carried out using the starting material (II) :) according to the same method and conditions as in the case of forming the first layer region 0.

That is, in the present invention, to form the second layer region (S) composed of a-8i (H,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon such as a method, a sputtering method, or an ion blating method.

For example, by glow discharge method, a-8i (H,X)
In order for the second ft, fjJ to be made of; A raw material gas for introducing hydrogen atoms (I) and/or halogen atoms (X) is placed in a deposition chamber whose interior is under reduced pressure, and a glow emitter is placed inside the deposition chamber. cause it to occur,
a on a predetermined support surface that has been previously placed in place;
It is impossible to form Jshi consisting of -8i(H,X). Also, when forming by sputtering, VJl, for example, Ar
When sputtering a target prepared by 81 in an atmosphere of an inert gas such as I-Ie or a mixed gas based on these residues, hydrogen atoms (H) and/or halogen atoms are sputtered. The gas for introducing atoms (3) may be placed in the deposition chamber for sputtering.

In the present invention, the second
The amount of hydrogen atoms or halogen atoms (3) or the sum of the amounts of hydrogen atoms and halogen atoms (+-t + X) contained in the layer region (S) is preferably 1 to 40 a
atomic%, more preferably 5-30 atomic%
, it is desirable that the amount is optimally set to 5 to 25 atomic%.

In the layer region constituting the photoreceptive layer, a layer region (PN) containing a substance that controls conduction properties (for example, a layer region (PN) containing the substance Ω by structurally introducing a group II atom or a group II atom) In order to form a photoreceptive layer, during layer formation, a starting material η for introducing a group I II atom or a starting material for introducing a group I atom is placed in a gaseous state in a deposition chamber. Possible starting materials for introducing Group I atoms include those that are gaseous at room temperature and pressure, or that can be easily gasified under layer-forming conditions. It is desirable to adopt such a starting material for introducing boron atoms.Specifically, for introducing boron atoms,
B2H6, B4HIO-R+Ho, B5H11, Ba
Hto, B6HI2. Boron hydride such as B6H14, BF
, , BCI, , BBr, and other boron halides. In addition, AIICIIs.

GaC& , Ga(CH,), , InC4, Tl
Cll5 etc. can also be mentioned.

The starting materials for introducing phosphorus atoms that are effectively used in the present invention as starting materials for introducing group V atoms include PH,
P, hydrogenated phosphorus such as crosspiece, PH, l,! 'F3゜PF,
, PCIl,1 , PCIH,PBr, , Pl
Examples include phosphorus halides such as r, , and PIs. In addition, AsH3, AsF3゜As(J3.AsBr3
, AsF, , SbH3, SbF, , SbF,
, 8b (Js.

5b(J, , HiH3, BiCA'3. B1Br
3 and the like can also be cited as effective starting materials for introducing Group V atoms. Supports used in the present invention include:
It may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, and Al1Cr.
t Mos Aus Nbs Ta% Vt Ti 1
Examples include metals such as Pt and Pd, and alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually 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.

Ats Cr%MO% Aub Ir, Nbs Ta
, Vb Tib Pt5Pd I In*Os, Sn
02, conductivity is imparted by providing a thin film made of ITO (In2O5+ Snow), etc., or if it is a synthetic resin film such as a polyester film, NiCr, At, Ags Pbs Z11%Nr
* Au% Cr * Mo, IrS Nb% T
Vacuum deposition of thin films of metals such as at V, Tis Pt, etc.
Provided on the surface by electron beam evaporation, sputtering, etc.
Alternatively, the surface is laminated with the metal to impart conductivity to the surface. The shape of the support may be any shape such as a cylindrical shape, a square shape, a plate shape, etc., and the shape is determined as desired. For example, the photoconductive member 100 of FIG. When used as a photographic image forming member, it is desirable to have an endless belt shape or a cylindrical shape for continuous high-speed copying. 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. In such cases, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.,
It is assumed to be 10μ or more.

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

FIG. 25 shows an example of a photoconductive member manufacturing apparatus.

In the gas cylinders 202 to 206 in the figure, raw material gas for forming the photoconductive member of the present invention is sealed.
H4 gas (purity 99.999%, hereinafter referred to as S i Ha/H
Abbreviated as e. ) cylinder, 203 is Ge diluted with T(e)
L gas (purity 99.999%, hereinafter abbreviated as GeL/He) cylinder, 204 is SiF4 gas diluted with He (
Purity 99.99%, hereinafter abbreviated as S i F4/H13.

) cylinder, 205 is a cylinder of B and Ha gas (purity 99.999%, hereinafter abbreviated as BaHa/He) diluted with He, and 206 is a cylinder of H2 gas (purity 99.999%).

To allow these gases to flow into the reaction chamber 201, make sure that the pulps 222 to 226 of the gas cylinders 202 to 206 and the leak pulp 235 are closed. After confirming that the auxiliary pulps 232 and 233 are open, first the main pulp 234 is opened to exhaust the reaction chamber 201 and each gas pipe. Next, the reading on the vacuum gauge 236 is about 5X.
When the pressure reaches 10 torr, the auxiliary pulp is 232.233
, close the outflow pulps 217-221.

Next, to give an example of forming a light-receiving layer on the cylindrical substrate 237, the gas cylinder 202') Si
H4/He gas, gas cylinder 203! 7 GeH
4/Heli switch, adjust the pressure of the outlet pressure gauge 227, 228 to lkp/c4 between the pulps 222, 223, respectively, and gradually open the inflow pulps 212, 213, and then open the FC in the mass flow controller 207, 208 Let each of them flow in. Subsequently, the outflow pulps 217 and 218 and the auxiliary pulp 232 are gradually opened to allow the respective gases to flow into the reaction seat 201. 5IH4/He gas flow rate and GeH at this time
Adjust the outflow pulp 217, 218 so that the ratio of 4/He gas flow rate becomes the desired value, and adjust the main flow while checking the reading of the vacuum gauge 236 so that the pressure inside the reaction chamber 201 becomes the desired value. Adjust the opening of the pulp 234. and base 2
The temperature of 37 is raised to 50-400° by heating heater 238.
After confirming that the temperature is set in the co range,
The power supply 240 is set to a desired power to generate a glow discharge in the reaction chamber 201 to form a first layer region (Q) on the substrate 237.
form.

When the first layer region (6) has been formed to the desired layer thickness, the outflow pulp 218 is completely closed and the gas cylinder 205 is filled with the BtHa/He gas.
I (e gas) is introduced into the reaction chamber 201 by the same pulp operation as the e-gas and controlled by the mass controller 210 according to the desired doping curve, and under similar conditions except that the discharge conditions are changed as necessary. By maintaining the glow discharge for a desired period of time in accordance with the above procedure, it is possible to form a second layer region (2) substantially free of germanium atoms on the first layer region.

In this way, an amorphous layer composed of the first layer region (S) and the second layer region (S) is formed on the base body 237.

During layer formation, in order to ensure uniform layer formation, the substrate 237 is moved by a motor 239 at a constant speed, and a cylindrical At
Each sample as an electrophotographic image forming member was formed on a substrate under the conditions shown in Table 1 (see Table 2).

When forming the layer region 09), the distribution concentration shown in FIG. 26 was formed for each sample by changing the flow rate ratio of BtH6 gas and PHs gas according to a predesigned change rate line.

Place each sample obtained in this way in a charging exposure experiment device.■5. Corona charging was performed at OkV for 0.3see, and a light image was immediately irradiated. The light image was created using a tungsten Lang light source, and a light intensity of 21 ux-sec was irradiated through a transmission type test chart. The cascading thus resulted in a good toner image on the surface of the photoreceptor layer. The toner image on the photoreceptive layer is
When transferred onto transfer paper using 5.0 kV (D corona charging), each sample had excellent resolution and a clear, high-density image with good gradation reproducibility was obtained.

In the above, the light source is replaced by a tungsten lamp81
0 nm L: DGaAs semiconductor laser (10mW)
The image quality of the toner transfer image was evaluated for each sample in the same manner as above, except that the electrostatic image was formed using Clear, high-quality images were obtained.

Example 2 The manufacturing apparatus shown in FIG.
Each sample as an electrophotographic image forming member was formed on the substrate under the conditions shown in Table 3 (see Table 4).
By changing the flow rate ratio of H and gas according to a predesigned change rate line, the distributed concentration shown in FIG. 27 was formed for each sample.

When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples produced high-quality toner transfer images.
When a repeated use test was conducted 200,000 times in an RH environment, no deterioration in image quality was observed in any of the samples.

Table 4 Example 3 A cylinder-shaped At
Samples (Samples N [L 31-1 to 37-12) as electrophotographic image forming members were prepared on a substrate under the conditions shown in Table 5 (Table 6).

The content distribution concentration of germanium atoms in each sample is the second
8, and the distribution concentration of impurity atoms is shown in FIGS. 26 and 27.

When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples provided high quality toner transfer images. Also, for each sample, 38°C 180%
When a repeated use test was conducted 200,000 times in an RI environment, no deterioration in image quality was observed in any of the samples.

Common layer forming conditions in the above embodiments of the present invention are shown below.

Substrate temperature: Germanium atom (Ge) containing layer: approx. 200°C Germanium atom (Ge) non-containing layer: approx. 250°C Discharge frequency: 13.56 MHz 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 germanium atoms in each layer region. figure,
FIGS. 11 to 24 are explanatory views for explaining the distribution state of impurity atoms in the photoreceptive layer, respectively. FIG. 25 is a schematic explanatory view of the apparatus used in the present invention, and FIG. to second
FIG. 8 is an explanatory diagram showing the distribution state of each atom in each example of the present invention. 100...Photoconductive member 101...Support 102...Photoreceptive layer Applicant Canon Co., Ltd. Agent Gi Marushima ml' (Dedicated 11111Q〒11C-11 111 Hai-C -111→-C C (FW) 0 (PI/) -C(p)i) 111-IC (#A/) 1st j copy fan 180 Taku IC10 C (PPJ ) 0 (PN) 110 (silk) 11111100 (py) 11111 C (PN)

Claims (1)

[Claims] (1) A support for a photoconductive member, a first layer region (G) made of an amorphous material containing germanium atoms on the support, and a first layer region (G) containing silicon atoms. The photoreceptive layer has a layered structure in which a second layer region (S) made of an amorphous material and exhibits photoconductivity is provided in order from the side of the support, and the photoreceptor layer has a conductive layer. In the photoreceptive layer, the maximum distribution concentration of the substance (C) in the layer thickness direction is in the second layer region (S), and ) at -
The photoconductive member is characterized in that the above-mentioned photoconductive material is contained in a state where it is distributed in a larger amount on the side of the support. (2) The photoconductive member according to claim 1, wherein the first layer region (G) contains silicon atoms. (3) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is non-uniform in the layer thickness direction. (4) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is uniform in the layer thickness direction. (5) The photoconductive member according to claim 1, wherein at least one of the first layer region (G) and the second layer region (8) contains hydrogen atoms. (6) The photoconductive material according to Claims 1 and 5, wherein at least one of the first layer region (G) and the second layer region (S) contains a halogen atom. Element. (Force) The photoconductive member according to claim 2, wherein the distribution state of germanium atoms in the first layer region (G) is such that more germanium atoms are distributed toward the support side. (8) The photoconductive member according to claim 1, wherein the substance (C) that controls conductivity is an atom belonging to Group Ⅰ of the periodic table. (9) The substance (C) that controls conductivity is an atom that belongs to group Photoconductive member 0 according to claim 1, which is an atom belonging to Group V of the table.