JPH0450586B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
The present invention relates to a photoconductive member for laser light that is sensitive to electromagnetic waves such as. 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 is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and 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 these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and stability over time, and it is necessary to improve overall 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 was often observed that residual potential remained during use. When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speeds, the response gradually decreases, etc. This often occurred. Furthermore, a-Si has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, 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 longer wavelength side cannot be used effectively. In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light that reaches the support increases, the support itself will absorb the light that passes through the photoconductive layer. When the reflectance is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater 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 with an a-Si material, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., 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, but how these constituent atoms are contained is determined. Problems may therefore arise in the electrical or photoconductive properties of the formed layer. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, etc. This often occurs. 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 includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "hydrogenated amorphous silicon"] ``a-Si(H,X)'' is used as a generic notation for The photoconductive materials designed and produced under this technology not only exhibit extremely superior properties in practical use, but also exceed conventional photoconductive materials in every respect, especially when used with laser light. We have discovered that it has extremely excellent properties as a photoconductive member for electrophotography (hereinafter sometimes abbreviated as photoconductive member), and that it has excellent absorption spectrum characteristics on the long wavelength side. It is based on points. 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 photoresponse. 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. It is an object of the present invention to provide a photoconductive member having sufficient performance. 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 to
Another object of the present invention is to provide a photoconductive member having high signal-to-noise ratio characteristics. The photoconductive member for laser light of the present invention includes a support for the photoconductive member, a first layer region made of an amorphous material containing silicon atoms and germanium atoms on the support, and a silicon atom. an amorphous layer having a layered structure provided in order from the support side, and a second layer region exhibiting photoconductivity made of an amorphous material containing The distribution concentration of germanium atoms in the layer is arranged in the layer thickness direction so that there is a part with a high concentration of 1000 atomic ppm or more within 5μ from the support side, and a part where the distribution concentration is considerably lower than that on the support side. The first amorphous layer is non-uniform, and is characterized in that the first amorphous layer contains atoms belonging to Group 1 or Group 3 of the periodic table. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, photoconductive properties, and 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, and it is highly sensitive and has high
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. 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 FIG. 1 has an amorphous layer 102 on a support 101 for photoconductive member.
The amorphous material 102 has a free surface 105 on one end surface. The amorphous layer 102 is made of a-Si containing germanium atoms from the support 101 side.
(H,X) (hereinafter abbreviated as "a-SiGe(H,X)") and a
-Si(H,X) and a second layer region (S) 104 having photoconductivity 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 are
1 (the side opposite to the side where the amorphous layer 1 is provided)
02 surface 105 side)
It is contained in the first layer region (G) 103 so that it is distributed more toward the 01 side. In the photoconductive member 100 of the present invention, at least the first layer region (G) 103 contains a substance (C) that controls conduction characteristics, and the first layer region (G) 103 has a desired amount of The conduction properties are given. In the present invention, the first layer region (G) 103
The substance (C) that controls the conduction properties contained in
It may be uniformly contained in the entire layer region of the first layer region (G) 103, and the first layer region (G) 1
It may be contained so as to be unevenly distributed in some layer regions of 03. Substance (C) that controls conduction properties in the present invention
When the substance (C) is contained in the first layer region (G) so as to be unevenly distributed in a part of the layer region (G), the layer region (PN) in which the substance (C) is contained
is preferably provided as an end layer region of the first layer region (G). In particular, when the layer region (PN) is provided as the end layer region on the support side of the first layer region (G), the substance (C) contained in the layer region (PN) By appropriately selecting the type and content thereof as desired, it is possible to effectively prevent charge of a specific polarity from being injected from the support into the amorphous layer. In the photoconductive member of the present invention, the substance (C) capable of controlling conduction properties is added to the first layer region (G) constituting a part of the amorphous material as described above. It is intended to be contained evenly throughout the layer region (G) or unevenly distributed in the layer thickness direction, but furthermore, it is contained in the second layer region (S) provided on the first layer region (G). ) may also contain the substance (C). When the substance (C) is contained in the second layer region (S), the type, amount and content of the substance (C) contained in the first layer region (G) are determined. Depending on the method, the type and content of the substance (C) to be contained in the second layer region (S), and the manner of its inclusion are appropriately determined. In the present invention, when the substance (C) is contained in the second layer region (S), preferably the substance (C) is contained in the layer region including at least the contact interface with the first layer region (G). It is desirable to include a substance. In the present invention, the substance (C) may be uniformly contained in the entire layer region of the second layer region (S), or may be uniformly contained in a part of the layer region. is also good. When both the first layer region (G) and the second layer region (S) contain a substance (C) that controls conduction characteristics, the substance (C) in the first layer region (G) It is desirable that the layer region containing the substance (C) and the layer region containing the substance (C) in the second layer region (S) be in contact with each other. Moreover, the first layer region (G) and the second layer region (S)
The substance (C) contained in the first layer region (G) and the second layer region (S) may be of the same kind or different kinds, and the content thereof may be Each layer region may be the same or different. However, in the present invention, when the substance (C) contained in each layer region is the same in both, the content in the first layer region (G) is sufficiently large. Alternatively, it is preferable that substances (C) of different types with different electrical properties are contained in each desired layer region. In the present invention, by containing the substance (C) that controls conduction characteristics at least in the first layer region (G) constituting the amorphous layer, the substance (C) is contained. Layer region [first layer region (G)
It is possible to arbitrarily control the conduction properties of the layer (either part or all of the layer region) as desired, but such materials include the so-called
Examples of impurities used in the semiconductor field include P-type impurities that give P-type conductivity to a-SiGe (H,X) that constitutes the amorphous layer to be formed. and n-type impurities that provide n-type conductivity characteristics. Specifically, P-type impurities include atoms belonging to the group of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium). Among them, B and Ga are particularly preferably used. Examples of n-type impurities include atoms belonging to a group of the periodic table (group atoms), such as P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc.
In particular, P and As are preferably used. In the present invention, the content in the layer region (PN) containing the substance controlling conduction properties is as follows:
The conductive properties required for the layer region (PN) or, if the layer region (PN) is provided in direct contact with the support, the relationship with the properties at the contact interface with the support. etc., can be selected as appropriate based on organic relevance. In addition, the relationship with other layer regions provided in direct contact with the layer region (PN) and the characteristics at the contact interface with the other layer regions is also considered, and the material controlling the conduction characteristics is determined. 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 usually 0.01 to 5×10 ⁴ atomic ppm, preferably 0.5 to 1×10 ⁴ atomic ppm, optimally,
It is desirable that the content be 1 to 5×10 ³ atomic ppm. In the present invention, the content of the substance (C) in the layer region (PN) containing the substance (C) that controls conduction characteristics is usually set to 30 atomic ppm or more,
Preferably 50 atomic ppm or more, optimally
By setting the concentration to 100 atomic ppm or more, for example, when the substance (C) to be contained is the above-mentioned p-type impurity, when the free surface of the amorphous layer is subjected to a polar charging treatment, the charge from the support side can be reduced. Injection of electrons into the amorphous layer can be effectively prevented, and when the substance (C) to be contained is the n-type impurity, the free surface of the amorphous layer becomes polar. When subjected to charging treatment, injection of holes from the support side into the amorphous layer can be effectively prevented. In the above case, as described above, the layer region (Z) excluding the layer region (PN) contains a substance (C) that controls the conductive properties contained in the layer region (PN). It may contain a substance (C) that governs the conduction characteristics of a conduction type polarity different from that of the conduction type polarity, or it may contain a substance (C) that governs the conduction characteristics of a conduction type of the same polarity. , it may be contained in an amount much smaller than the actual amount contained in the layer region (PN). In such a case, the content of the substance (C) that controls the conduction characteristics contained in the layer region (Z) depends on the polarity and content of the substance (C) contained in the layer region (PN). It is determined as desired depending on the amount, but usually 0.001~
1000atomic ppm, preferably 0.05-500atomic
ppm, preferably 0.1 to 200 atomic ppm. In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance (C) that controls conductivity, the content in the layer region (Z) is preferably is preferably 30 atomic ppm or less. In the present invention, the amorphous layer contains a layer region containing a substance controlling conductivity having a conductivity type of one polarity, and a substance controlling conductivity having a conductivity type of the other polarity. It is also possible to provide a so-called depletion layer in the contact region by directly contacting a layer region containing . For example, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in the amorphous layer so as to be in direct contact with each other to form a so-called p-n junction. Thus, a depletion layer can be provided. In the photoconductive member of the present invention, the germanium atoms contained in the first layer region (G) have the above-mentioned distribution state in the layer thickness direction, and are parallel to the surface of the support. It is desirable to have a uniform distribution state in the in-plane direction. 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 of all wavelengths from relatively short wavelengths to relatively long 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, and the distribution concentration C of germanium atoms in the layer thickness direction increases from the support side to the second layer region. Since the change decreases toward the layer region (S), there is excellent affinity between the first layer region (G) and the second layer region (S), and as will be described later. As,
By extremely increasing the distribution concentration C of germanium atoms at the end of the support side, when a semiconductor laser or the like is used, the long wavelength side, which is almost completely absorbed by the second layer region (S), can be Light can be substantially completely absorbed in the first layer region (G), and interference due to reflection from the support surface can be prevented. Further, in the photoconductive member of the present invention, each of the amorphous materials constituting the first layer region (G) and the second layer region (S) has a common constituent element of silicon atoms. Therefore, chemical stability is sufficiently ensured at the laminated interface. 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. 2 to 10, 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 _tB represents the first layer region (G) on the support side. ), and t _T indicates the position of the end surface of the first layer region (G) on the side opposite to the support side. That is, in the first layer region (G) containing germanium atoms, layers are formed from the t _B side toward the t _T side. FIG. 2 shows the first distribution state of germanium atoms contained in the first layer region (G) in the layer thickness direction.
A typical example is shown. In the example shown in FIG. 2, from the interface position t _B where the surface where the first layer region (G) containing germanium atoms is formed and the surface of the first layer region (G) contact, t ₁ Up to the position t1, the distribution concentration C of germanium atoms takes a constant value _C1 and is contained in the first layer region (G) in which germanium atoms are formed, and from the position _t1 the concentration _C2 decreases to the interface. It is gradually and continuously decreased until reaching position _tT . Interface position t _T
The distribution concentration C of germanium atoms is C ₃
It is said that In the example shown in FIG. 3, the distribution concentration C of the germanium atoms contained is from the position t _B to the position t _T
A distribution state is formed in which the concentration gradually and continuously decreases from C ₄ until reaching C ₅ at position t _T . In the case of Fig. 4, the distribution concentration C of germanium atoms is constant at a concentration _C6 from position t _B to position t ₂ , and gradually and continuously between position t ₂ and position t _T. At position t _T , the distribution concentration C
is substantially zero (substantially zero here means less than the detection limit amount). In the case of Fig. 5, the distribution concentration C of germanium atoms is gradually decreased continuously from the concentration c ₈ from position t _B to position t _T , and becomes substantially zero at position t _T. . In the example shown in FIG. 6, the distribution concentration C of germanium atoms between position t _B and position t ₃ is as follows:
The concentration C is a constant value of ₉ , and at the position t _T the concentration
It is said to be C ₁₀ . Between the position t ₃ and the position t _T , the distribution concentration C is linearly decreased from the position t ₃ to the position t _T . In the example shown in FIG. 7, the distribution concentration C takes a constant value of concentration C ₁₁ from position t _B to position t ₄ ,
From position _t4 to position _tT , the distribution state is such that the concentration decreases linearly from _C12 to _C13 . In the example shown in FIG. 8, from position t _B to position t _T
Up to , the distribution concentration C of germanium atoms decreases linearly from the concentration C ₁₄ to substantially zero. In FIG. 9, the distribution concentration C of germanium atoms from position t _B to position t ₅ is the concentration C ₁₅
The concentration C is linearly decreased to ₁₆ , and the position t ₅
An example is shown in which the concentration C ₁₆ is kept at a constant value between and the position t _T . In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration C ₁₇ at the position t _B , and is gradually decreased from this concentration C ₁₇ until reaching the position t ₆ , and then at t ₆ . Near the position, the concentration decreases rapidly to a concentration _C18 at position _t6 . Between position t ₆ and position t ₇ , the concentration is decreased rapidly at first, then slowly and gradually decreased to reach C ₁₉ at position t ₇ , and then between position t ₇ and position t ₈ Then, it is gradually decreased very slowly to reach the concentration C ₂₀ at position t ₈ . Between position _t8 and position _tT , the concentration is reduced from _C20 to substantially zero according to a curve shaped as shown in the figure. As described above with reference to FIGS. 2 to 10, some typical examples of the distribution state of germanium atoms contained in the first layer region (G) 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 high, and on the interface _tT side, the distribution state of germanium atoms has a part where the distribution concentration C is considerably lower than that on the support side. is provided in the layer region (G). The first layer region (G) constituting the amorphous layer constituting the photoconductive member in the present invention preferably contains germanium atoms at a relatively high concentration on the support side, as described above. It is desirable to have a localized area A. In the present invention, the localized region A is defined as the interface position by using the symbols shown in FIGS. 2 to 10.
It is desirable that it be provided within 5μ from _tB . In the present invention, the localized region A may be the entire layer region (L _T ) up to 5μ thick from the interface position t _B , or may be a part of the layer region (L _T ). In some cases. Whether the localized region A is a part or all of the layer region (L _T ) is determined as appropriate depending on the characteristics required of the amorphous layer to be formed. 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 usually 1000 atomic ppm or more, preferably 1000 atomic ppm or more relative to silicon atoms.
5000 atomic ppm or more, optimally 1×10 ⁴ atomic
It is desirable that the layer be formed in such a way that it can have a distribution state of ppm or more. That is, in the present invention, the amorphous layer containing germanium atoms has a layer thickness from the support side.
It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists within 5μ (layer region with a thickness of 5μ from t _B ). In the present invention, the content of germanium atoms contained in the first layer region is appropriately determined as desired so as to effectively achieve the object of the present invention, but is usually 1 to 9.5× 10 ⁵ atomic ppm,
Preferably 100 to 8×10 ⁵ atomic ppm, optimally
It is desirable that the content be 500 to 7×10 ⁵ atomic ppm. In the present invention, the layer thickness of 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. Considerable care must be taken in the design of the photoconductive member to ensure that the photoconductive member has the desired properties. In the present invention, the layer thickness of the first layer region (G)
T _B is typically 30 Å to 50 μ, preferably 40
It is desirable that the thickness be 50 Å to 30 μ, most preferably 50 Å to 30 μ. Further, the layer thickness T of the second layer region (S) is usually 0.5 to 90μ, preferably 1 to 80μ, and optimally 2
It is desirable that the thickness be ~50μ. The sum (T _B +T) of the layer thickness T _B of the first layer region (G) and the layer thickness T of the second layer region (S) is based on the characteristics required for both layer regions and the entire amorphous layer. It is determined as desired when designing the layers of the photoconductive member, based on the organic relationship between the characteristics and the properties required for the photoconductive member. In the photoconductive member of the present invention, the above (T _B
The numerical range of +T) is usually 1 to
It is desirable that the thickness be 100μ, preferably 1 to 80μ, most preferably 2 to 50μ. In a more preferred embodiment of the present invention,
The above layer thickness T _B and layer thickness T are usually T _B /
When satisfying the relationship T≦1, it is desirable that appropriate numerical values be selected for each. In selecting the numerical values of the layer thickness T _B and the layer thickness T in the above case, it is more preferable that T _B /T≦0.9,
Optimally, it is desirable that the values of layer thickness T _B and layer thickness T be determined so that the relationship T _B /T≦0.8 is satisfied. In the present invention, the content of germanium atoms contained in the first layer region (G) is 1×10 ⁵
In the case of atomic ppm or more, the layer thickness T _B of the first layer region (G) is desirably as thin as possible, preferably 30μ or less, more preferably
It is desirable that the thickness be 25μ or less, optimally 20μ or less. In the present invention, a first layer region (G) and a second layer region (S) constituting an amorphous layer as necessary
Specific examples of the halogen atom (X) contained therein include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. In the present invention, the first layer region (G) composed of a-SiGe (H, It is done by a deposition method. For example, in order to form the first layer region (G) composed of a-SiGe (H, A raw material gas for Ge supply that can supply raw material gas and germanium atoms (Ge), and a raw material gas for introducing hydrogen atoms (H) and/or raw material gas for introducing halogen atoms (X) as necessary. , the germanium atoms contained on the surface of a predetermined support, which has been placed at a predetermined position, are introduced at a desired pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge in the deposition chamber. It is sufficient to form a layer made of a-SiGe(H,X) while controlling the distribution concentration according to a desired rate of change curve. In addition, when forming by a sputtering method, for example, a target composed of Si or a target composed of Si is formed in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases.
Using two targets composed of Ge,
Or using a mixed target of Si and Ge,
Diluted with diluent gas such as He or Ar as necessary
A raw material gas for supplying Ge and, if necessary, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) are introduced into a deposition chamber for sputtering to form a plasma atmosphere of the desired gas. , said
The target may be sputtered while controlling the gas flow rate of the raw material gas for supplying Ge according to a desired rate of change curve. In the case of the ion plating 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 resistance heating method or electron beam method ( This can be carried out in the same manner as in the case of sputtering, except that the flying evaporates are heated and evaporated by EB method or the like and passed through a desired gas plasma atmosphere. Substances that can be used as the raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially because of its ease of handling during layer creation work and good Si supply efficiency. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Substances that can be used as raw material gas for Ge supply include:
_{GeH4 , Ge2H6 , Ge3H8 , Ge4H10} , _{Ge5H12 , Ge6}
Germanium hydride in a gaseous state or which can be gasified, such as H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , etc., can be mentioned as one that can be effectively used. In terms of Ge supply efficiency, etc.
Preferred examples include GeH ₄ , Ge ₂ H ₆ and Ge ₃ H ₈ . Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. The first layer region (G) made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When creating the first layer region (G) containing halogen atoms according to the glow discharge method, basically:
For example, silicon halide, which will be the raw material gas for supplying Si, germanium hydride, which will be the raw material gas for Ge supply, and gases such as Ar, H ₂ , He, etc., are mixed at a predetermined mixing ratio and gas flow rate. A first layer region (G) is deposited on the desired support by introducing a layer region (G) into a deposition chamber and generating a glow discharge to form a plasma atmosphere of these gases. However, in order to make it easier to control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be further mixed with these gases to form a layer. It may be formed. 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 halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen 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 addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient 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 in addition, HF, HCl,
Hydrogen halides such as HBr and HI, SiH ₂ F ₂ , SiH ₂
Halogen-substituted silicon hydrides such _{as I2} , _SiH2Cl2 , _SiHCl3 , _SiH2Br2 , _{SiHBr3 ,} and _GeHF3 , _{GeH2F2 ,
GeH3F , GeHCl3} , _GeH2Cl2 , _GeH3Cl ,
_{GeHBr3 , GeH2Br2} , _GeH3Br , _GeHI3 , _GeH2
Germanium hydrogenated halides such as I ₂ , GeH ₃ I,
Halides containing hydrogen atoms as one of their constituent elements, such as GeF ₄ , GeCl 4 , GeBr ₄ , GeI _{4 ,} GeF ₂ ,
Gaseous or gasifiable substances such as germanium halides such as GeCl ₂ , GeBr ₂ , GeI ₂ and the like can also be mentioned as useful starting materials for forming the first layer region (G). The halides containing hydrogen atoms in these substances introduce halogen atoms into the layer when forming the first layer region (G), and at the same time introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties. Since it will be introduced,
In the present invention, it is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, H ₂ , SiH ₄ , Si ₂
Silicon hydride such as H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ with germanium or a germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ ,
Germanium hydride such as Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si are allowed to coexist in the deposition chamber. This can also be done by causing electrical 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 usually 0.01 to 40 atomic%, preferably 0.05 to 40 atomic%.
It is desirable that it be 30 atomic%, optimally 0.1 to 25 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained therein, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (X) can be controlled. What is necessary is to control the amount of the starting material used, introduced into the deposition system, the discharge power, etc. In the present invention, in order to form the second layer region (S) composed of a-Si(H,X), the starting material (I) for forming the first layer region (G) described above is used. The first layer region (G) is formed using the starting material [starting material for forming the second layer region (S) ()] excluding the starting material that will become the raw material gas for G supply from among the above. It can be carried out according to the same method and conditions as in the case of forming. That is, in the present invention, a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used to form the second layer region (S) composed of a-Si (H, It is made by a vacuum deposition method. For example, in order to form the second layer region (S) composed of a-Si (H, Along with the raw material gas for supplying Si, a raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as needed is introduced into a deposition chamber whose interior can be reduced in pressure. to generate a glow discharge, and a
A layer consisting of -Si(H,X) may be formed.
In addition, when forming by a sputtering method, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or hydrogen atoms and halogen atoms contained in the second layer region (S) constituting the amorphous layer to be formed The sum of the amounts (H+X) is usually 1 to 40 atomic%, preferably 5 to 40 atomic%.
It is desirable that it be 30 atomic %, optimally 5 to 35 atomic %. A substance (C) that controls conduction properties, for example, group group atoms or group atoms, is structurally introduced into the layer region constituting the amorphous layer to form a layer region containing the substance (C) (PN ), during layer formation, a starting material for introducing group atoms or a starting material for introducing group atoms is placed in a gaseous state in a deposition chamber, and other materials for forming an amorphous layer are added. It may be introduced together with the starting material. As a starting material for introducing such group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such group atom include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ ,
Boron hydride _{such as B5H11} , _B6H10 , _{B6H12 , B6H14 ,} etc.
Examples include boron halides such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ ,
InCl ₃ , TlCl ₃ and the like can also be mentioned. In the present invention, effective starting materials for introducing a group atom include hydrogenated phosphorus such as PH ₃ and P ₂ H ₄ , PH ₄ I, PF ₃ ,
Examples include phosphorus halides such as _PF5 , _PCl3 , _PCl5 , _PBr3 , _PBr5 , and _PI3 . In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ ,
SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for the introduction of group atoms. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, 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,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al , Ag, Pb, Zn, Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of 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. However, in such cases, the thickness is usually 10μ or more in view 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 diagram include
The raw material gas for forming the photoconductive member of the present invention is sealed, for example, 110
2 is SiH ₄ gas diluted with He (99.999% purity,
Hereinafter, it will be abbreviated as SiH ₄ /He. ) cylinder, 1103 is He
_GeH4 gas diluted with (purity 99.999% or less)
Abbreviated as GeH ₄ /He. ) cylinder, 1104 is SiF ₄ gas diluted with He (purity 99.99%, hereinafter referred to as SiF ₄ /He)
It is abbreviated as ) cylinder, 1105 diluted with He
B ₂ H ₆ gas (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ /He) cylinder, 1106 is H ₂ gas (purity 99.999)
%) It is a cylinder. In order to flow these gases into the reaction chamber 1101, valves 112 of gas cylinders 1102 to 1106 are used.
2-1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112-1126 is closed.
Step 1116: After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, to give an example of forming an amorphous layer on the cylindrical substrate 1137, the gas cylinder 11
SiH ₄ /He gas from 02, GeH ₄ /He gas from gas cylinder 1103, B ₂ from gas cylinder 1105
H ₆ /He gas through valves 1122, 1123, 11
25 and outlet pressure gauges 1127 and 112 respectively.
Adjust the pressure of 8, 1130 to 1 Kg/cm ² , gradually open the inflow valves 1112, 1113, 1115, and then press the mass flow controllers 1107, 1108,
1110 respectively. Subsequently, the outflow valves 1117, 1118, 1120 and the auxiliary valve 1132 are gradually opened to supply each gas to the reaction chamber 11.
01. At this time, the outflow valve 111 is adjusted so that the ratio of the SiH ₄ /He gas flow rate, GeH ₄ /He gas flow rate, and B ₂ H ₆ /He gas flow rate becomes a desired value.
7, 1118, 1120, and reaction chamber 1
Vacuum gauge 1 so that the pressure inside 101 reaches the desired value
Adjust the opening of the main valve 1134 while checking the reading of 136. After confirming that the temperature of the base 1137 is set to a temperature in the range of 50 to 400°C by the heating heater 1138, the power supply 1137
140 to a desired power to generate a glow discharge in the reaction chamber 1101, and at the same time, the flow rate of GeH ₄ /He gas is controlled manually or by a method such as an externally driven motor according to a pre-designed rate of change curve. The distribution concentration of germanium atoms contained in the formed layer is controlled by gradually changing the opening of the valve 1118. In the manner described above, glow discharge is maintained for a desired period of time to form a first layer region (G) on the substrate 1137 to a desired layer thickness. First layer region (G) to desired layer thickness
At the stage where the outflow valve 1118 is formed, the outflow valve 1118
Following similar conditions and procedures, except for completely closing the battery and changing the discharge conditions as necessary,
By maintaining the glow discharge for a desired period of time, a second layer region (S) substantially free of germanium atoms can be formed on the first layer region (G). In order to contain the substance (C) that controls conductivity in the second layer region (S),
For example, a gas such as B ₂ H ₆ or PH ₃ may be added to other gases introduced into the deposition chamber 1101. In this way, the amorphous layer composed of the first layer region (G) and the second layer region (S) is transferred to the base 113.
Formed on 7. During layer formation, the base 1137 is preferably rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Reference examples and examples will be described below. Reference Example 1 Using the manufacturing apparatus shown in FIG. 11, the following steps were carried out on a cylindrical Al substrate under the conditions shown in Table 1 and according to the rate of change curve of the gas flow rate ratio shown in FIG. 12.
An electrophotographic image forming member was obtained by forming layers while changing the gas flow rate ratio of GeH ₄ /He gas and SiH ₄ /He gas with the elapsed layer formation time. The image-forming member thus obtained was installed in a charging exposure experimental device, corona charged at 5.0 KV for 0.3 seconds, and a light image was immediately irradiated using a tungsten lamp light source, and a light intensity of 2 lux.sec was applied to a transmission type. It was irradiated through a test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
Transferred onto transfer paper with 5.0KV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Reference Example 2 Using the manufacturing equipment shown in Fig. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the change rate curve of the gas flow rate ratio shown in Fig. 13 under the conditions shown in Table 2. Layer formation was carried out under the same conditions as in Reference Example 1, except that the ratio was changed with the elapsed time of layer formation, 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 Reference Example 1, an extremely clear image was obtained. Reference Example 3 Using the manufacturing equipment shown in Fig. 11, the gas flow rates of GeH ₄ /He gas and SiH 4 /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in Fig. 14 under the conditions shown in Table ₃ . Layer formation was carried out under the same conditions as in Reference Example 1, except that the ratio was changed with the elapsed time of layer formation, 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 Reference Example 1, an extremely clear image quality was obtained. Reference Example 4 Using the production equipment shown in Fig. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the change rate curve of the gas flow rate ratio shown in Fig. 15 under the conditions shown in Table 4. Layer formation was carried out under the same conditions as in Reference Example 1, except that the ratio was changed with the elapsed time of layer formation, 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 Reference Example 1, an extremely clear image quality was obtained. Reference Example 5 Using the production equipment shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the change rate curve of the gas flow rate ratio shown in FIG. 16 under the conditions shown in Table 5. Layer formation was carried out under the same conditions as in Reference Example 1, except that the ratio was changed with the elapsed time of layer formation, 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 Reference Example 1, an extremely clear image quality was obtained. Reference Example 6 Using the manufacturing equipment shown in Fig. 11, the gas flow rates of GeH ₄ /He gas and SiH _{4 /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in Fig. 17 under the conditions shown in Table 6} . Layer formation was carried out under the same conditions as in Reference Example 1, except that the ratio was changed with the elapsed time of layer formation, 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 Reference Example 1, an extremely clear image quality was obtained. Reference Example 7 Using the manufacturing equipment shown in Fig. 11, the gas flow rates of GeH ₄ /He gas and SiH _{4 /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in Fig. 18 under the conditions shown in Table 7} . Layer formation was carried out under the same conditions as in Reference Example 1, except that the ratio was changed with the elapsed time of layer formation, 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 Reference Example 1, an extremely clear image quality was obtained. Reference Example 8 In Example 1, Si ₂ was used instead of SiH ₄ /He gas.
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Reference Example 1, except that H ₆ /He gas was used and the conditions shown in Table 8 were used. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Reference Example 1, an extremely clear image quality was obtained. Reference example 9 In reference example 1, instead of SiH ₄ /He gas
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Reference Example 1, except that SiF ₄ /He gas was used and the conditions shown in Table 9 were used. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Reference Example 1, an extremely clear image quality was obtained. Reference Example 10 Same conditions as Reference Example 1 except that (SiH ₄ /He + SiF ₄ /He) gas was used instead of SiH ₄ /He gas and the conditions shown in Table 10 were changed. Layer formation was carried out 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 Reference Example 1, an extremely clear image quality was obtained. Reference Example 11 Using the production equipment shown in Fig. 11, the following steps were carried out on a cylindrical Al substrate under the conditions shown in Table 11, according to the rate of change curve of gas flow rate ratio shown in Fig. 12.
An electrophotographic image forming member was obtained by forming layers while changing the gas flow rate ratio of GeH ₄ /He gas and SiH ₄ /He gas with the elapsed layer formation time. The image-forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 KV for 0.3 seconds, and a light image was immediately irradiated using a tungsten lamp light source to transmit a light amount of 2 lux sec to a transmission type. It was irradiated through a test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
Transferred onto transfer paper with 5.0KV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Reference example 12 In reference example 11, when creating the first layer, B ₂
Same as Reference Example 11 except that the flow rate of H ₆ to (SiH ₄ + GeH ₄ ) and the flow rate of B ₂ H ₆ to SiH ₄ were changed as shown in Table 12 when creating the second layer. Each of the electrophotographic imaging members was prepared under the following conditions. Regarding the image forming member obtained in this way, reference example
When an image was formed on a transfer paper under the same conditions and procedures as in No. 11, the results shown in Table 12 were obtained. Reference example 13 In reference examples 1 to 10, the second layer creation conditions are
Each of the electrophotographic image forming members was produced under the same conditions as shown in each reference example except that the conditions shown in Table 13 were used. Using the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Reference Example 1, and the results shown in Table 13A were obtained. Reference example 14 In reference examples 1 to 10, the conditions for creating the second layer are
Each electrophotographic image forming member was produced under the same conditions as shown in each Example except that the conditions shown in Table 14 were used. Using the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Reference Example 1, and the results shown in Table 14 were obtained. Example 1 In Reference Example 1, the light source was an 810 nm GaAs semiconductor laser (10 mW) instead of the tungsten lamp.
Reference Example 1 was carried out under the same toner image forming conditions as in Reference Example 1, except that an electrostatic image was formed using
When the image quality of the toner transfer image was evaluated using an electrophotographic image forming member prepared under the same conditions as described above, a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained.

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[Table] ◎: Excellent ○: Good

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[Table] ◎: Excellent ○: Good or better Common layer forming conditions in Examples and Reference Examples of the present invention are shown below. Substrate temperature: germanium atom (Ge) containing layer...
...Approx. 200℃ Germanium atom (Ge)-free layer...Approx. 250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[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 diagrams for explaining the distribution state of germanium atoms in the amorphous layer, respectively. The explanatory diagram, FIG. 11, is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS.
FIG. 8 is an explanatory diagram showing the rate of change curve of the gas flow rate ratio in each embodiment of the present invention. 100...Photoconductive member, 101...Support, 1
02...Amorphous layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member, a first layer region made of an amorphous material containing silicon atoms and germanium atoms on the support, and an amorphous material containing silicon atoms. a second layer region exhibiting photoconductivity made of a material and an amorphous layer having a layered structure provided in order from the support side; Distribution concentration is from the support side
The layer is non-uniform in the layer thickness direction so as to have a portion with a high distribution concentration of 1000 atomic ppm or more within 5 μm and a portion where the concentration is considerably lower on the surface side than on the support side, and 1. A photoconductive member for laser light, characterized in that the amorphous layer contains atoms belonging to Group 1 or Group 3 of the periodic table. 2. The photoconductive member for laser light 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 for laser light according to claim 1, wherein at least one of the first layer region and the second layer region contains a halogen atom. 4. The photoconductive member for laser light according to claim 1, wherein at least one of the first layer region and the second layer region contains hydrogen atoms and halogen atoms. 5. Claim 2, wherein the amount of hydrogen atoms contained in the first layer region is 0.01 to 40 atomic%.
A photoconductive member for laser light as described in 2. 6. The photoconductive member for laser light according to claim 3, wherein the amount of halogen atoms contained in the first layer region is 0.01 to 40 atomic%. 7. The photoconductive member for laser light according to claim 4, wherein the sum of the amounts of hydrogen atoms and halogen atoms contained in the first layer region is 0.01 to 40 atomic%. 8. Claim 2, wherein the amount of hydrogen atoms contained in the second layer region is 1 to 40 atomic%.
A photoconductive member for laser light as described in 2. 9. The photoconductive member for laser light according to claim 3, wherein the amount of halogen atoms contained in the second layer region is 1 to 40 atomic %. 10. The photoconductive member for laser light according to claim 3, wherein the sum of the amounts of hydrogen atoms and halogen atoms contained in the second layer region is 1 to 40 atomic %. 11. The photoconductive member for laser light according to claim 1, wherein the amount of germanium atoms contained in the first layer region is 1 to 9.5 x ¹⁰⁵ atomic%. 12 The atom belonging to Group 1 of the periodic table is B,
The photoconductive member for laser light according to claim 1, which is selected from Ga. 13 The atom belonging to Group 1 of the periodic table is P,
The photoconductive member for laser light according to claim 1, which is selected from As. 14. The photoconductive member for laser light according to claim 3 or 4, wherein the halogen atom is selected from fluorine and chlorine.