JPH0229209B2 - - 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 photoconductive members for electrophotography that are 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 is a need to improve overall characteristics in terms of usage environment characteristics and stability over time, and there are areas that can be further improved. 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 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. There were many cases where spots appeared. 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 the photoconductive layer is composed of a-Si material, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties. In this case, problems may 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. Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs particularly when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that need to be solved in terms of stability over time. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive and comprehensive research on Si from the viewpoint of its applicability and applicability as a photoconductive member used in electrophotographic image forming members, we found that silicon atoms (Si) and germanium atoms (Ge) ) and containing at least either a hydrogen atom (H) or a halogen atom (X), a so-called hydrogenated amorphous silicon germanium atom, a halogenated amorphous silicon germanium, or a halogen-containing hydrogenated amorph Hereinafter, the structure of a photoconductive member having an amorphous layer exhibiting photoconductivity composed of asilcongermanium (hereinafter referred to as "a-SiGe(H,X)") will be described. A photoconductive member designed and produced under the specifications described not only exhibits extremely superior properties in practical use, but also surpasses conventional photoconductive members in every respect. This is based on the discovery that it has particularly excellent properties as a photoconductive member for electrophotography, and that it has excellent absorption spectrum properties on the long wavelength side. The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member for electrophotography that has a long lifespan, does not cause any deterioration phenomenon 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 for electrophotography 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 provide excellent adhesion between a layer provided on a support and the support and between each laminated layer, to provide a dense and stable structural arrangement, and to provide layer quality. It is an object of the present invention to provide a photoconductive member for electrophotography having high properties. 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 excellent electrophotographic properties with sufficient performance and with almost no deterioration of the properties observed even in a humid atmosphere. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. Yet another object of the present invention is high photosensitivity,
An object of the present invention is to provide a photoconductive member for electrophotography that has high signal-to-noise ratio characteristics and good electrical contact with a support. The electrophotographic photoconductive member of the present invention (hereinafter simply referred to as photoconductive member) has a support for an electrophotographic photoconductive member, a silicon atom, and 1 to 9.5×10 ⁵ with respect to the sum of the silicon atoms. A layer thickness of 1 consisting of an amorphous material containing atomic ppm of germanium atoms.
It has a photoreceptive layer exhibiting photoconductivity of ~100μ, and the distribution state of germanium atoms in the photoreceptor layer is non-uniform in the layer thickness direction, and the portion where the distribution concentration of germanium atoms is high on the support side is have,
On the side opposite to the support side, the distribution concentration has a part that is considerably lower than that on the support side, and the maximum value of the distribution concentration of germaunium atoms is 1000 atomic ppm or more with respect to silicon atoms, and The photoreceptive layer is characterized by containing 0.001 to 50 atomic percent of nitrogen atoms. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. Indicates 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. Furthermore, in the photoconductive member of the present invention, the photoreceptive layer formed on the support is strong and has excellent adhesion to the support, and can be continuously repeated at high speed for a long time. can be used. 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. The photoconductive member 100 shown in FIG. 1 consists of a support 101 for the photoconductive member and a-SiGe (H, The photoreceptive layer 102 has a photoreceptive layer 102. The germanium atoms contained in the photoreceptive layer 102 are continuous in the layer thickness direction of the photoreceptive layer 102 and on the side opposite to the side where the support 101 is provided (the side where the photoreceptive layer 102 is provided). surface 104 side)
It is contained in the photoreceptive layer 102 so that it is distributed in a larger amount on the support side (the surface 105 side of the photoreceptive layer 102). In the photoconductive member of the present invention, the distribution state of germanium atoms contained in the photoreceptive layer is as described above in the layer thickness direction, and in the in-plane direction parallel to the surface of the support. It is desirable that the distribution is uniform. 2 to 10 show typical examples of the distribution state of germanium atoms contained in the photoreceptive layer of the photoconductive member of the present invention in the layer thickness direction. 2 to 10, the horizontal axis shows the distribution concentration C of germanium atoms, the vertical axis shows the layer thickness of the photoreceptive layer showing photoconductivity, and t _B is the position of the surface of the photoreceptive layer on the support side. , t _T indicates the position of the surface of the photoreceptive layer on the side opposite to the support side. That is, the photoreceptive layer containing germanium atoms is formed from the t _B side toward the t _T side. FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the photoreceptive layer in the layer thickness direction. In the example shown in FIG. 2, germanium atoms extend from the interface position t _B to the position t ₁ where the surface of the support on which the photoreceptive layer containing germanium atoms is formed and the surface of the photoreceptive layer contact each other. The distribution concentration C of
A germanium atom takes a constant value of C ₁ ,
It is contained in the formed photoreceptive layer, and is gradually and continuously reduced from the distribution concentration C ₂ from the position t ₁ to the interface position t _T . At the interface position _tT , the distribution concentration C of germanium atoms is _C3 . 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. reduced, and 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 decreased linearly up 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 .} 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 until it reaches 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 photoreceptive layer in the layer thickness direction, in the present invention, germanium atoms are The light-receiving layer is provided with a distribution state of germanium atoms having a portion where the distribution concentration C of atoms is high, and a portion where the distribution concentration C is considerably lower on the interface _tT side than on the support side. There is. The photoreceptive layer constituting the photoconductive member of the present invention preferably has a localized region A containing germanium atoms at a relatively high concentration on the support side, as described above. 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 5 μm thick from the interface position t _B , or may be a part of the layer region L _T. Whether the localized area A is a part or all of the layer area L _T is determined as appropriate depending on the characteristics required of the photoreceptive 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 distribution concentration C _nax of germanium atoms is preferably 1000 atomic ppm or more, more preferably 5000 atomic ppm with respect to silicon atoms. Above, optimally 1×
It is desirable to form a layer so that a distribution state of 10 ⁴ atomic ppm or more can be achieved. 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 C _nax of the distribution concentration exists within 5 μm (layer region with a thickness of 5 μm from t _B ). In the present invention, the content of germanium atoms contained in the photoreceptive layer is appropriately determined as desired so as to effectively achieve the object of the present invention, but it is determined based on the total amount with silicon atoms. Preferably 1 to 9.5×10 ⁵ atomic ppm, more preferably 100 to 8
×10 ⁵ atomic ppm, optimally 500 to 7×
It is preferable to set it at 10 ⁵ atomic ppm. In the photoconductive member of the present invention, the distribution state of germanium atoms in the photoreceptive layer 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 is supported. Since the change decreases from the body side toward the free surface side of the photoreceptive layer, the desired characteristics can be achieved by arbitrarily designing the rate of change curve of the distribution concentration C as desired. A desired photoreceptive layer can be realized. For example, the distribution concentration C of germanium in the photoreceptive layer can be sufficiently increased on the support side and as low as possible on the free surface side of the photoreceptive layer.
By applying changes in the distribution concentration C to the distribution concentration curve of germanium atoms, high photosensitivity can be achieved for light in the entire wavelength range from relatively short wavelengths to relatively long wavelengths, including the visible light region. It is possible to plan. In addition, as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the end of the photoreceptive layer on the support side, when a semiconductor laser is used, the side of the laser irradiation surface of the photoreceptor layer is Light on the long wavelength side that is not fully absorbed can be substantially completely absorbed in the end layer region of the support side of the photoreceptive layer, effectively eliminating interference due to reflection from the support surface. It can be prevented. In the photoconductive member of the present invention, the photoreceptive layer contains a , nitrogen atoms are contained. The nitrogen atoms contained in the photoreceptive layer may be contained evenly in the entire layer area of the photoreceptive layer, or may be contained only in some layer areas of the photoreceptive layer so that they are ubiquitous. Also good. In addition, the distribution state of nitrogen atoms is such that the distribution concentration C(N) is
In the layer thickness direction of the photoreceptive layer, even if it is uniform, the distribution concentration C(N) is similar to the distribution state of germanium atoms explained using FIGS. 2 to 10.
may be non-uniform in the layer thickness direction. In other words, when the distribution concentration C(N) of nitrogen atoms is non-uniform in the layer thickness direction, the distribution state of nitrogen atoms is as follows:
This can be explained in the same way as the case of germanium atoms using FIGS. 2 to 10. In the present invention, when the main purpose is to improve photosensitivity and dark resistance, the nitrogen atom-containing layer region N provided in the photoreceptive layer occupies the entire layer area of the photoreceptive layer. When the main purpose is to strengthen the adhesion between the support and the light-receiving layer, it is provided so as to occupy the end layer region of the light-receiving layer on the support side. In the former case, the content of nitrogen atoms contained in the layer region N is relatively small in order to maintain high photosensitivity, and in the latter case, in order to ensure enhanced adhesion with the support. It is desirable that a relatively large amount be used. In addition, in order to achieve both the former and the latter at the same time, it is necessary to distribute it at a relatively high concentration on the support side and at a relatively low concentration on the free surface side of the photoreceptive layer, or In the surface layer region on the free surface side of the light-receiving layer, a nitrogen atom distribution state may be formed in the layer region N such that nitrogen atoms are not actively contained. In the present invention, the content of nitrogen atoms contained in the layer region N provided in the photoreceptive layer depends on the characteristics required of the layer region N itself or when the layer region N is in direct contact with the support. When provided, it can be selected as appropriate in terms of organic relationships, such as the relationship with the characteristics at the contact interface with the support. In addition, when another layer region is provided in direct contact with the layer region N, the characteristics of the other layer region and the relationship with the characteristics at the contact interface with the other layer region are also considered. and the nitrogen atom content is appropriately selected. The amount of nitrogen atoms contained in the layer region N is determined as desired depending on the properties required of the photoconductive member to be formed, but is preferably 0.001.
~50atomic%, more preferably 0.002~
It is desirable that the content be 40 atomic%, optimally 0.003 to 30 atomic%. In the present invention, whether the layer region N occupies the entire area of the photoreceptive layer, or even if it does not occupy the entire area of the photoreceptor layer, the ratio of the layer thickness _T0 of the layer area N to the layer thickness T of the photoreceptive layer is sufficiently large, it is desirable that the upper limit of the content of nitrogen atoms contained in the layer region N be sufficiently smaller than the above value. In the case of the present invention, if the layer thickness T ₀ of the layer region N accounts for two-fifths or more of the layer thickness T of the photoreceptive layer, The upper limit of the amount of nitrogen atoms is preferably:
30 atomic% or less, more preferably 20 atomic%
Hereinafter, the optimum value is preferably 10 atomic % or less. In the present invention, the layer region N containing nitrogen atoms constituting the photoreceptive layer has a localized region B containing nitrogen atoms at a relatively high concentration on the support side as described above. It is desirable to provide such a layer, and in this case, it is possible to further improve the adhesion between the support and the light-receiving layer. The localized region B is desirably provided within 5μ from the interface position _tB , if explained using the symbols shown in FIGS. 2 to 10. In the present invention, the localized region B may be the entire layer region L _T up to 5 μm thick from the interface position t _B , or may be a part of the layer region L _T. Whether the localized region is a part or all of the layer region L _T is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed. The localized region B has a distribution state of nitrogen atoms contained therein in the layer thickness direction, and the maximum value C _nax of the distribution concentration of nitrogen atoms is preferably 500 atomic ppm or more, more preferably 800 atomic ppm or more, and optimally
It is desirable to form a layer so that a distribution state of 1000 atomic ppm or more can be achieved. That is, in the present invention, the layer region N containing nitrogen atoms has a layer thickness of within 5 μm from the support side (t _B
It is desirable that the maximum value C _nax of the distribution concentration exists in the layer region of 5 μm to 5 μm layer. In the present invention, specific examples of the halogen atom (X) contained in the light-receiving layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as. In the present invention, the photoreceptive layer composed of A-SiGe (H, will be accomplished. For example, by the glow discharge method, a
- To form a photoreceptive layer composed of SiGe (H, The raw material gas for supply and, if necessary, the raw material gas for introducing hydrogen atoms (H) and/or the raw material gas for introducing halogen atoms (X) are kept in a desired gas pressure state in a deposition chamber whose interior can be reduced in pressure. A glow discharge is generated in the deposition chamber to control the distribution concentration of germanium atoms contained on the surface of a predetermined support, which has been previously installed at a predetermined position, according to a desired rate of change curve. Laa-SiGe
It is sufficient to form a layer consisting of (H,X). or,
For example, when forming by sputtering method,
Using 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, or using two targets made of this target and Ge, or , Si and
Using a mixed target of Ge, the source gas for supplying Ge diluted with a diluent gas such as He or Ar is added as necessary to hydrogen atoms (H) and/or halogen atoms. (X) Introducing an introduction gas into a deposition chamber for sputtering to form a plasma atmosphere of a desired gas, and controlling the gas flow rate of the raw material gas for supplying Ge according to a desired rate of change curve. Then, sputtering the target described above is sufficient. 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 a resistance heating method or an electron beam. Law (EB Law)
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 above method, and the flying evaporated material is passed through a desired gas plasma atmosphere. Substances that can be used as 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:
GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and other germanium hydrides in a gaseous state or that can be gasified are mentioned as those that can be effectively used, especially during layer formation work. GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferred in terms of ease of handling, good Ge supply efficiency, and the like. 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 using 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. A light-receiving layer made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When manufacturing a light-receiving layer containing halogen atoms according to the glow discharge method, basically silicon halide, which is a raw material gas for supplying Si, germanium hydride, and Ar, which are raw material gases for supplying Ge, are manufactured using the glow discharge method. ，
Gases such as H ₂ and He are introduced into a deposition chamber where a photoreceptive layer is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. A light-receiving layer can be formed on a desired support by using these gases, but in order to more easily control the ratio of hydrogen atoms introduced, hydrogen gas or hydrogen atoms may be added to these gases. A layer may also be formed by mixing a desired amount of a silicon compound gas containing . 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, HI, SiH ₂ F ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ ,
GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ ,
GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br,
GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I and other hydrogenated germanium halides, halides containing hydrogen atoms as one of their constituents, GeF ₄ , GeCl ₄ , GeBr ₄ ,
Germanium halides such as GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and other gaseous or gasifiable substances can also be mentioned as effective starting materials for forming the photoreceptor layer. Among these substances, halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming the photoreceptive layer. , is used as a suitable raw material for introducing halogen in the present invention. In order to structurally introduce hydrogen atoms into the photoreceptive layer, in addition to the above, H ₂ , SiH ₄ , SiH ₆ , Si ₃ H ₈ ,
Silicon hydride such as 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 , Ge ₅ H ₁₂ ,
Generating a discharge by coexisting germanium hydride such as 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 in a deposition chamber. But it can be done. In a preferred example of the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the photoreceptive layer of the photoconductive member to be formed is preferably 0.01~
40atomic%, more preferably 0.05-30atomic%,
The optimum range is preferably 0.1 to 25 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the photoreceptive layer, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (X) contained What is necessary is to control the amount of starting material used for this purpose introduced into the deposition system, the discharge power, etc. The layer thickness of the photoreceptive layer in the photoconductive member of the present invention is appropriately determined as desired so that photocarriers generated in the photoreceptor layer are efficiently transported, and is preferably 1 to 100 μm. More preferably 1~
It is desirable that the thickness be 80μ, and optimally 2 to 50μ. In the present invention, in order to provide the layer region N containing nitrogen atoms in the photoreceptive layer, when forming the photoreceptive layer, the starting material for introducing nitrogen atoms is used as the starting material for forming the photoreceptive layer. It may be used in conjunction with the above, and the amount thereof may be controlled and contained in the formed layer. When the glow discharge method is used to form the layer region N, a starting material for introducing nitrogen atoms is added to a material selected as desired from among the starting materials for forming the photoreceptive layer described above. As the starting material for introducing nitrogen atoms, most of the gaseous substances containing at least nitrogen atoms or gasified substances that can be gasified can be used. For example, a source gas containing silicon atoms (Si), a source gas containing nitrogen atoms (N), and hydrogen atoms (H) and/or halogen atoms (X) as necessary. or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are nitrogen atoms (N) and hydrogen atoms (H). It is also possible to use a mixture with a gas in a desired mixing ratio. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
You may mix and use the raw material gas which has nitrogen atom N as a constituent atom with the raw material gas which has a nitrogen atom N as a constituent atom. Nitrogen atoms N used when forming layer region N
Starting materials that can be effectively used as raw material gases for introduction include, for example, nitrogen, N ₂ ,
Mention may be made of gaseous or gasifiable nitrogen, such _as ammonia _NH3 , hydrazine _H2NNH2 , hydrogen azide _HN3 , _ammonium azide _NH4N3 , and nitrogen compounds such as nitrides and azides. In addition to this, halogenated nitrogen compounds such as nitrogen trifluoride F ₃ N and nitrogen tetrafluoride F ₄ N ₂ can be used, since in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced. can be mentioned. In the present invention, the layer region N may contain oxygen atoms in addition to nitrogen atoms in order to further enhance the effect obtained by nitrogen atoms.
Examples of raw material gases for introducing oxygen atoms into the layer region N include oxygen O ₂ and ozone.
O ₃ , nitric oxide NO, nitrogen dioxide NO ₂ , nitrogen monoxide N ₂ O, nitrogen sesquioxide N ₂ O ₃ , trinitrogen tetraoxide
N ₂ O ₄ , nitrogen pentoxide N ₂ O ₅ , nitrogen trioxide NO ₃ , silicon atom (Si), oxygen atom (O), and hydrogen atom (H)
For example, disiloxane whose constituent atoms are
H ₃ SiOSiH ₃ , trisiloxane H ₃ SiOSiH ₂ OSiH ₃
Examples include lower siloxanes such as. To form the layer region N containing nitrogen atoms by the sputtering method, single crystal or polycrystalline
This can be carried out by sputtering a Si wafer, Si ₃ N ₄ , or a wafer containing a mixture of Si and Si ₃ N ₄ in various gas atmospheres. For example, if a Si wafer is used as a target, nitrogen atoms and optionally hydrogen atoms or/and
The raw material gas for introducing halogen atoms is diluted with a diluting gas as necessary and introduced into a sputtering deposition chamber, and a gas plasma of these gases is formed to sputter the Si wafer. Good. Alternatively, by using Si and Si ₃ N ₄ as separate targets, or by using a mixed target of Si and Si ₃ N ₄ , a dilution gas atmosphere can be created as a sputtering gas. This is accomplished by sputtering in a gas atmosphere containing at least hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing nitrogen atoms, the raw material gas for introducing nitrogen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, when forming a layer region N containing nitrogen atoms when forming a photoreceptive layer, the distribution concentration C (W) of nitrogen atoms contained in the layer region W is adjusted in the layer thickness direction. In order to form a layer region N having a desired depth profile in the layer thickness direction by varying the distribution concentration C(N), in the case of glow discharge, the distribution concentration C(N)
This is accomplished by introducing a gas as a starting material for introduction of nitrogen atoms into the deposition chamber, while changing the gas flow rate appropriately according to a desired rate of change curve. For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manually or by using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like may be used to control the flow rate according to a rate of change curve designed in advance to obtain a desired content rate curve. When forming the layer region N by the sputtering method, the distribution concentration C(N) of nitrogen atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state (depth profile) of nitrogen atoms in the layer thickness direction. To form the
First, as in the case of the glow discharge method, the starting material for introducing nitrogen atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is changed as desired. done by. Second, the target for sputtering,
For example, if a mixed target of Si and Si ₃ N ₄ is used, the mixing ratio of Si and Si ₃ N ₄ can be changed in advance in the layer thickness direction of the target. will be accomplished. 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,Pd,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 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 the desired photoconductive member is formed, but when 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 a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is preferable to use
It is considered 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. 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 is NH ₃ gas (purity
99.999%) cylinder, 1106 is _H2 gas (purity
99.999%) 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 a light-receiving layer on the cylindrical substrate 1137, the gas cylinder 11
SiH ₄ /He gas from 02, GeH ₄ /He gas from gas cylinder 1103, gas from gas cylinder 1105
NH ₃ gas valves 1122, 1123, 112
5 and outlet pressure gauges 1127, 1128, 1
Adjust the pressure of 130 to 1Kg/cm ² and open the inflow valve 11.
12, 1113, 1115 gradually, and mass flow controllers 1107, 1108, 1110
Let them flow into each other. Subsequently, the outflow valve 11
17, 1118, 1120, auxiliary valve 1132
are gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, the SiH ₄ /He gas flow rate and
The outflow valves 1117 and 111 are adjusted so that the ratio between the GeH ₄ /He gas flow rate and the NH ₃ gas flow rate becomes a desired value.
8 and 1120, and also adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches the desired value. After confirming that the temperature of the base 1137 is set to a temperature in the range of about 50 to 400°C by the heater 1138, the power supply 114
is set 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 performing an operation of gradually changing the opening of 1118. Further, during layer formation, it is desirable that the base 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Examples will be described below. Example 1 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 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. Example 2 Using the manufacturing apparatus 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. 13 under the conditions shown in Table 2. Layers were formed under the same conditions as in 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 Example 1, an extremely clear image quality was obtained. Example 3 Using the manufacturing apparatus 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. 14 under the conditions shown in Table 3. Layers were formed under the same conditions as in 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 Example 1, an extremely clear image quality was obtained. Example 4 Using the manufacturing apparatus 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. 15 under the conditions shown in Table _4. Layers were formed under the same conditions as in 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 Example 1, an extremely clear image quality was obtained. Example 5 Using the manufacturing apparatus 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. Layers were formed under the same conditions as in 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 Example 1, an extremely clear image quality was obtained. Example 6 Using the manufacturing apparatus 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. Layers were formed under the same conditions as in 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 Example 1, an extremely clear image quality was obtained. Example 7 Using the manufacturing apparatus 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. Layers were formed under the same conditions as in 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 Example 1, an extremely clear image quality was obtained. Example 8 In Example 1, instead of SiH ₄ /He gas
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, except that Si ₂ 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 Example 1, an extremely clear image quality was obtained. Example 9 In Example 1, instead of SiH ₄ /He gas
An electrophotographic image forming member was obtained by forming layers under the same conditions as in 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 Example 1, an extremely clear image quality was obtained. Example 10 Same conditions as in 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 Example 1, an extremely clear image quality was obtained. Example 11 Using the manufacturing apparatus shown in FIG. 11, on a cylindrical Al substrate, according to the rate of change curve of the gas flow rate ratio shown in FIG. 12 under the conditions shown in Table 11,
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. Example 12 Using the manufacturing apparatus shown in FIG. 11, the No. 19
According to the rate of change curve of gas flow rate ratio shown in the figure,
An electrophotographic image forming member is formed by forming layers by changing the gas flow rate ratios of GeH ₄ /He gas and SiH ₄ /He gas, and of NH ₃ gas and SiH ₄ /He gas with the elapsed layer formation time. Obtained. 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 Nato 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. Example 13 In Example 1, when creating the first layer, NH ₃
Each electrophotographic image forming member was produced under the same conditions as in Example 1, except that the flow rate for (SiH ₄ +GeH ₄ ) was changed as shown in Table 13. Using the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 13 were obtained. Example 14 Electrophotographic image forming members were prepared in the same manner as in Example 1, except that the thickness of the first layer was changed as shown in Table 14. For each image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 14 were obtained. Example 15 A toner image similar to Example 1 except that in Examples 1 to 10, an 810 nm GaAs semiconductor laser (10 mW) was used instead of the tungsten lamp as the light source to form an electrostatic image. When evaluating the image quality of toner transfer images for each of the electrophotographic image forming members prepared under the same forming conditions as in Examples 1 to 10, it was found that the image quality was excellent in resolution and clear with good gradation reproducibility. A high-quality image was obtained.

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[Table] ◎: Excellent ○: Good △: Sufficient for practical use

[Table] ◎: Excellent ○: Good △: Practically sufficient Common layer forming conditions in the above examples of the present invention are shown below. Substrate temperature: germanium atom (Ge) containing layer...
Approximately 200℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[Brief explanation of drawings]

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 nitrogen atoms in the photoreceptive layer, respectively. 11 are schematic explanatory diagrams of the apparatus used in the present invention, and FIGS. 12 to 19 are explanatory diagrams showing the rate of change curves of the gas flow rate ratio in the embodiments of the present invention, respectively. be. 100...Photoconductive member, 101...Support, 102
...Photoreceptor layer.

Claims (1)

[Scope of Claims] 1 to 1 for the sum of the support for a photoconductive member for electrophotography, silicon atoms, and the silicon atoms.
9.5×10 ⁵ atomic ppm germanium atoms; is non-uniform in the layer thickness direction, and has a portion with a high distribution concentration of germanium atoms on the support side, and the distribution concentration on the side opposite to the support side is considerably lower than that on the support side. the photoreceptive layer contains 0.001 to 50 atomic percent of nitrogen atoms; Photoconductive material for photography. 2. The photoconductive member for electrophotography according to claim 1, wherein the photoreceptive layer contains hydrogen atoms. 3. The photoconductive member for electrophotography according to claim 1 or 2, wherein the light-receiving layer contains a halogen atom.