JPS6068343A - Photoconductive member - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (here, light in a broad sense refers to ultraviolet light, visible light, infrared light, X-rays, gamma rays, etc.). As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it has high sensitivity and a high signal-to-noise ratio [photocurrent (Ip)].
/ dark current (Id)), has absorption spectrum characteristics that match the spectral characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, has the desired dark resistance value, and is non-polluting to the human body during use. In addition, solid-state imaging devices are required to have characteristics such as being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention.
Publication No. 855718 describes an image forming member for electrophotography,
DE 2933411 describes an application to a photoelectric conversion reader. According to Heigo et al., a photoconductive member having a photoconductive layer composed of conventional a-8i has excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and furthermore, stability over time, which requires a comprehensive improvement in characteristics. For example, 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. If you continue to use the conductive material for a long time. As fatigue accumulates due to repeated use, a so-called ghost phenomenon occurs in which an afterimage occurs. Alternatively, repeated use at high speeds often causes disadvantages such as a gradual decrease in responsiveness. Furthermore, a-8i has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, 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 long wavelength side cannot be used effectively. Another problem is that a large amount of the irradiated light reaches the support without being sufficiently absorbed in 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 the image. This is a big problem especially when a semiconductor laser is used as a light source.Alternatively, when a photoconductive layer is made of an a-8i material, its electrical and photoconductive properties are In order to improve the structure, hydrogen atoms or halogen atoms such as fluorine atoms and chlorine atoms, boron atoms and phosphorus atoms to control the electrical conduction type, or other atoms to improve other properties are added. They are contained in the photoconductive layer as atoms, but depending on how these constituent atoms are contained, problems may arise in the electrical or photoconductive properties or voltage resistance of the formed layer. For example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer may not be sufficient, the injection of charge from the support side may not be sufficiently prevented in dark areas, or the transfer paper may There may be image defects in the transferred image that are thought to be caused by a localized discharge breakdown phenomenon commonly called "white spots," or, for example, when a blade is used for cleaning, it may be caused by rubbing. In addition, when used in a humid atmosphere, or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image rarely occurs. Moreover, when the layer thickness exceeds 10-odd microns, the layer may lift or peel off from the surface of the support, or the layer may peel off as the time elapses after it is left in the air after being removed from the vacuum deposition chamber for layer formation. This phenomenon often occurs when the support is a drum-shaped support that is normally used in the electrophotographic field, and is unstable over time. Therefore, while improving the properties of the A-8I material itself, all of the above-mentioned problems can be solved when designing photoconductive members. The present invention has been made in view of the above points, and is a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. for A-8I. As a result of comprehensive research and consideration from the viewpoint of its applicability and applicability, we have developed an amorphous material that uses silicon atoms as a matrix and contains at least either hydrogen atoms (5) or halogen atoms (3). F57Il11 Hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter [a-Si (H,X) J] will be used as a generic notation for these]
A photoconductive member designed and produced with the structure of a photoconductive member having an amorphous layer showing photoconductivity composed of In addition to the fact that it is superior in all respects to conventional photoconductive materials, it has particularly excellent properties as a photoconductive material for electrophotography, and on the long wavelength side. This is based on the discovery that it has excellent absorption spectrum characteristics. 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 have excellent adhesion between a layer provided on a support and the support and between each layer of laminated layers,
It is an object of the present invention to provide a photoconductive member that is dense and stable in terms of structural arrangement and has a high quality single layer. Another object of the present invention is to maintain charge retention during electrical resistance treatment for electrostatic image formation to such an extent that ordinary electrophotographic methods can be applied very effectively when applied as an image forming member for electrophotography. There is plenty of ability. Another object of the present invention is to provide a photoconductive member having excellent electrophotographic properties in which almost no deterioration in the properties is 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 crosstones, and high resolution. . Yet another object of the present invention is high photosensitivity. It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics and good electrical contact with the support. Another object of the present invention is to have excellent adhesion between a layer provided on a support and the support and between each layer of laminated layers,
It is an object of the present invention to provide a photoconductive member that is dense and stable in terms of structural arrangement and has a high quality single layer. Still another object of the present invention is to easily obtain high-quality images with no image defects or image blurring, high density, clear halftones, and high resolution during long-term use. The object of the present invention is to provide a photoconductive member for electrophotography that can be used for electrophotography. a first amorphous layer having a layer structure in which a first layer region and a second layer region made of an amorphous material containing silicon atoms and exhibiting photoconductivity are provided in order from the support side; and a second amorphous layer made of an amorphous material containing atoms and nitrogen atoms, and the distribution state of germanium atoms in the first amorphous layer is uneven in the layer thickness direction. It is characterized by being uniform. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical and optical properties. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical properties are stable, it is highly sensitive, 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, 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 a fast photoresponse. The amorphous layer formed has a strong layer structure and excellent adhesion to the support, and can be used continuously and repeatedly under pressure for a long time at high speed.Hereinafter, according to the drawings. 1 The photoconductive member of the present invention will be explained in detail. Fig. 1 is a schematic configuration diagram schematically shown to explain the layer structure of the photoconductive member of the first embodiment of the present invention. The photoconductive member 100 shown in FIG. 1 includes a first amorphous layer H) 102 on a support 101 for photoconductive member.
, a second amorphous layer (If) 105, and the amorphous layer (If) 105 has a free surface 106 on one end surface. The first amorphous layer (T) 102 is composed of a-8i (H,X) (hereinafter abbreviated as [a-5iGe (H,X) J) containing germanium atoms from the support 101 side. tt. The first layer region (cl103 and a-Si (H,X)
A second layer region (S) 10 consisting of and having photoconductivity
It has a layered structure in which 4 and 4 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) lo30 and in the in-plane direction parallel to the surface of the support 101, and The first layer region (C
Contained in e2O2. In the present invention, germanium atoms are not contained in the second layer region (S) provided on the first layer region (Q), and the first amorphous layer structure is By forming the transparent layer (I), a photoconductive member can be obtained that has excellent photosensitivity to light in the entire wavelength range from relatively short wavelengths to relatively short wavelengths, including the visible light region. In addition, the distribution state of germanium atoms in the first layer region (Q) and the second layer region (S) is that germanium atoms are continuously distributed in the entire layer region. ), and when a semiconductor laser or the like is used, the first layer region (0 In the photoconductive member of the present invention, the first layer region (Q
Since each of the amorphous materials constituting the and the second layer region (S) has a common constituent element of silicon atoms,
The laminated interface is sufficiently acidified to ensure chemical stability. In the present invention, the content of germanium atoms contained in the first layer region (cl) is determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 9. .5X105atomic ppm, more preferably Zoo~8X105ato105at
o s Optimal: 500~7 X 1.05 atoms
ic ppm is preferable. In the present invention, the first layer region (0 and the second layer region (S)
Since the layer thickness is one of the important factors for effectively achieving the object of the present invention, the design of the photoconductive member should be carefully selected so that the formed photoconductive member has sufficient desired properties. Sufficient care must be taken when doing so. In the present invention, the layer thickness TB of the first layer region (Q) is preferably 30X to 50μ, more preferably 40A to 40μ, and optimally 50A to 30μ. , the layer thickness T of the second layer region (S) is preferably 0.5
~90μ, more preferably 1-80μ, optimally 2-5
It is desirable that it be 0μ. The sum (TB+T) of the layer thickness TB of the first layer region (Q) and the layer thickness T of the second layer region (S) is based on the characteristics required for both layer regions and the thickness of the first amorphous layer (I ) is appropriately determined as desired when layering the photoconductive member, based on the organic relationship between the properties required for the whole.In the photoconductive member of the present invention, the above-mentioned (TB+T)
The numerical range is preferably 1 to 100μ. More preferably, it is 1 to 80μ, most preferably 2 to 50μ. In a more preferred embodiment of the present invention, as the layer thickness TB and the layer thickness T, appropriate values are selected for each when usually satisfying the relationship TB/T≦1. It is desirable that In selecting the numerical values of layer thickness TB and layer thickness T in the above case, more preferably, TB/T≦0.9°, optimally T B /T≦0. It is desirable that the values of layer thickness TB and layer thickness T be determined so that the following relationship is satisfied. In the present invention, the content of germanium atoms contained in the first layer region (O
pm or more, it is desirable that the layer thickness TB of the first layer region (Q) be as thin as possible, preferably 30
It is desirable that the thickness be less than μ, more preferably less than 25 μ, optimally less than 20 μ. In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and dark resistance, as well as improving the adhesion between the support and the first amorphous layer (1), One amorphous layer (I) contains oxygen atoms. The oxygen atoms contained in the first amorphous layer (I) may be evenly contained in the entire layer region of the first amorphous layer (I), or It may be contained and unevenly distributed only in a part of the layer region of the crystalline layer (1). In addition, even if the distribution state of oxygen atoms is uniform in the thickness direction of the amorphous layer, the distribution concentration CD)
may be non-uniform in the layer thickness direction. In the present invention, when the main purpose of the layer region (0) containing oxygen atoms provided in the first amorphous layer (I) is to improve photosensitivity and dark resistance, When the first amorphous layer (I) is provided so as to occupy the entire layer area and the main purpose is to strengthen the adhesion between the support and the amorphous layer, It is provided so as to occupy the support side end layer region of the amorphous layer (1). In the former case, the content of oxygen atoms contained in the 1-layer region 0) is kept relatively low in order to maintain high photosensitivity, and in the latter case, the content of oxygen atoms contained in the 1-layer region 0) is set to be relatively low in order to maintain high photosensitivity. Therefore, it is desirable to have a relatively large amount. Also, for the purpose of achieving both the former and the latter at the same time,
The first amorphous layer (I) may be distributed at a relatively high concentration on the support side and at a relatively low concentration on the free surface side of the first amorphous layer (1). In the surface layer region on the free surface side of the layer region 0), a distribution state of oxygen atoms such that oxygen atoms are not actively contained may be formed in the layer region 0). In the present invention, the content of oxygen atoms contained in layer region 0) K provided in the first amorphous layer (I) is as follows:
In organic relationships, such as the characteristics required for itself, or the relationship with the characteristics at the contact interface with the support when the layer region 0) is provided in direct contact with the support. and can be selected as appropriate. In addition, when another layer region is provided in direct contact with the layer region (0), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The content of oxygen atoms is appropriately selected taking into account the following. The amount of oxygen atoms contained in layer region 0) can be determined as desired depending on the properties required of the photoconductive member to be formed, but is preferably 0.001 to 50 atomic%, more preferably is 0.002 to 40 atomic%, optimally 0
．． It is desirable that the content be 0.003 to 30 atomic%. In the present invention, the layer region (0) is the first amorphous layer ([)
The layer thickness T that occupies the entire area of the first amorphous layer (I) or does not occupy the entire area of the first amorphous layer (I) (both layer area 0). When the proportion of the first amorphous layer (t) in the layer thickness T is sufficiently large, the upper limit of the content of oxygen atoms contained in the layer region 0) is made sufficiently smaller than the above value. It is desirable to In the case of the present invention, when the ratio of the layer thickness TO of the layer region 0) to the layer thickness T of the first amorphous layer (1) is two-fifths or more, the layer The upper limit of the amount of oxygen atoms contained in region 0) is preferably 30 atoms
It is desirable that the content be less than c%, more preferably less than 20 atomic%, most preferably less than 10 atomic%. 2 to 10 show typical examples of the distribution state of oxygen atoms contained in the layer region 0) of the photoconductive member according to the present invention in the layer thickness direction. 2 to 10, the horizontal axis shows the distribution concentration C of oxygen atoms, the vertical axis shows the layer thickness of layer region 0), tB is the position of the end surface of layer region 0) on the support side, tT indicates the position of the end surface of the layer region 0) on the side opposite to the support side. That is, in the layer region 0) containing oxygen atoms, the layer is formed from the tB side toward the tT side. FIG. 2 shows a first typical example of the distribution state of oxygen atoms contained in the layer region Ω in the layer thickness direction. In the example shown in FIG. 2, the distribution concentration of oxygen atoms is from the interface position tB where the surface where the layer region 0) containing oxygen atoms is formed and the surface of the layer region 0) to the position tl. C is contained in the layer region 0) where oxygen atoms are formed while taking a constant value of C1, and from the position t1, the concentration gradually and continuously decreases from the concentration C2 to the interface position 1T. At the interface position tT, the distribution concentration C of oxygen atoms is C3
It is said that In the example shown in FIG. 3, the distribution concentration C of the contained oxygen atoms is C4 from position tB to position tT.
The concentration C5 gradually decreases continuously from tT to the concentration C5.
The distribution state is formed as follows. In the case of FIG. 4, the distribution concentration C of oxygen atoms is kept at a constant value C6 from position tB to position t2, gradually and continuously decreased between position t2 and position tT, and is gradually and continuously decreased from position tB to position t2. In , the distribution concentration C is assumed to be substantially zero (here, substantially zero means the case where the amount is below the detection limit).
. In the case of FIG. 5, the distribution concentration C of oxygen atoms gradually decreases continuously from the concentration C8 from position tB to position tT, and becomes substantially zero at one position tT. In the example shown in FIG. 6, the distribution concentration C of oxygen atoms is
Between position tB and position t3, the concentration is a constant value C9, and at one position tT, the concentration is CIO. position t
3 and position tT, the distribution density C is linearly decreased from position t3 to position tT. In the example shown in FIG. 7, the distribution concentration C is at the position tB.
The concentration C11 takes a constant value up to position t4, and
4 to position tT, the distribution state is such that the concentration decreases linearly from the concentration C12 to the concentration cia. In the example shown in FIG. 8, the distribution concentration C of oxygen atoms decreases linearly from the concentration C14 to substantially zero from the position tn to the position tT. In FIG. 9, from position tB to position t5, the distribution concentration C of oxygen atoms decreases linearly from concentration C15 to concentration cte, and between position t5 and position tT, the concentration C16 is constant. An example of a value is shown. In the example shown in FIG. 10, the distribution concentration C of oxygen atoms is the concentration C17 at the position tB, and at first it decreases slowly from this concentration C17 until reaching the position t6, and then rapidly decreases near the position t6. position t
6, the density is C18. Between position t6 and position t7, the concentration is decreased rapidly at first, then slowly and gradually decreased to C19 at position t7, and between position t7 and position t8, it gradually decreases very slowly. and reaches the concentration C20 at the position ts. 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 oxygen atoms contained in the layer region 0) in the layer thickness direction, in the present invention, on the support side, The layer region I has a portion where the distribution concentration C of oxygen atoms is high, and has a portion where the distribution concentration C is considerably lower on the interface tT side than on the support side.
Kla is being kicked out. In the present invention, the layer region 0) containing oxygen atoms constituting the first amorphous layer m is a localized region 0) containing oxygen atoms at a relatively high concentration toward the support side, as described above. region(
B), and in this case, the support and the first amorphous layer (

The adhesion between [) can be further improved. The above localized region) is desirably provided within 5 μm from the interface position tB, if explained using the symbols shown in FIGS. 2 to 10. In the present invention, the localized region 03) is located at the interface position t
It may be the entire layer region (LT) up to 5μ thick from B, or it may be a part of the layer region (LT). Whether the localized region is a part or all of the layer region (LT) is determined as appropriate depending on the characteristics required of the first amorphous layer (I) to be formed. The localized region [F]) has the maximum distribution concentration Cm of oxygen atoms as the distribution state of the oxygen atoms contained therein in the layer thickness direction.
ax is preferably 500 atmic ppm or more,
It is desirable that the layer be formed so as to achieve a distribution state that is more preferably 800 atomic ppm or more, and optimally 1000 atomic ppm or more. That is, in the present invention, the layer region 0) containing oxygen atoms has a layer thickness within 5 μm from the support side (5 μm from tB).
In the present invention, if necessary, the first amorphous layer (1) is formed so that the maximum value Cmax of the distribution concentration exists in the first amorphous layer (1)
Examples of the norogen atoms (3) contained in the first layer region (0) and the second layer region (S) constituting the In the present invention, the first layer region (G) composed of % a -SiGe (H,X) can be formed by, for example, glow discharge method, sputtering method, Alternatively, it can be achieved by a vacuum deposition method that utilizes a discharge phenomenon such as an ion blating method.For example, by a glow discharge method, a-SiG
To form the first layer region (Q) consisting of e (H, A desired gas pressure state is maintained in a deposition chamber whose internal pressure can be reduced, by supplying raw material gas for Ge, and as necessary, raw material gas for introducing hydrogen atoms (2) and/or raw material gas for introducing halogen atoms (3). to generate a glow discharge in the deposition chamber, and 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. -8iGe(H,X)
What is necessary is to form a layer consisting of. In addition, when forming by sputtering method, for example, a target made of Si or the target G 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 e or Si
A raw material gas for supplying Ge diluted with a diluent gas such as He or Ar is used as a target containing a mixture of hydrogen atoms σj or/and Ge.
A gas for introducing rogen atom flash is introduced into a deposition chamber for sputtering to form a plasma atmosphere of a desired gas, and the gas flow rate of the raw material gas for supplying Ge is controlled according to a desired rate of change curve. All you have to do is sputter the target. In the case of the ion blating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in a deposition boat as evaporation sources, and the evaporation sources are heated using resistance heating or electrobeam. This can be carried out in the same manner as in the sputtering method, except that the evaporated material is heated and evaporated by a method such as the EB method and the flying evaporated material is passed through a desired gas plasma atmosphere. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH4 and Si2H6. Silicon hydride (silanes) in a gaseous state or that can be gasified, such as S l sHs * S i4H1g , can be cited as one that can be effectively used, especially because of its ease of handling during layer creation work and good Sl supply efficiency. SiH4゜Si2
H6 is preferred. GeH is a substance that can be used as a raw material gas for supplying Ge.
4jGezHs p Ge5Hs p Ge4Ht0
pGe5Ht2. Ge5Ht4tGe 7H16p
Ge 8H18p Ge 9H2G and other germanium hydrides in a gaseous state or that can be gasified are mentioned as those that can be effectively used.GeH4 ,Ge2H
6# Ge aHs is preferred. Many halogen compounds are effective as the raw material gas for introducing /S halogen atoms used in the present invention, such as halogen gas, halides, interhalogen compounds, and silane derivatives substituted with norogen. Or a halogen compound that can be gasified is preferably mentioned. Furthermore, it can be in a gaseous state or gasified, which contains silicon atoms and halogen atoms as constituent elements. Silicon hydride compounds containing halogen atoms are also effective in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine, iodine nohalogen gas, BrF, CIF, ClF3゜BrF5
, BrF3, IF3 + IFytXCI
, IBr, and other interhalogen compounds. As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF4, Si2F6, SiC4゜SiBr4
Preferred examples include silicon halides such as the following. When a photoconductive member characteristic of the present invention is formed by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen is used as a raw material gas capable of supplying Si together with a raw material gas for supplying Ge. A first layer region (■) consisting of a-8iGe containing halogen atoms can be formed on a desired support without using silicon oxide gas. When creating a layer region, basically, for example, silicon halide, which will be the raw material gas for S1 supply, germanium hydride, which will be the raw material gas for Ge supply, and a gas such as Ar, H2t He, etc. are mixed in a predetermined manner. These gases are introduced into the deposition chamber to form a first layer region (Q) in such a manner as to produce a glow discharge to form a plasma atmosphere of these gases.
Therefore, although the first layer region (Q) can be formed on the desired support, hydrogen gas or A desired amount of silicon compound gas containing hydrogen atoms may also be mixed to form a layer. In addition, each gas may be used not only singly but also as a mixture of multiple types at a predetermined mixing ratio. In order to introduce halogen atoms into the layer formed by either the sputtering method or the ion blasting method, a gas of the above-mentioned halogen compound or a silicon compound containing the halogen atoms is introduced into the deposition chamber. In the case of introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H2, or the above-mentioned silanes or /
Gases such as germanium hydride and the like may be introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gases. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, H(J, HBr, HI, etc.) are used. halogenation) Cm, 8iH2Fg, 8iHz
Iz. S 1H1 (Jz, 8 iHC-6g, S 1H2
Halogen-substituted silicon hydride such as Br2,81HBr s,
and Gears, GeH2F2. GeHaF, GeH(Ja, GeHzC#,
GeH+sCJ, GeHB r s. 9 GeH2Br 2 , GeH3Br I GeHI3
pGeH2I2, GeH3I, etc.] Halides containing hydrogen atoms as one of their constituent elements, such as germanium hydrogenation halides, GeF4゜GeC114, GeBr4
, GeI4, GeF2, GeC12, Ge
Br2. Gaseous or gasifiable substances such as germanium halides such as GeI2 can also be mentioned as effective starting materials for forming the first layer region (q). S rogenide is
When forming the first layer region (0), hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced at the same time as the introduction of /SO gen atoms into the layer. In order to structurally introduce hydrogen atoms into the first layer region (Q), in addition to the above, H2, SSH4, SizH6t
Germanium or a germanium compound for supplying Ge to silicon hydride such as Si3Hg and Si4H10;
Or GeH4, Ge 2H6, Ge SH8, Ge
4H1 (1. Ge 5H12* Ge6H14HGe7) (ts p
This can also be carried out by coexisting germanium hydride of Ge 8H18s G ('9H20, etc.0) and silicon or a silicon compound for supplying 81 in the deposition chamber to generate a discharge. In a preferred example of the present invention, The first layer region constituting the first amorphous layer (1) to be formed (the amount of hydrogen atoms contained in Q or the amount of halogen atoms (3) or the amount of hydrogen atoms and halogen atoms) The sum (H+X) is preferably 0.0
1-40 atomic%, more preferably 0.05-3
0 atomic%, optimally 0.1-25 atomic%
It is desirable that this is done. To control the amount of hydrogen atoms and/or halogen atoms (3) contained in the first layer region (5), for example, the support temperature and/or hydrogen atoms (E'l)% or halogen atoms can be controlled. The amount of the starting material used to contain (3) introduced into the deposition system, the discharge power, etc. may be controlled. In the present invention, in order to form the second layer region (S) composed of a-Si (H, , Ge When forming the first layer region (Q) using the starting material [starting material for forming the second layer region (S) (■)] excluding the starting material that becomes the raw material gas for supplying In other words, in the present invention, the second layer region (S) composed of a-8i (H, Alternatively, the second layer region (S) composed of a-8t(H,X) is formed by a glow discharge method. Basically, along with the raw material gas for supplying St that can supply the silicon atoms (Sl) described above, raw material gas for introducing hydrogen atoms (2) and/or for introducing halogen atoms (3) depending on the required pressure is used. is introduced into a deposition chamber whose interior can be made to have a reduced pressure, a glow discharge is generated in the deposition chamber, and a layer consisting of [a-8i(H, In addition, in the case of forming by the S/Z stumbling method, the Si is formed in an atmosphere of an inert gas such as Ar or He, or a mixed gas containing one of these gases. When sputtering the target, it is sufficient to introduce a gas for introducing hydrogen atoms (H) and/or rogen atoms into the sputtering deposition chamber. In the photoconductive member of the present invention, germanium The second layer region (S), which is provided on the first layer region (G) containing atoms and does not contain germanium atoms, contains a substance that controls conduction properties, thereby improving the layer region. The conduction properties of (8) can be arbitrarily controlled as desired. Examples of such substances include so-called impurities in the semiconductor field. a −S i (H,
For X), examples include an n-type impurity that provides n-type conduction characteristics and an n-type impurity that provides n-type conduction characteristics. Specifically, as well as n-type impurities, atoms belonging to Group Ⅰ of the periodic table (Group Ⅰ atoms), such as B (boron), U (aluminum), Ga (gallium), In (indium)
, 'l (thallium), etc., and B and Ga are particularly preferably used. Particularly suitable n-type impurities include atoms belonging to Group V of the periodic table (group II atoms), such as P (adjacent), As (arsenic), sb (antimony), Bi (bismuth), etc. The ones used for are P, As
It is. In the present invention, the content of the substance controlling the conduction properties contained in the second layer region (S) is determined based on the conduction properties required for the layer region (S) or the content of the substance controlling the conduction properties contained in the second layer region (S). In terms of organic relationships, such as the characteristics of other layer regions provided in direct contact and the relationship with the characteristics at the contact interface with the other layer regions,
It can be selected as appropriate. In the present invention, the content of the substance that controls conduction characteristics contained in the second layer region (S) is as follows. Preferably 0.001 to 1000 atomic pp
m, more preferably 0.05 to 500 atomic p
pm, preferably 0.1 to 200 atomic ppm. In order to structurally introduce a substance that controls conduction properties into the second layer region (S), such as Group 1 atoms or Group V atoms, a starting material for introducing Group 1 atoms must be prepared during layer formation. The substance or starting material for introducing Group 1 atoms may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the second layer region. Possible starting materials for introducing Group 1 atoms include those that are gaseous at room temperature and pressure, or
It is desirable to use a material that can be easily gasified at least under layer-forming conditions. Specifically, as a starting material for introducing such Group 1 atoms, B2 is used for introducing boron atoms.
Hs, B4d(to tB 5H9q B 5 F(1
1+ B 6 H10t B 6 H12t B 6 H
Boron hydride such as No. 14, BF 3. BCl3yBB
r3 etc.], boron rogenide, etc. In addition, A/Cd3, GaC/3゜Ga(CH3)5r
InCJ3, TICA'3, etc. can also be mentioned. In the present invention, effective starting materials for the introduction of Group Ⅰ atoms include PH3,
P2 [44 good hydrogen north neighbor, PH4I. PF3 t PFs + PCla, P(Js t
Examples include halogen ratios such as PBr3p PBrs p PIa. In addition, AsH3゜AsF3 #A
SC13y AsBr3 t AsF5 t SbH3
JSbF3. SbF5.5bCJ3.5b (J5, BiH3t B
iCl3 t B1Br3 and the like can also be mentioned as effective starting materials for introducing Group (I) atoms. In the present invention, in order to provide the layer region (0) containing oxygen atoms in the first amorphous layer H, the first amorphous layer ([)
When forming, the starting material for introducing oxygen atoms may be used together with the starting material for forming the first amorphous layer m, and the amount thereof may be controlled and contained in the layer to be formed. . When using the glow discharge method to form layer region 0), a material for introducing oxygen atoms is added to a starting material selected as desired from among the starting materials for forming the first amorphous layer (■) described above. Starting materials are added. As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing oxygen atoms (0) as constituent atoms, and hydrogen atoms (H) or... rogen atoms (X) as constituent atoms as necessary. or a raw material gas whose constituent atoms are silicon atoms (8i) and a raw material whose constituent atoms are oxygen atoms (0) and hydrogen atoms (H). Alternatively, a raw material gas containing silicon atoms (Si) and silicon atoms (Si), oxygen atoms (0
) and hydrogen atoms () can be mixed and used. Also, separately, silicon atoms (Sl) and hydrogen atoms-7 (H)
Even if a raw material gas having an oxygen atom (0) as a constituent atom is mixed with a raw material gas having an oxygen atom (0) as a constituent atom. -Nitrogen oxide (NO), nitrogen dioxide (NO2), :nitric oxide (N20), nitrogen sesquioxide (N203) +nitrogen tetroxide (N204), nitrogen sesquioxide (N205)
rNitrogen trioxide (NOa), whose constituent atoms are a silicon atom (8i), an oxygen atom (0), and a hydrogen atom (H),
For example, disiloxa 7 (B38 ios iH3)
, Triji t:+ Key jj-:y(H3S jO81
Examples include lower siloxanes such as H20s iH3). To form the first amorphous layer (I) containing oxygen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or a Si02 wafer or 81
This can be carried out by sputtering a wafer containing a mixture of Si02 and Si02 in various gas atmospheres. For example, if an 81 wafer is used as a target, the raw material gas for introducing oxygen atoms and optionally hydrogen atoms and/or hydrogen atoms is diluted with a diluting gas as necessary to prepare the material for sputtering. The 81 wafer 1 is introduced into the deposition chamber to form a gas plasma of these gases.
- can be sputtered. Alternatively, by using Si and S+02 as separate targets or by using a mixed target of Sl and 8102, in an atmosphere of dilution gas as a sputtering gas, or at least hydrogen atoms () This is accomplished by sputtering in a gas atmosphere containing T) or/and halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the example of glow discharge described above can be used as an effective gas also in the case of sputtering. In the present invention, when forming the first amorphous layer (T),
When providing a layer region (0) containing oxygen atoms, the distribution concentration C(0) of oxygen atoms contained in the nucleus layer region (0) is changed in the layer thickness direction to obtain a desired distribution state in the layer thickness direction. (de
In order to form a layer region (0) having a pth profile), in the case of glow discharge, the starting material gas for introducing oxygen atoms whose distribution concentration 0 (0) should be changed is changed by changing the gas flow rate as desired. This is accomplished by introducing it into the deposition chamber while changing the rate appropriately according to the rate curve. For example, the opening of a predetermined needle pulp provided in the middle of the gas passage system may be gradually changed by any commonly used method such as manual operation or an external drive motor. At this time, the rate of change in flow rate does not need to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a pre-designed rate-of-change curve to obtain a desired content rate curve. ◎ Layer region (0) When forming by sputtering method, the distribution concentration a (O) of oxygen atoms in the layer thickness direction is changed to form a desired distribution state (depth profile) of oxygen atoms in the layer thickness direction. First, as in the case of the glow discharge method, the starting material for introducing oxygen atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is changed as desired. done by. Second, when using a target for sputtering, for example, a mixed target of 8i and 8103, the mixing ratio of sI and 5i02 can be changed in advance in the layer thickness direction of the target. It is achieved by letting it happen. In the present invention, hydrogen atoms (H
) or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H×X) is preferably Fil ~
40 atomic%, preferably 5-3°ato
mrc%, preferably 5 to 25 atomic. In the photoconductive member 100 shown in FIG. , mainly moisture resistance,
It is provided in order to achieve the objectives of the present invention in terms of continuous repeated use characteristics, pressure resistance, use environment characteristics, and durability. Further, in the present invention, each of the amorphous materials constituting the first amorphous layer (D102 and the second amorphous layer (U) 105 has a common constituent element of silicon atoms). Therefore, chemical stability is sufficiently ensured at the laminated interface.In the photoconductive member 100 shown in FIG. The second amorphous layer (f
r) 103 has a free surface and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, pressure resistance, use environment characteristics, and durability. Further, in the present invention, each of the amorphous materials constituting the first amorphous layer (I) 102 and the second amorphous layer (II) 103 has a common constituent element of silicon atoms. Therefore, chemical stability is sufficiently ensured at the laminated interface. The second amorphous layer (II) in the present invention is a non-crystalline layer containing silicon atoms (8I), nitrogen atoms (N), and optionally hydrogen atoms (H) or/and halogen atoms. Crystalline material (hereinafter Ja (81xN1-y)y('Lx) t-
It is written as yJ. However, o<x-y<1). The formation of the second amorphous layer (II) composed of a (8ixN1-x)y(Hs
This is accomplished by a sputtering method, an electron beam method, or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, degree of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured.
In the second amorphous layer (U), nitrogen atoms and nitrogen atoms are formed together with silicon atoms, which makes it relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having desired characteristics. The glow discharge method or the sputtering method is preferably adopted because of the advantages that it can be easily introduced into the process.Furthermore, in the present invention, the glow discharge method and the sputtering method can be used in the same equipment system. In combination, a second amorphous layer (T
I) may also be formed. To form the second amorphous layer (II) by the glow discharge method, a-(S l x N 1 x ) y ('',
X)1. The raw material gas for formation is mixed with a dilution gas at a predetermined mixing ratio if necessary, and introduced into a vacuum deposition chamber where the support is installed, and the introduced gas is used to cause glow discharge. By gas plasma generation, a (""x
Nt-X)31(H%X)1-y may be deposited. In the present invention, a-(8IxNl-x)y(H,X)
As the raw material gas for forming ty, silicon atoms (S
i), nitrogen atom (NX hydrogen atom (H), halogen atom (
Most of the gaseous substances containing at least one of X) as a constituent atom or the gasified substances that can be gasified can be used. When using a raw material gas having 8i as a constituent atom as one of Si, NSH, and X, for example, a raw material gas having S: as a constituent atom, a raw material gas having N as a constituent atom,
If necessary, a raw material gas containing I] and/or a raw material gas containing X as a constituent atom may be mixed at a desired mixing ratio, or a raw material gas containing St as a constituent atom,
Raw material gas containing N and H as constituent atoms or/and N and X
A raw material gas having constituent atoms of 81. A raw material gas having three constituent atoms, N and H, or a raw material gas having three constituent atoms, St, N, and X, can be mixed and used. Separately, N is added to the raw material gas containing 81 and H as constituent atoms.
A raw material gas containing 84 and In the present invention, preferred halogen atoms (X) contained in the second amorphous layer (U) are F, C4; 3°Br, I, and particularly preferred are FlC,, e. It is. In the present invention, raw material gases that can be effectively used to form the second amorphous layer (TI) include:
Examples include substances that are in a gaseous state at room temperature and pressure, or substances that can be easily gasified. Layer forming methods for forming the second amorphous layer (II) from the above amorphous material include glow discharge method, sputtering method, ion implantation method, ion blating method, electron beam method, etc. Can be mentioned. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, the level of equipment capital investment, and the desired characteristics of the photoconductive member to be manufactured on a manufacturing scale. It is relatively easy to control the manufacturing conditions for manufacturing parts, and it is possible to introduce nitrogen atoms, hydrogen atoms and halogen atoms as necessary into the second amorphous layer (IF) along with silicon atoms. The glow discharge method or the sputtering method is preferably employed because of the advantages that it can be easily performed. Furthermore, in the present invention, in order to form the second amorphous layer (I) composed of a-8iN (H, A raw material gas for Si supply that can supply silicon atoms (Si), a raw material gas for introducing nitrogen atoms (N), and a raw material gas for introducing hydrogen atoms (N) as needed.
H) A raw material gas for introduction and/or halogen atoms (force introduction) is introduced into a deposition chamber whose interior can be reduced in pressure, a glow discharge is generated in the deposition chamber, and 5iN is applied to a predetermined position in advance.
It is sufficient to form a pot number consisting of (H, X). Δ Furthermore, when the second amorphous layer (II) is formed by sputtering, the following procedure is performed, for example. Firstly, when sputtering a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas containing these gases, nitrogen atoms (
N) Hydrogen atoms (H) are added to the raw material gas for introduction as necessary.
It may be introduced into a vacuum deposition chamber where sputtering is performed together with a raw material gas for introduction and/or for introduction of halogen atoms (X). Secondly, Si3 is used as a target for sputtering.
A second target formed by using a target composed of N4, or a target composed of 8i and a target composed of 8iBN4, or a target composed of 8i and 8i 3N4. amorphous layer (II
) can be introduced into nitrogen atoms (N). At this time, if the above-mentioned raw material gas for introducing nitrogen atoms (N) is also used, its flow rate can be controlled.
It is easy to arbitrarily control the amount of nitrogen atoms (N) introduced therein. The content of nitrogen atoms (N) introduced into the second amorphous layer (H) is determined by the force that controls the flow rate when the raw material gas for introducing nitrogen atoms (N) is introduced into the deposition chamber. N or nitrogen atom (N
) The proportion of nitrogen atoms (N) contained in the target for introduction can be arbitrarily controlled as desired by adjusting the proportion of nitrogen atoms (N) contained in the target for introduction, or by doing both. The starting materials used as raw material gas for supplying Si used in the present invention include 5ilH4, 812H6, Si3)
(g. Silicon hydride (silanes) in a gaseous state or that can be gasified, such as 5I4T (IQ), is cited as one that can be effectively used, especially for ease of handling in layer creation work, good St supply efficiency, etc. 8 i04 + S i 2H6 is preferred from the viewpoint of
can also be introduced. Effective starting materials for raw material gas for supplying 81 include:
In addition to the above-mentioned silicon hydride, silicon compounds containing /% halogen atoms (X), so-called halogen atom-substituted silane derivatives, specifically, for example, SiF4. Si2F6,5iO
J4tSiBr4 etc./. Preferably, silicon oxide is used. Saraniij, SiH2F2.8iH212,5iH20
−β21SiHO,,e31SiT(2Br2 +5i
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituents, such as HBr3 and other hydrogen atoms, are also effective for forming the second amorphous layer (U). It can be used as a starting material for supplying Si. Even when these silicon compounds containing halogen atoms (X) are used, as mentioned above, by appropriately selecting the layer forming conditions, X together with Si can be added to the second amorphous layer (II) to be formed. It can be introduced. The silicon halide compound containing a hydrogen atom in the above-mentioned starting material has electrical or photoelectric properties at the same time as the halogen atom (X) is introduced into the layer during the formation of the second amorphous layer (U). Since a hydrogen atom (H), which is extremely effective for control, is also introduced, it is used as a starting material for the introduction of a halogen atom (X), which is suitable for the present invention. In addition to the above-mentioned materials, effective starting materials that serve as the raw material gas for introducing halogen atoms (X) used in forming the second amorphous layer (TI) in the present invention include, for example, fluorine, Halogen gas of chlorine, bromine, and iodine, BrP
+O−gF+αgF3 *BrF3 *BrF3,
II3, II7, IO! , interhalogen compounds such as TBr, HF, HClg, HBr,
Examples include hydrogen halides such as HI. Starting materials that can be effectively used as raw material gas for introducing nitrogen atoms (N) used when forming the second amorphous layer (TI) are those containing N as a constituent atom or containing N.
For example, nitrogen (N2), ammonia (NHa), hydrazine (H2NNH2), hydrogen azide (HNa), ammonium azide (NH4N3) and H are constituent atoms.
), gaseous or gasifiable nitrogen, nitrogen compounds such as vacancies and azides, and the like. In addition to this,
Nitrogen trifluoride (FaN) r
Mention may be made of halogenated drilling compounds such as nitrogen tetrafluoride (F4N2). In the present invention, the diluent gas used when forming the second amorphous layer (It) by a glow discharge method or a sputtering method is a so-called rare gas, for example, He+Ne+A.
Preferred examples include r. The second amorphous layer (II) in the present invention is carefully formed so as to provide the desired properties. In other words, a substance whose constituent atoms are SI+N+H or/and X as required has a structure ranging from crystalline to amorphous depending on its preparation conditions, and electrically:
In the present invention, a-( S
The formation conditions are strictly selected as desired so that ixNl-x)y(rT,X) 1-y is formed. For example, if the second amorphous layer (U) is provided with the main purpose of improving pressure resistance, a(S'xNt-x)y(T
(, In addition, when a second amorphous layer (It) is provided for the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to some extent, and AA 81 xNl-x)y(H,X)1 is created as an amorphous material having a certain degree of sensitivity. On the surface of the first amorphous layer (T), a-(S 1xN1-x
)y(T(,X)i-a second amorphous layer (T)
On the surface of a-(S'xNl-x)y(H-X)! -y
When forming the second amorphous layer fl), the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer, and in the present invention, a−(Slx′Nj −X )y(T(
, In the present invention, an optimal range is appropriately selected in accordance with the method of forming the second amorphous layer (It) in order to effectively achieve the desired purpose, and the second amorphous layer (It) is The second amorphous Layer (TI)
For the formation of , glow discharge and sputtering methods are recommended because delicate control of the composition ratio of the atoms that make up the layer and control of the layer thickness are relatively easy compared to other methods. Advantageously, in these layer formation methods the second amorphous #(■)
When forming a layer, the discharge power during layer formation is created in the same manner as the support temperature described above.a (S'xNl-x)
It is one of the important factors that influences the characteristics of y(HlX)i-y. a having the characteristics for achieving the object of the present invention;
-(S'xNt-x)y(HeX) The discharge power condition for effectively creating t-y with good productivity is preferably ril, 0 to 300W, more preferably 2.0
~25oW1 Optimally 5.0~2oow is desirable. The gas pressure in the deposition chamber is preferably 0.01~] Torr
More preferably, it is 0.1 to Q and about 5 Torr. In the present invention, the desirable numerical ranges of the support temperature and discharge power for creating the second amorphous layer (IT) include the values in the above ranges, but these layer creation factors are as follows: The desired characteristics a − (8ixNs−x)y(”X) t−y are not determined independently and separately.
It is desirable that the optimum value of each layer forming factor be determined based on the mutual organic relationship so that the second amorphous layer (II) consisting of is formed. Second amorphous layer (TI) in the photoconductive member of the present invention
The amount of nitrogen atoms contained in K is the same as the production conditions of the second amorphous layer (W), so that the second amorphous layer (II) can obtain the desired characteristics to achieve the object of the present invention. It is an important factor in the formation of The amount of nitrogen atoms contained in the second amorphous layer (TI) in the present invention depends on the type and characteristics of the amorphous material constituting the second amorphous layer (U). 0, that is, the general formula a-(SixNt
-x)y(H2Xhy) The amorphous material represented by , O<a<1), an amorphous material composed of silicon atoms, nitrogen atoms, and hydrogen atoms (hereinafter referred to as [a-(81bN
1-・b). Hl-c". However, 0〈b, Cku1
), an amorphous material composed of a silicon atom, a nine-element atom, a hydrogen atom, and optionally a hydrogen atom (hereinafter referred to as [a
It is written as -(8idN1-d)e(H2X) +-eJ. However, Q(d*e<1), [classified. In the present invention, the second amorphous layer (II) is a-8I
-1]N1-3, the second amorphous layer (I
The amount of nitrogen atoms contained in r) is preferably 3]'X 10 to 60 atomic%, more preferably 1 to 5° atomic%, optimally 10 to 45
It is desirable to set it to omic%. That is, if expressed as a in a-BIBNl-8 above, a is preferably 0.4 to 0,99999, more preferably 0.5 to 0.
．． 99, optimally between 0.55 and 0.9. In the present invention, the second amorphous layer (H) is 8-(Sib
Nl-b). H. When composed of I, the amount of nitrogen atoms contained in the second amorphous layer (TI) is preferably I
X 10 to 55 atomic%, more preferably 1 to 55 atomic%, optimally 10 to 50 atomic%
It is desirable to set it to atomic%. The hydrogen atom content is preferably 1 to 40 atom
mic%, more preferably 2 to 35 atomic%, optimally 5 to 3 Qltomic%, and when the hydrogen atom content is within these ranges, the photoconductive member formed is , it can be fully applied as an excellent thing in practice. That is, the cut b is preferably 0.45 to 0.99999,
More preferably 0.45 to 0.99, optimally 0.15 to
0.9, C is preferably 0.6 to 0.99, more preferably 0.65 to 0.98, optimally 0.7 to 0.95. The second amorphous layer (U) is a-(S'dNt-d)e
When composed of (HlX)le, the content of nitrogen atoms contained in the second amorphous layer (Ir) is as follows:
Preferably, I X 10"'-3~9 Q atom
ic%, more preferably Id 1-90 atomic%
, optimally 10-55 atomic %, more preferably ld 1-18 atomic %, optimal KH 2-1
It is desirable that the halogen atom content be within this range, so that a photoconductive member produced when the halogen atom content is in this range can be applied to a practical surface. The content of hydrogen atoms contained as necessary is preferably l 9 atomic % or less, more preferably a 13
It is desirable that the amount is less than atomjc%. That is, the previous a-(SidNt-d)e (H+Xh-e
d. d is preferably 0.4 to 0.999.
99, more preferably 0.4 to n, 99, optimally 0.4
5-0.9, e is preferably 0.4 to 0.99999,
Preferably 0.4&~0.99, optimally 0.45-0.
9 is desirable. The number range of the layer thickness of the second amorphous layer (II) in the present invention is one of the important factors for effectively achieving the object of the present invention. In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose. The thickness of the second amorphous layer (n) depends on the amount of nitrogen atoms contained in the layer (Tf) and the thickness of the first amorphous layer (r). However, it is necessary to appropriately determine the desired characteristics based on organic relationships depending on the characteristics required for each layer region. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production. The layer thickness of the second amorphous layer (II) in the present invention is preferably 0.003 to 30μ, more preferably 0.00μ.
It is desirable that the thickness be 4 to 20μ, most preferably 0.005 to 10μ. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include Ni0r and stainless steel. A-go Or +Mo+Ao+NbtTa+V+Ti
Examples include metals such as tPt*Pd and alloys thereof. Polyester is used as the electrically insulating support. Polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride. Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, etc., and glass. Ceramic, paper, etc. are commonly used. 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, Nr Or e is applied to its surface.
Ae* Cr +Mo IALI , Ir l Nb
+Ta lvl T'+ , Pt ePd , In2
O3, 8n02, ITO (In203 +5n02
), etc., or if it is a synthetic resin film such as a polyester film, + Ni0r −A−e , Ag e pb
eZn. Ni+Au+C! r+Mo+ Ir+Nb+Ta, V+
Vacuum evaporation or electron beam evaporation of thin films of metals such as Ti+Pt. Conductivity is imparted to the surface by sputtering or the like, or by laminating the surface with the metal. The shape of the support body is cylindrical, belt-shaped,
It may have any shape such as a plate shape, and the shape is determined as desired. For example, if the photoconductive member 100 shown in FIG. , it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. Hyakuen et al. In such cases, the thickness is usually set to 10μ or more from the viewpoint of manufacturing and handling of the support, mechanical strength, etc. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained. FIG. 11 shows an example of a photoconductive member manufacturing apparatus. In the gas cylinders 1102 to 1106 in the figure, raw material gas for forming the photoconductive member of the present invention is sealed. %, below 8iH4/
It is abbreviated as He. ) cylinder, 1103 is G diluted with He.
e H4 gas (purity 99.999%, hereinafter referred to as G e H
4/T (abbreviated as e) cylinder, 1104 is diluted with He and contains 8 i F 4 gas (purity 99.99%, hereinafter 8
It is abbreviated as i F4 /He. ) cylinder, 1105 is No gas (purity 99.999), 11o6 is 02H4
It is a gas cylinder (99.999% purity). The valves 1122 to 1126 of the gas cylinders 1102 to 1106 are used to flow these gases into the reaction chamber 1101.
, make sure that the leak valve 1135 is closed, and also check that the inflow valves 1112 to 1116 and the outflow valve 11
17-1121. After confirming that 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.times.10@-6 torr, the auxiliary valves 1132, 1133 and the outflow pulps 1117 to 1121 are closed. Next, a first amorphous layer (T
) is an example of forming a gas cylinder 110.
2 to 8iH4/)Te gas, from gas cylinder 11o3, GeH4/He gas, and No gas from gas cylinder 1105.
Adjust to d, inflow pulp 1112, 1113.1114
Gradually open the mass flow controller 1107゜11
08.1109 respectively. Subsequently, outflow valves 1117, 1118, 1119, auxiliary valve 113
2 is gradually opened to allow gas to flow into each reaction chamber 1101. At this time, 81H4/He gas flow rate and Qe H4/
Adjust the outflow valves 1117, 1118, and 1119 so that the ratio of the He gas flow rate to the No gas flow rate becomes the desired value, and also adjust the reading of the vacuum gauge 1136 so that the pressure in the reaction chamber 1101 becomes the desired value. Main valve 1134 while watching
Adjust the aperture. After confirming that the temperature of the substrate 1137 is set to a temperature in the range of 50 to 400°C by the heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. Glow discharge is maintained for a desired time to form a first layer region (G) on the substrate 1137 to a desired layer thickness. At the stage where the first layer region (G) has been formed to the desired layer thickness, the discharge valve 1118 is completely closed and the discharge conditions are changed as necessary for the desired time according to the same conditions and procedures. By maintaining the glow discharge, the first layer region (G
) on which a second layer region (S) substantially free of germanium atoms can be formed. In this way,
A first amorphous layer (T) is formed. In order to contain a substance that controls conductivity in the second layer region (8), when forming the second layer region (S), for example, 8
A gas such as 2H6 or PH3 may be added to the gas introduced into the deposition chamber 1101. When a halogen atom is contained in the first amorphous #(I), glow discharge may be generated by further adding, for example, 5iP4 gas to the above gas. In addition, when the first amorphous layer (I) contains halogen atoms without hydrogen atoms, the above Si 1.
t, 4 (e gas and G e H4/) Instead of T e gas, S i F4 /He gas and G e F 47QT
You can use e-gas. The first amorphous layer (
To form the second amorphous layer (II) on T), for example, each of SiH4 gas and NH3 gas is introduced by the same valve operation as in the formation of the first amorphous layer (T). This is accomplished by diluting with a diluent gas such as He 2 as necessary to generate glow discharge according to desired conditions. In order to contain halogen atoms in the second amorphous layer (JT), for example, SiF4 gas and NH3 gas, or 5IH4 gas is added thereto and the second amorphous layer (JT) is formed in the same manner as above. ). Needless to say, when forming each layer, all the outflow valves other than the gas outflow valve are closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow out into the reaction chamber 1101. In order to avoid gas remaining in the gas piping leading from the valves 1117 to 1121 into the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, the auxiliary valves 1,132 and 1133 are opened, and the main valve 1134 is closed.
If necessary, fully open the system and evacuate the system to high vacuum for one day. When the flow rate ratio of nitrogen atoms contained in the second amorphous layer (II) is changed as desired, or when the layer is formed by sputtering, a mixed gas of Ar and NH3,
When forming the target, it can be controlled as desired by changing the sputtering area ratio of the silicon wafer and silicon nitride, or by changing the mixing ratio of silicon powder and silicon nitride powder and molding the target. The nitrogen atoms contained in the amorphous layer (IF) (
The amount of X) is the raw material gas for introducing halogen atoms, e.g.
This is accomplished by adjusting the flow rate when the iP4 gas is introduced into the reaction chamber 1101. 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 A cylinder-shaped A,
An electrophotographic image forming member was formed on the e substrate under the conditions shown in Table 1. The thus-obtained monk-forming member was installed in a charging exposure experiment device.+7)5. Corona charging was performed at OkV for 0.311 eC, and a light image was immediately irradiated using a tungsten lamp light source with a light intensity of 21 ux and AEC through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the bond forming member by cascading a charged developer (containing toner and carrier) over the surface of the bond forming member. The toner image on my forming member was transferred to G15. When transferred onto transfer paper using OkV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 2 An electrophotographic image forming member was formed using the manufacturing apparatus shown in FIG. 11 in the same manner as in Example 1 except that the conditions shown in Table 2 were used. Using the thus obtained image forming member, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, except that the charge polarity and the charge polarity of the developer were opposite to those in Example 1. The image was extremely clear. A great image was obtained. Example 3 An electrophotographic image forming member was formed using the manufacturing apparatus shown in FIG. 11 in the same manner as in Example 1 except that the conditions shown in Table 3 were used. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 4 In Example 1, G e H4/T (e gas and SiH
An electrophotographic image forming member was prepared in the same manner as in Example 1, except that the content of germanium atoms contained in the first layer was changed as shown in Table 4 by changing the gas flow rate ratio of 4/He gas. were created respectively. 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 4 were obtained. Example 5 Electrophotographic image forming members were prepared in the same manner as in Example 1 except that the thickness of the first layer was changed as shown in Table 5. 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 5 were obtained. Example 6 Using the manufacturing apparatus shown in FIG. 11, a first amorphous layer (T) was formed on a cylindrical substrate under the conditions shown in Table 6.
An electrophotographic image forming member was formed in the same manner as in Example 1 except that . The image forming member obtained in this way was installed in a charging exposure experiment apparatus.Q5. Corona charging was performed at OkV for 0.3 see, and a light image was immediately irradiated using a tungsten lamp light source and a light amount of 21 ux, sec' was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the image forming member by cascading a charged developer (including toner and carrier) over the surface of the image forming member. The toner image on the imaging member is transferred o5. When transferred onto transfer paper using OkV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 7 In Example J, the light source was replaced with a tungsten lamp.
The toner image was formed under the same toner image forming conditions as in Example 1, except that the electrostatic image was formed using a 10 nm GaAs-based conductor laser (1 (knW)). When the image quality of the toner-transferred image was evaluated using the electrophotographic image forming member, it was found that a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained. Example 8 Amorphous layer ( Each of the electrophotographic image forming members (sample plate 1
2-201~12-208.12-301~12-30
8.24 samples (12-601 to 12-608) were created. Each of the electrophotographic image forming members thus obtained was individually placed in a copying machine, and corona charging was performed at C) 5 kV for 0.2 seconds, and a light image was irradiated. A tungsten lamp is used as a light source, and the light t ld 1 , O1uxsec
And so. The latent image was developed with a charged developer (containing toner and carrier) and transferred to regular paper. The transferred image was extremely good. Toner that was not transferred and remained on the electrophotographic imaging member was cleaned with a rubber blade. Even when such steps were repeated over 100,000 times, no image deterioration Vi was observed in any case. Table 8 shows the results of the overall image quality evaluation of the transferred image of each sample and the evaluation of durability through repeated and continuous use. Example 9 Sputtering was used when forming the amorphous layer (II). , by changing the target area ratio of the mixed gas of Ar and NH3 and the silicon nitride, the amorphous II
An image forming member was prepared in the same manner as in Example except that the content ratio of silicon atoms and nitrogen atoms in the (IT) was changed. For each of the image forming members thus obtained, the image forming, developing, and cleaning steps as described in Example 1 were repeated about 50,000 times, and then image evaluation was performed, and the results shown in Table 9 were obtained. Obtained. Example 10 When forming the amorphous layer (It), SiH4 gas and NH3
Each of the image forming members was created in the same manner as in Example 1, except that the content ratio of silicon atoms and nitrogen atoms in the amorphous layer (It) was changed by changing the gas liquid ratio. . For each image forming member thus obtained, Example 1
After repeating the steps up to transfer about 50,000 times using the method described in 1., image evaluation was performed, and the results shown in Table 10 were obtained. Example 11 When forming the amorphous layer (n), S-th gas]4 gas, SiF4
The amorphous layer (It) was formed by changing the supply ratio of gas and NH3 gas.
Each of the image forming members was produced in exactly the same manner as in Example 1, except that the content ratio of silicon atoms to nitrogen atoms in the sample was changed. After repeating the image forming, developing and cleaning steps as described in Example 1VC about 50,000 times for each of the image forming members thus obtained, image evaluation was performed and the results shown in Table 11 were obtained. Example 12 Each of the imaging members was prepared in the same manner as in Example 1, except that the thickness of the amorphous layer (TI) was changed. The image forming, developing and cleaning steps as described in Example 1 were repeated to obtain the results shown in Table 12. Table 4 Table 5 0: Excellent 0: Good 6 Common layer forming conditions in the Examples of the present invention shown in Table 7, Table 12 and above are shown below. Substrate temperature: Germanium atom (Ge) content: approx. 200°C Germanium atom (Ge) free content: approx. 250°C Discharge frequency: 13.56 MHz Reaction chamber pressure during reaction: 0.3 Torr

[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 explanatory diagrams for explaining the distribution state of oxygen atoms in an amorphous material, respectively. , Figure 11 is
FIG. 2 is a schematic explanatory diagram of an apparatus used to produce the photoconductive member of the present invention in Examples. 100... Photoconductive member 101... Support body 102.
...First amorphous layer (T) 105...Second amorphous layer (TI) Applicant Canon Co., Ltd. 0 1111 → -C Procedural amendment (own ship October 1982) Patent Application No. 149752, dated May 24, 1982, 2, Name of the invention Photoconductive member 3, Relationship with the case of the person making the amendment Patent applicant address 3-30-2 Shimomaruko, Ota-ku, Tokyo Name (100
)Representative of Canon Co., Ltd. Ryu Kaku 3 Part 4, Agent address: 3-30-25 Shimomaruko, Ota-ku, Tokyo 146, Specification subject to amendment 6, Specified locations of the specification of contents of amendment as shown in the table below. to correct.

Claims (1)

[Claims] a support for a photoconductive member; and an amorphous material containing silicon atoms and germanium atoms on the support;
a first amorphous layer having a layer structure in which a first layer region and a second layer region made of an amorphous material containing silicon atoms and exhibiting photoconductivity are provided in order from the support side; and a second amorphous layer made of an amorphous material containing silicon atoms and nitrogen atoms, and the first amorphous layer contains oxygen atoms. A photoconductive member.