JPS6059360A - Photoconductive member - Google Patents

Abstract

PURPOSE:To stabilize electrical, optical and photoconductive characteristics at all times by distributing nonuniformly in the layer thickness direction Ge into the 1st layer region on a base side in the 1st layer and incorporating nitrogen into the 1st layer. CONSTITUTION:The 1st layer 102 provided successively with the 1st layer region 104 constituted of an amorphous material contg. Si and Ge and the 2nd photoconductive layer region 105 constituted of an amorphous material contg. Si is provided on a base 101. Ge in the region 104 is nonuniformly distributed in the layer thickness direction and nitrogen is incorporated into the layer 102. The Ge is distributed preferably more toward the base side in the region 104. The 2nd layer 103 constituted of an amorphous material contg. Si and C is provided on the layer 102.

Description

[Detailed description of the invention] The present invention is based on light (here, light in a broad sense, ultraviolet light).

The present invention relates to a photoconductive part I that is sensitive to electromagnetic waves such as visible light, infrared light, Xa, gamma rays, etc.

As a photoconductive material forming a photoconductive layer in a solid-state imaging device, an image forming part for electrophotography in the image forming field, or a document reading device, it has a 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, and has a desired dark resistance value.
Solid-state imaging devices are required to have characteristics such as being harmless to the human body during use and being able to easily remove afterimages within a predetermined time. In the case of an electrophotographic imaging member incorporated into an electrophotographic apparatus, the above-mentioned non-toxicity during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as a-si) is a photoconductive material that has recently attracted attention.
It is described in Japanese Patent No. 55718 as an image forming unit for electrophotography, and in German Publication No. 2933411 as an application to a photoelectric conversion/reading device.

Hyakunen et al., photoconductor 10 paulownia having a photoconductive layer composed of conventional A-81 has excellent dark resistance value, photosensitivity, electrical, optical, photoconductive properties of photoresponsive monk, moisture resistance, etc. The reality is that there are points that need to be further improved in terms of use environment characteristics and stability over time in order to achieve a comprehensive improvement in characteristics.

For example, when applying it to electrophotographic image forming systems, when trying to simultaneously achieve high photosensitivity and high dark resistance, in the past, it has often been observed that residual potential remains during use, and this type of light 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 speed, the response gradually decreases. There were many cases where spots appeared.

Furthermore, a-81 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. Alternatively, there is still room for improvement in that it is not possible to effectively use light on the longer wavelength side when using commonly used lights or fluorescent lamps as a light source. .

In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases, the reflectance of the support itself to the light transmitted through the photoconductive layer may decrease. When the value is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" in the image.

This effect becomes larger as the irradiation spot is made smaller in order to increase the resolution, and it becomes a big problem especially when the semiconductor laser is used at a temperature of about 100 ml.

Furthermore, when forming a photoconductive layer using A-8S material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type Boron atoms, phosphorus atoms, etc. for control purposes, or other atoms for improving other properties, are contained in the photoconductive layer as constituent atoms, but depending on how these constituent atoms are contained, However, problems may arise in the electrical or photoconductive properties of the formed layer.

Therefore, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charges from the support side to the other side is not sufficiently blocked in a dark area. This occurs in many cases.

Furthermore, if the layer thickness exceeds 10-odd microns, the layer will float and peel off from the surface of the support as time passes after it is left in the air after being taken out of the air storage room for layer formation. Otherwise, phenomena such as cracks occurring in the layer were likely to occur. This phenomenon is
This problem often occurs particularly when the support is a drum-shaped support normally used in the field of electrophotography, and is a problem that should be solved in terms of stability over time.

Therefore, while improvements in the characteristics of the A-8I material itself are being made, efforts must be made to solve all of the above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the above-mentioned points, and is concerned with the applicability and applicability of a-8I as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive research and consideration from this point of view, we have found that amorphous lateral slopes, so-called hydrogenated amorphous silicon, and halodanized amorphous silicon, are made of silicon atoms and contain at least either hydrogen atoms (6) or halogen atoms. , or halogen-containing hydrogenated amorphous silicon [-a-
81 (H, In addition to exhibiting extremely superior properties, it also exceeds conventional photoconductive members in every respect, particularly as a photoconductive member for electrophotography, and has extremely superior properties at long wavelengths ( This is based on the discovery that the absorption and shedding torque characteristics of II+ are excellent.

The present invention has stable electrical, optical, and photoconductive properties at all times, is an all-environment type with almost no restrictions on usage environments, has excellent photosensitivity on the long wavelength side, and is resistant to light fatigue. The main object of the present invention is to provide an optical Nf conductive member which has a long lifespan, exhibits no 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 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 improve layer quality. The purpose is to provide a high photoconductivity I.

Another object of the present invention is that when used as an intermediary for forming electrophotographic images, it is possible to improve the process during '41 electrophotographic processing for forming electrostatic images to such an extent that ordinary electrophotographic methods can be applied very effectively. It is an object of the present invention to provide a photoconductive member having sufficient charge retention ability and excellent electrophotographic properties with almost no deterioration of the properties observed even in a humid atmosphere.

Still another object of the present invention is to produce a high-quality product with high density, )--clear foottones, and high resolution.5. It is an object of the present invention to provide a photoconductive member for electrophotography that can easily produce images.

Yet another object of the present invention is high photosensitivity.

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

The photoconductive member of the present invention includes a support for a photoconductor, a first layer region made of an amorphous material containing silicon atoms and germanium atoms, and an amorphous layer region containing silicon atoms. a first layer (1) of a layered structure provided in order from the support side; a second layer region made of amorphous material containing silicon atoms and carbon atoms; a photoreceptive layer composed of a second layer and a second layer, wherein the distribution state of dalmanium atoms in the first layer region is non-uniform in the layer thickness direction; The layer (1) is characterized by the presence of nitrogen atoms.

The photoconductive member of the present invention, which is prepared in such a manner as to have the various layer configurations described above, can solve all of the above-mentioned problems,
It exhibits extremely excellent electrical, optical, and photoconductive Q4'' properties, electrical pressure resistance, and use 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 has high sensitivity and a high signal-to-noise ratio. It is light fatigue resistant and can be used repeatedly! [! It has excellent J properties, high density, clear halftones, and can stably and repeatedly produce high-quality images with high resolution.

In addition, the photoconductive member of the present invention has a strong layer itself formed on the support, and has excellent adhesion to the support, making it possible to repeatedly use it continuously at high speed for a long time. can.

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.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The conductive member of the present invention will be described in detail below with reference to the drawings.

FIG. 1 is a schematic configuration diagram for explaining the layer configuration of a photoconductive member according to a first embodiment of the present invention.

The photoconductive member 100 shown in FIG.
102 and a second layer (n) i 03, said second layer (II) 103 having a free surface 106 on one end face. First layer (1) 102 is support body 101
a-8i (H,X) containing siddarmanium atoms on the side
(Hereafter, the first layer region (G) 104 composed of a-6IGe (abbreviated as I(,X)J) and a-81 (H,
A second layer region (S) composed of X) and having photoconductivity
105 are laminated in order. Dalmanium atoms contained in the first layer region (G) 104 are continuous in the layer thickness direction of the tenth layer region (G) 104 and on the side where the support 101 is provided. On the opposite side (second layer (n) 103 side), the support 1.01 (!11) is distributed more in the first layer region 0) 104. contained within.

In the photoconductive member of the present invention, the distribution state of kermanium atoms contained in the first layer region (G) is as follows:
In this direction, it is desirable to have the above-mentioned distribution state, and to have a uniform distribution state in the in-plane direction parallel to the surface of the support.

In the present invention, the second layer region (S) provided on the first layer region (S) does not contain kermanium atoms, and the first layer (S) is not included in this various layer structure. ), it is possible to obtain a photoconductive member that has excellent photosensitivity to light of all wavelengths from relatively short wavelengths to relatively short wavelengths, including the visible light region.

Moreover, the distribution state of germanium atoms in e (>1 layer region 0) is such that germanium atoms are connected in the entire layer region U,
: distribution, and the distribution concentration C of dalmanium atoms in the layer thickness direction decreases from the support side toward the second layer region (S). G) and the second
It has excellent affinity with the layer region (S) of When a semiconductor laser or the like is used, the second layer can prevent the accompanying interference, and by making the distribution concentration C of dalmanium atoms extremely large at the end of the support, as will be described later. Light on the long wavelength side, which is almost completely absorbed in the region (S), can be substantially completely absorbed in the first layer region (S), thereby preventing interference due to reflection from the support surface. I can do it.

Further, in the photoconductive member of the present invention, the first layer region (G
) and the second layer region (S) each have a common constituent element of silicon atoms, ensuring sufficient chemical stability at the laminated interface. It has been acidified.

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

In FIG. 2 to FIG. 1Q, the horizontal axis shows the distribution concentration C of germanium atoms, the vertical axis shows the layer thickness of the first layer region O), and tB is gfA11 of the first layer region O) on the support side. 'j
1, and t indicates the position of the end surface of the first layer region 0) on the side opposite to the support side. That is, the first layer region (G) containing germanium atoms is formed as a layer from the tB side toward the ptT side.

FIG. h'K2 shows a first typical example of the distribution state of dalmanium atoms contained in the first layer region O) in the layer thickness direction.

In the example shown in FIG. 2, the interface position t□ where the surface of the support where the germanium atom-containing first layer region ←) is formed and the surface of the first layer region (G) contacts Up to the position, the distribution concentration C of dahmanium atoms takes a constant value C, and the dahmanium atoms are contained in the first layer region (G) where they are formed, and from the position U to the interface position The concentration C2jJl is gradually and continuously decreased until tTK. At the interface position 1T, the distribution concentration C of germanium atoms is C3.

In the example shown in FIG. 3, the distribution concentration C of germanium atoms to be included gradually and continuously decreases from the concentration C4 from the position 1B to the concentration C1+ at the position tT. The distribution state is formed as follows.

In the case of Fig. 4, the distribution concentration C of kermanium atoms from position 1B to multiple positions t2 is a constant value of concentration C6,
The distribution concentration C is gradually and continuously decreased between the position ft1t+ and the position FJt, and the distribution concentration C is substantially zero at the position tT (here, substantially zero means that the amount is below the detection limit). ).

In the case of FIG. 5, the distribution concentration C of germanium atoms is
The concentration is gradually decreased continuously from the concentration c8 from the position tB to the multi-position tT, and becomes substantially zero at the position MtT.

In the example shown in FIG. 6, the distribution concentration C of kermanium atoms is between the position tB and the position
A constant value of 9 is used, and the concentration is set to CtO at position tT. Between the position t3 and the position tT, the area density C is linearly decreased from the position t3 to the multiple position t.

In the example shown in FIG. 7, the distribution concentration C is 1? T
From tB to multiple positions t4, the concentration C1l takes a constant value, and from position t4 to multiple positions t, the concentration decreases linearly from C12 to 3.

In the example shown in FIG. 8, from position 1 to multi-position t7, the distribution concentration C of dalmanium atoms decreases linearly from the concentration CI4 to substantially zero.

In FIG. 9, from position 1B to multi-position t8, the distribution concentration C of germanium atoms is the same as the concentration.

An example is shown in which the concentration is linearly decreased to CI6, and the concentration is kept at a constant value of C16 between position t5 and position tT.

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is -7 at position tB, and this concentration C17 decreases slowly at first until position t6, and near position ts. is rapidly decreased to a concentration C11l at position t6.

Between position t6 and position t7, the concentration is decreased rapidly at first, and then gradually decreased to reach the concentration CtS at position t7, and between position t7 and position t8, it decreases extremely slowly. position 1. reaches C20 at 6 degrees. Between the position t8 and the position 1T, the concentration is reduced according to a curve shaped as shown in the figure so that the concentration a actually becomes zero from C20.

As described above with reference to FIGS. 2 to 10, some typical examples of the distribution state of germanium atoms contained in the first layer region O) in the layer thickness direction, in the present invention, , on the support side, there is a part where the distribution concentration C of dalumanium atoms is high, and on the interface t side, there is a part where the distribution concentration C is considerably lower than on the support side. is provided in the first layer region (G).

The first layer constituting the photoconductive part I in the present invention
The layer region (G) preferably has a relatively high concentration of damanium atoms (a wide localized region) on the support side as described above.

In the invention, the localized region (A) is
Explaining using the symbols shown in FIG. 0, it is desirable to provide the interface within 5 μ from the interface position tB.

In the present invention, the localized region (4) is located at the interface position t
It may be the entire layer region (LT) with 5 μNt from B, or it may be a part of the layer region (LT).

Whether the localized region (A) is a part or all of the layer region (L,) is appropriately determined according to the characteristics required of the first layer (1) to be formed.

In the localized area history), the distribution state of the kalmanium atoms contained therein in the layer thickness direction is expressed as follows:
The layer is formed in such a manner that the concentration is preferably 1000 atomic ppm or more, more preferably 5000 atomic ppm or more, and optimally IXIQ atomic ppm or more.

That is, in the present invention, the first layer region (containing dallmanium atoms) has the maximum distribution concentration CI within 5 μm in layer thickness from the support side (region with a thickness of 5 μm from 1B).
Preferably, it is formed in such a way that Tlax is present.

In the present invention, the content of dalmanium atoms contained in the first layer region (1) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 9. 5 x 10 atomic ppm.

Preferably 100-8. OX 105atomic
ppm, optimally 500-7 X 10 atoms
c ppm.

In the present invention, the first layer region (G) and the second layer region (S
) is one of the important factors for effectively achieving the object of the present invention. Section H setting n1
Sufficient care needs to be taken when

In the present invention, the layer thickness TB of the first layer region (G) is '
lf preferably 30i~50μ, better 1 or 4°X~
40μ, optimally 5oX to 30μ.

Further, the layer thickness T of the second layer region (S) is preferably 0.5
~90μ, more preferably 1 to 80μ, optimally 2 to 5
It is assumed to be 0μ.

The layer thickness TB of the first layer region (1) and the layer thickness T of the second layer region (S) (T, l+T) are the characteristics required for both layer regions and the first layer (1). It is suitably determined as desired in the layer designation 1 of the photoconductive layer, based on the mutual relationship with the characteristics required in all cases.

In the photoconductive member of the present invention, the numerical range of (TB + T) is preferably 1 to 1 ooμ.

It should be set at 1 to 80μ for good harvesting, and preferably 2 to 50μ.

In a more preferred embodiment of the present invention, the above-mentioned layer thickness TB and layer thickness T are set to appropriate numbers for each of them so as to satisfy the following relationship: Tn/T≦1. (tt
4 is most likely to be selected.

In selecting the numerical values of layer thickness TB and layer thickness T in the above case, it is preferable that TB/T≦0.9. Optimally T
The values of layer thickness TB and layer thickness T are determined so that the relationship B/T≦0.8 is satisfied.

In the present invention, the content of dalmanium atoms contained in the first layer region (G) is I x 10 atomic
ppm or more, the layer thickness TB of the first layer region (G)
It is desirable that the thickness be as thin as possible, preferably 30μ or less, more preferably 25μ or less, optimally 20μ or less.
It is considered to be less than μ.

In the photoconductive part of the present invention, the distribution state of kermanium atoms in the first layer region 0) is as follows:
Dalmanium atoms are continuously distributed in the entire layer region of Since a decreasing change is given, the first layer (1) having the required characteristics can be realized as desired by arbitrarily designing the change rate curve of the distribution concentration C as desired. I can do it.

For example, the distribution concentration C of germanium in the first layer region (1) is sufficiently increased on the support side;
) on the second layer (II) side, by giving a change in the distribution concentration C to the distribution concentration curve of dalmanium atoms so as to reduce it as much as possible. Photosensitivity can be achieved for light of wavelengths in the entire range up to wavelengths.

Furthermore, as will be described later, by making the distribution concentration C of kermanium atoms extremely thick at the support side end of the first layer region G), laser irradiation when using a semiconductor laser can be avoided. Light on the long wavelength side that cannot be absorbed sufficiently in the second layer region (S) on the surface side can be substantially completely absorbed in the layer region (S), and the light reflected from the support surface can be substantially completely absorbed. It is possible to effectively prevent interference caused by

In the photoconductive layer 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 layer (1), One layer (I) contains Ij2, a nitrogen atom.

The nitrogen atoms contained in the first layer (1) are
It may be evenly contained in the entire layer region of 1), or it may be contained and unevenly distributed only in a part of the layer region of the first layer (summer).

Further, the distribution state of nitrogen atoms may be such that the distribution concentration C(e)) is uniform in the layer thickness direction of the first layer (1), or as shown in FIGS. 2 to 10. Similar to the distribution state of dalmanium atoms described above, the distribution state may be non-uniform.

The distribution state of nitrogen atoms in the case where the distribution concentration C(f)) of nitrogen atoms is non-uniform in the layer thickness direction is shown in Figures 2 to 1.
It can be explained in the same way as the case of a dalmanium atom using the diagram 0.

In the present invention, when the main purpose is to improve photosensitivity and dark resistance, the layer region axis containing nitrogen atoms provided in the first layer (1) is ), and the main purpose is to strengthen the adhesion between the support and the first layer (1),
It is provided so as to occupy the support side end layer region (g) of the first layer (1).

In the former case, the content of nitrogen atoms contained in the layer region is relatively small in order to maintain high photosensitivity, and in the latter case, in order to ensure strong adhesion to the support. It is a heavy burden that this is done relatively often.

Also, for the purpose of achieving both the former and the latter at the same time,
Either the concentration is distributed at a relatively high concentration on the support side and the concentration is distributed at a relatively low concentration on the 20R (II) side of the first layer (1), or the concentration is distributed at a relatively low concentration on the ) second layer (n)
In the surface candy region on the side, it is sufficient to form a distribution state of nitrogen atoms in the layer region ring such that nitrogen atoms are not contained in the fR polarity.

In the present invention, the layer region (
The content of nitrogen atoms contained in 6) depends on the properties required for the layer region (b) itself, or when the layer region (c) is provided in direct contact with the support, It can be selected as appropriate based on the organic relationship, such as the relationship with the characteristics at the contact interface with the body.

In addition, when another layer region is provided in contact with the layer region axis, the characteristics of the lumbosacral layer region and the characteristics at the contact interface with the lumbosacral layer region are also determined. The nitrogen atom content is appropriately selected in consideration of the above.

The concentration of nitrogen atoms contained in the layer region (c) can be determined as desired depending on the characteristics required of the photoconductive part I to be formed, but is preferably 0.001 to 50 atoms.
mic%, more preferably 0.002-40atom1
c %, optimally 0.003-30 atomic
It is assumed to be q6.

In the present invention, even if the layer area (to) occupies the entire area of the first layer (1) or the entire area of the first layer (summer) is not aged, the layer thickness of the layer area If the ratio of 'r)+ to the layer thickness T of the first layer (1) is large enough, the layer area □□□
It is desirable that the upper limit of the content of nitrogen atoms contained in the above-described value be sufficiently reduced.

In the case of the present invention, when the ratio of the layer thickness TI+ of the layer region (transfer) to the layer thickness T of the first layer (1) is two-fifths or more, The upper limit of the amount of nitrogen atoms contained in ) is preferably 30 atomic% or less,
Preferably less than 20 atomic units, optimally 1
It is set to be 0 atomic% or less.

In the present invention, the nitrogen atom-containing layer region constituting the first layer (I) is a region containing nitrogen atoms at a relatively high concentration on the support side as described above. Current area (
B) is preferable, and in this case, the adhesion between the support and the first layer (1) can be further improved.

The localized region Φ) is desirably provided within 5 μ of the interface position tB, if explained using the symbols shown in FIGS. 2 to 10.

In the present invention, the above localized region) is at the interface position 1B.
It may be the entire layer region (LT) up to 5 μN, 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 appropriately determined according to the characteristics required of the first layer (1) to be formed.

The localized region (13) has the maximum distribution concentration C of nitrogen atoms as the distribution state of the nitrogen atoms contained therein in the layer thickness direction.
maX is preferably 500 atomic ppm or more, more preferably 800 atomic ppm or more,
Optimally, the layer is formed so that a distribution state of 1000 mlc'Tlpm or more can be obtained.

That is, in the present invention, the layer region (G) containing nitrogen atoms is within 5μ in layer thickness from the support side (from 1R to 5μ).
It is desirable to form the layer so that the maximum value Cmax of the distribution concentration exists in a layer region of μ thickness.

In the present invention, the rhodan atoms (3) contained in the first layer region (G) and second layer region (S) constituting the first layer (1) as necessary include: Specific examples include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred.

In the present invention, in order to form the first layer region composed of a-8i Ge (Hp This is accomplished by a vacuum deposition method that utilizes this phenomenon.

For example, a-5IGe(H,
In order to form the first layer region (X) composed of Raw material gas for Ge supply and hydrogen atoms ◇0 as necessary
Is the raw material gas for introduction and/or the raw material gas for introduction of Rodan atoms (3) reduced in pressure inside? The gas is introduced into a deposition chamber under a desired pressure state to generate a glow discharge in the deposition chamber, thereby increasing the distribution concentration of germanium atoms to be impregnated on the surface of a predetermined support that has been placed in a predetermined position in advance. a-8IGe (H
, X) is formed. In addition, when forming by sputtering method (for example, Ar, He
The inert Gasnu of Houji is a target made from +1 to St in an atmosphere of mixed gas based on Monk's gas,
Alternatively, the target and the Ge'''c target can be used, or a mixed target of Si and Go can be used, and if necessary, He or Ar can be used.
A rough gas for supplying Ge, diluted with a diluent gas such as While forming a gas plasma atmosphere,
The target may be sputtered while controlling the gas flow rate of the raw stone gas for supplying Ge according to a desired rate of change curve.

In the case of the ion blating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline kermanium 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. It can be carried out in the same manner as in the case of the sintering method, except that it 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 at iθ.

Materials that can be used as raw stone gas for supplying St used in the present invention include 5iH41512H6# St, H
81Si4H1゜ etc. in gas state or gasified? Water-bedded silicon (silanes) can be effectively used, and 81H4 and Si2H6 are particularly preferred in terms of ease of handling during layer creation work and good separate supply efficiency. Can be mentioned.

GeH is a substance that can be used as raw gas for supplying Ge.
4+ Ge2H6t G551 (61Ge14H10r
Ge5T112 e Ge6H141Ge 7H16
+ Go 8it, 81 Ge? ) Dalmanium hydride in a gaseous state or that can be gasified, such as I20', is cited as one that can be effectively used, especially in terms of ease of handling during layer formation, good Go supply efficiency, etc. , GeH41G
e 2xr6+Gs 3HB is preferred.

"Raw material for introducing halogen atoms used in the present invention"
Many halogen compounds are effective as gases, for example, rhodan gas, rhodanides, interhalogen compounds, rhodan-substituted silanes, which are in the gaseous state or can be gasified. Rodan compounds are hailed as preferred.

Furthermore, silicon atoms and rodan atoms (1 to
In the present invention, silicon hydride compounds containing rhodan atoms in a gaseous state or which can be gasified as constituents can also be mentioned as effective.

Specifically, the rhodane compounds that can be suitably used in the present invention include halogen atoms of fluorine, chlorine, bromine, and iodine, BrF*C1F, C4F6 +BrF
5+BrF, IF, IF7, ICj,
(such as IBr) can be mentioned.

Examples of silicon compounds containing a halogen atom, so-called silane derivatives substituted with 1F by a rhodane atom, include 5IF4, 812F6, 5iC64, and SiBr4.
Preferred examples include silicon halides such as the following.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using a silicon compound containing such a rhodan atom, the raw material gas that can supply Si together with the raw gas for supplying Ge is used. Even if silicon hydride gas is used, a-8IGe containing halogen atoms can be
It is possible to form a first layer region (G) consisting of ".

When creating a cml layer containing halogen atoms according to the glow discharge method, basically, for example, silicon halide is used as a raw material gas for supplying 81, and hydrogenated silicon is used as a raw gas for supplying Ge. Rumanium and gases such as Ar+H2, He, etc. are introduced at a predetermined mixing ratio and gas flow rate into a deposition chamber that forms the first M region, and a glow discharge is generated to remove these gases. A first layer region (G) is deposited on the desired support by forming a plasma atmosphere.
However, in order to make it easier to control the ratio of hydrogen atoms introduced, water bed gas or a silicon compound containing hydrogen atoms may be optionally mixed with these gases. A layer may be formed by doing so.

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

In both the sputtering method and the ion silating method, in order to introduce halodane atoms into the layer to be formed, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. What is necessary is to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, raw gas for introducing hydrogen atoms, for example, ■■2, or gases such as the above-mentioned shida silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. What is necessary is to form a plasma atmosphere of the gases.

In the present invention, the above-mentioned halogen compounds or halodane-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms;
In addition, HF, HCt, HBr.

HI Kasa's hydrogen halide, SiH2F2.511 (2I
2.

5iH2CA2.5IHC63, 5iH2Br2, 5
Halokun-substituted silicon hydride such as iHBr3, and GeHF
3T GeH2F2rGel (3F + GeHBr
3 * GeH2Ct2 + GeHBr3 r Ge
HBr3 tGeH7Br2 + GeHBr3- hydrogenated dalmanium halide, I-rhodanide with hydrogen atoms as one of its constituents, GeF4 lGeC
L4F GeBr41 GeI41 GeF21 Ge
Germanium halides such as C121GeBr2°GeI2, gaseous or gasifiable substances can also be used as starting materials for forming the first layer.

Among these substances, rhodanides containing hydrogen atoms are
Hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced into the layer at the same time as location atoms are introduced into the layer during the formation of the first layer region.・Used as the original tI for Rodin introduction.

Water I atom! To introduce it spontaneously into the beginning of the layer region of 'ri1, H2, or 81r14.5121
Silicon hydride such as 16pSI3H6,5i4H1゜, and G
kelmanium or a kelmanium compound for supplying e, or (?eH4lGe 2H6,Ge
511B, Ge 4H10lGe 51112, G
e 6H14rGe 71 (16, Ge 6HI B
Dalmanium hydride such as lGe qH20 and silicon or a silicon compound for supplying Sl are deposited in Pj.
! ? @S can also be performed by coexisting in I7 and causing discharge.

In a preferred embodiment of the invention, the first layer (1
) The amount of hydrogen atoms ([(), or the sum of the amounts of hydrogen atoms and halodane atoms (3), or the sum of the amounts of hydrogen atoms and halodane atoms (H'X) I like L
< is 0.01 to 40 atomic%, preferably 0605 to 30 atomic%, most preferably 01 to 25
It is assumed to be atomlc%.

Hydrogen atoms (6) contained in the 2p-1 layer region (G)
or/and to control the amount of halodane atoms flash, for example, the support temperature or/and hydrogen atom CO or halogen J
What is necessary is to control the amount of the starting material used to contain f, T, and the element (3) introduced into the deposition system, the discharge force, etc.

In the present invention, in order to form the second layer region (S) composed of a-81(H,X), the starting material (I) for forming the first layer region (G) described above is used. In the middle, the first layer region (G) is formed using the starting material (starting material Ql for forming the second layer region (S)) excluding the starting material that becomes the raw material gas for G supply. It can be carried out according to the same method and conditions as in the case of forming.

That is, in the present invention, in order to form the second layer region (S) composed of a-8t (H, This is accomplished by using the vacuum bonding method. For example, a -81(H,X
) to form the second layer region (S) consisting of S, which can supply the aforementioned silicon atoms (Si).
Introducing a raw material gas for introducing hydrogen atoms (b) and/or for introducing local atoms (3) as necessary together with the raw material gas for supplying t 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 -5l (H
, X) may be formed. In addition, in the case of forming by the sintering method or the tuttering method, for example, Ar+He
When sputtering a target composed of St in an atmosphere of # inert gas or a mixed gas based on these gases, a gas for introducing hydrogen atoms (Jo or/and halogen atoms (3)) is used for sputtering. It is sufficient to introduce it into the deposition chamber.

In the photoconductive member of the present invention, conduction properties are controlled in the second layer region (S) provided on the first layer region (G) containing r-rumanium atoms and not containing kelmanium atoms. The layer region (
The conduction properties of S) can be arbitrarily controlled as desired.

Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-8l (11,
), a p-type impurity that gives p-type conductivity characteristics, and i
Examples include n-type impurities that provide type conductivity characteristics.

Specifically, as the p-type impurity, atoms belonging to Group ■ of the periodic table (Group ■ atoms), such as B (boron), A
Examples include L (aluminum), Ga (gallium), In (indium), and Tt (thallium), with B and Ga being particularly preferred.

Examples of n-type impurities include atoms belonging to Group V of the periodic table (Group V atoms), such as P (*), A11 (arsenic), and S
b (antimony), Bi (bismuth), etc., especially,
Preferably used are P and As.

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). It can be selected as appropriate based on the organic relationship, such as the characteristics of other layer regions provided in direct contact and the relationship with the characteristics at the fused interface with the lumbosacral layer region.

In the present invention, the content of the substance controlling conduction properties contained in the second layer region (S) is preferably 0.00
1 to 1000 atomic ppm, preferably 0.05 to 500 atomic ppm *optimally o, i to 200 atomic ppm.

In order to structurally introduce a substance that controls the conduction properties into the second layer region (S), for example, a group Ⅰ atom or a group ① atom, a starting material for introducing a group ① atom is used during layer formation. Or part ■
The starting material for introducing group atoms is introduced in a gaseous state into the deposition chamber in a second
It may be introduced together with other starting materials for forming the layer region. As the starting material for such introduction of ff' group III atoms, it is desirable to employ materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. . Specifically, such starting materials for introducing a group Ⅰ atom are as follows:
B2H6, B4H101B5H9, B51111,
B6) 11 o, B6H12, B6H14, etc. boron hydride, BF5+BCl3 JBr3 etc. Of) Halo r
Examples include boron y-chloride. In addition, AtCl3+GaC
63°Ga (CR2) 5 + I nct3,
Mention may also be made of TlCl3 and the like.

Effectively used in the present invention as a starting material for introducing a group V atom is pn3 for introducing a phosphorus atom.
, hydrogen ratios such as P2H4, PH4I, PF 5 +
PF 5 r PCl3 *PC45+PBr3+P
Examples include phosphorus halides such as Br3+PI3. Ko (7
), AsH3, AsF5 +AsC4+AsBr3
+AsF5 ysbH4.

SbF5 +SbF5.5bCL5 +5bCt5,
BIH5, BICt3, B1Br3, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

In the present invention, in order to provide a layer region containing nitrogen atoms in the first layer (I), a starting material for introducing the nitrogen atoms is added during the formation of the first layer (I). The first layer (I) described above
It may be used together with the starting material for formation, and may be contained in the formed mass while controlling its amount. Layer area (to)
When a glow discharge method is used to form the first layer (I), a starting material for introducing nitrogen atoms is added to one selected as desired from among the starting materials for forming the first layer (I) 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 raw material gas whose constituent atoms are silicon atoms (S*), a raw material gas whose constituent atoms are nitrogen atoms (c), and, if necessary, hydrogen atoms α◇ or and rodan atoms G9 as constituent atoms. The raw material gas is used by mixing it at a desired mixing ratio, or the raw material gas containing silicon atoms (Sl) and nitrogen atoms (H) and hydrogen atoms (JO) are used.
Alternatively, a raw material gas containing silicon atoms (S+), nitrogen atoms (C), and silicon atoms (S+) may be mixed together at a desired mixing ratio. It can be used in combination with a raw material gas having three hydrogen atoms (6) as its constituent atoms.

Alternatively, a raw material gas containing a silicon atom (Sl) and a hydrogen atom α as its +19 constituent atoms may be mixed with a raw material gas containing a nitrogen atomic axis as its constituent atoms.

In order to form a layer region containing nitrogen atoms by the sintering method, a monocrystalline or polycrystalline Sl wafer or Si3N4 wafer, or 81 and Si
This can be carried out by using a wafer containing a mixture of 5N4 and sputtering it in various gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halodane atoms can be diluted with a diluting gas as necessary. It is sufficient to introduce the above-mentioned 81 water into a deposition chamber, form a gas plasma of these gases, and snow the 81 water.

Another option is to use Si and S15N4 as separate targets, or by using a mixed target of Sl and 815N4, in an atmosphere of diluted gas as a snowyatter gas, or at least hydrogen. Atom (6) or/and Rodan atom 00f: This is achieved by sputtering in a gas atmosphere containing the constituent atoms. As the raw material gas for introducing nitrogen atoms, it can also be used as an effective gas in the case of sputtering, where the raw material gas force for introducing nitrogen atoms in the raw material gas shown in the example of glow discharge ≦≦.

In the present invention, when a layer region (6) containing nitrogen atoms is provided during the formation of the first layer (I), the distribution concentration C of nitrogen atoms contained in the layer region (6) (N) in the layer thickness direction to obtain the desired distribution state (depth) in the layer thickness direction.
In order to form a layer region φ0 having a profile), in the case of glow discharge, the gas of the starting material for introducing nitrogen atoms whose distribution concentration C(N) is to be changed is changed at a gas flow rate according to a desired rate of change curve. With appropriate changes, 71&
This is accomplished by introducing the ffl into the room. for example,
The opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by some commonly used means such as manually or by 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 predetermined rate of change curve to obtain a desired content rate curve. When forming a layer region (to) by sputtering method, the distribution concentration of nitrogen atoms in the layer thickness direction C (
In order to change N) in the layer thickness direction and form a desired distribution state (depth profile) of nitrogen atoms in the layer thickness direction, firstly, as in the case of the glow discharge method, a starting point for introducing nitrogen atoms is used. This is accomplished by using the substance in a gaseous state and appropriately varying the gas flow h1 when introducing the gas into the deposition chamber as desired. Second, if a mixed target of Si, Si, and N4 is used as a sputtering target, the mixing ratio of 81 and Si3N4 should be adjusted in advance in the layer thickness direction of the target. This can be achieved by allowing it to change.

In the present invention, the amount of hydrogen atoms α contained in the second layer region (S) constituting the first layer (I) to be formed,
Or the amount of halodane atoms (3) or the sum of the amounts of hydrogen atoms and no-rodane atoms (H+X) is preferably 1 to 40
atomic% + preferably 5 to 30 atomic%
r is optimally set at 5 to 25 atomic%.

In the photoconductive member 100 shown in FIG. 1, a second layer (It) 10 is formed on a first layer (I) 102.
3 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, electrical pressure resistance, use environment characteristics, and durability.

Furthermore, in the present invention, since each of the amorphous materials constituting the first layer (I) 102 and the second layer (II) 103 has a common constituent element of silicon atoms,
Chemical stability is sufficiently ensured at the laminated interface.

The second layer (It) in the present invention consists of silicon atoms (S
l), a carbon atom (C), and optionally a hydrogen atom ◇ or/and a halodane atom (3) (hereinafter r a (s iXC1x ) y (it , x )
+ -y j and M myself. 0 (x, y<1
).

The formation of the second layer (II) consisting of a (S l x CI x ) y (H,
This is accomplished by the snotering method, ion plantation method, ion brating method, and electron beam method.

The first manufacturing method is selected as appropriate depending on factors such as manufacturing conditions, equipment capital investment load, manufacturing regulations, and desired characteristics of the photoconductive material to be manufactured. However, it is relatively easy to control the manufacturing conditions for producing a conductive member having desired characteristics.In addition to silicon atoms, carbon atoms and
The glow discharge method or the sputtering method is preferably employed because of the advantages that it can be easily introduced into the second layer (n).

Furthermore, in the present invention, the second layer aI) may be formed by using both the glow emission method and the sputtering method in the same apparatus system.

To form the second layer (■) by glow discharge method,
The raw material gas for forming a-(SIXCl-x)y(H, A (81XC1 -z)y(HbX)iy may be deposited.

In the present invention, a-(SiXC1-X)y(H,,X
)1-y The raw material gas for forming y is silicon atoms (
Most of the gaseous substances or gasified substances that have at least one constituent atom of the following atoms (Sl), carbon atoms ((5, hydrogen atoms α℃, ) and lorokenone atoms (3) can be used.

When using a raw material gas whose constituent atoms are Si as one of Si, C, H, and In accordance with A raw material gas containing 81 as a constituent atom and/or a raw material gas containing
and H as constituent atoms, or St,
A raw material gas having three constituent atoms, C and X, can be mixed and used.

Alternatively, a raw material gas containing St and I (as constituent atoms) may be mixed with a raw material gas containing C as constituent atoms, or a raw material gas containing Sl and X as constituent atoms may be mixed with C. A mixture of raw material gases having constituent atoms may be used.

In the present invention, preferred examples of the normal location atoms (3) contained in the second layer (n) are 'j;', C6,
Br, (2), V, and Ct are particularly desirable.

In the present invention, the raw material gases that can be effectively used to form the second layer (II) include:

Examples include substances that are in a gaseous state at room temperature and pressure, or substances that can be easily gasified.

In the present invention, hydrogen gases such as silanes (Stmune) such as SiH4, 512H6ySi5HB+Si4H4g, etc., which have Sl and H as constituent atoms, are effectively used as the raw material gas for forming the second layer (n). silicon oxide gas, C and H
For example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and 2 to 3 carbon atoms.
Examples include acetylene hydrocarbons, halogens, hydrogen halides, interhalogen compounds, hydrogen halides, halokene-substituted silicon hydrides, and silicon hydrides.

Specifically, the saturated hydrocarbons include methane (CH4),
Ethane (C2■6), Proy4 (CsFta),
n-Butane (n C4H1o), intane (C5H12
), ethylene hydrocarbons include ethylene (C2H4
), propylene (C3H6), butene-1 (C4H[
]), ]butene-2C4H8), isobutylene (C4H
8), pentene (C5H4o) b.Acetylene hydrocarbons include acetylene (C2■2), methylacetylene (C3H4), butyne (C4H6); simple halodane includes halogen gases such as fluorine, chlorine, bromine, and iodine;
Hydrogen halides include FH, HI, HCl, HB
r.

Examples of haO intergonic compounds include B rF , C1F , C
tF 3 r CLF 5 eBrF5. BrF5. I
F7. IF5+IC4+IBr, as silicon halide 5IF4,512F6+5iCt(+5iC43B
r+5IC42Br2ySICLBr3 +5IC4I
+5IBr4, -5 as halodane-substituted silicon hydride
IH2F2HyoS IH2Ct2.8iHC4, S 1H
3cA.

5II (3Br, 5iH2Br2, 5iHBr3, as silicon hydride, 5IH4eS12HB+5i4H1
(Silane), etc. can be mentioned.

In addition to these, CF4+CC44+CBr4+CHF3.
CH2F2. CH3F.

CA15C1, Cll3Br, CH5I, C2H5
Halodane-substituted paraffinic hydrocarbons such as C4, SF4.
Fluorinated sulfur compounds such as SF6, 5t(CH3)4 +
Alkyl silicides such as Si(C2H5)4 and s+cz(c
n3)5,5tcz2(cIr3)2. s+cz3cH
Silane derivatives such as halodane-containing alkyl silicides of 3@ can also be mentioned as effective.

These second layer (II) forming substances contain silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms in a predetermined composition ratio in the second layer (11) to be formed. They are selected and used as desired when forming the second layer (n).

For example, inclusion of silicon atoms, carbon atoms, and hydrogen atoms can be easily achieved and a layer with desired characteristics can be formed81.
(CH5)4 and the amount of S (HCt3.5t) (2C62) to contain the location atom.

a-(81XC1-X)y(Ct+H)1 by introducing 5iC74 or s1H3cz in a predetermined mixing ratio into the apparatus for forming the second layer (II) in a gas state to generate glow discharge. A second layer (It) consisting of -y can be formed.

To form the second layer (■) by the sputtering method, a monocrystalline or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Sl and C is used as a target. etc. as necessary.
Sputtering may be performed in various gas atmospheres containing Rodan atoms and/or hydrogen atoms as constituent elements.

For example, if a Si wafer is used as a target, the raw material gas for introducing C, H or/and The Sl wafer may be sputtered by introducing these gases to form a sulfur plasma.

Alternatively, Sl and C may be used as separate targets, or by using a single mixed target of St and C, if necessary, in a gas atmosphere containing hydrogen atoms and/or halogen atoms. This is done by sputtering. As the raw material gas for introducing C, H and Get used no.

In the present invention, the second layer (TI) is formed using a glow discharge method.
The diluent gas used in the formation by the S. Gutterling method is a so-called noble gas, such as Tier N
e+Ar shade can be mentioned as a suitable one.

The second layer (II) in the present invention is carefully formed so that its required properties are imparted as desired.

In other words, a substance whose constituent atoms are St, C, and if necessary I (or/and It exhibits properties ranging from photoconductive to non-photoconductive, and from photoconductive to non-photoconductive.

In the present invention, a
(stxcl-z)y(H, For example, in order to provide the second layer (1■) with the main purpose of improving electrical surface pressure property* (S i xC1x
) y (H,

In addition, when the second layer (II) 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 a certain extent, and it becomes less resistant to the irradiated light. As an amorphous material with a sensitivity of about a (s IxC+ −X )y (H,X) + y
is created.

a (81Xc1-x)y(a
, X) +-y when forming the second layer (In,
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 (S!XC, -x)y (
It is desirable that the temperature of the support during the formation of the layer is tightly controlled so that it can be formed to the desired value.

In the present invention, the formation of the second layer 01) is carried out by appropriately selecting an optimal range in accordance with the method of forming the second layer (IT) in order to effectively achieve the desired purpose. , preferably from 20 to 400°C, more preferably from 50 to 350°C, most preferably from 100 to 300°C. To form the second layer (It), glow discharge is used to form the second layer (It), as it is relatively easier to delicately control the composition ratio of the raw material that makes up the layer and control the layer thickness compared to the oil method. Although it is advantageous to adopt a method or a sputtering method, these layer forming methods can be used to form the second layer (I
When forming I), the temperature of the support as well as the important factor that influences the characteristics of a - (S l x C1x )y There is one.

a- having the characteristics for achieving the object of the present invention;
(81XC3-X)yXl-y is preferably produced at a discharge power of 10 to 300 W, more preferably from 20 to 250 W, in order to effectively produce the product.

Optimally, it is set at 50 to 200W.

The gas pressure in the deposition chamber is preferably 0.01 to 1. Torr
, more preferably about 0.1 to 0.5 Torr.

In the present invention, the values of the support temperature and discharge power for forming the second layer (II) are preferably within the ranges described above, but these layer formation factors are determined independently and separately. It is not determined, but the desired characteristics a-(stXc, -X)y()1. It is desirable that the optimum value of each layer creation factor be determined based on mutual organic relationship so that the second layer (II) consisting of X), -y is formed.

The amount of carbon atoms contained in the second layer (II) in the photoconductive member of the present invention, as well as the conditions for forming the second layer (n), is determined to provide the desired characteristics to achieve the object of the present invention. This is an important factor in the formation of the second layer (II).

The amount of carbon atoms contained in the second rrJ (II) in the present invention can be determined as desired depending on the type and characteristics of the amorphous material constituting the second layer (II). It is.

RIJ, nil general formula a-(StxCl-X)y
The amorphous material represented by (H, 0
(a(1), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as r a (S1bC1-
b) Written as ctll-J.

IF5, 0(b, c(1), silicon atom and carbon atom-
An amorphous material (hereinafter referred to as r a-(StdCl-4) e
(H,X)+-eJ and i myself. Output 0 (d, e (
It is classified as 1).

In the present invention, the second layer (II) is a S l aC
1-a, the carbon atoms iIi contained in the second layer (n) are preferably I x 10' to 90
atomic%, 1-80 atomic for Yoshiharu
The optimum value is 10-75 atomic%.

That is, if a is expressed in the above 11 8 l aC1-a, a is preferably 0.1 to 0.99999, more preferably 02 to 0.99, most preferably 0.25 to 0. It is 9.

In the present invention, the second layer (If) is a-(SIbC1
-b) cHl.

When the second layer (11) is composed of
c, more preferably 1 to 90 atomic%
, optimally 10 to 80 atomlc%. The content of hydrogen atoms is 5, preferably 1 to 40 atoms.
1%, preferably 2 to 35 atomic%, optimally 5 to 30 atomic%, and the photoconductive region formed when there is a hydrogen-containing concentration in this range is as follows:
It is excellent in practice and can be fully applied.

That is, if expressed as above a (SlbC+-b)c"11-c, b is preferably o, i~0.99999, more preferably 0.1~0.99, optimally 0.15 ~0.
9, C is preferably 0.6 to 0.99, more preferably 0
．． 65-0.98, optimally O67-0.95.

The second layer (II) is a-(Sl, IC1-d), (
H,,X-)1-e consists of a second layer (
11) The content of carbon atoms contained in
0 atomic%, optimally 10-80 atomic%
c%. h) The content of f7 atoms is preferably 1 to 20 atomic%, more preferably 1 to 18 atomic%.
ato+nlc row, optimally 2 to 15 atomic rows. A photoconductive member produced when the amount of no-rodene atoms a is within these ranges can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably 19 atomic% or less, more preferably 13 atomic% or less."1. Ru.

That is, the previous a (Sl, 1 self-published 几(n, X) + - e's d
If it is displayed as 5e, d is preferably 01 to 0.9!1
999, preferably 0.1 to 0.99, most preferably 0.999.
15-0.9, e is preferably 0.8-0.99, more preferably 0.82-0.99, optimally 0.85-0.
It is 98.

The number range of the second WJ (layer) 9 in the present invention is an important factor for effectively achieving the object of the present invention.
It is one.

This may be determined as desired depending on the intended purpose so as to effectively achieve the purpose of the present invention.

Moreover, the layer thickness of the second layer (II) is determined depending on the amount of carbon atoms contained in the layer (II) and the layer thickness of the first layer (1). It is necessary to appropriately determine the desired value based on the organic relationship depending on the characteristics required for the layer region.

In addition, it is desirable to consider the economical aspects including productivity and mass production.

The layer thickness of the second layer (n) in the present invention is preferably 0
The thickness is preferably 0.003 to 30μ, preferably 0.004 to 20μ, most preferably 0.005 to 10μ.

The support used in the present invention may be electrically conductive or electrically insulating. As the conductive support, for example,
NlCr % stainless steel, A'-r Cr+Mo +A
u + Nb + Ta r V 'r Ti + P
Examples include metals such as t r Pd and alloys thereof.

As an electrically insulating support, polyester, polyethylene, ? Films or sheets of synthetic resins such as recasenate, cellulose, acetate, polypropylene, polycyclized vinyl, poly(vinylidene), polystyrene, polyamide 1", glass, ceramics, 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, NlCr *At
+ Cr + Mo * Au, Ir r Nb
, Ta + V + Ti rPt , Pd , I
n2O3+ 5n02 + ITO(In203+ 5
Conductivity is imparted by providing a thin film made of NiCr+
Atr Ag * Pb + Zn + Ni r Au +
Cr + Mo + Ir + Nb r Ta #
A thin film of gold λjet of V r Ti +r'tζ7 is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., and the surface is laminated with a metal whose conductivity is 11L. given. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined depending on the needs. If it is used as a forming member, it is preferably in the shape of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within the range. Unfortunately, in cases like this,
In terms of manufacturing and handling of the support, mechanical strength, etc.
Preferably it is 10μ or more.

Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained.
``'C'C Explanation FIG. 11 shows an example of the details of a photoconductive member manufacturing apparatus.

In the gas cylinders 1102 to 1106 in the figure, raw material zrs for forming the photoconductive part paulownia of the present invention is sealed; for example, 1102 is 5IH4 gas ( Purity 99.999%, hereinafter referred to as Si
D cylinder abbreviated as H4/He, 1103 is GeH4 gas diluted with Hll (purity 99.999%, hereinafter abbreviated as GeK 4/14e) cylinder, 1104 is 5IF4 gas diluted with He (purity 99.99%, hereinafter abbreviated as 81 F 4 / He) cylinder, 1105
is Nus gas (99.999% purity) cylinder, 1106
Chill with I■2 gas (purity 99.999) cylinder.

In order to cause the gases to flow into the reaction chamber 1101, the valves 1122 to 112 of the gas cylinders 1102 to 1106 are used.
6. Check that the leak valve 1135 is closed, and also check the inflow valves 1112 to 1116 and the outflow valve 1.
117 to 1121, confirm that the auxiliary valves 1132 and 1133 are open, and first open the main valve 1134.
(Vl) to exhaust the inside of the reaction chamber 1101 and each gas pipe.

Next [Vacuum @t 1136 reading is about 5 X 10'L
When it becomes orr, the auxiliary valves 1132, 1133.
Close outflow valves 1117-1121.

Next, to give an example of forming the first layer (1) on the cylindrical substrate 1137, SiH4/H1'l gas is supplied from the gas cylinder 1102 to the pump 1103.
Qel(4/ I(e)f, gas cylinder 1105, J
NH3 gas, valve 1122.1123.1125
Open the outlet pressure y-j1127, 112B, and adjust the pressure of 11aO to 1y/cnI2, and open the inflow valve 1112°1.
113, 1115 are gradually opened to allow flow into mass flow controllers 1107, 1108, and 1110, respectively.

Subsequently, the outflow pal 7'l 117.

1118 and 1120, the auxiliary valves 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, S i H4/He is the gas flow rate and GeR4/H
e Adjust the outflow valves 1117, 1118, and 1120 so that the ratio of the gas flow rate to the NH3 gas flow rate becomes the desired value, and adjust the reading of the vacuum gauge 1136 so that the pressure inside 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 about 50 to 400°C by the heating heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. tr to occur and at the same time to a pre-designed rate of change curve.
: The flow rate of the GeH4/He gas is controlled manually or by means such as an externally driven motor by gradually changing the opening of the valve 1118, thereby controlling the flow rate of the GeH4/He gas contained in the formed layer. Control the distribution concentration of rumanium atoms.

In the manner described above, glow discharge is maintained for a desired period of time to form a first layer region (G) on the substrate 1137 with a desired layer thickness V. At the stage where the first layer region (G) has been formed to the desired layer thickness, the same conditions and procedures are followed except that the outflow valve 1118 is completely closed and the discharge conditions are changed as necessary. By maintaining the time glow group "iN", it is possible to form a second layer region (S) substantially free of germanium atoms on the first layer region (6).

In order to have a substance that controls conductivity in the second layer region (S), a gas such as B21t6 r PH3 is added to the deposition chamber 1101 when forming the second layer region (S). All you have to do is add it to the gas introduced inside.

When halodane atoms are contained in the layer (1) of tIX-, glow discharge may be generated by further adding, for example, S-4if gas to the above gas.

In addition, when the first layer (1) contains norodane atoms without hydrogen atoms, the above 81) I4/H4
gas and GeH4/ )io gas, SiF4/
He gas and GeF4/He gas may be used.

To form the second layer (n) on the first layer (I) formed to the desired thickness as described above, the same valve operation as in the formation of the 10th layer (1) is performed. For example, S IH4
This is accomplished by diluting each of C2H4 gas and C2H4 gas with a diluent gas such as He as necessary to generate glow discharge according to desired conditions.

In order to contain halodane atoms in the second layer (It),
For example, 5IF4 gas and C2H4 gas, or Si
A second JrI(II
).

Needless to say, all the gas outflow valves other than 4 i revs, which are necessary for forming each layer, are closed.
In addition, when forming each layer, the gas used to form the previous layer flows into the reaction chamber 1101 and outflow nozzles 1117 to 1121.
In order to avoid gas from remaining in the gas piping leading to the reaction chamber 11o1, the outflow hull 7' 1117 to 1121 is closed, the auxiliary pulp 1132 and 1133 is opened, and the main valve 1134 is fully opened to create a high vacuum in the system. Perform the operation to exhaust air according to the center spacing.

For example, in the case of glow discharge, the amount of carbon atoms contained in the second W (II) is 81H4ifs and C
The flow rate ratio of the 2H4 gas introduced into the reaction chamber 11o1 can be changed as desired, or in the case of forming a layer by sputtering, the sputtering serum ratio of the silicon-free wafer and the graphite wafer that forms a layer can be changed. Alternatively, it can be controlled as desired by changing the mixing ratio of silicon powder and graphite powder and molding TARDAT. The amount of halodane atoms (2) contained in the second layer (II) is such that the flow ii1 when a raw material gas for introducing halogen atoms, for example, Stp"4 gas, is introduced into the reaction chamber 1101 is MI7iI! It is accomplished by

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

Examples will be described below.

Example 1 A cylindrical At
Ge ■ I4 / He gas and S
An electrophotographic image forming member was obtained by forming layers while changing the gas flow rate ratio of I H4/He gas with the elapsed time of layer formation.

The image forming member obtained in this way is installed in a VfF electric ζ□λ optical production device e5. Corona charging was performed at OkV for 0.3 seconds, and a light image was immediately irradiated. A tungsten lamp light source was used for light image irradiation, and a light of 2 Lux/9eQ was irradiated through a transmission type test chart.

Immediately thereafter, a chargeable developer (containing toner and carrier) was cascaded onto the surface of the imaging member, thereby obtaining a positive toner image on the surface of the imaging member. When the toner image on the image forming member was transferred onto transfer paper using corona charging at 05,000 kW, a clear, high-density image 51 with excellent resolution and good gradation reproducibility was obtained.

Example 2 Using the manufacturing apparatus shown in FIG. 11, Ge
Ha/He! Su and S! Layer formation was carried out under the same conditions as in Example 1, except that the gas flow rate ratio of H4/He gas was varied with the elapsed time of layer formation to obtain an electrophotographic image forming member.

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, and an extremely clear image quality was obtained.Example 3 Using the manufacturing apparatus shown in FIG. , according to the rate of change curve of the gas flow rate ratio shown in FIG.
Layer formation was carried out under the same conditions as in Example 1, except that the flow rate ratio of 14/He gas and SiH4/He gas was varied 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, Ge
The gas flow meter ratio of H4/f-Te gas and SIH4/He gas was changed with the elapsed layer formation time, and the other conditions were the same as in Example 1, and layer formation was performed to form an electrophotographic image forming member. Obtained.

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, Ge
Layer formation was carried out by changing the gas OL MH ratio of H4/He gas and H4/ne gas with the elapsed layer formation time, and other conditions were the same as in Example 1. I got the parts.

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 production apparatus shown in FIG. 11, Ge
H, +/)He gas and SiH4/l (e gas) gas flow ratio was changed with the elapsed layer formation time, and other conditions were the same as in Example 1, layer formation was carried out to form an electrophotographic image forming member. I got it.

Using the thus obtained image forming area, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and an extremely clear image quality was obtained.

Example 7 Using the manufacturing apparatus shown in FIG. 11, Ge
The gas flow rate ratio of H/T (e gas and SiH4/H" gas was changed with the elapsed time of layer formation, and the other conditions were the same as in Example 1. Layer formation was carried out to form an electrophotographic image forming member. Obtained.

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, and an extremely clear image quality was obtained. ◇Example 8 In Example 1, S H14 /S for He gas
Layer formation was carried out using 12H6/He gas and under the conditions shown in Table 8, except for the same conditions as in Example 1, 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 2, an extremely clear image quality was obtained.

Example 9 In Example 1, SiF was used instead of SHI4/Ile.
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, except that 4/He gas was used and the conditions shown in Table 9 were used.

Like this! When an image was formed on a transfer paper using the prepared hoe forming member under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 10 In practical example 1, s+u4/H” is replaced by (5I
Using H4/He+SIF/)le) gas, the first
Layer formation was carried out under the same conditions as in Example 1, except that the conditions shown in Table 0 were used to obtain an electrophotographic image forming member.

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; an extremely clear image quality was obtained.

Example 11 Electrophotographic image forming members were produced in the same manner as in Examples 1 to io, except that the conditions for forming the second layer were as shown in Table 11. did.

With respect to the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1.
The results shown in Table 1A were obtained.

Example 12 Electrophotographic image forming members were prepared in the same manner as in Examples 1 to 10, except that the conditions for forming the second layer were as shown in Table 12. did.

With respect to the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1.
The results shown in Table 2A were obtained.

Example] 3 Using the manufacturing apparatus shown in FIG. 11, G was produced according to the rate of change curve of the gas flow rate ratio shown in FIG. 19 under the conditions shown in Table 13.
The gas flow rate ratios of eH4/He gas and SiH4/He gas, and NH3 gas and SIH4/l (e gas) were varied as well as the elapsed time for layer formation, and the other conditions were the same as in Example 1. Forming was carried out to obtain an electrophotographic imaging 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 14 Using the manufacturing apparatus shown in FIG. 11, %G was adjusted according to the rate of change curve of the gas flow rate ratio shown in FIG. 20 under the conditions shown in Table 14.
eI(/He gas and 5IH4/He gas.

The gas flow rate ratio of NH3 gas and H4/He gas was changed with the elapsed layer formation time, and the other conditions were as in Example 1.
In the same manner as above, layer formation is performed to form rq! for electrophotography. A forming member was obtained.

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 15 Examples 1 to 10 were the same as Example 1 except that an 810 nm QQaAs semiconductor L/- laser (0 mW) was used as a light source instead of a tungsten lung. Examples 1 to 2 under the same toner image forming conditions.
When the image quality of toner transfer images was evaluated for each of the electrophotographic image forming members prepared under the same conditions as No. 10,
Clear, high-quality images with excellent resolution and good gradation reproducibility were obtained.

Example 16 Each of the electrophotographic image forming members (trials n, 8) was prepared according to the same conditions and procedures as in Example 1, except that the conditions for forming layer (II) were changed to the conditions shown in Table 15. -401~12-4
08.12-701-12-708.12-801~1
2-808 (72 samples) were created.

Each of the electrophotographic image forming members obtained in this way was individually installed in a copying machine, and under the same conditions as described in the example, For each, the overall quality of the transferred image was evaluated, and the durability was evaluated by continuous use of I and I.

Table 16 shows the results of the overall image quality evaluation of the transferred image of each sample and the durability evaluation by repeated continuous tests.

Example 17 The process was exactly the same as Example J, except that when forming layer (II), the content ratio of silicon atoms and carbon atoms in one layer (n) was changed by changing the coupe area ratio between the silicon wafer and graphite. Each of the imaging members was made by the method. For each of the image forming portions thus obtained, the steps of image formation, development, and cleaning as described in Example 1 were repeated approximately 50,000 times, and then image evaluation was performed, and the results shown in Table 17 were obtained. Ta.

Example 18 Same as Example 1 except that when forming layer Ql), the flow rate ratio of ]NH4 gas and C2I■4 gas was changed to change the content ratio of silicon atoms and carbon atoms in layer (II). Each of the image forming members was created in exactly the same manner. After repeating the steps up to transfer approximately 50,000 times using the method described in Example 1 for each of the image forming portions thus obtained,
When image evaluation was performed, the results shown in Table 18 were obtained.

Example 19 When forming layer 0), SiH4 gas, SiF4 gas, C
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 and carbon atoms in layer Φ) was varied by changing the flow rate ratio of 2H4 gas. After repeating the image forming, developing, and IJ-coating steps as described in Example 1 approximately 50,000 times for each image forming member thus obtained, image evaluation was performed, and the results shown in Table 19 were obtained. Ta.

Example 20 Each of the imaging members was produced in exactly the same manner as in Example 1, except that the layer thickness of layer (n) was changed.

As described in Example 1, the steps of image formation, development, and cleaning were repeated and the results shown in Table 20 were obtained.The common layer creation conditions in the embodiments of the present invention of O and above are as shown below. It is.

Substrate temperature: kermanium atom (Ge) containing layer...
...About 200℃ germanium atom (Go)-free layer・
・・About 250℃ Discharge frequency: 13.56 MEIz Reaction chamber pressure during reaction: 3 Torr

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive part A of the present invention, and FIGS.
FIG. 11 is a schematic explanatory diagram of the apparatus used for producing the photoconductive member of the present invention, and FIGS. 12 to 20 are explanatory diagrams for explaining the distribution state of germanium atoms in G). It is an explanatory view showing a change rate curve of gas flow rate ratio in an example of the present invention. 100... Photoconductive member 101... Support body 102.
...First layer (1) 103...Second layer (11) 10
4...First layer region (G) 105...Second layer region (S) C Otsuta's flow rate ratio gas tear amount good Amendment Showa f&'l''+, +f'A'i Nfl No. 147
7 Relationship with 'A7 No. j11i'1 Applicant 11 Place (1st tide)'') K), ': 61% It't', 3-30-2 Shimomaruko, Hita-ku, f name 4h.)
(100) Canon +'13 Nikai 7. 4 agents Akira! 1Illi',j, "Details of the amendment, Column 8, Amendment I, as shown in the attached sheet" The following paragraph 4f in the specification of the present application has been amended. Note ■, s < 3ct Sada Insert the following sentence between the 11th and 12th lines. "Nitrogen atoms (b) used in forming layer space ships
Starting materials that can be effectively used as raw material lotus for introduction include N as a constituent atom or N and H as constituent atoms, such as nitrogen (N2), anthaninia (Nt(
3), shidrazine (f(zNHH2), hydrogen azide (H
Examples include monoatomic compounds such as nitrogen, nitride, and azide in the form of scum or that can be converted into nitrogen, such as N3), an7nium azide (NE (4N3)).In addition, nitrogen ξ atoms Nitrogen halides such as nitrogen trifluoride (1'3N') and nitrogen tetrafluoride (CF4N2) can be mentioned because in addition to the introduction of (b), it is also possible to introduce into the y atom. .

Claims (1)

[Scope of Claims] (A support for phosphorescence and a first layer region IG made of an amorphous material containing silicon atoms and dalmanium atoms on the support) , a second JrI region (S) made of an amorphous material containing silicon atoms and exhibiting photoconductivity.
and has a first layer of a layered structure provided in order from the support side, and a second layer made of an amorphous material containing silicon atoms and carbon atoms, and the first layer A photoconductive part characterized in that the distribution state of germanium atoms in the region (G) is non-uniform in the layer thickness direction, and the first layer contains nitrogen atoms. (2) The photoconductive member according to claim 1, wherein at least one of the first layer region ←) and the second layer region (S) contains hydrogen atoms. (3) The photoconductive member according to claim 1 or 2, wherein at least one of the first layer region (IG) and the second layer region (8) contains a halogen atom. (4) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer region width is an 8 distribution state in which germanium atoms are distributed more toward the support side.