JPS6083953A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member having superior photosensitivity by forming a photoconductive layer contg. N and consisting of an amorphous layer contg. Ge and an amorphous layer contg. Si on a support and an amorphous layer contg. Si and O on the photoconductive layer. CONSTITUTION:A layered region 104 made of an amorphous material contg. Ge atoms or further contg. H atoms, halogen atoms, etc., if necessary and a photoconductive layered region 105 made of an amorphous material contg. Si atoms or further contg. H atoms, halogen atoms, etc., if necessary are successively laminated on a support 101 to form the 1st layer 102. At this time, in order to improve the photosensitivity and adhesive strength, N atoms are incorporated into the layer 102 so that they are distributed uniformly or ununiformly in the thickness direction. The 2nd layer 103 of an amorphous material contg. Si atoms and O atoms is then formed on the layer 102 to obtain the desired photoconductive member 100.

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 photoconductive members that are sensitive to electromagnetic waves such as visible light, infrared light, X-rays, and gamma rays.

Photoconductive materials that form photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, and document reading devices have high sensitivity and low S/N ratio [photocurrent (Ip)/
It has a high dark current (Id), has absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, has a desired dark resistance value, and is harmless to the human body during use. Furthermore, solid-state imaging devices are required to have characteristics such as being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned harmlessness during use is important.

Based on these points, amorphous silicon (hereinafter referred to as a-8I) is a photoconductive material that has recently attracted attention.
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

However, a photoconductive member having a photoconductive layer composed of conventional a-8i has poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance, etc. The reality is that there are points that can be further improved in terms of usage environment characteristics and stability over time, and it is necessary to improve overall characteristics.

For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use; If a photoconductive member is used repeatedly for a long period of time, fatigue due to repeated use will accumulate, resulting in the so-called ghost phenomenon that causes an afterimage, or if used repeatedly at high speeds, the responsiveness will gradually decrease. In many cases, such inconveniences arise.

Furthermore, A-8L 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 it with semiconductor radars currently in practical use. Furthermore, when a commonly used halogen lamp or fluorescent lamp is used as a light source, there remains room for improvement in that long wavelength light cannot be used effectively.

In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases,
If the support itself has a high reflectance for light passing through the photoconductive layer, interference due to multiple single reflections will occur within the photoconductive layer, which is one of the causes of "picket" in the image. .

This effect becomes larger as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source.

Furthermore, when forming a photoconductive layer using an A-81 material, in order to improve its electrical and photoconductive properties, it is necessary to use a hydrogen atom or a fluorine atom such as a hydrogen atom, or an electrically conductive type atom. Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms to control the properties of the photoconductive layer, and other atoms are included in the photoconductive layer to improve properties. In some cases, problems may arise with the electrical or photoconductive properties of the formed layer.

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

Furthermore, when the layer thickness exceeds 10-odd microns, the layer may lift or peel off from the support surface, or the layer may peel off as the time elapses after it is left in the air after being taken out of the Makabe deposition chamber for layer formation. This resulted in problems such as the formation of cracks. This phenomenon is
In particular, there are drawbacks to be solved in terms of stability over time, which often occur when the support is a drum-shaped support commonly used in the field of electrophotography.

Therefore, while efforts are being made to improve the properties of the A-8i material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing the light guide member.

The present invention has been made in view of the above points, and focuses on the applicability and applicability of A-81 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 discovered an amorphous material that uses silicon atoms as its base material and contains at least one of either hydrogen atoms (2) or halogen atoms (2), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, Or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as a generic term [a-8
i (H, Not only does it have extremely superior properties in practical use, but it also surpasses conventional photoconductive materials in every respect, especially as a photoconductive material for electrophotography. This is based on the discovery that it has excellent absorption vector characteristics on the long wavelength side.

The present invention has stable 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 resistant to light fatigue. The main object of the present invention is to provide a photoconductive member which is extremely durable, does not cause the phenomenon of aging 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 radars, and has fast photoresponse.

Another object of the present invention is to provide excellent adhesion between the layer provided on the support and the support, and between each of the layers to be layered.
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 high layer quality.

Another object of the present invention is to: 'When applied as an image forming member for electrophotography, the charge generated during charging processing for electrostatic image formation is such that ordinary electrophotography can be applied very effectively. It is an object of the present invention to provide a photoconductive member having sufficient retention ability and excellent electrophotographic properties in which almost no deterioration of the properties is observed even in a humid atmosphere.

Still another object of the present invention is to provide a photoconductive member for electrophotography, which has high magnetism and can easily produce high-quality images with clear halftones and high resolution.

Yet another object of the invention is foveal 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 the photoconductive member, a first layer region (G) made of an amorphous material containing r-rumanium atoms, and an amorphous material containing silicon atoms. A first layer having a layered structure in which a second layer region (S) exhibiting photoconductivity is provided in order from the support side, and an amorphous material containing silicon atoms and oxygen source molecules. It is assumed that tp!ja has a photoreceptive layer constituted by a second layer and a nitrogen atom is contained in the first layer.

The photoconductive member of the present invention designed to have the above-described layer structure can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. Indicates pressure resistance and usage environment characteristics.

In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, cylinder sensitivity is high, and it has a high signal-to-noise ratio. - It has excellent light fatigue resistance and repeated use characteristics, has a high density, /--7) - has a clear image, and has a high resolution.
High quality images can be stably and repeatedly obtained.

In addition, the photoconductive member of the present invention has a photoreceptive layer formed on a support, which is strong and has excellent adhesion to the support, and can be used continuously at high speed for a long time. Can be used repeatedly.

Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, particularly excellent matching with semiconductor radar, and fast photoresponse.

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

FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention.

The photoconductive member 100 shown in FIG. 1 includes a support 101 for the photoconductive member, and a first layer (1
) 102 and a second layer (II) 103, #second layer (1) 103 having a free surface 106 on one end surface.

The first layer (1) 102 includes siglumanium atoms from the support 101 side, silicon atoms, hydrogen atoms, if necessary,
A first layer region (G) 104 made of an amorphous material (hereinafter abbreviated as "a-Ge(St,H,X)J") containing at least one of the following atoms: and a-
3l (H,

Glumanicum atoms contained in the first layer region (G) 104 are continuous in the layer thickness direction of the first layer region (G) 104 and in the in-plane direction parallel to the surface of the support 101. It is contained in the first layer region (c) 104 so as to be uniformly distributed.

In the present invention, germanium atoms are not contained in the second layer region (S) provided in the first layer region (G) and soil, and the first layer region (S) provided in the first layer region (G) does not contain germanium atoms. By forming (1), it is possible to obtain a photoconductive member that has excellent photosensitivity to light in the entire range of wavelengths from relatively short wavelengths to relatively short wavelengths, including the visible light region.

In addition, when a semiconductor laser or the like is used, the second layer region (
Light on the long wavelength side, which is almost completely absorbed by S), can be virtually completely absorbed in the 10th layer region (G) K, 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
) contains silicon atoms, the first layer region (G
) and the second layer region (S) each have a common constituent element of silicon atoms, so chemical stability can be sufficiently ensured at the laminated interface. has been done.

In the present invention, the content of germanium atoms contained in the first layer region (G) may be appropriately determined as desired so as to effectively achieve the object of the present invention. Preferably 1 to 10
105 atomic ppm, more preferably 100
It is desirable to set it to 9.5-9.5 X 10 atomic ppm, optimally 500-8 X 10 atomic 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. Great care must be taken during design.

In the present invention, the layer thickness Tn of the first layer region (G) is preferably 30X to 50μ, more preferably 40X to 40μ.
It is desirable that μ is optimally set to 50× to 30 μ.

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

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

In the photoconductive member of the present invention, the numerical range of (TB+T) is preferably 1 to 100μ, more preferably 1 to 80μ, and most preferably 2 to 50μ.

In a highly preferred embodiment of the present invention, the layer thickness TB and layer thickness T are preferably TB/T≦1.
When satisfying the following relationship, it is desirable to select appropriate numerical values for each of them.

In selecting the numerical values of layer thickness TB and layer thickness T in the above case, it is preferable that Tn/T≦0.9, and optimally Tn/T≦0.9.
It is desirable that the values of layer thickness TB and layer thickness T be determined so that the relationship B/T≦0.8 is satisfied.

In the present invention, the content of germanium atoms contained in the first layer region (G) is I x 105105ato
ppm or more, the layer thickness TB of the first (0 layer region (G)) is desirably <thin>, preferably 30μ or less, more preferably 25μ or less, most preferably 20μ. The following is desirable.

In the photoconductive member of the present invention, the first layer (1) is used for the purpose of increasing photosensitivity and dark resistance, as well as improving the 1:1 adhesion between the support and the first layer (1). Nitrogen atoms are contained in the layer (1). The nitrogen atoms contained in the first layer (]) may be evenly contained in the entire layer area of the first layer (+), or may be contained in a part of the first layer (1). It may be contained and unevenly distributed only in the layer region.

Further, the distribution state of nitrogen atoms may be such that the distribution concentration C (c) is uniform or non-uniform in the layer thickness direction of the first layer (1).

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

In the former case, the content of nitrogen atoms in the layer region (g) is kept relatively low in order to maintain high photosensitivity, while in the latter case, it ensures enhanced adhesion with the support. It is desirable to have a relatively large amount for measurement purposes.

Also, for the purpose of achieving both the former and the latter at the same time,
The first layer (
+) in the second layer (It) 0111, or in the second layer (It) of the first layer (1).
In the interface layer region on the n) side, it is sufficient to form a nitrogen atom distribution state in the layer region (g) so that nitrogen atoms are not actively contained.

In the present invention, the layer region () provided in the first layer (])
The content of nitrogen atoms contained in the layer depends on the characteristics required for the layer region (g) 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 properties at the contact interface.

In addition, when another layer region is provided in direct contact with the layer region (to), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The nitrogen atom content is appropriately selected with consideration given to the following.

The amount of nitrogen atoms contained in the layer region (g) is determined as desired depending on the properties required of the photoconductive member to be formed, but is preferably 0.001 to 50 atoms.
ic%, preferably 0.002 to 40 atoms
c%, most preferably 0.003 to 30 atomic%.

In the present invention, even if the layer region (b) occupies the entire area of the 10th layer (1) or the entire area of the first layer (1), the layer thickness of the layer area (g) When the proportion of TH in the layer thickness T of the first layer (1) is sufficiently large, the upper limit of the content of nitrogen atoms contained in the layer region is sufficiently smaller than the above value. is desirable.

In the case of the present invention, when the ratio of the layer thickness TN of the layer region (b) to the layer thickness T of the first layer (1) is two-fifths or more, the layer region (b) The upper limit of the amount of nitrogen atoms contained in (b) is preferably 30 atoms or less, more preferably 20 atomic% or less, and most preferably lQ atomic% or less.

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

In Figure 2 and Figure 10, the horizontal axis shows the nitrogen atom distribution concentration C (c), the vertical axis shows the layer thickness of the layer region (c), and tB
indicates the position of the end surface of the layer region (g) on the support side, and t indicates the position of the end surface of the layer region (g) on the opposite side to the support side.

That is, in the layer region (6) containing nitrogen atoms, the layer formation lasts from the tB side toward the t side.

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

In the example shown in FIG. 2, oxygen atoms extend from the interface position tB where the surface where the layer region (b) containing nitrogen atoms is formed and the surface of the layer region (6) contact to the position t1. Nitrogen atoms are contained in the layer region (to) where they are formed, while the distribution concentration C (to) takes a constant value of Ci, and at the position t1
The concentration is gradually and continuously reduced from C2 to the interface position t. Interface position t.

In this case, the distribution concentration C(g) of nitrogen atoms is C3.

The distribution concentration C@ of elementary atoms gradually and continuously decreases from the concentration C4 until it reaches the position tT from the position tB.

A distribution state is formed in which the concentration becomes Cs.

In the case of FIG. 4, from position tB to position tz'l: the distribution concentration C of nitrogen atoms is set to a constant value of concentration C6, and from position 1
．． and the position tT, the distribution concentration C(g) is gradually and continuously reduced, and at the position tT, the distribution concentration C(g) is substantially zero (here, substantially zero means that the density is below the detection limit). ).

In the case of FIG. 5, the distribution concentration C of nitrogen atoms is gradually decreased from the concentration C8 over and over again from position t8 to position t, and becomes substantially zero at position tT. has been done.

In the example shown in Figure 6, the distribution concentration C(g) of nitrogen atoms is a constant value of concentration C9 between positions tB and CIG at position t.

Between position t3 and position t, the distribution density C is linearly linear from position ts to position 1T. c.
, h18 1 In the example shown in FIG.
, from position t4 to position t4, the concentration C1l is constant, and from position t4 to position tT, the concentration decreases in a linear function from cl to concentration Cl11.

In the example shown in FIG. 8, the distribution concentration C(b) of nitrogen atoms decreases linearly from the concentration 014 to substantially zero from position 0 to multi-position tT.

In FIG. 9, from position tll to position 1. Up to , the nitrogen atom distribution a degree C(g) decreases linearly from a degree Cl1l to shi age C11l, and between the position Rts and the position tT, it once becomes a constant value of C11l. An example is shown.

In the example shown in FIG. 10, C is the distribution concentration C(to) of nitrogen atoms at the position C1? and position t6
Until reaching , the concentration CI7 is gradually decreased at first, and around the position t6, it is rapidly decreased to the concentration C1B at the position t6.

Between position t6 and position 51t7, the decrease is rapid at first, and then slowly and gradually decreased until position t7.
So, between the concentration C1 and the position t7 and the position ts,
Very slowly 9 gradually decreased at position tII,
The concentration reaches Ca11. Between position 1° and position tT, the concentration C! ◎It is reduced according to the curved edge of the shape as shown in the figure so that it becomes substantially zero.

As shown in FIGS. 2 to 10 above, some typical examples of the distribution state of nitrogen atoms contained in the layer region in the layer thickness direction have been explained. On the body side, there is a part where the distribution concentration C(N) of nitrogen atoms is high, and on the interface t side, the distribution concentration C(N) of nitrogen atoms has a part where the distribution concentration C(N) is considerably lower than on the support side. A distribution state is provided in the layer region.

In the present invention, the nitrogen atom-containing layer region (G) constituting the first #(1) is a region where nitrogen atoms are contained at a relatively high risk due to the force on the support side, as described above. Current area (
B) is desirable, and in this case, the adhesion between the support and the first layer (1) can be further improved.

If the localized region (B) is explained using the symbols shown in FIGS. 2 to 9 and 10, it is preferable that the localized region (B) be provided within 5 μ of the interface position @t.

In the present invention, the localized region (B) is located at the interface position t
, may be the entire layer region (LT) up to 5μ thick, or may be a part of the layer region (LT).

Whether the localized region 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.

The maximum value Cm @
Above, preferably 80 Q atomic ppm
As mentioned above, it is desirable to form layers so as to obtain a distribution state that is optimally -1000' atomic ppm or more.

That is, in the present invention, the layer region containing nitrogen atoms has a layer thickness within 5 μm (1 cm*) from the support side.
It is desirable to form it so that x exists.

In the present invention, the halogen atoms (3) contained as necessary in the first layer region (G) and second layer region (19) constituting the 10th layer (1) are specifically 7,
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 (2) composed of a-Go (81, H, It is made by a vacuum deposition method using . By glow discharge method, a-Go(St.

In order to form the first layer region (b) composed of H,
.

Raw material gas for supply and, if necessary, silicon atoms (S
The raw material gas for S1 supply that can supply hydrogen atoms (
6) Introducing a raw material gas for introduction and/or a raw material gas for introducing halogen atoms (g) into a deposition chamber whose interior can be reduced in pressure at a desired gas pressure to generate a glow discharge within the deposition chamber; When germanium atoms are placed in a predetermined position in advance and are contained in the first layer region (G) with a non-uniform concentration distribution, the distribution concentration of germanium atoms is controlled according to a desired rate of change curve while a-Go( A layer consisting of Si, LX) may be formed.

In addition, when forming by sputtering method, for example, Ar
, a target made of Si in an atmosphere of an inert gas such as He or a mixed gas based on these gases,
Alternatively, the target and a target composed of Ge may be used, or a mixed target of Si and Ge may be used, and He may be added as necessary.

A raw material for supplying Ge diluted with a diluent gas such as Ar is introduced into a deposition chamber for buttering with a gas for introducing hydrogen atoms (b) and/or halogen atoms (t) as necessary. , by creating a plasma atmosphere of the desired gas. At this time, the distribution concentration of germanium atoms in the first layer region (G) can be arbitrarily controlled by sputtering the target while controlling the gas flow rate of the raw material gas for supplying Ge according to a desired rate of change curve. I can do it.

In the case of the ion grating method, for example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition beat as evaporation sources, respectively, and the evaporation sources are heated using a resistance heating method or an electron beam method. (EB method) etc., except for heating and evaporating and passing the flying evaporated material through the desired f-szolazma atmosphere.
This can be done in the same manner as in the case of the Sufu9 Tsutaring method.

Substances that can be used as the raw material gas for supplying St used in the present invention include 5iH41Si2H6, Si, H8
゜81 Hydrogenation in a gaseous state such as H or which can be gasified 1
0 silicon (silanes) can be used effectively, and 5LH4,81□H6 is particularly preferred in terms of ease of handling during layer-forming work and good St supply efficiency.

Parts that can be used as raw material gas for supplying Ge include GeH
4lG@2H,6+ Ge3H8# Ge4H10j
Gl! 15) L121 G"6H1-4*"7H141
GeaHla Reference G@9H20 etc. (Dtf), Shape M (D
In addition, germanium hydride that can be converted into Fiff and X can be effectively used, and in particular, Gem4@
Ge2H6#Ge3H8 is preferred.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halides, interhalogen compounds, and gaseous states such as halogen-substituted 72-conductors. Preferred examples include halogen compounds that can be converted into gas or gasified.

Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, and bromine.

Halogen gas in eyelids, BrF I CJtF + C
4F6 s BrF5 lBrF31IF3. IF7
, IC! , IBr, and other interhalogen compounds.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF, *Si, FA, 5iCJA, 5iBr,
etc. (D/'logonized silicon can be mentioned as a preferable example.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, a raw material gas capable of supplying Si together with a raw material gas for supplying Ge is used. The first layer region (G) made of a-8iGe containing halogen atoms can be formed on a desired support without using silicon hydride gas.

When creating the first layer region (G) containing halogen atoms according to the glow discharge method, for example, silicon halide, which serves as a raw material gas for supplying Si, germanium hydride, which serves as a raw material gas for supplying Ge, and Ar + H2s. A gas such as He is introduced into the deposition chamber for forming the first layer region (G) at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. By doing this, the first layer region (G) can be formed on the desired support, but in order to more easily control the ratio of introducing hydrogen atoms, it is possible to form the first layer region (G) on the desired support. Furthermore, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed to form a layer.

Moreover, each gas may be used not only singly but also in combination at a predetermined mixing ratio.

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

In addition, when introducing hydrogen atoms, a raw material gas for hydrogen atom introduction, such as H2, or the above-mentioned silanes or/
A plasma atmosphere of the gas rA may be formed by introducing a gas such as germanium hydride into a deposition chamber for sputtering.

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, He, HBr.

HI etc. (7) 80l/r' Hydrogen heptaide, SiH2F
2.5iH2I2.5IH2C12゜5iHCj, ,
Halodane-substituted silicon hydrides such as 5iH2Br2.5iHBr3, and GeHF3. GeHBr3. GeH3
F, GeHBr3゜GeH2Cノ. , GeHsC, GeHBr3, Ge2H6j, GeHBr3, and other halides containing hydrogen atoms as one of their constituent elements, GeF41GeC*GeBr41 Ge
14 +GeF2+GeCノ2. GeBr2IGe■2
Substances in a gaseous state or capable of being gasified, such as germanium chloride, etc., can also be mentioned as useful starting materials for forming the first layer region (G).

Among these substances, halides containing hydrogen atoms are extremely effective hydrogen atoms for controlling electrical or photoelectric properties at the same time as introducing halogen atoms into the layer when forming the first layer region (G). Since halogen is also introduced, it is used as a suitable raw material for halogen introduction in the present invention.

In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, H2, SiH4, Si2H6°5
With germanium or a germanium compound for supplying Ge to silicon hydride such as t3H8, 5i4H1o, or GeH41Ge2H6j Ge3H81Ge4H1
01Ge5H121Ge6H14,Ge7H160,G
Germanium hydride such as e8H18, Ge, H2o and S
This can also be achieved by causing a discharge by causing silicon or a silicon compound to coexist in the deposition chamber for supplying t.

In a preferred example of the present invention, the amount of hydrogen atoms (the amount of rice grains, the amount of halogen atoms (maximum), or the amount of hydrogen atoms and halogen atoms contained in the layer region (G) of l1g1 constituting the photoreceptive layer to be formed) The sum of the fireflies (H×) is preferably 0
．． 01-40 atomic%, more preferably 0.0
5-30 atom IC%, optimally 0.1-25 at
It is recommended that it be defined as omic%.

Hydrogen atoms (U or/) contained in the first layer region (G)
To control the amount of halogen atoms (3), for example, the temperature of the support or/and the introduction of the starting material used to contain the halogen atoms (3) into the deposition apparatus system. It is sufficient to control the amount, discharge power, etc.

In the present invention, in order to form the second layer region (S) composed of a-8t(H,X), the starting materials for forming the first layer region (G) described above are used. Using the starting material (starting material (II) for forming the second layer region (S)) excluding the starting material that becomes the raw material gas for supply, the first This can be carried out according to the same method and conditions as in the case of forming the layer region (G).

That is, in the present invention, in order to form the second layer region (S) composed of a-3i (H, This is accomplished by utilizing a vacuum deposition method. For example, by glow discharge method, a-8i(H,X)
In order to form the second layer region (S) consisting of, basically, along with the raw material gas for supplying St that can supply the silicon atoms (St) described above, hydrogen atoms @ A raw material gas for introducing or/and rhodan atoms (3) is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated within the deposition chamber. A layer consisting of a-8i(H,X) may be formed on the surface of the support. In addition, in the case of sputtering a target made of St in an atmosphere of an active gas such as Ar, He, or a mixed gas containing these gases, hydrogen Gas for introducing atoms (6) and/or atoms (3) may be introduced into the deposition chamber for sputtering.

In the photoconductive member of the present invention, the second layer region (S) provided on the first layer region (G) containing dalmanium atoms and not containing germanium atoms has conductive properties. By containing a substance that controls the conductivity of the layer region (S), the conductive properties of the layer region (S) can be controlled as desired.

Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-8i (H,X) constituting the second layer region (S) to be formed
On the other hand, p-type impurities that give p-type conductivity characteristics and n-type impurities that give n-type conduction characteristics can be mentioned.

Specifically, p-type impurities include atoms belonging to Group Ⅰ of the periodic table (Group Ⅰ atoms), such as B (boron), At(
Among them, B and Ga are particularly preferably used. As n-type impurities, atoms belonging to group V of the periodic table (group V atoms), such as P
(9)), As (arsenic), sb (antimony), Bi (bismuth), etc., and p and Aa are particularly preferably used.

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 properties contained in the second layer region (S) is preferably 0.
．． 001 to 1000 atomic ppm, preferably 0.05 to 500 atomic ppm, most preferably 0.1 to 200 atomic ppm.

In order to structurally introduce a substance that completely controls the conduction properties into the second layer region (S), for example, a group II atom or a group V atom, it is necessary to introduce a substance for introducing a group II atom during layer formation. The starting material or the starting material for introducing Group V atoms may be introduced in gaseous form into the deposition chamber together with other starting materials for forming the second layer region.

As the starting material for introducing the group (I) atoms, it is desirable to use a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for the introduction of group Ⅰ atoms include B2H6, B4 horse OT for the introduction of boron atoms.
B5H91B5H11' B6H10゜B6H42,
Boron hydride such as B6H44, BF3. BC15rBB
Boron halides such as r3+ are praised. In addition, A
tCl3. GaCl2. Ga(CH3), , I
nC/! , , TtCl.

etc. can also be mentioned.

In the present invention, effective starting materials for introducing Group V atoms include PH3,
Hydrogenated phosphorus such as P2H4, PH4I, PF3゜PF
5. Pct, , PCl5 * PBr, , P
Br3. Examples include nologonated phosphorus such as PH6. In addition, AsH2, AsF3 rAsC4s, As
Br, , AsF5, SbH3, SbF5. Sb
F5゜5bCL3. SbC! 5, BkH3*B
1CA3, B1Br5, etc. can also be mentioned as effective starting materials for the introduction of the 1st substance.

In the present invention, providing a nitrogen atom-containing layer region in the photoreceptive layer (1) means that the photoreceptor layer (1) is provided with a layer region containing nitrogen atoms.
During the formation of 1), the starting material for introducing nitrogen atoms is used together with the starting material for forming the photoreceptive layer (I), and the amount thereof is controlled in the formed layer. It is better to include it. When the glow discharge method is used to form the layer region (2), a nitrogen atom-introducing material selected from among the starting materials for forming the photoreceptive layer (1) as desired is added. starting materials are added. As such a starting material for introducing nitrogen atoms, most of the gaseous substances containing at least nitrogen atoms or substances that can be gasified can be used.

For example, a raw material gas whose constituent atoms are silicon atoms (St), a raw material gas whose constituent atoms are nitrogen atomic axes, and a raw material gas whose constituent atoms are hydrogen atoms (6) or halogen atoms (3) as necessary. or use a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing nitrogen atoms (6) and hydrogen atoms (6) in a desired mixing ratio. They can also be used by mixing them at a desired mixing ratio.

Alternatively, raw gas containing silicon atoms (St) and hydrogen atoms (b) as constituent atoms may be mixed with raw material gas containing nitrogen atoms (6) as constituent atoms.

Nitrogen atoms used in forming layer region (6)
) Starting materials that can be effectively used as raw material gases for introduction include nitrogen (N2), ammonia (N
Mention may be made of nitrogen compounds such as gaseous or gasifiable nitrogen, nitrides and azides, such as H3), hydrazine (H2NNH2), hydrogen azide (HN3), ammonium azide (NH4N3), etc. In addition to this, in addition to introducing nitrogen atoms (N), it is also possible to introduce halodane atoms (3), such as nitrogen trifluoride (F, N) and nitrogen tetrafluoride (F4N2). Nitrogen compounds can be mentioned.

In the present invention, in order to further enhance the effect obtained by nitrogen atoms in the middle layer region, in addition to nitrogen atoms,
Furthermore, it can contain oxygen atoms.

The raw material gas for introducing oxygen atoms into the layer region (6) is 1, for example, oxygen (02) #ozone (
03) , -nitrogen oxide (No) , nitrogen dioxide (No2
), -nitrogen dioxide (N20), nitrogen sesquioxide (N2
05), trinitric oxide (N204), nitrogen sesquioxide (
N20. ), nitrogen trioxide (NO, ), silicon atom (St), oxygen atom (0), and hydrogen atom (6) as constituent atoms, for example, disiloxane (H3SiO8iH3
), )Disiloxane (H3S iO81H20S
Examples include lower siloxanes such as 1H3).

K to form a layer region (transfer) containing nitrogen atoms by a sputtering method is a single crystal or polycrystalline S1 wafer or a 513N4 wafer, or a mixture of St and Si.
This can be carried out by using a wafer containing a mixture of 3N4 as a target and subjecting it to wafers in various gas atmospheres.

For example, if an S1 wafer is used as a target, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms or/and halodane atoms is diluted with a diluting gas as necessary, and introduced into a deposition chamber for y-tar,
The SL wafer may be sputtered by forming a gas plasma of these gases.

Alternatively, St and Si 3N4 may be used as separate targets, or a mixed target of sl and 513N4 may be used. Hydrogen atom (
6) or/and by sputtering in a gas atmosphere containing halogen atoms (3) as constituent atoms. As the raw material gas for introducing nitrogen atoms, the raw material gas for introducing nitrogen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, when a layer region containing nitrogen atoms is provided when forming the photoreceptive layer (I),
By changing the distribution concentration C axis of nitrogen atoms contained in the layer region (to) in the JvI thickness direction, a desired distribution state in the layer thickness direction (
In the case of a glow discharge, the starting material gas for the introduction of nitrogen atoms should be varied in the distribution concentration C (to) to form a layer region with a depth profile.

This is accomplished by introducing the gas into the deposition chamber while changing the flow rate of the gas appropriately according to the desired change in surface line area. 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 manually or by using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear temperature; for example, a microcomputer or the like may be used to control the flow rate according to a rate of change curve designed in advance to obtain a desired content rate curve.

When forming a layer region (goods) by a sputtering method, the distribution concentration C axis of nitrogen atoms in the layer thickness direction is varied in the layer thickness direction to obtain a desired distribution state (de) of nitrogen atoms in the layer thickness direction.
K forming the pth profile) is, firstly,
As in the case of the glow discharge method, the starting material for introducing nitrogen atoms is used in a gaseous state, and the gas flow rate at which the gas is introduced into the deposition chamber is appropriately changed as desired.

Second, if a target for sputtering is to be used, for example, a mixture of Si and 82 sN4, the mixing ratio of sl and Si 3N4 should be determined.

This is accomplished by changing the layer thickness direction of the target in advance.

In the present invention, hydrogen atoms (
6) or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 1 to 1.
40 atomic%, preferably 5 to 30 atomic%
mic%, preferably 5 to 25 atomic%.

The second layer (11) in the present invention consists of silicon atoms (S
t), oxygen atom (0), and hydrogen atom ([(
) or/and halogen atoms (hereinafter referred to as '[a'''''xol-x)y(H2N)1-, J'. However, 414 times are formed with O(xy<1).

The formation of the second layer (II) composed of a-(siXol-x)y(H,X)1- is performed by glow discharge method,
This can be accomplished by the zoster ring method, the ion immersion 2° launch method, the ion routing method, the electron beam method, or the like. 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. The second layer (11
) The glow discharge method or the sintering method is preferably employed because of the advantage that it can be easily introduced into the liquid.

Furthermore, in the present invention, the second layer (n) may be formed by using a glow discharge method and a sputtering method in the same device system.

To form the second layer (n) by glow discharge method i
a −(S i xo 1- x )y (Hs
) 1- The raw material gas for y formation is mixed with a dilution gas at a predetermined mixing ratio if necessary, and introduced into a vacuum deposition chamber where a support is installed, and the introduced gas is used to perform glow discharge. The gas is turned into a gas glaze by causing the a-(StxO
l-x)y(H,X)1-.

All you have to do is deposit it.

In the present invention, a-(SixO4-x)y(H, x)
1-. Silicon atoms (Si
), oxygen atom (0), hydrogen atom (6), halogen atom (
Most of the gaseous substances containing at least one of the constituent atoms of 3) or the gasified substances that can be gasified can be used.

When using a raw material gas having 81 as a constituent atom as one of Sir O, H*
Source gas containing H as a constituent atom or/and X as necessary
A raw material gas having constituent atoms of 8% and a raw material gas having constituent atoms of 0.
and a raw material gas containing H as constituent atoms or/and a raw material gas containing 0 and X as constituent atoms, also at a desired mixing ratio, or a raw material gas containing Sl as constituent atoms, A raw material gas containing three constituent atoms of Si, O, and H or a raw material gas containing three constituent atoms of Si, O, and X can be used in combination.

Alternatively, a raw material gas containing St and H as constituent atoms may be mixed with a raw material gas containing 0 as constituent atoms, or a raw material gas containing St and X as constituent atoms may be mixed with O. Raw material gases serving as constituent atoms may be mixed and used.

In the present invention, Fr C4p Br is suitable as the halodane atom (3) contained in the second layer (If).
r I, especially F and C1 are preferred.

In the present invention, materials that can be used as the raw material gas effectively used to form the second layer (■) include those in a gaseous state at room temperature and pressure, or substances that can be easily gasified. can be mentioned.

Further, when forming the second layer (It) by the sintering method or the tuttering method, for example, the following procedure is performed.

Firstly, when a target made of Si is exposed to a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixture of these gases,
A raw material gas for introducing oxygen atoms (0) may be introduced into a vacuum deposition chamber in which sputtering is performed together with a raw material gas for introducing hydrogen atoms (6) and/or halogen atoms (3) as necessary.

Secondly, 510 is used as a target for sputtering.
The second layer is formed by using a target made of 2, or a target made of Si 419 and a target made of SiO2, or a tarduct made of St and 5I02. Oxygen atoms (0) can be introduced into (If). On this occasion.

If the above raw material gas for introducing oxygen atoms (0) is also used, the amount of oxygen atoms (0) introduced into the second layer (It) can be arbitrarily controlled by controlling its flow rate. It is easy to do.

The content of oxygen atoms (0) introduced into the second layer (II) can be determined by controlling the flow rate when the raw material gas for introducing oxygen atoms (0) is introduced into the deposition chamber, or by controlling the flow rate when the raw material gas for introducing oxygen atoms (0) is introduced into the deposition chamber. Adjust the proportion of oxygen atoms (0) contained in the target for introducing atoms (0) when creating the target, or
By doing both, it is possible to control as desired.

The starting material used as the raw material gas for supplying Si used in the present invention is SiH4r St. H6,5i3H
B.

Silicon hydride (silanes) in a gaseous state or that can be gasified, such as S i 4H4°, can be effectively used, especially in terms of ease of handling in layer creation work, good S1 supply efficiency, etc. Preferred examples include SiH3F Si2H6.

Using these starting materials, S
H may also be introduced along with i.

Effective starting materials that serve as raw material gas for supplying Si include:
In addition to the above-mentioned silicon hydride, silicon compounds containing rhodane atoms (3), so-called silane derivatives substituted with rhodane atoms, specifically, for example, 5iF41St2F6.
Preferred examples include halides such as SiC2 and SiBr4.

Furthermore, SiH2F2.5iH2I2.5in2Ct2
,5il(CA3゜S 1H2Br 2.S 1HB
81 for the formation of the second layer (11) for which rhodanide is also effective, such as halogenated silicon hydride such as r 6, etc., which is in a gaseous state or can be gasified, and has a hydrogen atom as one of the constituent elements) It can be mentioned as a starting material for supply.

Even when using a silicon compound containing these rhodan atoms (3), by appropriately selecting the layer forming conditions as described above for fc, can be introduced.

The silicon rhodanide compound containing hydrogen atoms in the above-mentioned starting material can be used to simultaneously introduce a halogen atom (3) into the layer during the formation of the second layer (II), and to improve gaseous or photoelectric properties. Since hydrogen atoms (b), which are extremely effective for control, are also introduced,
In the present invention, the preferred starting material is Rodan atom (3).

In addition to the above-mentioned materials, examples of effective starting materials as raw material gases for introducing halogen atoms (3) used in forming the second layer (II) in the present invention include fluorine, chlorine, bromine, etc. , iodine gas, BrF
, ClF, ClF3. BrF5. BrF3.
IF3゜IF7 r IC4'+ Interrogonic compounds such as IBr, HF.

Examples include hydrogen halides such as 14C1, HBr, and HI.

Oxygen atoms (0
) An effective starting material that can be used as a raw material gas for introduction is oxygen (0°), which has 0 as its constituent atoms, or has N and O as its constituent atoms.

Ozone (03), -nitrogen oxide (No), nitrogen dioxide (No2).

-Nitrogen dioxide (N20), nitrogen sesquioxide (N203)
, trinitrogen tetraoxide (N204), nitrogen sesquioxide (N20
5), nitrogen trioxide (No5), silicon atom (St
), an oxygen atom (0), and a hydrogen atom (6) as constituent atoms, for example, disiloxane (H,5iO8iH3),
) Disiloxane (1(3SiO8i)I20SiH,)
Examples include lower siloxanes such as.

In the present invention, the second layer (II) is formed by glow discharge method or Suno J. The diluent gas used when forming by the tuttering method is a so-called rare gas, such as He HNe.

Ar, etc. can be cited as suitable women.

The second layer (It) in the present invention is carefully formed to provide the desired properties.

In other words, a substance whose constituent atoms are St, 0, and H or/and X as necessary has a structure ranging from crystalline to amorphous depending on its preparation conditions, and electrically.
In the present invention, a-( S
In order to form rxol-, )y(H, For example, to provide the second layer (II) with the main purpose of improving pressure resistance, a-(sixo,-x)y(n,
x) 1-, is made as an amorphous material with pronounced electrically insulating behavior in the environment of use.

In addition, when the second layer (II) is provided with 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 the degree of electrical insulation is reduced to a certain extent with respect to the irradiated light. As an amorphous material with a sensitivity of a
-(SixO4-x)y(H,X)1-7 is created.

a −(S r xol −x
)y (H*
), the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer.In the present invention, a-(SixO
+-x)y(H,X)4. It is desirable that the temperature of the support during layer formation be strictly controlled so that the layer can be formed as desired.

In the present invention, the formation of the second layer (If) is carried out by appropriately selecting an optimal range in accordance with the method of forming the second layer (n) in order to effectively achieve the desired purpose. but preferably 20 to 400°C, more preferably 50 to 350°C,
The optimum temperature is preferably 100 to 300°C. To form the second layer (II), glow discharge method and Although it is advantageous to adopt the snow e-tsuttering method, when forming the second layer (II) using these layer forming methods, the discharge power during layer formation is adjusted as well as the support temperature described above. a-(SIXo
It is one of the important factors that influences the characteristics of l-X)y(H,X)1□.

A that describes the characteristics by which the object of the present invention is achieved.
-(SiXO, -X), (H%
W, preferably 50 to 200 W.

The gas pressure in the deposition chamber is preferably 0.01 to 1 Torr.
More preferably, it is about 01 to Q, 5 Torr.

In the present invention, the preferable numerical ranges for the support temperature, discharge, and armature for forming the second layer (■) include the above-mentioned ranges, or these layer forming reactors are independent. They are not determined separately, but are mutually organically related so that a second layer (If) consisting of a-(SixOl-x)y(H,X)1-y with desired characteristics is formed. It is desirable that the optimum value of each layer creation factor be determined based on the following.

The amount of oxygen atoms contained in the second layer (It) in the photoconductive member of the present invention is determined according to the desired characteristics to achieve the object of the present invention, as well as the production conditions of the second layer (It). is an important factor in the formation of the second layer (n) obtained.

The amount of oxygen atoms contained in the second layer (1) in the present invention is determined as desired depending on the type and characteristics of the amorphous material constituting the second layer (n). It is something that can be done.

That is, the general formula a-(SixOl-x)y(H,
The amorphous material represented by
"a-8i aol -a J. However, O('a
(1), an amorphous material composed of silicon raw material, oxygen atoms, and hydrogen atoms (hereinafter referred to as "'-(Sibol-b)c
It is written as "Horse-0". However, 0(b, c(j), an amorphous material (hereinafter referred to as r a-(S i 1
01-6)r(H,X)1-eJ. However, 0
(d, e(1), K classified.

In the present invention, the second layer (11) is a-8taO1-
When the second layer (n) is composed of K, the amount of oxygen atoms contained in the second layer (n) is expressed as a in a-8ta01-a, where a is preferably 0.33 to 0.99999, and so on. It is preferably 0.5 to 0.99, most preferably 0.6 to 0.9.

In the present invention, the second layer (II) is a-(SibOl
-b).

When composed of Hl-c, the amount of oxygen atoms contained in the second layer (n) is a-(SiHOl-b)cHl-c
b is preferably 0.33 to 0.999
99, preferably 0.5 to 0.9, optimally 0.6 to
0.9, C is preferably 0.6 to 0.99, more preferably 0.65 to 0.98, most preferably 0.7 to 0.95.

The second layer (II) is a-(Stdot-,1)e(
H+X)1-e, the second layer (II
) The content of oxygen atoms contained in a −(
S 1,10 + -d (H,
9. Preferably 0.5~o, 99, optimally 0.6~
0.9, e is preferably 0.8 to o, 99, preferably 0
．． 82-0.99, optimally 0.85-0.98"?'
It is desirable to have one.

The number range of the layer thickness of the second layer (ff) in the present invention is as follows.

This is one of the important factors for effectively achieving the purpose 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 layer (It) also depends on the amount of oxygen atoms contained in the layer (■) and the thickness of the first layer (I). It needs to be determined as desired based on the organic relationship depending on the characteristics required for the area.

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 layer (II) in the present invention is preferably o, oo 3 to 30μ, preferably 0.004 to 2
It is desirable to set it to 0μ, optimally O,'005 to 10μ.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, AJ, and Cr.

Mo, Au, Nb, Ta, V, T
Examples include metals such as i, Pt, and Pd, and alloys thereof.

As electrically insulating supports, polyester, polyethylene, polycarbonate, cellulose acetate, polyzolopyrene, polyvinyl chloride, polyvinylidene chloride, ? Films or sheets of synthetic resins such as lintylene, polyamide, glass, ceramics, 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, NiCr is applied to its surface.

ur Cr + Mo I Au I I r HNb
+ Ta + V+ T i I P t r Pd
+ In2O5+ 5n02 +ITO (InzQ,
Conductivity is imparted by providing a thin film made of s + 5n02), etc., or if it is a synthetic resin film such as a polyester film, NiCr.

A4Ag, Pb, Zn, Ni, Au, Cr, Mo, I
A thin film of metal such as R, Nb, Ta, V, TI, PT, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the above metal to make the surface conductive. Granted. The shape of the support is cylindrical.

The photoconductive member 1 shown in FIG.
If 00 is used as an electrophotographic image forming member, it is preferably in the form of an endless belt or a cylinder for continuous high-speed copying. The thickness of the support is appropriately determined so as to form a photoconductive member of the desired thickness, but if flexibility is required as a photoconductive member, the thickness of the support may be determined appropriately. It is made as thin as possible within the range.

However, in such a case, the thickness is preferably 10 μm or more in view of manufacturing and handling of the support, mechanical strength, etc.

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

FIG. 11 shows an example of a photoconductive member manufacturing apparatus.

(7) Gases from 1102 to 1106 in the figure? A raw material gas for forming the photoconductive member of the present invention is sealed in the chamber, and as an example, 1102 is a gas diluted with He (purity 99.999%, hereinafter referred to as S). i
It is abbreviated as H4/He. )? 1103 is Ge H4 gas diluted with He (purity 99.999%, hereinafter Ge
H4/') Ia. ) Gimpe, 1104 is 5IF4 gas diluted with Ha (purity 99.9c+%, hereinafter St
It is abbreviated as 'F'4/He. ) Tempe, 1105 is Su, gas (99.999% purity) cylinder, 1106 tdH2 Ganu (purity 99.999%) Himpe.

In order to flow these gases into the reaction chamber 1101, valves 1122 to 1126 of gas cylinders 1102 to 1106,
Make sure the leak valve 1135 is closed,
In addition, inflow valves 1112 to 1116, outflow pulp 111
After confirming that the auxiliary nozzles 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe.

Next, the vacuum gauge 1136 reads approximately 5 X 10-' to
Assistance at the time of applying force to rr/? Valve 132, 1133,
Close outflow pulps 1117-1121.

Next, to give an example of forming the first layer (1) on the cylindrical substrate 1137, Si H4Ae gas is formed from the gas cylinder 1102, and GeH is formed from the gas cylinder 1103.
4/He gas, open the gas valve 1105, open the bell 1122.11211125 and adjust the pressure of the outlet pressure gauge 1127, 1128.1130 to 1ψ da,
Gradually open the inflow valves 1112, 1113.
10 respectively. Subsequently, the outflow valve 111
7, 1118, 1120, the auxiliary valves 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, adjust the outflow pulp 1117°1118.1120 so that the ratio of the SiF4 gas (e gas flow rate, the GeH4/He gas extraction amount, and the NH3 gas flow rate) becomes the desired value,
Further, the opening of the main valve 1134 is adjusted while checking the reading of the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches a desired value. After confirming that the temperature of the substrate 1137 is set to a temperature in the range of approximately 50 to 400°C by the heater 1138, the power source 1140 is set to the desired power to generate a glow discharge in the reaction chamber 1101. The 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 pulp 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 C)
A second layer region (S) substantially free of germanium atoms can be formed in the soil.

In order to contain a substance that controls conductivity in the second layer region (S), for example, when forming the second layer region (S), B
It is preferable to add a gas such as 2H6 or PH3 to the gas introduced into the deposition chamber 1101.

To form the second layer (It) on the first layer (1) soil formed to the desired layer thickness as described above, the same valve operation as in the formation of the first layer (]) is required. For example, SiH4
This is accomplished by diluting each of the gases and NOO20 with a diluent gas such as He as necessary to generate glow discharge according to desired conditions.

In order to contain NO-Rhodan atoms in the second layer (II), for example, SiF4 gas and NOO20 or SiH
The second layer (IF) is formed in the same manner as above by adding 4 gases.

Is there a necessary gas outflow when forming each layer? Needless to say, all the outflowing pulp outside the valve is closed, and when forming each layer, the gas used to form the previous layer is connected to the reaction chamber 1101 and the gas piping from the outflowing pulps 1117 to 1121 to the reaction chamber 1101. In order to avoid remaining in
4 is fully opened and the system is once evacuated to a high vacuum, as necessary.

The amount of oxygen atoms contained in the second layer (n) is, for example,
In the case of glow discharge, the flow rate ratio of 5IH4 and NOO20 introduced into the reaction chamber 1101 is changed as desired, or in the case of layer formation by sputtering, No is mixed in the sputtering gas (Ar). When forming the target, silicon wafer and S+02
It can be controlled as desired by changing the nupatta area ratio of the plate or by changing the mixing ratio of silicon powder and 5I02 powder and molding the target. The amount of halogen atoms (T) contained in the second layer (II) is determined by the raw material gas for introducing halogen atoms, such as S I F4.
This is accomplished by adjusting the flow rate when the gas is introduced into the reaction chamber 11o1.

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

Examples will be described below.

Example 1 Using the manufacturing apparatus shown in FIG. 11, layers were formed on a cylindrical M substrate under the conditions shown in Table 1 to obtain an electrophotographic image forming member.

The image forming member obtained in this way was installed in a charging exposure experiment apparatus, and 05. Corona charging was performed at OkV for 0.3 seconds, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light amount of 2 uX and Bee 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 set at θ5. 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 Layer formation was performed 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 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, 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 good image quality was obtained.

Example 3 Layer formation was carried out in the same manner as in Example 1 except that the manufacturing apparatus shown in FIG. 11 was used and the conditions shown in Table 3 were used 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 In Example 1, GeH4/He Ganu and S r H4
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 Ae Ganu. Created each.

Regarding 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 the table 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 M 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, layers were formed on a cylindrical M substrate under the conditions shown in Table 6 to obtain an electrophotographic image forming member.

The image forming member obtained in this way was installed in a charging exposure experiment apparatus, and 05. Perform corona charging for 0.3 seconds at OkV,
A light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light amount of 2 ux, see was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the bottom surface of the imaging member by cascading a 2-chargeable developer (containing toner and carrier) over the surface of the imaging member. When the toner image on the image forming member was transferred onto a transfer paper by corona charging at 05,000 kV, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Example 7 In Example 1, the light source was replaced with a tungsten lamp.
An electrophotographic image was created under the same toner image forming conditions as in Example 1, except that the electrostatic image was formed using a 10 nm Q GaAs-based semiconductor radar (10 mW). When the image quality of the toner-transferred image of the forming member was evaluated, a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained.

Example 8 Second 7g! Each of the electrophotographic image forming members (sample A 11- 401~11-408.11-501~11
-508.24 samples of 11-601 to 12-608) were created.

Each of the electrophotographic image forming members thus obtained was individually installed in a copying machine, and under the same conditions as described in each example, each of the electrophotographic image forming members corresponding to each example was , we evaluated the overall image quality of the transferred image and evaluated its durability after repeated continuous use.

Table 8 shows the overall image quality evaluation of the transferred image of each sample and the durability evaluation after repeated continuous use.

Example 9 When forming the second layer (■), silicon wafer and S x 0
Example 1 was carried out in exactly the same manner as in Example 1, except that the target area ratio of 2 and the mixing ratio of Ar and No were changed to change the content ratio of silicon atoms and oxygen atoms in the second layer (II). Each of the imaging members was made by the method. For each of the image forming members thus obtained, the steps of image formation, development, and cleaning 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. .

Example 10 When forming the second layer (U), the flow rate ratio of 5IH4 gas and No gas was changed to change the content ratio of silicon atoms and oxygen atoms in the second layer (II). Example 1
Each of the imaging members was made in exactly the same manner as described above.

After repeating the steps up to transfer approximately 50,000 times using the method described in Example 1 for each image forming member thus obtained,
When the image was evaluated, the results shown in Table 10 were obtained.

Example 11 When forming the second layer (II), SiH4 gas, S r
The second layer (1
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 oxygen atoms in (2) was changed. After repeating the image forming, developing and cleaning steps as described in Example 1 approximately 50,000 times for each of the image forming members thus obtained, image evaluation was performed and results as shown in Example 11 were obtained.

Example 12 Each of the imaging members was prepared by the same method as in Example 1 except that the thickness of the second layer (II) was changed. The cleaning process was repeated to obtain the results shown in Table 12.

Common layer forming conditions in the embodiments of the present invention shown in Table 12 and above are shown below.

Substrate temperature: Glumanium atom (Ge) containing layer...
...about 200°C Germanium atom (Ge)-free layer ...about 250°C Discharge frequency: 13.56 M
Hz Reaction chamber pressure during reaction: 0.3 Torr

[Brief explanation of drawings]

FIG. 1 is a schematic layer configuration diagram for explaining the layer configuration of the photoconductive member of the present invention, and FIGS. 2 to 10 are respectively layer regions (N
), an explanatory diagram for explaining the distribution state of nitrogen atoms in
FIG. 1 is a schematic explanatory diagram of an apparatus used for producing a photoconductive part of the present invention in an example. 100... Photoconductive member 101... Support body 102.
...First layer (1) 103...Twentieth layer (It) 1
04...First layer region (G) 105...Second layer region (S) -m-→-C 0 11--→-C 1111→-C C □-10 Procedural amendment Showagu? Mr. Manabu Shiga, Commissioner of the Japan Patent Office, visited Japan in February 2013.Relationship with the amendment case Applicant (,tF'R(''n)j) 3-I, Shimomaruko, Ota-ku, Tokyo (No. 1-2) “8 (-f) (10 Canon Co., Ltd. 4, substitute 1 person Address: Shigesu Building 330, 2-6-2 Marunouchi, Chiyoda-ku, Tokyo Amended Document The following matters have been amended in the specification of this application. Note 1, page 50, line 19, "0.5-0.8" is corrected to "0.5-0.99J."

Claims (1)

[Claims] (1) A support for a photoconductive member, and on the support,
A first layer region (G) made of an amorphous material containing germanium atoms and a second layer region (S) made of an amorphous material containing silicon atoms and exhibiting photoconductivity are connected to the support. The first layer has a layered structure provided in order from the body side, and the second layer is made of an amorphous material containing silicon atoms and oxygen atoms, and the first layer contains nitrogen atoms. A light guide forming member characterized by containing. <2) The photoconductive member according to claim 1, wherein at least one of the 810 layer region (G) and the 20th layer region (S) contains hydrogen atoms. (3) The light according to claim 1 or 2, wherein a halogen atom is contained in at least one of the first layer region (G) and the second layer region (S). conductive member.