JPS6057983A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain the titled photoconductive member of total environment type having stabilized electric, optical and photoconductive characteristics at all times and also having excellent photosensitivity on the long wave side and optical fatigue resistance by a method wherein the condition of distribution of Ge atoms in the first layer region of a photoreceptive layer is unevenly formed in layer thickness direction, and a substance which controls condutivity is contained in the first layer region. CONSTITUTION:A photoreceptive layer 102 has the layer construction wherein the first layer region 103 consisting of a-Si(H, X)[a-SiGe(H, X)] containing Ge atoms and the second layer region 104 consisting of a-si (H, X) and having photoconductivity are laminated successively from the side of supporting member 101. The germanium atoms to be contained in the first layer region 103 are continuously formed in the layer thickness direction of the first layer region 103, and they are contained in the first layer region 103 in such a manner that they are more abundantly distributed on the side of the supporting member 101 than the side 105 which is reverse to the side where the supporting member 101 is provided. In this photoconductive member 100, a substance C which controls conductivity is contained at least in the first layer region 103, and the desired conductive characteristics are given to the first layer region 103.

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, gamma rays, etc.

As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive and has a photocurrent (I) of 8N ratio [photocurrent (I)].
/dark current (Id)), has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has a desired dark resistance value, and is harmless to the human body during use. In addition, solid-state imaging devices are required to have characteristics such as being able to easily dispose of afterimages within a predetermined period of time. Especially,
In the case of an electrophotographic imaging member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned harmlessness during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as a-8i) is a photoconductive material that has recently attracted attention.
No. 55718 describes application to electrophotographic image forming members;
DE 2933411 describes an application to a photoelectric conversion reader.

However, the conventional photoconductive member having a photoconductive layer composed of A-8L has a low dark resistance value and a low light sensitivity.

Further improvements are required in terms of electrical, optical, and photoconductive properties such as photoresponsiveness, use environment properties such as moisture resistance, and stability over time. The reality is that there are points that could be made.

For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it was often observed that residual potential remained during use. When 4-electric components are used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes afterimages, or when used repeatedly at high speeds, the response gradually decreases. There were many cases where inconveniences occurred.

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. Furthermore, when a commonly used halodan lamp or fluorescent lamp is used as a light source, there remains room for improvement in that the source material on the longer wavelength side cannot be used effectively.

Additionally, if the amount of light that is irradiated is not absorbed sufficiently in the photoconductive layer and reaches the support, the support itself will absorb more of the light that passes through the photoconductive layer. When the reflectance is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "M" in the image.

This shadow becomes larger as the irradiation spot is made smaller in order to improve the resolution, and it becomes a big problem especially when a semiconductor laser is used as the light source.

Furthermore, when the entire photoconductive layer is composed of a-8i material, halogen atoms such as hydrogen atoms or fluorine atoms are added to improve the electrical and photoconductive properties, and to control the electrical conductivity type. In addition, boron atoms, phosphorus atoms, etc., or other atoms to improve properties, are contained in the photoconductive layer as constituent atoms, but depending on how these constituent atoms are contained, the formation Problems may arise with the electrical or photoconductive properties of the applied layer.

That is, for example, the lifetime of photocarriers generated in the formed photoconductive N layer due to light irradiation (5) is not sufficient, or the injection of charge from the support side is not sufficiently prevented in the dark area. There are many cases where this happens.

Furthermore, when the layer thickness exceeds 10-odd microns, the layer may lift or peel off from the surface of the support as time passes after it is left in the air after being removed from the vacuum deposition chamber for layer formation. This tends to cause phenomena such as cracks in the layers. This problem often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are issues that need to be resolved in terms of stability over time. There is.

Therefore, while efforts are being made to improve the properties of the a-8i material itself, 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 points, and is
As a result of continued comprehensive research and study from the viewpoint of application as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., and its applicability. , amorphous Hamura which has a silicon atom as a matrix and contains at least either a hydrogen atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "hydrogenated amorphous silicon"] The layer structure of a photoconductive member having a photoreceptive layer exhibiting photoconductivity is as explained below Photoconductive materials that have been specially designed and produced not only exhibit extremely superior properties in practical use, but also exceed conventional photoconductive materials in all respects, especially for use in electrophotography. This is based on the discovery that it has extremely excellent properties as a photoconductive member, and that it has excellent absorption spectrum properties on the long wavelength side.

The present invention has stable electrical, optical, and photoconductive properties at all times, is an all-environment type 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 that is extremely durable, does not exhibit any deterioration phenomenon even after repeated use, and has no or almost no residual potential observed.

Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers in particular, and has fast photoresponse.

Another object of the present invention is to have excellent adhesion between a layer provided on a support and the support and between each layer of laminated layers,
It is an object of the present invention to provide a photoconductive member that is dense and stable in terms of structural arrangement and has high layer quality.

Another object of the present invention is that when applied as an image forming member for electrophotography, the present invention has a charge retention property during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively. It is an object of the present invention to provide a photoconductive member which has excellent electrophotographic properties, which are sufficiently thick and whose properties hardly deteriorate even in a humid atmosphere.

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

Yet another object of the present invention is high photosensitivity.

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 comprises a support for the photoconductive member, a first layer region made of an amorphous material containing silicon atoms and dalmanium atoms, and an amorphous material containing silicon atoms. a second layer region exhibiting photoconductivity and a photoreceptive layer having a layered structure provided on the side of the support,
The distribution state of germanium atoms in the first layer region is non-uniform in the layer thickness direction, the first layer region contains a substance that controls conductivity, and the light receiving j- It is characterized by containing carbon atoms.

The photoconductive member of the present invention, which is carefully designed to have the above-mentioned layer structure, can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, and photoconductive properties. Indicates electrical voltage resistance and operating environment characteristics.

In particular, when applied as an electrophotographic image forming member (9), 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 has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

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 continuously repeated at high speed for a long time. can be used.

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

(10) 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 has a photoreceptive layer 102 entirely on a support 101 for the photoconductive member, and the photoreceptor M102 has a free surface 105 on one end surface.

The light-receiving layer 102 is made of ylumanium JJ from the support 101 side.
i, a-st(H,x) containing child (hereinafter ra-8
A first layer region (G) 103 composed of +Ge (H, 104 are laminated in order.

The germanium atoms contained in the first layer region (G) 103 are continuous in the thickness direction of the first layer region (G) 103 and are provided with the support 101. It is contained in the first layer region (G) 103 so that it is more distributed on the support 101 side than on the opposite side (the surface 105 side of the photoreceptive layer 102).

In the photoconductive member 100 of the present invention, at least the first
A substance (C) that controls the conduction properties in the layer region (G) 103
is contained, giving the layer region (2) 103 of the flute 1 the desired conductive properties.

In the present invention, the substance (C) controlling the conduction properties contained in the first layer region p) 103 is the substance (C) contained in the first layer region p) 103.
It may be uniformly contained in the entire layer area of 103,
Moreover, it may be contained so as to be unevenly distributed in a part of the layer region of the first layer region C) 103.

In the present invention, the first layer region G) is made such that the substance C) that controls the conduction properties is present in a part of the first layer region G).
), the layer region (PN) containing the substance Ill') is preferably provided as an end layer region of the first layer region G). In particular, when the layer region (PN) is provided as the end layer region on the support side of the first layer region G), the type of the substance C) contained in the layer region (PN) and By appropriately selecting the silk content as desired, it is possible to effectively prevent charge of a specific polarity from being injected from the support into the photoreceptive layer.

In the photoconductive member of the present invention, the substance (C) capable of controlling conduction properties is contained in the first layer region constituting a part of the photoreceptive layer, as described above. Although it is contained evenly over the entire region ←) or unevenly distributed in the layer thickness direction, it is further contained in the 20th layer region M (S) provided on the first layer region ←). The substance (C) may also be contained therein.

When the substance (C) is contained in the second layer region (S), the substance (C) contained in the first layer region
Depending on the type, content, and method of inclusion, the second
The type and amount of the substance (C) to be contained in the layer region (S), and the manner in which it is contained are determined as appropriate.

In the present invention, the substance (
C) When containing W, preferably at least a little
It is desirable to include the substance in the layer region including the contact interface with the layer region @).

In the present invention, the substance (C) is added to the second layer region (1
3) It may be contained uniformly in the entire layer region of (S), or it may be contained uniformly in a part of the layer region.

In the case where both the first layer region G) and the second layer region (S) contain a substance (C) that controls conduction characteristics, the substance (C) in the first layer region (G) is contained. It is desirable that the layer region containing the substance C) and the layer region containing the substance C) in the second layer region (S) are provided so as to be in contact with each other. Moreover, the substance (C) contained in the first layer region (C) and the second layer region (S) is contained in the first layer region (G) and the second layer region (S). They may be of the same type or different types, and their content may be the same or different in each layer region.

However, in the present invention, if the substance (C) contained in each layer region is the same in both, the content in the first layer region IG) should be increased sufficiently, or Alternatively, it is preferable that substances C) having different electrical properties are contained in each desired layer region.

In the present invention, at least the first layer region constituting the photoreceptive layer (14) contains a substance C) that controls the conduction properties.
By containing gold, the conductive properties of the layer region (which may be part or all of the first layer region) containing the substance (C) can be controlled as desired. However, examples of such substances include so-called impurities in the semiconductor field.
In the present invention, a-
For 8iGa (H,

Specifically, the p-type impurity is an atom belonging to Group ■ of the periodic table (Group ■ atom), for example, B (boron) + ht
(aluminum), Ga (gallium).

Examples include In (indium), Tt (thallium), etc., and B and Ga are particularly preferably used. Examples of n-type impurities include atoms belonging to Group Ⅰ of the periodic table (Group Ⅰ atoms), such as P (phosphorus) and As<arsenic).

Examples include sb (antimony), Bl (bismuth), etc., and particularly preferably used are P and As.

In the present invention, the content in the layer region (PN) containing the substance (C) that controls conduction properties is determined by the conduction properties required for the layer region (PN) or the content of the substance (C) that controls conduction properties. P.N.
) is provided in direct contact with the support, it can be appropriately selected depending on the organic relationship, such as the relationship with the properties at the contact interface with the support.

In addition, the relationship with other layer regions provided in direct contact with the layer region (PN) and the characteristics at the contact interface with the other layer regions is also taken into consideration, and the substance C that controls the conduction characteristics is selected. ) content is selected appropriately.

In the present invention, the content of the substance (C) that controls conduction properties contained in the layer region (PN) is preferably 0.01 to 5 x 10 ato+nlc ppm,
More preferably 0.5-l x 10 atomic p
pm + optimally 1 to 5 x 103103ato ppm
It is desirable that this is done.

In the present invention, the content of the substance (C) in the layer region (PN) containing the substance (C) that controls the conduction properties is preferably 30 atomic ppm, more preferably 50 atomic ppm. Atomic ppm or more, optimally 100
For example, when the substance (C) to be contained is the above-mentioned p-type impurity, when the free surface of the photoreceptive layer is subjected to polar charging treatment, light from the support side is The substance (C) that can effectively prevent the injection of electrons into the receptor layer and
In the case of the above-mentioned n-type impurity, when the free surface of the photoreceptive layer is charged to e polarity, it is possible to effectively prevent the injection of holes from the support side into the photoreceptor layer. I can do it.

In the above case, as mentioned above, the layer region (PN
) In the layer area (2) excluding 1 ft, there is a layer area (P
N) may contain a substance (C) that controls the conduction characteristics of a conduction type polarity different from the conduction type polarity of the substance (C) that governs the conduction characteristics contained in N), or The substance (c) t having a conductivity type and controlling the conduction characteristics may be contained in a much smaller amount than the actual amount contained in the layer region (PN).

In such a case, the content of the substance (C) that controls the conduction properties contained in the layer region (@) is as follows:
The polarity and content (17) of the substance (C) contained in PN)
) It is determined as desired depending on the amount, but
Preferably 0.001 to 1000at1000ato+
Preferably 0.05 to 500 atomic ppm
a Optimally, it is desirable to set it to 0.1 to 200 atomic ppm.

In the present invention, when the layer region (PN) and the layer region +2) contain the same kind of conductivity controlling substance (C)', the content in the layer region +2) is preferably It is desirable to set it to 30 atomic ppm or less.

In the present invention, the photoreceptive layer contains a layer region containing a conductivity-controlling substance having one polar conductivity type, and a layer region containing a conductivity-controlling substance having a conductivity type of the other polarity. It is also possible to provide a so-called depletion layer in the contact region by directly contacting the interlayer region. For example, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in the photoreceptive layer so as to be in direct contact with each other to form a so-called p-n junction. A depletion layer can be provided.

In the photoconductive member of the present invention, the distribution state of the germanium atoms contained in the first layer region (18) O) is as described above in the layer thickness direction. It is desirable to have a uniform distribution in the in-plane direction parallel to the surface.

In the present invention, the second layer region (S) provided on the first layer region (S) does not contain germanium atoms, and a light-receiving layer is formed in such a layer structure. By doing so, 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.

In addition, the distribution state of germanium atoms in the first layer region @) is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration C of germanium atoms in the layer thickness direction is the second layer from the support side. Since a change is given that decreases toward the layer region (S), the first layer region O) and the second layer region (S
), and as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the edge of the support, it is possible to The light on the long wavelength side, which is almost completely absorbed in the second layer region (S), can be substantially absorbed in the first layer region (G), and the light is absorbed by the light by reflection from the support surface. Interference can be prevented.

Furthermore, in the photoconductive member of the present invention, the first layer region O)
Since each of the amorphous materials constituting the and the second layer region (S) has a common constituent element of silicon atoms,
Chemical stability is sufficiently ensured at the laminated interface.

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

2 to 10, the horizontal axis shows the distribution concentration of germanium atoms c'f%, the vertical axis shows the layer thickness of the first layer region @), and tB shows the layer thickness of the first layer region G) on the support side. tT indicates the position of the end surface of the first layer (#←) on the side opposite to the support side. That is, in the first layer region O) containing germanium atoms, no layer formation occurs from the tB side to the tT side.

FIG. 2 shows a first typical example of the distribution state of ke-rumanium atoms contained in the first layer region ←) in the layer thickness direction.

In the example shown in FIG. 2, from the interface position 1B where the surface of the support on which the first layer region (1) containing germanium atoms is formed and the surface of the layer (1) of the confectionery 1 are in contact, t1
Up to the position, germanium atoms are contained in the first layer region where germanium atoms are formed, while the distribution concentration C of germanium atoms takes a constant value C1, and the concentration C2 is higher than the concentration C2 at the interface position tT. has been gradually and continuously reduced until . At the interface position tT, the distribution concentration C of germanium atoms is C3.

In the example shown in FIG. 3, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration C4 from the position tIl to the position 1T, and reaches the concentration C5 at the position tT. It forms a distribution state.

In the case of Fig. 4, the distribution concentration C of germanium atoms is a constant value of concentration C6 (21) from position tB to position t2, and gradually and continuously decreases between position t2 and position tT. At the position 1T, the distribution concentration C is substantially zero (substantially zero here means the detection limit is not reached).

In the case of FIG. 5, the distribution concentration C of germanium atoms is
The concentration C8 is gradually decreased continuously from position tB to position tT, and becomes substantially zero at position tT.

In the example shown in FIG. 6, the distribution concentration C of germanium atoms is a constant value of concentration C2 between position 1B and position t3, and the concentration is C1° at position t. Between position t3 and position tT, the distribution density C decreases linearly from position t3 to position tT.

In the example shown in FIG. 7, the distribution concentration C is at the position tB.
The concentration C1 is kept at a constant value up to position t4.
The distribution state is such that the concentration decreases in a linear function from the concentration C12 to the concentration C13 up to the 4th position tT.

In the example shown in FIG. 8, position tT (2
2) Until the distribution concentration C of germanium atoms reaches the concentration C4
From 4 onwards, it decreases in a linear manner, essentially reaching zero.

In FIG. 9, the distribution concentration C of germanium atoms at 1 from position tB to position #t5 is concentration c;
16″!, and the positions t5 and tT
An example in which the concentrations are set to constant values of c and 6 is shown between n and .

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is at the concentration c, 7 at the position tB, and from this concentration c, 7, it decreases slowly until it reaches the position t6. In the vicinity of the position, the Fi concentration is rapidly reduced to c, 8 at the position t6.

Between position t6 and position t7, the concentration decreases rapidly at first, then gradually decreases to a concentration of C19 at position t7, and then gradually decreases very slowly between position t7 and position t8. and reaches the concentration C2o at position &-18. Between position t8 and position LTO, the concentration C2o is reduced to substantially zero according to a curve shaped as shown in the figure.

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

The first layer region (G) constituting the photoreceptive layer constituting the photoconductive member in the present invention preferably contains germanium atoms at a relatively high concentration on the support side, as described above. It is desirable to have a localized region (A)'.

In the present invention, the localized @ area (4) is
To explain using the symbols shown in Figure 0, the interface position 1-rtB
It is more desirable that the distance be within 5μ.

In the present invention, the localized region α) is located at the interface position tB
It may be the entire layer region (LT) with 5μR1, or it may be a part of the layer region (LT).

Whether the localized region (g) is a part or all of the layer region (LT) is determined as appropriate depending on the characteristics required of the light-receiving layer to be formed.

The localized region (A) has a distribution state of germanium atoms contained therein in the layer thickness direction such that the maximum distribution concentration Cmax of germanium atoms is preferably 1000 atomic ppm or more with respect to silicon atoms. It is desirable that the layer be formed in such a manner that the distribution state is preferably 5000 atomic ppm JJ or more, and optimally I x 10 atomic ppm or more.

That is, in the present invention, the photoreceptive layer containing germanium atoms is formed such that the maximum value Cmax of the distribution concentration exists within 5μ in layer thickness from the support side (layer region 5μ thick from tB). It is preferable that the

In the present invention, the content of germanium atoms contained in the first layer region may be determined as desired according to the requirements (25) so as to effectively achieve the object of the present invention, but preferably 1 to 9.5 x 10 ato
micPPm% Preferably 100-8 X 10
atomic ppm% optimally 500~7 x 10
It is desirable to set it to atomic ppm.

In the present invention, the first layer region (S) and the second layer region (S)
The thickness of the photoconductive member is one of the important factors for effectively achieving the object of the present invention. Great care must be taken during autopsy.

In the present invention, the layer thickness TB of the first layer region) is preferably 30X to 50μ, more preferably 40X to 40μ.
, the optimum value is preferably 501 to 30μ.

Further, the layer thickness T of the second layer section (S) is preferably 0.5
~90μ, more preferably 1-80μ, optimally 2-5
It is desirable that it be 0μ.

The sum (TB + T) of the layer thickness TB of the first layer region (G) and the layer thickness T of the second layer region (S) is determined by the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. (26)
) is suitably determined as desired when designing the layers of the photoconductive member, based on the organic relationship between them.

In the photoconductive member of the present invention, the numerical range of (T, 10T) is preferably 1 to 100μ, more preferably 1 to 80μ, and most preferably 2 to 50μ. desirable.

In a highly preferred embodiment of the present invention, the above layer thickness TB and layer thickness T are preferably T, /T≦1
It is desirable that appropriate numerical values be selected for each so as to satisfy the following relationship.

In selecting the numerical values of layer thickness TB and layer thickness T in the above case, more preferably TB/T≦0,9, optimally T
, /T≦0.8. It is desirable that the values of the layer thickness TB and the layer thickness T be determined so as to satisfy the relationship: , /T≦0.8.

In the present invention, the content of germanium atoms contained in the first layer region is lXl0 atomic pp
m or more, the layer thickness TB of the first layer region O) can be made thinner, preferably 30 μυ
The thickness is preferably 25μ or less, most preferably 20μ or less.

In the present invention, if necessary, the first
Specific examples of the halogen atoms contained in the layer region (G) and the second layer region (S) include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It is possible to honor it as something.

In the present invention, in order to completely form the first layer region composed of a-8iGe (H+X), a vacuum deposition method using a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion silating method is used. done by. For example, a-8IGe(T(,X
) to form the first layer region (G)' consisting of
A raw material gas for supply, a raw material gas for Ge supply that can supply germanium atoms (Ge), and a raw material gas for introducing hydrogen atoms (@) or/and a raw material gas for introducing halogen atoms as necessary, The gas is introduced at a desired pressure into a chamber 9 < g whose interior can be reduced in pressure to cause a glow discharge in the chamber, and the gas contained in the chamber is placed on the surface of a predetermined support structure that has been previously installed at a predetermined position. a-8iGe (H
, X) may be formed. In addition, when forming by sputtering method, for example, in an atmosphere of an inert gas such as Ar or Ha, or a mixed gas containing these gases as a base, a tart composed of Sl or the tart? , ) and Gs.
A raw material gas for supplying Ge diluted with a diluent gas such as He or Ar is used as a mixture of hydrogen atoms and/or halogen atoms ( b) Introducing the introduction gas into the deposition chamber for dusting or tuttering to form a plasma atmosphere with the desired gas, and controlling the gas flow rate of the raw material gas for supplying Ge according to the desired rate of change curve. However, all you have to do is set the target mentioned above.

In the case of the ion blating method, for example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition date as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam method. (EB method) etc. (29) It can be carried out in the same manner as in the sputtering method, except that the flying evaporates are passed through the atmosphere surrounding the desired glass plasma.

As a substance that can be used as a source gas for separate supply used in the present invention, silicon hydride (silanes) in a gaseous state or capable of being gasified, such as 5IH4, Si2H6, 813H8゜5i4H,o, is effectively used. Among them, 5IH4 and Si2H6 are particularly preferred in terms of ease of handling during layer creation work, good SI supply efficiency, etc.

Examples of substances that can be used as raw materials for supplying Ge include GeH.
a r G112H6+ G(13H8* Ge4J(
1*Ge5H12*Ge6H, 41Go, H26T
Ge6H, 81G69H20 and other germanium hydrides in a gaseous state or that can be gasified can be effectively used. In particular, GaH + Ge H , Ge, H.B.
4 26 are listed as preferred.

(30) Many halogen compounds are effective as the raw material gas for introducing rodan atoms used in the present invention, such as gases such as halodane gas, halodanides, interhalogen compounds, and halodane-substituted silane derivatives. Preferable mention may be made of halogen compounds in the state or which can be gasified.

Furthermore, 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 used as an effective compound in the present invention.

Specifically, halodane compounds that can be suitably used in the present invention include fluorine, chlorine, bromine, and iodine.
'N gas, BrF, C1F, ClF5. BrF
5°BrF, , HF3. IP, , IC1, HB
Examples include compounds between /N C1)f.

Examples of silicon compounds containing halogen atoms, so-called halogen atom-substituted silane derivatives include, for example, Si
Preferred examples include halogenated silicon such as F4.812F6.5iC14 and B1Br4.

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 that can be supplied st '1 together with a raw material gas for supplying Ge is used. a-8I containing rodan atoms on a desired support without using silicon hydride gas
A first layer region ←) made of Ge can be formed.

When creating the entire first layer region (G) containing No-Rhodan atoms according to the glow discharge method, basically, for example, S1
Halogenated silicon as a raw material gas for supply, germanium hydride as a raw material gas for Ge supply, and Ar*H2C
Gases such as He, etc., are 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 remove these gases! A first layer area (
However, in order to more easily control the proportion of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is also mixed with these gases. A layer may be formed by doing so.

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

In order to introduce 7.rodan atoms into the layer formed in either the speckling method or the ion silating method, a gas of the above-mentioned)-rodan compound or a silicon compound containing the above-mentioned halogen atoms is deposited. It is sufficient to introduce the gas into the chamber to form a plasma atmosphere of the gas.

In the case of introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as B2, or the above-mentioned silanes and/or germanium hydride gases, is introduced into the deposition chamber for snow-tapping. What is necessary is to form a plasma atmosphere of the gases.

(33) In the present invention, the above-mentioned no-rodane compounds or silicon compounds containing no-rodane are effectively used as the raw material gas for introducing no-rodane atoms, but in addition, HF, HCt, Hydrogen halides such as HBr, HI, SiH2F2, 5iH2I2, 5iH2C
t2゜5IHC13, 5IH2Br2, 5iHBr3 and other norodane-substituted silicon hydrides, and GeHF3. GeB
2F2, Gea, F' *GeHCl5, GaH2
C22°GeHCt, GeHBr5. Ge)I2Br2
．． GeH, Br, GeHI, , GeB2I2゜GeH3
I % hydrogenated halodanide etc. containing hydrogen atoms as one of its constituent elements, GeF4*Ge
Cl4+G11Br4, GoI4+GeF2+
Gaseous or gasifiable substances such as germanium halides such as GeC12tGeBr2, GeI2, etc. may also be mentioned as useful starting materials for the formation of the first layer region.

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

(34) K for structurally introducing hydrogen atoms into the first layer region (G)
U, other than the above, H2, or SiH4, Si2H6゜8
1,H8,5i4H,. silicon hydride such as s GeH4, Ge 2H61Gll 5HB *G
@4H10+ Ge 5”12, G66H, 4°G
e 7Ht 6. Ge 6HI B +Ge, H2o
This can also be carried out by causing discharge to occur by coexisting germanium hydride such as the like and silicon or a silicon compound for supplying Si in the deposition chamber.

In a preferred example of the present invention, the amount of hydrogen atoms (b) contained in the first layer region (G) of the photoconductive member to be formed, or the amount of halogen atoms (3), or the amount of hydrogen atoms and halogen atoms The sum of the atoms (Hx) is preferably 0.01 to 4.
0 atomic%, more preferably 0.05-30
atomicl! , optimally 0.1-25 atoms
It is desirable to set it to c%.

Hydrogen atoms (b) or U contained in the first layer region (G)
In order to control the amount of halodane atoms flashed, for example, the support temperature or/and hydrogen atoms (b) or halogen atoms (
It is sufficient to control the amount of the starting material used to incorporate 3) into the deposition system, the discharge power, etc.

In the present invention, the second
To form the layer region (S), the starting material (1) for forming the first layer region (G), excluding the starting material that will become the raw material gas for supplying G, is used. It can be carried out using the [starting material (■) for forming the second layer region (S)] and following the same method and conditions as in the case of forming the first procedure M (G).

That is, in the present invention, in order to form the second layer region (S) composed of a-8i (H, This is accomplished by a vacuum deposition method that utilizes this phenomenon. For example, by glow discharge method, a-8i(H,X)
Basically, in order to form the second layer region (S) composed of 84
Along with the raw material gas for supply, hydrogen atoms (I(
) Introduction and/or halodane atoms (3) A raw material gas for introduction is introduced into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge in the deposition chamber, and A layer consisting of a-8i(H,X) may be formed on the supporting surface. In addition, when forming by a sputtering method, for example, when sputtering a target made of Si in an atmosphere of an inert gas such as Ar or Hs or a mixed gas based on these gases, A gas for introducing hydrogen atoms (or/and halodan atoms (3)) may be introduced into the deposition chamber for sputtering.

In the present invention, the amount of hydrogen atoms (6) or the amount of halogen atoms (3) contained in the second layer region (S) constituting the photoreceptive layer to be formed, or the amount of hydrogen atoms and halogen The sum of the amounts of atoms (H+X) is preferably 1 to 40 atoms
It is desirable that the number of IC chips is preferably 5 to 30 atomic chips.

A layer region containing the substance (C) by structurally introducing a substance (C) that completely controls the transmission properties, for example, group (I) atoms or group (I) atoms into the layer region constituting the photoreceptive layer. (PN)
In order to form a photoreceptive layer in a deposition chamber (37), a starting material for introducing a group (III) atom or a starting material for introducing a group (iii) atom is in a gaseous state during layer formation. It may be introduced together with other starting materials. It is desirable to use a starting material for the introduction of group (III) atoms that is gaseous at room temperature and pressure, or that can be easily gasified under layer-forming conditions. . Specifically, starting materials for introducing such group (I) atoms include 82H6, 84H, and the like for boron atom introduction. ,
B5H2r B5H1, r B6H1°.

Boron hydride such as B6H12, B6H14, BF, *
BCl3. Examples include boron halides such as BBr3. In addition, AtCt3°GaCl2. Ga(CH3
), , InCl2. TtCt3 etc. can also be mentioned.

In the present invention, effective starting materials for the introduction of Group Ⅰ atoms include PH3+P for the introduction of phosphorus atoms.
Hydrogen ratios such as 2H4 t PH4I , PF, , pF5
．． PCl,.

PCl5. PBr3. Plr5. Hatff of PI3 etc.
)1" phosphorus. In addition, AsHAsF
AsCt+Al1Br3+AlF3+31 451
5 8bH3, SbF5. SbF5, 5bCt, 5bCt
5. BiG,, BiCt, #old Br.

and the like can also be mentioned as effective starting materials for introducing Group Ⅰ atoms.

In the photoconductive member of the present invention, for the purpose of (1) increasing photosensitivity and (38) increasing dark resistance, and further improving the adhesion between the support and the photoreceptive layer, the photoreceptive layer is It contains carbon atoms. The carbon atoms contained in the photoreceptive layer may be uniformly contained in the entire layer region of the photoreceptive layer, or may be contained unevenly in only some layer regions of the photoreceptor layer. good.

In addition, even if the distribution concentration C (C) of carbon atoms is uniform in the thickness direction of the photoreceptive layer, the distribution state of carbon atoms is different from that of germanium atoms explained using FIGS. 2 to 1O. Like the distribution state, it may be non-uniform.

In other words, the distribution state of carbon atoms when the distribution concentration c (q) of carbon atoms is non-uniform in the layer thickness direction is shown in Figs.
It can be explained in the same way as the germanium atom using the O diagram.

In the present invention, when the main purpose of the layer region (C) containing carbon atoms provided in the photoreceptive layer is to improve photosensitivity and dark resistance, the entire layer region of the photoreceptive layer is If the main purpose is to strengthen the adhesion between the support and the photoreceptive layer, the photoreceptor is provided to occupy the end area of the photoreceptor layer on the side of the support.

In the former case, the content of carbon atoms contained in the layer region (C) is relatively low in order to maintain high photosensitivity, and in the latter case, to ensure 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,
Carbon atoms may be distributed at a relatively high concentration on the support side and at a relatively low concentration on the free surface side of the photoreceptive layer, or carbon atoms may be distributed in a surface layer region on the free surface side of the photoreceptive layer. It is sufficient to form a distribution state of carbon atoms in the layer region (Q) such that carbon atoms are not actively contained.

In the present invention, the content of carbon atoms contained in the layer region (C) provided in the light-receiving layer depends on the characteristics required for the layer region (C) itself or when the layer region (C) is a support. When provided in direct contact with the support, it can be appropriately selected depending on the organic relationship, such as the relationship with the properties at the contact interface with the support.

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

The amount of carbon atoms contained in the layer region (C) is determined as desired depending on the properties required of the photoconductive member to be formed, but is preferably 0.001 to 50 atoms.
mi@%, preferably 0.002 to 40 atoms1
The optimum content is desirably 0.003 to 30 atomlc%.

In the present invention, even if the layer region (Q occupies the entire area of the photoreceptive layer or does not occupy the entire area of the photoreceptive layer, the layer region (
When the ratio of the layer thickness 'rc of C) to the layer thickness T of the photoreceptive layer is sufficiently large, the upper limit of the content of carbon atoms contained in the layer region (C) should be sufficiently smaller than the above value. 41) It is desirable to be able to do so.

In the case of the present invention, if the ratio of the layer thickness TC of the layer region (C) to the layer thickness T of the photoreceptive layer is two-fifths or more, The upper limit of the amount of carbon atoms contained is preferably 30 atomle% or less, preferably 20 atomle% or less, and optimally 10 atomle% or less.
It is desirable that the content be atomic % or less.

In the present invention, the layer region (C) containing carbon atoms constituting the photoreceptive layer has a localized region CB) containing carbon atoms at a relatively high concentration on the support side as described above. In this case, the adhesion between the support and the light-receiving layer can be further improved.

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

(=12) Localized region (B) Whether to form part or all of the e-layer region (LT) is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed.

The localized region (B) has a distribution state of carbon atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration C (C) of carbon atoms is preferably 500 atomic ppm.
As described above, it is desirable to form layers so as to obtain a distribution state of preferably 800 atomic ppm or more, most preferably 1001000 atomic ppm or more.

That is, in the present invention, a layer region containing carbon atoms (@ is a layer thickness from the support side of 5 μm or less (5 μm from tn)
It is desirable to form the layer so that the maximum value Cmax of the distribution concentration C (C) exists in the thick layer region).

In the present invention, in order to provide a carbon atom-containing layer region (C) ffi in the photoreceptive layer, the starting material for introducing carbon atoms is added to the above-described starting material for forming the photoreceptive layer. It may be used together with the starting material and contained in the formed layer while controlling its amount.

When a glow discharge method is used to form the layer region (C) ffi, a starting material for introducing carbon atoms is added to one selected as desired from among the starting materials for forming the photoreceptive layer described above. As the starting material for introducing carbon atoms, most of the gaseous substances containing at least carbon atoms or gasified substances that can be gasified can be used.

For example, a raw material gas containing silicon atoms (St)e as constituent atoms, a raw material gas containing carbon atoms (C) as constituent atoms, and a raw material containing all constituent atoms as hydrogen atoms α◇ or halogen atoms (3) as necessary. or a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing carbon atoms (C) and hydrogen atoms (B) as constituent atoms. are mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (St) and silicon atoms (81) *carbon atoms (C
) and hydrogen atoms αη can be mixed and used.

Alternatively, a raw material gas containing carbon atoms (Q) may be mixed with a raw material gas containing silicon atoms (St) and hydrogen atoms.

Examples of those having C and H as constituent atoms include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like.

Specifically, methane (CH4) is a saturated hydrocarbon.
s-ethane (C2H6), pro-Al-(C5Ha), n-
Pig 7 (n-C4H1(1) e Pentane (C5H1
2) #Ethylene hydrocarbons include ethylene (C2H
4) e-propylene (CxH6)t-butene-1 (04H
B) y-butene-2 (C4H8) t-isobutylene (0
4H8) t-pentene (CsHlo) n-acetylene hydrocarbons include acetylene (02H2), p-methylacetylene (CsH4) -butyne (04H4), and the like.

In addition to these, alkyl silicides such as 5i(CH3)4ySI(C2H5)4 can be cited as raw material gases containing St, C, and H as constituent atoms.

In the present invention, the layer region (C) may further contain oxygen atoms and/or nitrogen atoms in addition to carbon atoms in order to further enhance the effects obtained by carbon atoms.

(45) As the raw material gas for introducing oxygen atoms into the layer region (C), for example, oxygen (02) t ozone (
03) *-Nitrogen oxide (NO) #Nitrogen dioxide (NO2)
-m=nitric oxide (N20) -nitrogen sesquioxide (N20s
) Trinitric oxide (N204) p Trinitric oxide (N
205), nitrogen trioxide (NO3) - silicon atom (S
t), oxygen atom (0), and hydrogen atom (b) as constituent atoms, for example, disiloxane (H3SiO8iH3) #
to! J'/oki? 7Q15810SiH20S
Examples include lower siloxanes such as IH3) and the like.

Nitrogen atoms (goods) for introducing nitrogen atoms into the layer region (C)
Starting materials that can be effectively used as raw material gases for introduction include those having N as a constituent atom, or N,! :H is a constituent atom, such as nitrogen (N2) e ammonia (
NH3), hydrazine (H2NNH2) #hydrogen azide (HN5), ammonium azide (NH4N s
), gaseous or gasifiable nitrogen, and nitrogen compounds such as nitrides and azides. In addition to this,
In addition to the introduction of nitrogen atom (b), no-rodan atom (3)
Nitrogen trifluoride, (FsN)
I can list rhodanide nitrogen compounds such as F 4N 2 (46).

To form a layer region containing carbon atoms (Q) by a sputtering method, a monocrystalline or polycrystalline 81 wafer, a C wafer, or a wafer containing a mixture of St and C is targeted. etc'f
This can be done by smearing in an atmosphere surrounded by various gases.

For example, if an S1 wafer is used as a tar ff,), the raw material gas for introducing carbon atoms and optionally hydrogen atoms and/or halodane atoms can be diluted with a diluting gas as necessary for sputtering. The St wafer may be sputtered by introducing the St wafer into a deposition chamber to form a gas plasma of these gases.

Alternatively, SI and C may be used as separate targets, or by using a mixed target of SI and C, in an atmosphere of dilution gas as a sputtering gas, or at least hydrogen atoms (RO) may be generated. ) or/and by sputtering in a gas atmosphere containing halodan atoms (t) as constituent atoms. As the raw material gas for introducing carbon atoms, the raw material gas for introducing carbon atoms in the raw material gas shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, when forming a photoreceptive layer, if a layer region (C'l 'z) containing carbon atoms is provided, the layer region (
By changing the distribution concentration C (C) of carbon atoms contained in Q in the layer thickness direction, a desired distribution state in the layer thickness direction (dspth
To form a layer region (C) with a profile), in the case of a glow discharge, a starting material gas for introducing carbon atoms whose distribution concentration CC) is to be changed is introduced, and its gas flow rate is adjusted to the desired rate of change curve. This is accomplished by introducing the material into the deposition chamber while changing it accordingly. 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; for example, a microcomputer or the like can be used to control the flow rate according to a rate-of-change curve designed in advance to obtain a desired content rate curve.

When forming the layer region (C) by a sputtering method, the desired distribution state (d) of carbon atoms in the layer thickness direction is obtained by changing the distribution concentration C (C) of carbon atoms in the layer thickness direction.
Firstly, as in the case of the glow discharge method, the starting material for introducing carbon atoms is used in a gaseous state, and the gas when introducing the nuclear gas into the deposition chamber is used. This is accomplished by appropriately changing the flow rate as desired.

Second, if a sputtering target is used, for example, a mixed target of Sl and C, the mixing ratio of Sl and C should be adjusted in advance in the layer thickness direction of the target. This is done by keeping things changing.

In the present invention, the amount of hydrogen atoms (6) or the amount of halogen atoms (3) contained in the second layer region (S) constituting the photoreceptive layer to be formed, or the amount of hydrogen atoms and/or % rod/sum of amounts of atoms (H+X) is preferably 1 to 40 atoms
ie% m, preferably 5 to 30 atomic%p, most preferably 5 to 25 atomic%.

(49) The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, fi, and t.

Cr, MotAu, Nb + Ta, V, TI
, Pt, Pd, or alloys thereof.

As the electrically insulating support, I-lyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, 7y! vinyl chloride, polyvinylidene chloride,
Films or sheets of synthetic resins such as polystyrene and polyamide, glass, ceramic, paper, etc. are usually used.

Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, N I Cr rA is applied to its surface.
LvCr 1Mo + Au l I r + Nb , T
a , vlT'i , p t gPd HIn 2oA
I 5n02, t'r.

Conductivity can be imparted by providing a thin film made of (In2O3+5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr, A/,
.

Ag, Pb, Zn, Nl, Au, Cr, Mo, Ir, N
b, a thin film of gold (50) such as 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. Gender is revealed. 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. For example, the photoconductive member 100 shown in FIG. 1 is used as an image forming member for electrophotography. If so, it is desirable to use an endless belt or a cylindrical shape for continuous high-speed copying. The thickness of the support is
It is determined as appropriate to form a photoconductive member as desired, but if flexibility is required as a photoconductive member, it is possible as long as the function as a support is fully exhibited. The limit is thinned out. 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.

Gas tanks 1102 to 1106 in the figure are sealed with raw material gas for forming the photoconductive member of the present invention. As an example, 1102 is a 5IH4 gas diluted with He ( Purity 99.999chi, below 81H4/
It is abbreviated as He. ) is NMB, 1103 is G diluted with He.
a H4 gas (purity 99.999%, hereinafter referred to as G eH4
/) It is abbreviated as ie. ) cylinder, 1104 is B2H6 gas diluted with He (purity 99.99%, hereinafter B2H4
74 (abbreviated as @) cylinder, 1105 is C2I (4if
1106 is a H2 gas (purity 99.999 cm) gas cylinder.K is a gas cylinder 41102-1 for flowing these gases into the reaction chamber 1101.
106 pulp 1122-1126, leak pulp 11
35 is closed, and the inflow pulp 1
112-1116. Outflow pulp 1117-1121. After confirming that the auxiliary pulps 1132 and 1133 are open, first open the main pulp 1134'i and open the reaction chamber 11.
01, and exhaust the inside of each gas pipe. Next, the vacuum gauge 113
When the reading of 6 is about 5 X 10-'torr IIC, auxiliary valve 1132.1133, outflow pulp】1
Close 17-1121.

Next, to give an example of forming a light-receiving layer on the cylindrical substrate 1137, gas bomb-'! S from 1102
iH4/He gas, Gax*umpe1103! J) GeH
4/He gas, gas 71=”n-21i 04’)
B 2Hb/l (e gas, gas cylinder 1105
Open the pulps 1122-1125, adjust the pressure of the outlet pressure gauges 1127-1130 to 1 kg/cIrL2, gradually open the inflow pulps 1112-1115, and let the 2H4 gas flow into the mass 70 (con)0-ra 1107-1110, respectively. let Continuing (53) Outflow pulp 1117-1120. Auxiliary valve 113
2 was gradually opened to allow each gas to flow into the reaction chamber 1]ol. At this time, S+H4/He gas flow rate and Ge■4/
FTe gas flow 1' and B2H6/He are
The outflow valve 11 is adjusted so that the ratio with the gas flow l is the desired value.
17 to 1120, and also adjust the opening of the main pulp 1134 while checking the reading of the vacuum gauge 1136 so that the pressure in the reaction chamber 11o1 becomes a desired value.

After confirming that the temperature of the substrate 137 is set to a temperature in the range of 50 to 400°C by the heating heater 1138, the power source 1140'fr is set to the desired power and the glow in the reaction chamber 1101 is set. Generate a discharge and at the same time G e H4/
The aperture of the pulp 1118 is gradually changed by adjusting the flow rate of He gas manually or using an external drive motor, etc., to control the distribution concentration of germanium atoms contained in the formed layer. In this way, Boron atoms (B) and carbon atoms (C) are contained on the substrate 1137, and according to the rate of change curve (54
) A distribution state of germanium atoms is formed.
Layer region (B, C) composed of 8iGe(H,X)
is formed to the desired layer thickness. At the stage when the layer regions (B, C) have been formed to the desired layer thickness, the outflow groove 1118.
1119 and 1120 and changing the discharge conditions as necessary. Atom (B), carbon atom (C
), to N') K is ^^ and no germanium atom (Ge) is contained, a-8l (H.

A layer region (S) composed of X) is formed, and the formation of the photoreceptive layer is completed.

During the formation of the above-mentioned photoreceptive layer, when a desired period of time has elapsed after the start of the layer formation, C2H4 on the B2H6,/He gas gas is stopped from flowing into the deposition chamber, thereby preventing boron atoms from being contained. The layer thicknesses of the layer region (B) containing carbon atoms and the layer region (C) containing carbon atoms can be arbitrarily controlled.

Also, C2 to the deposition chamber 1101 according to the desired rate of change curve.
By controlling the gas flow rate of H4 gas, the layer region (
The distribution of carbon atoms contained in C) can be formed as desired.

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 Using the manufacturing apparatus shown in FIG. 11, GeH4/He gas and SiH4/He gas and SiH4/
An electrophotographic image forming member was obtained by forming layers while changing the gas flow rate ratio of Hs gas with the elapsed time of layer formation.

The image forming member thus obtained was placed in a charging exposure experiment device.5. Corona charging was performed at OkV for 0.3 mec, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light amount of 2 Lux-seC was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the image forming member by cascading a charged developer (containing toner and carrier) over the surface of the image forming member. When the toner image on the image forming member was transferred onto a transfer paper by corona charging at OkV, a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained.

Example 2 (57) Using the manufacturing apparatus shown in FIG. 11, the gas b11. shown in FIG. 13 was produced under the conditions shown in Table 2. According to the rate of change curve of the quantity ratio, G eI (4/'fl e gas and S i H4,/'f
(The gas flow rate ratio of e gas was changed with 1-preparation elapsed time, and the other conditions were the same as in Example 1 to form layers to obtain an electrophotographic image forming member.

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

Example 3 Using the manufacturing apparatus shown in FIG. 11, Ge was produced according to the rate of change curve of the gas flow rate ratio shown in FIG.
H4/1 (gas flow rate ratio of e gas and S i H4//IIe gas was changed with gold layer formation elapsed time, and other conditions were the same as in Example 1 to form a layer 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 4 (58) Using the manufacturing apparatus shown in FIG. 11, AEU was produced according to the rate of change curve of the gas flow rate ratio shown in FIG.
The gas flow rate ratio of 41H gas and S i H47' to 'le gas was changed with the elapsed gold layer formation time, and the other conditions were the same as in Example 1 to form the layer, thereby producing an electrophotographic image forming member. Ta.

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 production equipment shown in Fig. 11, GeH
4/He was S and 81H4, and the gas flow rate ratio of E gas was changed with the elapsed layer formation time, and the other conditions were the same as in Example 1 to form a layer to obtain an image forming member for basket photography. .

The image forming member thus obtained was the same as Example 1.
When an image was formed on transfer paper under the desired conditions and procedure, a clear image quality was obtained after it was polished.

Example 6 Using the production apparatus shown in FIG. 11, GeH
4/r (gas flow control ratio of e gas and SiH4/Ha gas was changed with the elapsed time of gold layer creation; other conditions were as in Example 1.
Layer formation was carried out in the same manner as described above to obtain an electrophotographic image forming member.

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

Example 7 Using the manufacturing apparatus shown in FIG. 11, GeH
The gas flow rate ratio of 4/He gas and S1H4A (e gas was changed with the elapsed layer formation time, and the other conditions were as in Example 1.
Layer formation was carried out in the same manner as described above to obtain an electrophotographic image forming member.

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

Example 8 In Example 1, S was used instead of 5il (4/'Hs gas).
An electrophotographic image forming member was obtained by forming all layers under the same conditions as in Example 1, except that a 1□H6 e-gasu was used and the conditions shown in Example 8 were changed.

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

Example 9 In Example 1, 5iH474 (Si instead of e gas)
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, except that F4/) (・gas was used and the conditions shown in Table 9 were used.

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

Example 10 In Example 1, SiH4/'T (instead of e gas (
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, except that 5su4/)Is + 81F4e) gas was used and the conditions shown in Table 10 were used.

(61) When an image was formed on a transfer paper using the thus prepared image forming member under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 11 A cylindrical At
On the substrate, under the conditions shown in Table 11 and according to the rate of change curve of the gas flow rate ratio shown in FIG.
An electrophotographic image forming member was obtained by forming layers by changing the gas flow rate ratio of H4,/f (e gas) with the elapsed time of layer formation.

The image forming member obtained in this way is used as a band! Install it in the exposure experiment equipment 5. 0.3111 (Okv) (corona charging was performed for 1 hour, and a light image was immediately irradiated. A tungsten Lanzo light source was used for the light image, and a light amount of 2 Lux IC was irradiated through a transmission type test chart.

Immediately thereafter, by cascading the charged developer (including toner and carrier) over the entire surface of the image forming member,
A good toner image was obtained on the imaging member surface. Q5. When transferred onto transfer paper using Okv's Corona Fi Electron, a clear, high-density image with excellent resolution (62) and good gradation reproducibility was obtained.

Example 12 In Example 11, when creating the first layer, the flow rate of B2H6 to (5sH4 + GeH4) was changed, and when creating the second layer, the flow rate of B2H6 to SiH4 was changed as shown in Table 12. Each of the electrophotographic image forming members (samples j'Fx 1201 to 1
208)'! il-I made a slave.

Using the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 11, and the results shown in Table 12 were obtained.

Example 13 An electrophotographic image forming member was prepared in the same manner as in Examples 1 to 10, except that the conditions for creating the second layer were as shown in Tables 13 and 14. each (sample A
1301-1310.1401-1410) were created.

For each of the image forming members thus obtained, Example 1
When an image was formed on a transfer paper under the same conditions and procedures as above, the results shown in Tables 13A and 14A were obtained.

Example 14 A toner image similar to Example 1 except that an 810 nm GaAs semiconductor radar (10 mW) was used as the light source instead of the tungsten lamp to form an electrostatic image. When the image quality of the toner transfer image was completely evaluated for an electrophotographic image forming member prepared under the same forming conditions as in Example 1, it was found that it was a clear, high-quality image with excellent resolution and good gradation reproducibility. Image obtained.

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

Substrate temperature: germanium atom (Go) containing layer...
・ Approximately 200℃ germanium atom (Go)-free layer...
・About 250℃ Discharge frequency: 13.56 MHz Reaction chamber pressure during reaction: 0.3 Torr

[Brief explanation of the drawing]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are illustrations for explaining the distribution state of germanium atoms in the photoreceptive layer, respectively. figure,
FIG. 11 is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS. 12 to 18 are explanatory diagrams showing the rate of change curves of the gas flow ratio in the embodiments of the present invention, respectively. 100...Photoconductive member' 1.01...Support 10
2... Photoreceptive layer 103... First layer region (G) 1
04...Second layer region (S) (73) Figure 12 Gas fL power supply flow rate, this. 17 rods

Claims (6)

[Claims] (1) A support for a photoconductive member, a first layer region disposed on the support and made of an amorphous material containing silicon atoms and germanium atoms, and an amorphous material containing silicon atoms. a second layer region made of a material and exhibiting photoconductivity; and a photoreceptive layer having a layered structure provided in order from the side of the support; The distribution state is non-uniform in the layer thickness direction, the first layer region contains a substance controlling conductivity, and the photoreceptive layer contains carbon atoms. A photoconductive member. (2) The photoconductive part according to claim 1, wherein at least one of the first layer region and the second layer region contains hydrogen atoms. (3) The photoconductive member according to claim 1 or 2, wherein at least one of the first layer region and the second layer region contains a halogen atom. (4) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer region is such that more germanium atoms are distributed toward the support side. (5) The photoconductive member according to claim 1, wherein the substance that controls conductivity is an atom belonging to Group Ⅰ of the periodic table. (6) The photoconductive member according to claim 1, wherein the substance that controls conductivity is an atom belonging to Group V of the periodic table.