JPH0785171B2 - Photoreceptive member having ultra-thin layered structure - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to light (here, light in a broad sense, which means ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.). BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreceptive member which is sensitive to electromagnetic waves, particularly a photoreceptive member having an improved charge injection blocking layer and a photosensitive layer, and a deposited film forming apparatus by a plasma CVD method suitable for manufacturing the photoreceptive member.

[Description of Prior Art]

As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an image forming member for electrophotography in an image forming field, or a document reading device, it has high sensitivity and an SN ratio (photocurrent (Ip) / dark current (Id)). ], Having an absorption spectrum characteristic adapted to the spectrum characteristic of an electromagnetic wave for illumination, having a fast photoresponsiveness and having a desired dark resistance value, being non-polluting to the human body during use, Solid-state image pickup devices are required to have characteristics such that afterimages can be easily processed within a predetermined time, etc. In particular, electrophotographic image formation incorporated in an electrophotographic device used as an office machine in an office. In the case of a member, the pollution-free property at the time of use is an important point.

Amorphous assilicon (hereinafter referred to as a-Si) is a light-receiving material that has recently received attention based on such a point. For example, German Patent Publication Nos. 2746967 and 2855718 disclose the same. The use as an electrophotographic image forming member and the application to German Patent Publication No. 2933411 describe a photoelectric conversion reader.

However, the conventional light-receiving member having a light-receiving layer composed of a-Si has the following problems in terms of electrical resistance, darkness, photosensitivity, photoresponsiveness, and other electrical, optical, and photoconductive characteristics, and operating environment characteristics. ,
Furthermore, in terms of stability over time and durability, each has been individually improved in characteristics, but in reality there is a lot of room for further improvement in measuring overall characteristics. is there.

For example, when applied to an image forming member for electrophotography, a-Si
In the photosensitive layer composed of the material, hydrogen atoms or halogen atoms such as fluorine atoms and chlorine atoms in order to improve the electrical and photoconductive properties, and p-type impurities for controlling the electrical conductivity type. A group III atom such as a boron atom or n
Group V atoms such as phosphorus atoms, which are type impurities, or other atoms have been contained for the purpose of improving other characteristics. Depending on how these constituent atoms are contained, It is often observed that a residual potential remains during use, and if this type of photoreceptor member is used repeatedly for a long time, fatigue will accumulate due to repeated use, resulting in a so-called ghost phenomenon that causes an afterimage. There are few inconveniences.

In addition, in order to shift the maximum absorption of photosensitivity to the short wavelength side or the long wavelength side by adjusting the bandgap of a-Si,
It is also known to contain a so-called band gap adjusting agent.

For example, when at least one selected from oxygen atom (O), carbon atom (C) and nitrogen atom (N) is contained in the a-Si material, the band gap is expanded and the maximum absorption of photosensitivity is obtained. Is known to shift to the short wavelength side. Also, germanium atom (G
When at least one of e) or tin atom (Sn) is contained, the bandgap is reduced and the maximum absorption of photosensitivity shifts to the long wavelength side.

However, on the other hand, when such a band gap adjusting agent is contained, there is a problem in that a defect level is created in the forbidden band, and the occurrence of this defect level is caused by the above-mentioned III group addition in the a-Si material. There is a problem that it hinders the doping effect of group atoms or group V atoms, making satisfactory doping of these atoms difficult.

In order to solve this problem, it has been attempted to increase the amount of the group III atom or the group V atom to be supplied for the doping treatment into the a-Si material. Since the total amount of those atoms that do not act as a dopant does not act as a dopant, unless they constantly monitor and adjust the supply amount of those atoms to the reaction system, they will cause the generation of defect levels. Exists.

As described above, in order to control the bandgap of the photosensitive layer composed of a-Si, it is necessary to add a bandgap adjusting agent so as not to cause the generation of defect levels. In order to efficiently control the band gap, it is very difficult to adjust the supply amounts of various atoms contained in a-Si as desired, and it is important to freely control the band gap. It is an issue.

Furthermore, when the photosensitive layer composed of a-Si is subjected to a charging treatment, the purpose is to prevent electrons from being injected into the photosensitive layer from the support side, and to prevent charge injection between the support and the photosensitive layer. It is known to provide layers. Then, regarding the charge injection blocking layer, a-Si, polycrystalline silicon (hereinafter, referred to as “poly
-Si ") or a so-called non-single crystal silicon containing both (hereinafter referred to as" Mon-Si "(note that what is commonly referred to as microcrystalline silicon is classified into a-Si).
It has been proposed to use doped p-type impurities or n-type impurities.

However, the Non-Si film doped with p-type impurities or n-type impurities is functionally satisfactory, but has a problem that the adhesion to the support is poor and the film is easily peeled off from the support. The problem is even more pronounced when the film is poly-Si.

As a measure to solve this problem, it has been proposed that the Non-Si film doped with a p-type impurity or an n-type impurity further contains one or more of oxygen atom, carbon atom and nitrogen atom. .

However, there are still problems with this method. That is, according to this method, the effect of improving the adhesion between the support and the film and expanding the band gap of the film can be expected, but a defect level is created in the forbidden band. There's a problem. The occurrence of this defect level hinders the doping of the p-type impurity or the n-type impurity into the Non-Si film to form the p-type semiconductor or the n-type semiconductor, so that satisfactory doping of these impurities becomes difficult. There is a problem.

In order to solve this problem, the amount of p-type impurities or n-type impurities supplied to the Non-Si film for the doping process is increased. However, even in this method, since all of the supplied impurities do not act as dopants, unless the supply of these impurities to the reaction system is constantly monitored and adjusted,
There is a problem that it may lead to the occurrence of defect levels.

Further, the above-mentioned kind of light receiving member has a so-called multi-layered structure in any case, and its production is generally performed by plasma CVD.
A deposition film forming apparatus by the method is optimally adopted. In manufacturing such a desired light receiving member, generally, optimum film forming conditions are set for each layer, and the layer forming operation is separately performed according to the conditions. Therefore, according to the apparatus by the conventional plasma CVD method, the solution of the problems relating to the above-mentioned photosensitive layer and charge injection blocking layer is set by the operation of the formation process of the layer, and the conditions of the problem solution are set. Therefore, since it is performed by performing the film forming operation of the layer, the operation of the subsequent layer formation is further complicated, and the device itself is improved when the light receiving member having a desired multilayer structure is efficiently mass-produced. Is required.

[Object of the Invention]

INDUSTRIAL APPLICABILITY The present invention solves the above-mentioned problems related to the photosensitive layer and the charge injection blocking layer in the constituent layers and has an improved multilayer structure which achieves a desired function, and is used for an electrophotographic photoreceptor or the like, The main object is to provide a light receiving member and a device suitable for efficient mass production.

That is, the main object of the present invention is to obtain p without the defect level.
It is an object of the present invention to provide a light receiving member which is doped with a type impurity or an n type impurity in a desired state and has a desired band gap.

Another object of the present invention is to provide a light-receiving member having an improved charge injection blocking layer which has no defect level and is doped with p-type impurities or n-type impurities in a desired state. is there.

Another object of the present invention is to provide an electrophotographic light-receiving member for electrophotography, which has almost no problem of residual potential and no problem of image defect and has improved electrical withstand voltage.

[Constitution and effect of the invention]

The present inventors have overcome the above-mentioned problems with respect to a light-receiving member and a manufacturing apparatus for the same, which are used in a photoconductor for electrophotography having at least a photosensitive layer composed of s-Si and a charge injection blocking layer in the related art. As a result of earnest research to achieve the above-mentioned purpose, silicon atoms with a layer thickness of 10 Å ~ 150 Å, 30ato
A first layer composed of a non-single crystalline material containing an atom (a substance that controls conductivity) belonging to Group III or Group V of the periodic table with a concentration of mic ppm to 5 × 10 ⁴ atomic ppm And a second layer composed of a non-single-crystal material containing a silicon atom and at least one selected from an oxygen atom, a carbon atom and a nitrogen atom with a layer thickness of 10 Å to 150 Å and alternately laminated multiple times. And the charge injection blocking layer with a thickness of 10Å ~ 15
At 0Å silicon atom and 1 × 10 ^-3 atomic ppm to 1 × 10 ³ atom
A third layer composed of an amorphous material containing an atom belonging to Group III or Group V of the periodic table with a concentration of ic ppm, and a silicon atom, an oxygen atom, and a carbon with a layer thickness of 10Å to 150Å A photoreceptive member having a photosensitive layer formed in this order by alternately laminating a fourth layer composed of an amorphous material containing at least one selected from atoms and nitrogen atoms; By doing so, it has been found that the above-mentioned problems of the photosensitive layer and the charge injection blocking layer can be solved, the band gap can be easily controlled, and a light receiving member having an excellent charge injection blocking effect can be obtained. Got And then
Based on the above-mentioned findings using a conventional deposited film forming apparatus by the plasma CVD method, at least two kinds of ultra-thin films of at least some of the constituent atoms of the photosensitive layer and the charge injection blocking layer are made to be laminated a number of times. It has been found that there is a problem to be overcome in forming the photosensitive layer and the charge injection blocking layer.

That is, in the conventional apparatus using the plasma CVD method, since the number of film forming chambers in the reaction container is essentially one, the source gas to be introduced into the film forming chamber is replaced with a predetermined gas each time each ultrathin film is formed. The point is that the layer (film) to be formed is an ultra-thin film in any case, and since the layer thickness is extremely thin, the timing and operation of exchanging the source gas are important. Can't be achieved easily here. That is, not only is the type of raw material gas different for each layer, but the flow rate is also different, and therefore the type and flow rate of the raw material gas must be changed frequently, but this is difficult to cope with with conventional equipment. Is.

Another problem with the conventional plasma CVD apparatus is that when raw material gases of different compositions were alternately introduced into the film forming chamber, unnecessary gas was not allowed to remain in the film forming chamber. Therefore, it is necessary to completely exhaust the residual gas after each film-forming operation, which consumes extra time and cannot achieve the desired film-forming efficiency, while at the same time adversely affecting the quality of the film produced. There is a problem that occurs.

The present inventors have obtained the following findings as a result of repeated research to solve these problems. That is, the reaction vessel of the deposited film forming apparatus by the plasma CVD method is partitioned by a partition plate to form a plurality of film forming chambers, and a film forming raw material gas is introduced into each film forming chamber to form each film forming chamber. A plasma was generated in the film chamber, the cylindrical substrate was rotated against it, and the surface of the cylindrical substrate was passed through each film forming chamber, that is, the plasma region. Can be efficiently performed, and a light receiving member having a desired photosensitive layer and a charge injection blocking layer can be efficiently produced. According to this device, the above-mentioned problems as in the conventional device are not present at all, and the light receiving member is In the film-forming process, it has been found that the film-forming process can be continuously operated without interrupting the film-forming process for the purpose of gas exchange, exhaustion, etc. in the conventional apparatus, and further, mass production thereof is possible.

The present invention has been completed based on the above-mentioned experimentally confirmed knowledge, and a photosensitive layer having a specific structure that stably adheres to a support and does not peel off and has a desired function stably. Mass production of a light receiving member that has a charge injection blocking layer and exhibits stable and desired characteristics as a whole, and the light receiving member that does not require an opportunity to interrupt the film forming operation for source gas exchange, exhaust, etc. The device is provided.

The light receiving member provided by the present invention comprises a support, a layer of silicon atoms having a layer thickness of 10Å to 150Å, and 30 atomic ppm to 5 × 1.
A first layer made of an amorphous material containing an atom belonging to Group III or Group V of the periodic table with a concentration of 0 ⁴ atomic ppm, a silicon atom with a layer thickness of 10Å to 150Å, and an oxygen atom ,
A charge injection blocking layer formed by alternately laminating a second layer composed of a non-single crystal containing at least one selected from carbon atoms and nitrogen atoms, and a layer thickness of 10Å
~ 150Å with silicon atom and 1 × 10 ^-3 atomic ppm〜1 × 10 ³
A third layer composed of an amorphous material containing atoms belonging to Group III or Group V of the periodic table with a concentration of atomic ppm, and silicon atoms, oxygen atoms, and carbon atoms with a layer thickness of 10Å to 150Å And a fourth layer composed of an amorphous material containing at least one selected from nitrogen atoms, alternately stacked a plurality of times, in this order. .

Hereinafter, the light receiving member of the present invention will be described with reference to the drawings. In the following, the case where the light receiving member of the present invention is for electrophotography will be described, but the present invention is not limited to this.

FIGS. 1 (A) to 1 (C) are diagrams schematically showing typical examples of the layer constitution of the light receiving member for electrophotography of the present invention.

In the example shown in FIG. 1 (A), a charge injection blocking layer 102, a photosensitive layer 103 and a surface layer 104 are provided in this order on a support 101.

The support 101 used in the present invention may be either conductive or electrically insulating. As the conductive support, for example, NiCr, stainless steel, Al, Cr, Mo,
Examples include metals such as Au, Nb, Ta, V, Ti, Pt, and Pb, and alloys thereof.

Examples of the electrically insulating support include a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyamide, glass, ceramics, paper and the like. It is preferable that at least one surface of these electrically insulating supports is subjected to a conductive treatment, and a light receiving layer is provided on the surface side subjected to the conductive treatment.

For example, if it is glass, NiCr, Al, Cr,
Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , IT
Conductivity is imparted by providing a thin film made of O (In ₂ O ₃ + SnO ₂ ) or the like, or synthetic resin film such as polyester film is NiCr, Al, Ag, Pb, Zn, Ni, A
A thin film of a metal such as u, Cr, Mo, Ir, Nb, Ta, V, Tl or Pt is provided on the surface by vacuum vapor deposition, electron beam vapor deposition, sputtering or the like, or the surface is laminated with the metal, It imparts conductivity to the surface. The shape of the support is an endless belt or a cylinder, and the thickness thereof is appropriately determined so that a desired light receiving member can be formed. However, when flexibility is required as the light receiving member, It can be made as thin as possible within the range where the function as a support is sufficiently exhibited. However, in terms of mechanical strength and the like in terms of manufacturing and handling of the support, it is usually 10 μm or more.

The photosensitive layer 103 of the light receiving member of the present invention is an amorphous material having a silicon atom as a base, particularly an amorphous material having a silicon atom as a base and containing at least either a hydrogen atom (H) or a halogen atom (X). A relatively small amount of the material, so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon (hereinafter referred to as “a-Si (H, X)” as a generic name for these). An ultra-thin film made of an amorphous material containing a substance that controls the conductivity of a-Si (H,
X) is a layer having an ultrathin film laminated structure in which an ultrathin film made of an amorphous material containing at least one selected from oxygen atom, carbon atom and nitrogen atom is alternately laminated a plurality of times. It is desirable that the ultrathin film has a thickness of 10 to 150Å, preferably 10 to 100Å, and optimally 15 to 80Å.

The halogen atom contained in the photosensitive layer 103,
Specific examples thereof include fluorine, chlorine, bromine and iodine, and particularly preferable examples include fluorine and chlorine. And hydrogen atoms (H) contained in the photosensitive layer 103
Or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H + X) is preferably 1 to 40.
Atomic%, more preferably 5 to 30 atomic% is desirable.

Further, as the substance contained in the photosensitive layer 103 for controlling the conductivity, a p-type impurity or an n-type impurity in the so-called semiconductor field is used. As the p-type impurity, an atom belonging to Group III of the periodic table (hereinafter simply referred to as “Group III atom”), specifically, B (boron), Al (aluminum), Ga (gallium) ), In (Indium), Tl
(Thallium) and the like, but preferable ones are B and Ga.
Is. Further, as the n-type impurities, atoms belonging to Group V of the periodic table (hereinafter simply referred to as “Group V atoms”), specifically, P (phosphorus), As (arsenic), Sb ( Antimony), Bi (bismuth) and the like can be mentioned, but P and As are particularly preferable. The amount of the group III atom or the group V atom contained in the photosensitive layer 102 is from 1 × 10 ⁻³ to
1 × 10 ³ atomic ppm, preferably 5 × 10 ^{−2 to} 5 × 10 ² atom
ic ppm, optimally 1 × 10 ⁻¹ to 2 × 10 ² atomic ppm is desirable.

Further, the amount of oxygen atoms, carbon atoms and nitrogen atoms contained in the photosensitive layer 102 is 0.001 to 50 atomic%, preferably 0.0
02-40 atomic%, optimally 0.003-30 atomic% is desirable.

In the light receiving member of the present invention, the layer thickness of the photosensitive layer is
It is one of the important factors for efficiently achieving the object of the present invention, and it is necessary to take great care in designing the light receiving member so that the light receiving member is provided with desired characteristics. , Usually 3 to 100μ, but preferably 5 to 80
μ, optimally 7 to 50 μ.

The light-receiving member of the present invention has a charge injection blocking layer 102 between the support 101 and the photosensitive layer 103 described above, and the charge injection blocking layer 102 contains a relatively large amount of the layer III atoms. Alternatively, Non-Si (H, X) containing a group V atom [hereinafter, Non-SiM (H, X
X) ”. However, M represents a Group III atom or a Group V atom. ] Non-Si (H, X) [hereinafter, "Non-Si (O, C, N) (hereinafter, referred to as" Non-Si (O, C, N) ( H,
X) ”. ] Having an ultrathin film laminated structure in which the ultrathin film constituted by the above is alternately laminated a plurality of times, and the film thickness of each ultrathin film is 10 to 150Å, preferably 10 to 100
Å, optimally 15 to 80Å.

The group III atom or the group V atom contained in the charge injection blocking layer 102 has the same polarity or the opposite polarity to that contained in the photosensitive layer 103 described above. Group III atoms or V contained in the blocking layer 102
The amount of group atoms must be relatively high,
× 10 ⁴ atomic ppm, preferably 50 to 1 × 10 ⁴ atomic ppm,
Optimally, 1 × 10 ^{2 to} 5 × 10 ³ atomic ppm is desirable.

The amount of at least one selected from oxygen atom, carbon atom and nitrogen atom contained in the charge injection blocking layer 102 is 0.001 to 50 atomic%, preferably 0.002 to 40 atomic.
%, Optimally 0.003 to 30 atomic% is desirable.

The layer thickness of the charge injection blocking layer 102 of the light receiving member of the present invention is 300.
Å ~ 10μ, preferably 400 Å ~ 8μ, optimally 500 Å ~ 5
It is desirable to set to μ.

By the way, the charge injection blocking layer in the light receiving member of the present invention
102 is a Non-SiM having an ultra thin film laminated structure as described above.
(O, C, N) (H, X), that is, a-SiM (O, C, N) (H, X) or p
It is composed of oly-SiM (O, C, N) (H, X),
That is, the non-single-crystal material is composed of an amorphous material, a polycrystalline material, or a mixture of both (microcrystalline material is included in the amorphous material), but the latter poly-SiM (O, C, N) (H,
The layer composed of X) is appropriately formed by various methods, for example, the methods described below.

One of the methods is to raise the substrate temperature to a high temperature, specifically 400 to 4
This is a method of setting a temperature of 50 ° C. and depositing a film on the substrate by a plasma CVD method.

Another method is to first form an amorphous film on the surface of the substrate, that is, plasma C on the substrate whose substrate temperature is about 250 ° C.
In this method, a film is formed by the VD method, and the amorphous film is subjected to an annealing treatment to form poly. The annealing treatment is carried out by heating the substrate to 400 to 450 ° C. for about 20 minutes or by irradiating it with laser light for about 20 minutes.

On the photosensitive layer 103 in the light receiving member of the present invention, the surface layer 1
04 is provided. The surface layer contains at least one selected from oxygen atom, carbon atom and nitrogen atom.
-Si (H, X) [hereinafter referred to as "a-Si (O, C, N) (H, X)". ] Or an amorphous material having a nitrogen atom and a boron atom as a matrix [hereinafter referred to as "a-BN (H, X)". ] Or an amorphous material having a carbon atom as a matrix [hereinafter, referred to as "a
-C (H, X) ". ] Is composed.

The purpose of providing the surface layer 104 on the light receiving member of the present invention is to improve moisture resistance, continuous repeated use characteristics, electrical breakdown voltage, use environment characteristics, durability and the like.

In particular, when a layer made of a-Si (O, C, N) (H, X) is used as the surface layer, each of the amorphous materials constituting the surface layer and the photosensitive layer has a common silicon atom. Since it has the constituent atoms described above, chemical stability can be secured at the interface between the surface layer 104 and the photosensitive layer 103.

When the surface layer composed of such a-Si (O, C, N) (H, X) is used, the amount of oxygen atoms, carbon atoms or nitrogen atoms contained in the surface layer is increased, and Although various properties are improved, when the amount is too large, the layer quality is deteriorated and the electrical and mechanical properties are also deteriorated. Therefore, the amount of these atoms is 0.001 to 90 atomic%, preferably 1 to 90 atomic
%, Optimally 10 to 80 atomic% is desirable.

Further, in the light receiving member of the present invention, the layer thickness of the surface layer 104 is also one of the important factors for efficiently achieving the object of the present invention, and may be appropriately determined according to the desired object. However, depending on the amount of constituent atoms contained in the surface layer or the properties required for the surface layer, it is necessary to determine the mutual and organic relationships. In addition, it is necessary to take into consideration the economical efficiency in consideration of productivity and mass productivity. Therefore, the layer thickness of the surface layer of the light receiving member of the present invention is 3
The density is set to x10 ^{-3 to} 30 µ, more preferably 4 x 10 ^{-3 to} 20 µ, and particularly preferably 5 x 10 ^{-3 to} 10 µ.

In the example shown in FIG. 1 (B), the charge injection blocking layer 102 shown in FIG. 1 (A) described above further contains at least one of germanium atom and tin atom.
This is an example in which 102 also has a function as a long-wavelength absorption layer. That is, the layer 105 provided between the support 101 and the photosensitive layer 103 includes a p-type impurity or an n-type impurity, and at least one selected from oxygen atom, carbon atom and nitrogen atom, and further germanium atom or tin. Non-Si (H, X) containing at least one of the atoms [hereinafter referred to as "Non-Si (Ge,
Sn) M (O, C, N) (H, X) ". ] Is composed. By containing a germanium atom or a tin atom in the layer 105, when a long-wavelength light source such as a semiconductor laser is used, light on the long-wavelength side, which is hardly absorbed in the photosensitive layer 103, is contained in the layer 105. To allow for substantially complete absorption, which results in support 10
1 It is possible to prevent interference caused by reflection from the surface.

In order to obtain a charge injection blocking layer having an ultra-thin film laminated structure containing at least one of germanium atom and tin atom, Non-Si containing p-type impurities or n-type impurities is used.
An ultra-thin film structure layer composed of (H, X), and oxygen atoms,
At least one of germanium atom or tin atom should be contained in either or both of the ultra-thin film structure layers composed of Non-Si (H, X) containing at least one selected from carbon atom and nitrogen atom. The layers may be alternately laminated many times.

The amount of germanium atom or tin atom contained to absorb light on the long wavelength side is 1 to 9.5 × 10 ⁵ atomic ppm,
Preferably 1 × 10 ^{2 to} 9 × 10 ⁵ atomic ppm, optimally 5 ×
It is desirable to set 10 ² to 8 × 10 ⁵ atomic ppm.

In the example shown in FIG. 1 (B), the photosensitive layer 103 and the surface layer 1
04 is the same as that in FIG. 1 (A) described above.

Finally, in the example shown in FIG. 1 (C), a layer 106 having a long wavelength absorption function and a layer 102 having a charge injection blocking function are provided as separate layers on a support 101 in this order, and The photosensitive layer 103 and the surface layer 104 are provided on the top. In the example, the layer 106 is made of Non-Si (H, X) [hereinafter, referred to as “Non
-Si (Ge, Sn) (H, X). ] And other layers, that is, the charge injection blocking layer 102, the photosensitive layer 103, and the surface layer 104 are the same as those shown in FIG. 1 (A).

In the light-receiving member of the present invention having a layer structure that becomes hard, the photosensitive layer comprises an ultrathin film composed of a-Si (H, X) containing a relatively small amount of group III atom or group V atom; −Si (O, C, N)
Since ultra-thin films composed of (H, X) are alternately laminated multiple times, the problematic defect level occurs in the case of a conventional single-layered photosensitive layer. Satisfactory control of the bandgear can be efficiently achieved without any. Furthermore, as the charge injection blocking layer, an ultra-thin film composed of Non-Si (H, X) containing a relatively large amount of Group III atoms or Group V atoms, and a-Si (O, C,
N) (H, X) ultra-thin films are alternately stacked a plurality of times, so that a relatively large amount of conventional group III and group V atoms and oxygen Atoms, carbon atoms and at least one selected from nitrogen atoms are contained at the same time, and the disadvantages such as the decrease in doping effect and the occurrence of defect levels, which occur in the charge injection blocking layer having a single-layer structure, are all solved, which is excellent. It is also possible to obtain a light receiving member that exhibits the effect of preventing charge injection.

Next, a deposition film forming apparatus by the plasma CVD method, which is suitable for manufacturing the light receiving member having the ultrathin film laminated structure layer of the present invention, will be described in detail with reference to the drawings, but the present invention is not limited thereto. Not something.

FIG. 2 is a diagram schematically showing a typical example of a deposited film forming apparatus by the plasma CVD method of the present invention. FIG. 2 (A) is a schematic vertical sectional view of the entire apparatus, and FIG. 2 (B) is 1 is a schematic cross-sectional view of the entire device.

In FIG. 2, 201 is an aluminum support drum for forming an amorphous film having silicon atoms as a base material on its surface. (Hereinafter, simply referred to as “drum”.) The drum 201 is configured to rotate about a central axis by a rotation drive mechanism 202, and a heating heater 203 is arranged inside the drum 201. The heater for heating 2
03 is used to heat the drum to a predetermined temperature before film formation, to hold the drum at a predetermined temperature during film formation, or to perform an annealing treatment after film formation.

Reference numeral 204 denotes a cathode electrode, which forms a counter electrode coaxial with the drum 201 which is an anode electrode. Reference numeral 205 denotes a high frequency power supply, which supplies high frequency power to the cathode electrode 204 to cause discharge with the grounded anode electrode drum 201. 206 and 207 are insulators that insulate the anode electrode 201 and the cathode electrode 204.

The airtight reaction chamber formed by the cathode electrode 204 and the insulators 206, 207 is exhausted by the exhaust device 208 via the exhaust valves 209, 210. Reference numerals 211 and 212 are vacuum gauges provided immediately before the exhaust valves 209 and 210.

The discharge space between the drum 201 and the cathode electrode 204 is composed of two partition plates 213, 21 made of an insulating material that does not allow the raw material gas to pass therethrough.
It is divided into two areas by 4 and the partition plates 213, 2
14 is in contact with the cathode electrode 204, but 0 with the drum 201.
It keeps a slight distance of 5 to several mm.

In the two regions formed by the partition plates 213, 214, a raw material gas supply pipe 215, which has a large number of raw material gas ejection holes, is provided.
The raw material gas is supplied by the 216,
The other ends of the source gas supply pipes 215 and 216 are connected to a source gas cylinder 217.
~ 225,227 ~ 235 is connected. Raw material gas cylinder 217-2
25,227 to 235 are sealed with raw material gases, for example, gas cylinders 217 and 227 have SiH ₄ gas and gas cylinders 218 and 228, respectively.
H ₂ gas, gas cylinders 219,229 CH ₄ gas, gas cylinders 220,230 GeH ₄ gas, gas cylinders 221,231 N ₂ cylinders, gas cylinders 222,232 NO gas, gas cylinders 223,233
Is sealed with B ₂ H ₆ gas, gas cylinders 224, 234 with PH ₃ gas, and gas cylinders 225, 235 with SiF ₄ gas. Gas cylinders 217-225, 227-235 have valves 217a-225a, 22 respectively.
7a ~ 235a are provided, gas pressure legule letter 217b
〜225b, 227b〜235b, Inflow valve 217c〜225c, 227c〜235
The raw material gas is supplied to the raw material gas supply pipes 215 and 216 via the mass flow controllers 217d to 225d and 227d to 235d and the outflow valves 217e to 225e and 227e to 235e, respectively.

An outline of the operation of the plasma CVD apparatus of the present invention having a hardened configuration will be described below.

Gas cylinders 217-225,227-235 valves 217a-225a, 227a
Make sure that ~ 235a is closed, then add the inflow valve 21
7c ~ 225c, 227c ~ 235c and outflow valves 217e ~ 225e, 227e ~
Confirm that 235e is open, open the exhaust valves 209 and 210 to evacuate the reaction chamber and each raw material gas supply pipe, and when the vacuum gauges 211 and 212 reach approximately 5 × 10 ^-6 torr, the outflow valve 217e Close ~ 225e, 227e ~ 235e.

Next, the drum 201 is heated by the heater 203 until it reaches a predetermined temperature of 50 to 400 ° C.

Next, SiH ₄ gas from gas cylinders 217,227, H ₂ gas from 218,227, CH ₄ gas from 219,229, GeH ₄ from 220,230
Gas, same as 221,231 N ₂ gas, same as 222,232 NO gas, same
223, 233 diluted 3000ppm with more H ₂ gas was B ₂ H ₆ gas (hereinafter referred to as "B ₂ H ₆ / H ₂ gas".), From the 224, 234, H ₂
PH ₃ gas diluted with gas to 3000 ppm (hereinafter referred to as “PH ₃ / H ₂ gas”) and SiF ₄ gas from the same 225 and 235 are opened by valves 217a to 225a and 227a to 235a respectively, and pressure regulator 217b to After adjusting to 2Kg / cm ² by 225b, 227b ~ 235b,
The inflow valves 217c to 225c and 227c to 235c are gradually opened to flow into the mass flow controllers 217d to 225d and 227d to 235d, respectively. Next, gradually open the outflow valve for the raw material gas required for forming the film, and separate each gas into two partition plates.
Drum 201 and cathode electrode 204 separated by 213, 214
The raw material gas introduction pipes 215 and 216 are made to flow into the regions A and B formed between. At this time, the mass flow controller 21 adjusts the flow rate of the source gas in each region to a predetermined value.
Set 7d ~ 225d, 227d ~ 235d, and partition plates 213, 2
In order to prevent the raw material gases introduced into the respective regions from mixing with each other through a slight gap between the drum 14 and the drum 201, the vacuum gauges 2 so that the gas pressures in the regions A and B become equal and desired values.
While looking at 11,212, adjust the opening of the exhaust valves 209, 210. Then, after recognizing that the temperature of the drum 201 is set to a predetermined temperature, after rotating the drum, high frequency power is supplied to the cathode electrode 204 by the high frequency power supply 205, and the high frequency power is supplied between the drum 201 and the cathode electrode 204. A glow discharge is caused to occur in the area A, and different plasma states are formed in the area A and the area B.

The surface of the drum 201, which is heated to a predetermined temperature of 50 to 400 ° C. by the heater 203, rotates about the central axis as an area A
And area B alternately, which results in A on the drum surface.
The layers and the B layers will be alternately laminated.

The thickness of the A layer and the B layer is made thin by increasing the rotation speed of the drum, and made thick by decreasing the drum rotation speed, and the thickness ratio of the A layer and the B layer is set by changing the positions of the partition plates 213 and 214. region
It is possible to control by changing the ratio of the transit times of A and B.

FIG. 2 (C) is a partially enlarged view for explaining the rotation speed of the drum and the position of the partition plate for making the thickness of each layer a desired value. In the figure, 201 is a drum, 204 is a cathode electrode, 213 and 214 are partition plates, and the space between the drum 201 and the cathode electrode 204 is the area A due to the partition plates 213 and 214.
And area B.

Here, the film forming rate on the drum surface in the regions A and B, respectively,
a (Å / sec), b (Å / sec), the angle formed by the partition plates 213 and 214 with the center of the drum in areas A and B, 360x, respectively
(Degree), 360 (1-x) (degree) (where 0 <x <1),
If the number of rotations of the drum is y (revolutions / second), there are two areas
The layer thickness A (Å), B (Å) of the layer formed alternately by A and B is
The following formula: It is represented by. From the two equations, the following equation: Is guided.

That is, the angle of the partition plate before starting the film forming operation,
Area A side Fix the partition plates 213 and 214 so that the number of rotations of the drum during the film forming operation is It turns out that you should set to.

When the thickness of the film formed on the drum surface reaches a predetermined value, the high frequency power supply is stopped to stop the discharge, and the outflow valve 21
Close 7e to 225e and 227e to 235e.

By the above operation, the ultra thin film laminated structure layer is formed,
To form layers other than the ultra-thin layered structure layer, use regions A and B
Then, a mixed gas having the same mixing ratio may be introduced at a flow rate proportional to the volume ratio of each region, and the same operation as described above may be performed. At this time, it goes without saying that all the outflow valves other than the outflow valves for the raw material gas required when forming the respective layers are closed, and when forming the respective layers, the raw materials used for forming the previous layers are used. It is necessary to close the outflow valve and fully open the exhaust valves 209 and 210 to temporarily exhaust the system to a high vacuum in order to avoid gas remaining in the reaction chamber and in the gas pipe from the outflow valve to the reaction chamber. According to.

Another embodiment apparatus shown in FIG. 3 schematically shows an apparatus obtained by partially changing the embodiment apparatus shown in FIG. 2, and FIG. 3 (A) is a schematic cross-sectional view thereof. Figure (B) is a schematic vertical cross-sectional view thereof.

The apparatus of the embodiment shown in FIG. 3 has partition plates 213, 214 and a drum 201.
In order to completely prevent the mixture of the raw material gas from between the partition plate and the drum, a means for exhausting gas is added, and the partition plates 213 and 214 are provided with exhaust ports 236 and 237, respectively, and exhaust valves 238 and 239 are used. It is connected to the exhaust device 208. In FIG. 3, all other reference numerals shown in the drawing indicate the same parts as those shown in FIG.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples 1 to 8, but the present invention is not limited thereto.

All layers formed in the following examples are amorphous layers (layers made of an amorphous material).

Example 1 Using the manufacturing apparatus shown in FIG. 2, a layer was formed on the surface of a cylindrical Al substrate under the layer forming conditions shown in Table 1 for electrophotography having the layer structure shown in FIG. 1 (A). A light receiving member was obtained.

The obtained light receiving member is installed in a charging exposure experimental device,
Corona charging was performed at 0.5 KV for 0.3 seconds, and a light image was immediately irradiated. A tungsten lamp light source is used for irradiation of the light image,
A scene of 0.71ux · sec was taken through a transmissive test chart.

Immediately thereafter, the surface of the light receiving member was subjected to a cascade development with a chargeable developer to obtain a good toner image on the surface of the light receiving member. Then, the toner image is 0.5 KV
When it was transferred onto a transfer paper by the corona charging method, a clear high density image having excellent resolution and good gradation reproducibility was obtained.

That is, in this embodiment, since the charge injection blocking layer and the photosensitive layer do not have a defect level, an excellent function of not generating a residual potential or a ghost even when used for a long time can be achieved, and the residual potential can be improved. Since there is almost no problem of (1), the resolution is excellent, there is no problem of image defects, and there is a resolved electric resistance, so that an image with good gradation and clear high density can be obtained.

Example 2 An electrophotographic light-receiving member having the layer structure shown in FIG. 1 (C) was obtained in the same manner as in Example 1 except that the layer forming conditions were those shown in Table 2.

Using the obtained light-receiving member, corona charging, light image irradiation with a tungsten lamp, development, and transfer were carried out in the same manner as in Example 1, and excellent resolution, good gradation reproducibility, and clear image were obtained. A high density image was obtained.

Further, this electrophotographic light-receiving member was charged in the same manner as in Example 1 and imagewise exposed with a semiconductor laser having a wavelength of 788 nm. When development and transfer were performed in the same manner as in Example 1, a clear image without interference fringes was obtained.

Examples 3 to 5 Electrophotographic light-receiving members were obtained in the same manner as in Example 1 except that the layer forming conditions at the time of forming the first layer were changed to those shown in Table 3.

An image was formed using each of the obtained light receiving members in the same manner as in Example 1 (however, in Example 3, the charging was electrified and the development was performed using a chargeable developer). , But transferred by charging.) However, it has excellent resolution.
A clear, high-density image with good gradation reproducibility was obtained.

Examples 6 to 8 Electrophotographic light-receiving members were obtained in the same manner as in Example 1 except that the layer forming conditions at the time of forming the second layer were changed to those shown in Table 4.

An image was formed in the same manner as in Example 1 using each of the obtained light receiving members. As a result, a clear, high-density image having excellent resolution and good gradation reproducibility was obtained.

Comparative Example A photoreceptor member for electrophotography was obtained under the layer forming conditions shown in Table 5.

When the spectral sensitivity characteristics of the obtained light receiving member and the spectral sensitivity characteristics obtained in Example 1 are compared, the light receiving member obtained in Example 1 has a shorter spectral sensitivity characteristic than that of the comparative example. It turned out that it was modulated to the side.

Next, a light receiving member obtained in Comparative Example (Table 5),
In the light receiving member obtained according to Example 1 (Table 1), the amount of B ₂ H ₆ gas alone was changed variously in the layer forming conditions of the first layer, and the chargeability in each case was changed. I made a comparison. (However, the chargeability was measured by subjecting each of the light-receiving members to corona discharge at 7.5 KV for 0.15 seconds and measuring the surface potential of a vibration capacitance type after 0.2 seconds. As a result, the first layer had a single-layer structure. The light receiving member of Example 1 in which the first layer has an ultrathin film laminated structure is more preferable than the light receiving member of this comparative example.
The amount of B ₂ H ₆ showed a high charging ability from low concentration region, the same B ₂
It was found that H ₆ showed higher charging ability at the concentration.

Example 9 Using the manufacturing apparatus shown in FIG. 2, the first layer was formed on the surface of a cylindrical Al substrate under the layer forming conditions shown in Table 6 with the substrate temperature of 400 ° C. The third layer was formed under the same conditions as in Example 1 except that the substrate temperature was 250 ° C. to obtain an electrophotographic light-receiving member having the layer structure shown in FIG. 1 (A). Samples for crystallinity evaluation were prepared under the same conditions as the first layer shown in Table 6 except that the layer thickness was set to 1000Å on a glass substrate (7059 manufactured by Corning Incorporated).

When the produced samples for crystallinity evaluation were analyzed by X-ray diffraction, a sharp peak was observed at around 28.5 degrees, and it was confirmed that they were polycrystalline materials. Therefore, it was found that the first layer produced under the conditions shown in Table 6 was a polycrystalline material.

Using the obtained light-receiving member, corona charging, light image irradiation with a tungsten lamp, development, and transfer were carried out in the same manner as in Example 1. As a result, excellent resolving power, good gradation reproducibility, and clear sharpness were obtained. An image of the density was obtained.

Next, the same as Example 1 except that the substrate temperature was 250 ° C., except that the first layer was formed on the cylindrical Al substrate having the substrate temperature of 400 ° C. under the conditions shown in Table 7. The layers were formed under various conditions to obtain a light receiving member for electrophotography. A glass substrate (Corning 70
59) A sample for crystallinity evaluation was prepared under the same conditions as the first layer shown in Table 7 above.

When the produced sample for crystallinity evaluation was analyzed by X-ray diffraction, a steep peak was observed at around 28.5 degrees, and it was confirmed to be a polycrystalline material. Therefore, it was found that the first layer produced under the conditions of Table 7 was a polycrystalline material.

When the charging ability of the above-described light receiving member having a multi-layered first layer and the light receiving member having a single-layered first layer is compared,
The light receiving member having a multi-layered first layer showed a charging ability about 1.6 times higher than that of the light receiving member having a single-layered first layer.

As is clear from the results of the above Examples and Comparative Examples, according to the light receiving member of the present invention, in order to improve the characteristics in the photosensitive layer and the charge injection blocking layer composed of the a-Si material in the prior art. The residual potential that occurs when other atoms are contained in the material, and the problem that fatigue accumulation remains after a long time of use and an afterimage is generated, which causes a ghost phenomenon, that is, to cause a defect level in the forbidden band. The problems that occur in are preferably resolved.

That is, according to the present invention, since the doping efficiency of the dopant is improved, the charge injection blocking layer can block the injection of charges from the support in a smaller amount, and the photosensitive layer can be characterized in a smaller amount. It is possible to improve the defect level, reduce the defect level, and have an excellent function that does not cause residual potential or ghost even after long-term use. It is possible to provide a light receiving member that has no electric shock and has improved electrical pressure resistance.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a typical example of the layer structure of the light receiving member of the present invention. FIG. 2 is a diagram schematically showing a typical embodiment of the apparatus for producing the light receiving member of the present invention, wherein FIG. 2A is a schematic cross-sectional view, FIG. FIG. 3C is a partially enlarged view of FIG. FIG. 3 is a view schematically showing another embodiment of the apparatus for producing the light receiving member of the present invention, FIG. 3 (A) is a schematic cross-sectional view,
Figure (B) is a schematic vertical sectional view. Regarding FIG. 1, 101 ... Support, 102 ... Charge injection blocking layer, 103 ... Photosensitive layer, 104 ... Surface layer, 105 ... Charge injection blocking layer that also serves as long-wavelength absorption layer, 106 ... Long Wavelength absorption layer Regarding FIGS. 2 and 3, 201 ... drum, 202 ... rotation mechanism, 203 ... heating heater, 204 ... cathode electrode, 205 ... high frequency power supply, 206,
207 ... Insulator, 208 ... Exhaust device, 209, 210, 238, 239 ...
Exhaust valve, 211,212 ... vacuum gauge, 213,214 ... partition plate,
215,216 …… Raw material gas supply pipe, 217 to 225,227 to 235 …… Raw material gas cylinder, 217a to 225a, 227a to 235a …… Valve, 217
b〜225b, 227b〜235b …… Gas pressure regulator, 217c
~ 225c, 227c ~ 235c ... Inflow valve, 217d ~ 225d, 227d
〜235d …… Massflo controller, 217e〜225e, 227e
~ 235e …… Outflow valve, 236,237 …… Exhaust port

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-60-11849 (JP, A) JP-A-62-154673 (JP, A) JP-A-62-166352 (JP, A) JP-A-62- 166353 (JP, A)

Claims (1)

[Claims] 1. A non-container containing, on a support, a silicon atom having a layer thickness of 10Å to 150Å and an atom belonging to Group III or V of the periodic table with a concentration of 30 atomic ppm to 5 × 10 ⁴ atomic ppm. First layer composed of single crystalline material and layer thickness 10Å〜150
A charge formed by alternately stacking a second layer composed of a non-single-crystal material containing a silicon atom and at least one selected from oxygen atom, carbon atom and nitrogen atom a plurality of times in Å. Amorphous containing an injection blocking layer, a silicon atom with a layer thickness of 10Å to 150Å, and an atom belonging to Group III or V of the periodic table with a concentration of 1 × 10 ^-3 atomic ppm to 1 × 10 ³ atomic ppm 3rd layer composed of quality material and layer thickness 10Å〜15
A photosensitive layer formed by alternately stacking a fourth layer composed of an amorphous material containing a silicon atom and at least one selected from an oxygen atom, a carbon atom, and a nitrogen atom at 0Å a plurality of times. A light-receiving member having layers in this order.