JPH0785177B2 - Photoreceptive member having ultra-thin layered structure - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a light receiving member used for an electrophotographic photoreceptor or the like, and particularly to a light receiving member having an improved charge injection blocking layer.

[Description of Prior Art]

Conventionally, as a light-receiving member used for an electrophotographic photoreceptor or the like, in addition to excellent matching in the light-sensitive region as compared with other types of light-receiving members, it has a high Pickers hardness and is less prone to pollution. From the viewpoint of few problems, for example, JP-A-54-8
A light receiving member made of an amorphous material having a silicon atom as a base, that is, so-called amorphous silicon (hereinafter referred to as "a-Si") as disclosed in JP 6341 and JP-A-56-83746. Is attracting attention.

By the way, such a light receiving member has a photosensitive layer composed of a-Si on a support, and when the photosensitive layer is subjected to a charging treatment, electrons are injected from the support side into the photosensitive layer. It is known to provide a charge injection blocking layer between the support and the photosensitive layer in order to prevent the charge injection. And
Regarding the charge injection blocking layer, so-called non-single-crystal silicon containing a-Si, polycrystalline silicon (hereinafter referred to as “poly-Si”) or both (hereinafter referred to as “Non-Si”) What is commonly referred to as microcrystalline silicon is classified into a-Si.], It has been proposed to use one doped with 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 for the doping process into the Non-Si film is increased. However, even in this method, since all the supplied impurities do not act as dopants, unless the supply of these impurities to the reaction system is constantly monitored and adjusted, the defect level is generated. There is the problem of being spoiled.

[Object of the Invention]

The present invention is a photoreceptor member for electrophotography having an improved multi-layered structure which solves the above-mentioned problems related to the charge injection blocking layer in the constituent layers and achieves a desired function. The main purpose is to provide.

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

Still 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.

[Structure of Invention]

The present inventors have conducted diligent research to solve the above-mentioned problems and achieve the above-mentioned object of the present invention with respect to a conventional light-receiving member used for an electrophotographic photoreceptor having a charge injection blocking layer. As a result of stacking, first, in the light receiving member, as a charge injection blocking layer, a layer region in which two kinds of ultrathin film layers having different constituent atom ratios are alternately laminated a plurality of times is provided, It has been found that when the thin film interface having a continuous concentration distribution of the constituent atoms is used, the above-mentioned problems of the charge injection blocking layer can be solved.

The present invention has been completed based on this finding. The light receiving member provided by the present invention is a support, and at least a silicon atom having a layer thickness of 10Å to 150Å on the support,
A first layer composed of a non-single crystalline material containing an atom belonging to Group III or Group V of the periodic table, and a layer thickness of 10Å ~
Second layers composed of 150 Å of non-single crystalline material containing at least silicon atoms are alternately laminated a plurality of times, and the vicinity of the interface between the first layer and the second layer is in the range of 5 Å to 70 Å The region is composed of a charge injection blocking layer in which the concentration distribution of at least one constituent atom of the first layer and the second layer is continuously changed, and an amorphous material containing silicon atoms as a matrix. It is a light receiving member having an ultrathin film laminated structure characterized by having at least a photosensitive layer.

1 and 2 show an ultrathin film laminated structure of the present invention (FIG. 1 shows an ultrathin film laminated structure having different band gaps, and FIG. 2 shows an ultrathin film laminated structure to which a valence electron control agent is added. ) Is a schematic explanatory view of FIG. 1 (a), 2 (a)
The figure is a schematic explanatory view of a band structure of an ultrathin film laminated structure, and FIGS. 1 (b) and 2 (b) are schematic explanatory views of distribution of components of the ultrathin film laminated structure.

The band structure of the ultrathin film laminated structure of the present invention is the first (a)
As shown in FIGS. 2A and 2B, the ultrathin films are connected smoothly and the concentration distribution of at least one constituent atom between the ultrathin films is shown in FIGS. 1B and 2B. ) As shown in the figure, it has a characteristic of continuous continuity.

As in the ultra-thin film laminated structure of the present invention, at least one constituent element continuously and smoothly changes between the respective ultra-thin films, so that the ultra-thin film of each ultra-thin film constituent element depends on the support temperature during formation of the ultra-thin film. Also, due to mutual diffusion between the ultrathin films of each ultrathin film constituent atom by using the electrophotographic light-receiving member having the ultrathin film laminated structure under corona charging for a long time, It is possible to prevent deterioration of the electrophotographic characteristics (for example, photosensitivity, residual potential, dark decay, etc.) of the light receiving member with time. The characteristics of the electrophotographic light-receiving member can be further stabilized.

Further, by adopting the ultra-thin film laminated structure of the present invention, the interface state between the ultra-thin films is reduced and the transfer of charges is improved as compared with the case where the ultra-thin films are clearly separated and laminated. .

Furthermore, in the charge injection blocking layer of the ultrathin film laminated structure of the present invention, the interface state between the ultrathin films is reduced, so that the injection of charges from the support through the interface state is reduced and the charging ability is further improved. To do.

Furthermore, by adopting the ultrathin film laminated structure of the present invention, the adhesion between the ultrathin film layers is improved.

In order to achieve the above object in the ultrathin film laminated structure of the present invention, the width of the distribution of constituent atoms in the vicinity of the ultrathin film interface is
It is usually 5Å to 70Å, preferably 10Å to 60Å, more preferably 15Å to 50Å.

The contents of the present invention will be described below with reference to the illustrated embodiments. Although the illustrated example of the light receiving member is for electrophotography, the present invention is not limited thereto.

FIGS. 3 (A) to 3 (F) are diagrams schematically showing typical examples of the layer constitution of the light receiving member for electrophotography of the present invention.

In FIGS. 3A to 3F, 301 is a support, 302 is a charge injection blocking layer, 303 is a photosensitive layer, and the photosensitive layer may be a charge transporting layer 307 and a charge generating layer 308. Is a surface layer and 306 is an infrared absorption layer.

The support 301 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 , I
Conductivity is provided by providing a thin film made of TO (In ₂ O ₃ + SnO ₂ ) or the like, or synthetic resin film such as polyester film is made of NiCr, Al, Ag, Pb, Zn, Ni,
A thin film of a metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Tl, or Pt is provided on the surface by vacuum deposition, electron beam deposition, sputtering, or the like, or the surface is laminated with the metal, Conductivity is given to the surface. The shape of the support is an endless belt or a cylinder, and its thickness is appropriately determined so that a desired light receiving member can be formed. However, when flexibility is required as the light receiving member, The thickness can be made as thin as possible within the range where the function as a support is sufficiently exhibited. However, in manufacturing and handling the support,
From the viewpoint of mechanical strength, etc., it is usually 10 μm or more.

The photosensitive layer 303 of the light receiving member of the present invention is a non-single crystal material having a silicon atom as a base, particularly a silicon atom as a base,
Amorphous material containing at least one of a hydrogen atom (H) and a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter these generic expressions As "a-Si (H, X)"
It is written as. ] The halogen atom (X) specifically includes fluorine, chlorine, bromine, iodine and the like, and fluorine and chlorine are particularly preferable. it can. The amount of hydrogen atoms (H) or halogen atoms (X) contained in the photosensitive layer 303.
Or the sum of the amount of hydrogen atoms and halogen atoms (H +
X) is preferably 1 to 40 atomic%, more preferably 5
It is desirable to set it to ~ 30 atomic%.

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, and more preferably 7 to 50 μ.

In the light receiving member of the present invention, when the photosensitive layer is composed of the charge generation layer and the charge transport layer, the layer thickness of the charge generation layer is usually 0.
1 to 50 μm, preferably 0.2 to 30 μm, more preferably 0.2
The thickness of the charge transport layer is usually 3 to 100 μm.
m, preferably 5 to 80 μm, more preferably 7 to 50
μm.

The charge generation layer may be sandwiched between the charge transport layers, and in this case, the layer thicknesses of the entire charge generation layer and the entire charge transport layer may satisfy the layer thickness.

The light receiving member of the present invention includes the support 301 and the photosensitive layer 303.
And a charge injection blocking layer 302 between the charge injection blocking layer 302 and the charge injection blocking layer 302. The charge injection blocking layer 302 is an ultrathin film laminated structure in which at least two kinds of ultrathin films having at least part of constituent atoms are laminated multiple times. Is a layer having. That is, No containing a p-type impurity or an n-type impurity that has the effect of preventing charge injection
n-Si (H, X) [hereinafter referred to as "Non-SiM (H, X)".
(However, M represents a p-type impurity or an n-type impurity.)]
Ultra thin film layer composed of, etc., oxygen atom that exerts an adhesion effect with the support, etc., Non-SiM (H, X) containing at least one selected from carbon atom and nitrogen atom [hereinafter,
It is written as "Non-SiM (O, C, N) (H, X)". ] An ultra thin film layer and the like constituted by the above are alternately laminated a plurality of times.

The p-type impurities described above include atoms belonging to Group III of the periodic table (hereinafter simply referred to as “Group III atoms”), specifically, B (boron), Al (aluminum), Ga ( Although gallium), In (indium), Tl (thallium), etc. can be used, B and Ga are particularly preferable.
The n-type impurity is an atom belonging to Group V of the periodic table (hereinafter simply referred to as “Group V atom”), specifically, P (phosphorus), As (arsenic), Sb (antimony). , Bi (bismuth) and the like can be used, but P and As are particularly preferable. The amount of the group III atom or the group V atom contained in the charge injection blocking layer 302 is 30 to 5 × 10 ⁴ atom.
ic ppm, preferably 50 to 1 × 10 ⁴ atomic ppm, optimally 1 × 10 ^{2 to} 5 × 10 ³ atomic ppm.

The amount of at least one selected from oxygen atoms, carbon atoms and nitrogen atoms contained in the charge injection blocking layer 302 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 302 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.

The layer thickness of each ultra-thin film layer constituting the charge injection blocking layer 302 is 10 to 150Å, preferably 10 to 100Å, optimally 15 to
80Å is preferable.

By the way, the charge injection blocking layer in the light receiving member of the present invention
302 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
Although it is composed of oly-SiM (O, C, N) (H, X), etc., the latter layer composed of poly-SiM (O, C, N) (H, X) is various. The above method, for example, the method described below is appropriately formed.

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.

Needless to say, such poly-SiM (O, C, N)
On the charge injection blocking layer 302 made of (H, X), a-Si (H, X,
A photosensitive layer 303 composed of X) is formed.

In the present invention, the charge injection blocking layer composed of Non-SiM (O, C, N) (H, X) is required to be the ultra-thin film laminated structure layer as described above. The above-mentioned photosensitive layer 303 formed on the layer 302 can also be an ultrathin film laminated structure layer.

That is, the photosensitive layer 303 made of a-Si (H, X) or the like contains a Group III atom or a Group V atom having the effect of controlling the conductivity of the photosensitive layer, and the light of the photosensitive layer is The sensitivity can be improved. In addition, for the purpose of improving the film quality of the photosensitive layer and increasing the dark resistance of the photosensitive layer,
At least one selected from oxygen atom, carbon atom and nitrogen atom can be contained.

When the photosensitive layer composed of a-Si (H, X) or the like contains such other constituent atoms, an ultrathin film stack in which at least two kinds of ultrathin films differing in at least a part of the constituent atoms are stacked a plurality of times. With the structure, the band gap can be adjusted.

This will be described with reference to FIGS. 11 (A) and 11 (B).

Figures 11 (A) and (B) are explanatory diagrams of the energy band. In the figure, E _F is the Fermi energy, E _C is the conduction band edge energy, E _V is the valence band edge energy, and E _g is the bandgear tape. Is represented.

FIG. 11 (A) is a diagram for explaining a case where two kinds of ultra thin films having different band gears are laminated. That is, a-Si (H,
When at least one selected from nitrogen atom, carbon atom and nitrogen atom is contained in X), a-Si
The present inventors have confirmed that the bandgap is larger than that of (H, X), and also confirmed the following. For example, an ultrathin film layer composed of a-Si (H, X) and an a-Si (O, C, N) (H, X) thin film layer having different band gaps are laminated. Then, in the ultrathin film layer having a narrow band gap, a subband as shown by a broken line in the figure is formed by the quantum effect.
The sub-band is formed at a position energetically higher than the ends of the conduction band and the valence band, and as a result, the band gap of the photosensitive layer in which the ultrathin layer is laminated is wider than the band gap of a layer having a narrow band gap. It will be. And FIG. 11 (B) shows that a containing a p-type impurity
-Si (H, X) ultra-thin film layer (hereinafter referred to as "p-type ultra-thin film layer") and a-Si (H, X) containing n-type impurities.
It is a figure explaining the case where the ultrathin film layer (it calls a "n type ultrathin film layer" hereafter) comprised by X) was laminated | stacked by turns.
In this case, on the side of the conduction band, the n-type ultra-thin film layer sandwiched by the p-type ultra-thin film layer, and the conduction band edge energy by the quantum effect.
Subbands are formed on the higher energy side than E _C.
Similarly, in the valence band side, the sub-band by the quantum effect to a higher energy side than the low-band edge energy E _V is formed in the p-type ultra-thin layer. Each subband seeps into the p-type ultrathin film layer on the conduction band side and into the n-type ultrathin film layer on the valence band side. As a result, light absorption occurs between the conduction band sub-band and the valence band exuding sub-band, so that the band gap of the photosensitive layer in which the p-type ultra-thin film layer and the n-type ultra-thin film layer are laminated is The band gaps are peculiar to the p-type ultra-thin film layer and the n-type ultra-thin film layer, respectively.

From the above, specifically, the photosensitive layer 303 is formed by, for example, aS
An ultra thin film layer structure layer in which an ultra thin film layer composed of i (H, X) and an ultra thin film layer composed of a-SiM (H, X) are alternately laminated a plurality of times, or an a-Si (H , X) and an ultra thin film layer and aS
An ultra-thin film structure layer in which an ultra-thin film structure layer composed of i (O, C, N) (H, X) is alternately laminated multiple times, or a-Si
Ultra-thin layer composed of M (H, X) and a-Si (O, C, N) (H,
It is possible to form an ultrathin film laminated structure layer in which the ultrathin film structural layer composed of X) is alternately laminated a plurality of times.

On the photosensitive layer 303 in the light receiving member of the present invention, the surface layer 3
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
Notated as -C (H, X). ] Is composed.

The purpose of providing the surface layer 304 on the light receiving member of the present invention is to improve moisture resistance, continuous repeated use characteristics, electrical pressure resistance, 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 304 and the photosensitive layer 303.

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 304 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. 3 (B), the charge injection blocking layer 305 shown in FIG. 3 (A) described above is further made to contain at least one of germanium atom and tin atom.
This is an example in which 305 also has a function as a long-wavelength absorption layer. That is, the layer 305 provided between the support 301 and the photosensitive layer 303 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 305, when a long-wavelength light source such as a semiconductor laser is used, light on the long-wavelength side, which is hardly absorbed by the photosensitive layer 303, is generated in the layer 305. To allow for substantially complete absorption, which results in support 30
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,
Non-Si (H, containing at least one selected from carbon atoms and nitrogen atoms and p-type impurities or n-type impurities)
At least one of germanium atom and tin atom may be contained in one or both of the ultrathin film structure layers constituted by X), and these layers may be alternately laminated many times.

The amount of dermanium 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.

The photosensitive layer 303 and the surface layer 3 in the example shown in FIG.
04 is the same as that in FIG. 3 (A) described above.

Finally, in the example shown in FIG. 3 (C), the layer 306 having a long wavelength absorption function and the layer 302 having a charge injection blocking function are provided as separate layers on the support 301 in this order, and A photosensitive layer 303 and a surface layer 304 are provided on the top. In the example, the layer 306 is formed of Non-Si (H, X) [hereinafter, referred to as “Non
-Si (Ge, Sn) (H, X). ], The other layers, that is, the charge injection blocking layer 302, the photosensitive layer 303 and the surface layer 304 are the same as those shown in FIG. 3 (A). FIGS. 3D to 3F show the photosensitive layer 303 formed by the charge generation layer 308 and the charge transport layer 307 in FIGS. 3A to 3C.

FIG. 4 is a schematic explanatory view of a deposited film forming apparatus for producing the ultrathin film laminated structure of the present invention by RF discharge or microwave discharge.

The deposited film forming apparatus includes a deposition chamber 1 capable of high vacuum, a peripheral wall 2 also serving as an electrode for power introduction, an upper wall 3, a bottom wall 4, an insulator 5, a heater 7 for heating, a gas introduction pipe 8, a gas release hole. 9,
Valve 10, exhaust pipe 11, exhaust valve 12, voltage applying means 13,
Internal pressure sensor 15, gas supply system 20, gas cylinders 201-205,
Valves 211-215, mass flow controllers 221-225, inflow valves 231-235, outflow valves 241-245, pressure regulator 25
1 to 255, a mass flow controller 221-225, an outflow valve 241-245, and a microcomputer (not shown) for controlling the exhaust valve 12, and a cylindrical substrate 6 is installed in the reaction vessel 1. .

For example, the ultrathin film laminated structure of the present invention was formed by the above-described apparatus as follows. 201 as the first source gas for ultra thin film formation
The second raw material gas was put in 202, and the first raw material gas and the second raw material gas dilution gas were put in 203.

First, the interior of the deposition chamber 1 is sufficiently evacuated before the formation of the ultra-thin film laminated structure, and the mass flow controllers 221, 222, 223 and the inflow valves 241, 242, 243 are moved to the seventh position by a micro computer.
As shown in the figure, each source gas was controlled and introduced into the deposition chamber 1. The flow rate change region in FIG. 7 was controlled by controlling the openness of the inflow valves 241 and 242 by a microcomputer. Then, at the same time as the introduction of each raw material gas, a predetermined electric power was introduced from the voltage applying means 13 which was an RF power source or a microwave power source to the peripheral wall 2 which also served as an electrode. The total layer thickness of the ultra-thin layered structure was controlled by keeping it for a predetermined time according to the flow rate change pattern shown in FIG.

FIG. 5 shows that the ultrathin film laminated structure of the present invention is activated by at least two kinds of gases in different spaces, introduced into the deposition chamber through different paths, and reacted in the deposition chamber.
It is a schematic explanatory view of a deposited film forming apparatus for forming.

The deposition film stacking apparatus is provided with a deposition chamber 50 capable of high vacuum.
1, support 502 for base 503, heater 504 for heating, conductor 50
5, gas supply cylinder 506,507,508,509, gas introduction pipe 510,
Internal pressure sensor 511, thermal activation chamber 512, electric furnace 513, solid Si
Granules 514, compound introduction tube 515 for active species (A), active species (B)
Conduit 516, activated species (B) conduit 517, 524, 525, valve 51
8. Exhaust valve 520, exhaust pipe 521, microwave plasma generators 522 and 527, and microwave activation chambers 523 and 526.

An example of a method of forming the ultrathin film laminated structure of the present invention with the above-described deposited film forming apparatus is shown below.

The gas supply cylinder 509 was used as a hydrogen gas cylinder, the gas supply cylinder 506 was used as a first source gas cylinder, and the gas supply cylinder 507 was used as a second source gas cylinder.

First, before the formation of the ultra-thin film laminated structure, the inside of the deposition chamber 501 is sufficiently evacuated, and the mass flow controllers 506b, 507b, 509b and the supply valves 506d, 507d, 509d are controlled by a microcomputer as shown in FIG. Each raw material gas was controlled to the flow rate of, and introduced into each microwave activation chamber 523,526. By the microwave activation chambers 523 and 526, hydrogen gas and
The first source gas and the second source gas were activated and each active species was introduced into the deposition chamber 501. The total layer thickness of the ultra-thin layered structure was controlled by maintaining the flow rate shown in FIG. 8 for a predetermined time.

FIG. 6 is a schematic diagram of a deposited film forming apparatus for forming the ultrathin film laminated structure of the present invention by the oxidation reaction between a gaseous source gas and a gaseous halogen-based oxidizing agent that oxidizes the gaseous source gas. FIG.

The deposited film forming apparatus, gas supply cylinders 601-604, gas introduction pipes 601a-604a, mass flow meters 601b-604b,
Gas pressure gauges 601c-604c, inflow valves 601d-604d, 601e-
604e, pressure gauges 601f to 604f, gas introduction pipes 609 and 610, substrate holder 612, substrate heating heater 613, substrate temperature monitor thermocouple 616, substrate 618, vacuum exhaust valve 619, deposition chamber 620.
It consists of

For example, the ultrathin film laminated structure of the present invention was formed by the above-described apparatus as follows. The first source gas for ultra thin film formation
Into 604, the second source gas was placed in 603, and the halogen-based oxidant that oxidizes with each of the source gases was placed in 601.

First, before forming the ultra-thin film laminated structure, the inside of the deposition chamber 620 is sufficiently evacuated, and the mass flow controllers 604b, 603b, 610b and the inflow valves 604d, 603d, 601d are controlled by a micro computer as shown in FIG. The halogen-based oxidant was controlled and introduced into the deposition chamber 620.

The raw material gas and the halogen-based oxidant are introduced into the gas introduction pipes 610 and 609.
A chemical reaction occurs at the tip of the substrate to generate active species and a deposited film is formed on the substrate 618.

The total layer thickness of the ultra-thin layered structure was controlled by maintaining the flow rate change pattern shown in FIG. 9 for a predetermined time.

The present invention will be described below with reference to examples.

Example 1 Using the manufacturing apparatus shown in FIG. 4 and under the layer forming conditions shown in Table 1, a third layer was formed on the surface of an Al cylinder substrate by the RF discharge decomposition method.
An electrophotographic light-receiving member having the layer structure shown in FIG.

The charge injection blocking layer having the ultra-thin film laminated structure of the present invention is composed of N ₂ gas (second raw material gas) SiH ₄ gas and
B ₂ H ₆ / H ₂ gas (first raw material gas), H ₂ gas (dilution gas)
Was controlled.

The obtained light receiving member is installed in a charging exposure experimental device,
Corona charging was performed at 5.0 KV for 0.3 seconds, and a light image was immediately irradiated. For the irradiation of the light image, a tank stainless lamp light source is used,
A light quantity of 0.7 lux · sec was applied through a transmission type 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 5.0 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.

Example 2 An electrophotographic light-receiving member having a layer structure shown in FIG. 3 (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 11 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.

Example 12 Electrophotographic light-receiving member formed into layers under the layer forming conditions shown in Table 1 (that is, electrophotographic light-receiving member having an ultrathin film laminated structure as the first layer) and layer formation shown in Table 5 In the electrophotographic receiving member formed under the conditions (that is, the electrophotographic light receiving member having the first layer as a single layer structure), the B ₂ H ₆ gas of the respective layer forming conditions of the first layer is By varying only the amount,
The chargeability of each case was compared. However, the chargeability was measured at 7.5 KV for each electrophotographic light-receiving member.
Was charged for 0.15 seconds and then 0.2 seconds later, the surface potential of the vibration capacitance type was measured.

The results are shown in FIG. As is clear from the figure,
The electrophotographic light-receiving member having the ultra-thin layered first layer (represented by --------- in the figure) is the electrophotographic light-receiving member having the single-layered first layer (see the figure). It is revealed that the amount of B ₂ H ₆ shows higher charging ability from a low concentration region, and the same B ₂ H ₆ concentration shows higher charging ability.

Example 13 The layer forming conditions were set to those shown in Table 5 (base temperature: about 280 ° C., internal pressure during deposition: about 3 × 10 ⁻³ Torr), and the first layer was formed by using the deposited film forming apparatus shown in FIG. The ultrathin film laminated structure of the present invention was used to obtain a photoreceptive member for electrophotography by microwave plasma discharge.

NP9030 (manufactured by Canon Inc.) using the obtained light receiving member
When images were formed, clear, high-density images with excellent resolution and good gradation reproducibility were obtained.

Example 14 The layer forming conditions were set to those shown in Table 6 (base temperature: about 280 ° C., deposition chamber pressure: about 0.5 Torr), and an electrophotographic light-receiving member was obtained using the deposition film forming apparatus shown in FIG. . The obtained light receiving member was attached to a cylinder having an outer diameter of 80 mm and a length of 358 mm.

NP9030 (manufactured by Canon Inc.) using the obtained light receiving member
When images were formed, clear, high-density images with excellent resolution and good gradation reproducibility were obtained.

Example 15 The layer forming conditions were set to those shown in Table 7 (base temperature: about 280 ° C., deposition chamber pressure: about 0.5 Torr), and a photoreceptive member for electrophotography was obtained using the deposited film forming apparatus shown in FIG. . The light receiving member thus obtained was attached to an Al cylinder having an outer diameter of 80 mm and a length of 358 mm.

NP9030 (manufactured by Canon Inc.) using the obtained light receiving member
When images were formed, clear, high-density images with excellent resolution and good gradation reproducibility were obtained.

[Outline of Effects of the Invention] Like the ultrathin film laminated structure of the present invention, at least one constituent element continuously and smoothly changes between the respective ultrathin films, so that the temperature of the support during the formation of the ultrathin film causes Mutual diffusion between the ultrathin films of the ultrathin film components over time Also, by using the electrophotographic light-receiving member having the ultrathin film laminated structure under corona charging for a long period of time, the ultrathin film components of each ultrathin film component over time It is possible to prevent deterioration of electrophotographic characteristics (for example, photosensitivity, residual potential, dark decay, etc.) of the light receiving member with time due to mutual diffusion. Moreover, the characteristics of the light receiving member for electrophotography can be further stabilized.

Further, by adopting the ultra-thin film laminated structure of the present invention, the interface state between the ultra-thin films is reduced and the transfer of charges is improved as compared with the case where the ultra-thin films are clearly separated and laminated. .

Further, in the charge injection blocking layer of the ultra-thin film laminated structure of the present invention, the interface state between the ultra-thin films is reduced, so that the injection of charges from the support through the interface state is reduced and the charging ability is further improved. To do.

Furthermore, by adopting the ultrathin film laminated structure of the present invention, the adhesion between the ultrathin film layers is improved.

[Brief description of drawings]

1 and 2 are explanatory views of the ultrathin film laminated structure of the present invention. FIG. 3 is an explanatory diagram of a light receiving member having an ultrathin film laminated structure layer of the present invention. FIG. 4, FIG. 5 and FIG. 6 are explanatory views of a deposited film forming apparatus for producing the ultrathin film laminated structure of the present invention. FIG. 7, FIG. 8 and FIG. 9 are explanatory views of the flow rate when producing the ultrathin film laminated structure of the present invention. FIG. 10 is an explanatory diagram of the charging ability used in the examples of the present invention. FIG. 11 is an explanatory view of the ultrathin film laminated structure of the present invention. Regarding Fig. 4, 1 ... Film deposition chamber, 2 ... Peripheral wall that also serves as an electrode for power introduction, 6 ... Cylindrical substrate, 8 ... Gas introduction pipe, 12 ... Exhaust valve, 20 ... Raw material Gas supply system Referring to FIG. 5, 501 ... Film deposition chamber, 503 ... Substrate, 512
...... Thermal activation chamber, 523 ...... Microwave activation chamber, 510 ......
Raw material gas introducing pipe 601 to 604 ... About the raw material gas supply cylinder, 60
9,610 ... Raw material gas introduction pipe, 618 ... Substrate, 620 ... Film deposition chamber

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-61-193489 (JP, A) JP-A-62-43653 (JP, A) JP-A-62-161155 (JP, A) JP-A-62- 214619 (JP, A) JP 60-140354 (JP, A) JP 60-11849 (JP, A)

Claims (5)

[Claims] 1. A support and a layer thickness of 10Å to 150 on the support.
Å containing at least a silicon atom and a first layer composed of a non-single crystalline material containing an atom belonging to Group III or Group V of the periodic table, and containing at least a silicon atom having a layer thickness of 10 Å to 150 Å Second non-single crystalline material composed of
Are alternately laminated a plurality of times, and a region in the range of 5Å to 70Å near the interface between the first layer and the second layer is at least one of the constituent atoms of the first layer and the second layer. Photoreceptor having an ultra-thin layered structure having at least a charge injection blocking layer whose concentration distribution is continuously changed, and a photosensitive layer made of an amorphous material containing silicon atoms as a matrix. Element. 2. The light receiving member according to claim 1, wherein the second layer further contains at least one selected from oxygen atom, carbon atom and nitrogen atom. 3. The light receiving member according to claim 1, wherein the second layer further contains an atom belonging to Group III or Group V of the periodic table. 4. The light receiving member according to claim 1, further comprising a surface layer on the photosensitive layer. 5. The surface layer has a silicon atom as a matrix and an amorphous material containing at least one selected from an oxygen atom, a carbon atom and a nitrogen atom, or an amorphous material having a nitrogen atom and a boron atom as a matrix. The light receiving member according to claim 4, which is made of a high quality material or an amorphous material having carbon atoms as a matrix.