JPH0785172B2 - 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 photosensitive layer.

[Description of Prior Art]

Conventionally, as a light-receiving member used for an electrophotographic photoreceptor, etc., in addition to excellent matching in the light-sensitive region as compared with other types of light-receiving members, it also has a high Pickers hardness From the viewpoint that there is little problem of
Amorphous materials having a silicon atom (Si) as a matrix and so-called amorphous silicon (hereinafter referred to as "a-Si") as disclosed in JP 6341 and JP-A-56-83746.
Attention has been paid to a light receiving member composed of

By the way, such a light receiving member is formed on the support by a-Si,
Particularly preferably hydrogen atom (H) or halogen atom (X)
A-Si containing at least one of
It is expressed as "a-Si (H, X)". ] And at least a photosensitive layer having photoconductivity, said a
It is known that a-Si (H, X) is doped with an impurity in order to control the conductivity of a photosensitive layer composed of -Si (H, X). Of p-type impurities belonging to Group III of the periodic table (hereinafter simply referred to as “Group III atoms”) or n-type impurities of Group V of the periodic table (hereinafter simply referred to as “group III atoms”). , "Group V atom") is used.

It is also known to contain a so-called band gap adjusting agent in order to adjust the band gap of a-Si (H, X) to shift the maximum absorption of photosensitivity to the short wavelength side or the long wavelength side. .

For example, when at least one selected from oxygen atom (O), carbon atom (C) and nitrogen atom (N) is contained in a-Si (H, X), the band gap is increased and It is known that the maximum absorption of sensitivity shifts to the short wavelength side. In addition, germanium atom (G
When at least one of e) or tin atom (Sn) is contained, the band gap decreases 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 that a defect level is created in the forbidden band, and the occurrence of this defect level is caused by the a-Si described above.
There is a problem that the doping effect of group III atoms or group V atoms on (H, X) is impeded, and satisfactory doping of these atoms becomes difficult.

In order to solve this problem, the amount of Group III or Group V to be supplied for the doping process to a-Si (H, X) has been increased, but this method also provides Since the total amount of those atoms that do not act as a dopant does not act as a dopant, unless the amount of supply of these atoms to the reaction system is constantly monitored and adjusted, it will rather cause the generation of defect levels. Exists.

As described above, in order to control the band gap of the photosensitive layer composed of a-Si (H, X), it is necessary to add a band gap adjusting agent so as not to cause the generation of defect levels. At present, in order to efficiently achieve such satisfactory bandgap control, it is extremely difficult to adjust the supply amounts of various atoms contained in a-Si (H, X) as desired. Therefore, free control of the band gap is a serious issue.

[Object of the Invention]

INDUSTRIAL APPLICABILITY The present invention is used for an electrophotographic photoreceptor or the like which solves the above-mentioned problems associated with a photosensitive layer made of a non-single crystal material such as a-Si (H, X) and has a desired function. An object of the present invention is to provide a light receiving member and a device suitable for efficient mass production thereof.

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

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.

Another main object of the present invention is to provide a light-receiving member having an ultra-thin film laminated structure that does not change its characteristics over time due to mutual diffusion of constituent atoms between the ultra-thin films.

Another object of the present invention is to provide a light receiving member in which the interface state of the ultrathin film interface constituting the ultrathin film laminated structure is reduced.

[Structure of Invention]

The inventors of the present invention have earnestly studied in order to overcome the above-mentioned problems and achieve the above-mentioned object regarding a light-receiving member used for an electrophotographic photoreceptor or the like having at least a photosensitive layer composed of a non-single crystal material. As a result, the photosensitive layer of the light receiving member has a layer region in which two kinds of ultrathin films having different ratios of constituent atoms are alternately laminated a plurality of times.
In the case of using the one in which the distribution of the concentration of the constituent atoms is continuous at the interface of the ultra-thin film of the kind, the above-mentioned problems of the photosensitive layer are solved and the band gap thereof is easily controlled. I got the knowledge that it was possible.

The present invention has been completed based on the knowledge.
The light receiving member provided by the present invention comprises a support, a first layer composed of a non-single crystalline material containing at least silicon atoms and having a layer thickness of 10Å to 150Å, and a layer thickness on the support. A second layer composed of a non-single crystalline material containing at least a silicon atom of 10Å to 150Å and at least one selected from oxygen atom, carbon atom and nitrogen atom is alternately laminated a plurality of times, and The region in the range of 5Å to 70Å near the interface between the first layer and the second layer is the first and second regions.
Is a photoreceptive member having an ultrathin film laminated structure, characterized in that it has at least a photosensitive layer in which the concentration distribution of at least one of the constituent atoms of the layer is continuously changed.

1 and 2 show an ultrathin film laminated structure of the present invention. First
The figure shows that in the case of ultra-thin layered structures with different band gaps,
FIG. 2 is a schematic explanatory view of an ultrathin film laminated structure in the case of doping. FIGS. 1 (a) and 2 (a) are schematic explanatory views of a band structure of an ultrathin film laminated structure.
FIG. 2B and FIG. 2B are schematic explanatory views of distribution of constituent elements 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 FIG. 2 and FIG. 2 (a), the ultrathin films are connected smoothly and at least one constituent atom is present in each of the ultrathin films as shown in FIGS. 1 (b) and 2 (b). It has the characteristic that it changes smoothly as shown. (Figure E _c is the conduction band edge energy, E _v represents the valence band edge energy) as the ultra-thin film laminate structure of the present invention, at least one constituent atoms continuously smoothly between each ultrathin By changing the temperature, the mutual diffusion of atoms in each ultrathin film due to the temperature of the substrate during formation of the ultrathin film over time, or the electrophotographic light-receiving member with an ultrathin film laminated structure can be stored under corona charging for a long time. It is possible to prevent deterioration of electrophotographic characteristics (for example, photosensitivity, residual potential, dark decay, etc.) of a light receiving member due to mutual diffusion of ultrathin film constituent atoms with time due to use. it can. 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 photoconductive layer (or charge generation layer) of the ultrathin film laminated structure of the present invention, the interface state between the ultrathin films is reduced, so that the charge generation efficiency at the time of light absorption is improved.

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

FIGS. 11 (A) and 11 (B) are explanatory diagrams of energy bands, in which E _F is Fermi energy, E _c is conduction band edge energy, E _v is value electron band edge energy, and E _g is band gap. Is represented.

FIG. 11 (A) is a diagram for explaining a case where two kinds of ultrathin films having different band gaps are laminated.

As described above, when the a-Si (H, X) film contains at least one selected from oxygen atom, carbon atom and nitrogen atom, the band of the a-Si (H, X) film has Although it is known that the gap is widened, for example, a
-Si (H, X) ultra thin film layer and a-Si (H, X) containing at least one selected from oxygen atom, carbon atom and nitrogen atom [hereinafter referred to as "a-Si ( O, C, N) (H,
X) ”. ] Like an ultra thin film layer,
When ultra-thin film layers having different band gaps are stacked, sub-bands as shown by the broken line in the figure are formed by the quantum effect in the ultra-thin film layer having a narrow band gap. The subband is formed at a position higher in energy than the edges of the conduction band and the valence band, and as a result, the bandgap of the photosensitive layer in which the ultrathin film layers are stacked a plurality of times is smaller than that of the layer having a narrow bandgap. It will be wider than the band gap. (In the figure, it is assumed that the valence band side has higher energy toward the lower side and the conduction band side has higher energy toward the upper side.) FIG. 11 (B) shows p-type impurities. A-Si (H, X) containing
(Hereinafter referred to as "p-type ultra-thin film layer") composed of a. It is a figure explaining the case where it is laminated | stacked by turns. In this case, on the conduction band side, the n-type ultrathin film layer sandwiched by the p-type ultrathin film layers forms a subband on the energy side higher than the conduction band edge energy E _c due to the quantum effect. Similarly, on the valence band side, subbands due to the quantum effect are formed on the energy side higher than the valence band edge energy E _v in the p-type ultrathin film 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 stacked is , An a-Si (H, X) layer containing p-type impurities and an a-Si (H, X) layer containing n-type impurities.
It becomes narrower than the band gap of each X) layer.

FIG. 3 shows an example of the electrophotographic light-receiving member having the ultrathin film laminated structure of the present invention. FIG. 3 (a) shows an electrophotographic light-receiving member constituted by only the ultrathin film laminated structure 301 of the present invention on the substrate 300. Third (b), (c),
FIG. 3D shows an electrophotographic light-receiving member for which the ultrathin film laminated structure 301 of the present invention is used as a charge generation layer and which has a charge transport layer 302.

FIG. 3 (e) shows an electrophotographic light-receiving member comprising a substrate 300, a charge injection blocking layer 303, an ultrathin film laminated structure 301 of the present invention, and a surface layer 304. FIG. 3 (f) shows a substrate 300.
And a charge injection prevention layer 303, a layer having the ultrathin film laminated structure 301 of the present invention as a charge generation layer, and a charge transport layer 302.

3 (g) and 3 (h) show a substrate 300 and a charge injection prevention layer 303,
A photoreceptive member for electrophotography comprising a layer having the ultrathin film laminated structure 301 of the present invention as a charge generation layer, a charge transport layer 302, and a surface layer 304.

The support 300 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, ceramic, 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, Pb, In ₂ O ₃ , SnO ₂ , I
TO (In ₂ O ₃ , SnO ₂ ) to provide conductivity by providing a thin film, or synthetic resin film such as polyester film, 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 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 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 ultrathin film laminated structure layer 301 of the light receiving member of the present invention is made of a non-single crystal material, that is, specifically, as the ultrathin film laminated structure layer 301, for example, a-Si (H, X) is used. An ultra-thin film laminated structure layer in which an ultra-thin film formed and an ultra-thin film formed of a-Si (O, C, N) (H, X) are alternately laminated a plurality of times, a-Si
An ultra thin film laminated structure layer in which an ultra thin film composed of (H, X) and an ultra thin film composed of a-SiM (H, X) are alternately laminated a plurality of times, a-Si (O, C, N) ) (H, X) ultra thin film and a-
Ultra thin film laminated structure layer in which ultra thin films composed of SiM (H, X) are alternately laminated a plurality of times, ultra thin films composed of a-Si (H, X) and a-Si (Ge, Sn) An ultra-thin film structure layer in which an ultra-thin film composed of (H, X) is alternately laminated multiple times, a-Si
Ultra thin film composed of (O, C, N) (H, X) and a-Si (Ge, S)
n) An ultra-thin film laminated structure layer in which an ultra-thin film composed of (H, X) is alternately laminated can be cited. (However, the photosensitive layer of the present invention is not limited to these examples.) [In addition, "a-Si (O, C, N) (H, X)" means an oxygen atom, a carbon atom and a nitrogen atom. A-Si (H, X) containing at least one selected from the atoms is referred to as "a-SiM (H, X)"
Is a-Si (H, X) containing a Group III atom or a Group V atom
“A-Si (Ge, Sn) (H, X)” is an a-containing at least one of a germanium atom and a tin atom.
Si (H, X) shall be written respectively. ] And, the film thickness of each ultra-thin film forming such an ultra-thin film laminated structure layer is 10
~ 150Å, preferably 10 ~ 100Å, optimally 15 ~ 80Å.

Specific examples of the halogen atom (X) contained in the ultrathin layered structure layer 301 include fluorine, chlorine, bromine and iodine, and particularly preferable examples are fluorine and chlorine. The amount of hydrogen atoms (H) or halogen atoms (X) contained in the ultra-thin layered structure layer 301.
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%.

Further, as the group III atom contained in the ultrathin film laminated structure layer 301, specifically, B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), etc. Although it can be used, B and Ga are particularly preferable. Further, as the group V atom, specifically,
P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc. can be used, but particularly preferable ones are
P and As. The amount of the group III atom or the group V atom contained in the ultrathin layered structure layer 301 is 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, oxygen atoms contained in the ultrathin film laminated structure layer 301,
The amount of carbon and nitrogen atoms is 0.001 to 50 atomic%, preferably 0.002 to 40 atomic%, optimally 0.003 to 30 atomic
It is desirable to set it as%.

Furthermore, the amount of germanium atoms or tin atoms contained in the ultrathin layered structure layer 301 is 1 to 6 × 10 ⁵ atomic.
ppm, preferably 10-3 × 10 ⁵ atomic ppm, optimally 1 ×
It is desirable to set 10 ^{2 to} 2 × 10 ⁵ atomic ppm.

Further, in the light receiving member of the present invention, an ultrathin film laminated structure layer
The layer thickness of 301 is one of the important factors for efficiently achieving the object of the present invention, and is important in designing the light receiving member so that the light receiving member is provided with desired characteristics. It is necessary to pay sufficient attention, and when it is used as a charge generating and transporting layer, it is usually 3 to 100 µ, preferably 5 to 80 µ, and most preferably 7 to 50 µ.

When used as a charge generation layer, it is usually 0.1 to 50 μm.
However, it is preferably 0.2 to 30 μ, and most preferably 0.2 to 10 μ.

The charge transport layer 302 may be composed of the same constituent elements as the ultrathin layered structure layer 301, and preferably the charge transport layer 302.
Is preferably wider than the ultra-thin layered structure layer 301.

The thickness of the charge transport layer is preferably 3-100 μm,
It is preferably 5 to 80 µ, and most preferably 7 to 50 µ.

(Hereinafter, the charge generation layer and the charge transport layer are collectively referred to as a photosensitive layer.) The charge injection blocking layer 303 is such that electrons are injected from the support side into the photosensitive layer when the photosensitive layer is subjected to a charging treatment. The charge injection layer 303 is a layer provided to prevent
-Si, polycrystalline silicon (hereinafter referred to as "poly-Si"), or so-called non-single-crystal silicon containing both (hereinafter referred to as "Non-Si") [Note that microcrystalline silicon Those commonly referred to as are classified into a-Si. ]
A p-type impurity or an n-type impurity and / or an oxygen atom,
It is composed of at least one selected from carbon atoms and nitrogen atoms.

As the group III atom which is a p-type impurity or the group V atom which is an n-type impurity, the same ones as used in the above-mentioned photosensitive layer are used as they are, but a charge injection blocking layer
The amount of the group III atom or the group V atom contained in 303 is relatively high. That is, 30 to 5 × 10 ⁴ atomic pp
m, preferably 50 to 1 × 10 ⁴ atomic ppm, optimally 1 × 10
It is desirable to set ^{2 to} 5 × 10 ³ atomic ppm.

Further, by containing at least one selected from oxygen atom, carbon atom and nitrogen atom, the effect of improving the adhesion to the support is exhibited. The amount of these atoms contained in the charge injection blocking layer 303 is 0.0
It is desirable that the amount is 01 to 50 atomic%, preferably 0.002 to 40 atomic%, and most preferably 0.003 to 30 atomic%.

Further, the layer thickness of the charge injection blocking layer 303 of the light receiving member of the present invention is 300Å to 10µ, preferably 400Å to 8µ, and most preferably 50.
It is desirable to set 0Å to 5μ.

By the way, the charge injection blocking layer 303 in the present invention is a non-Si (H) containing at least one selected from the group III atom or the group V atom and / or the oxygen atom, the carbon atom and the nitrogen atom as described above. , X) [hereinafter, "Non-SiM (O,
Notated as C, N) (H, X). ] That is, a-SiM (O, C, N)
(H, X) or poly-SiM (O, C, N) (H, X) or a mixture of both, but poly-Si (O, C, N)
There are various methods for forming the layer composed of (H, X), and the following method can be given as an example.

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 annealed to form a 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.

A surface layer 304 is provided on the photosensitive layer of the light receiving member of the present invention. The surface layer contains a-Si (H, H, containing at least one selected from oxygen atom, carbon atom and nitrogen atom.
X) [hereinafter referred to as "a-Si (O, C, N) (H, X)."]
Alternatively, an amorphous material having a nitrogen atom and a boron atom as a matrix [hereinafter referred to as "a-BN (H, X)". ] Alternatively, 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 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 forming 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.

When the surface layer composed of such a-Si (O, C, N) (H, X) is used, the amount of oxygen atoms, carbon atoms, and 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
It is 3 × 10 ^{−3 to} 30 μ, more preferably 4 × 10 ^{−3 to} 20 μ, and particularly preferably 5 × 10 ^{−3 to} 10 μ.

Long-wavelength absorption layer (not shown) in the light receiving member of the present invention
Is provided on the support or on the charge injection blocking layer 303, and contains Non-Si (H, X) containing at least one of germanium atom (Ge) and tin atom (Sn).
[Hereinafter, described as Non-Si (Ge, Sn) (H, X). ] Is composed. The long-wavelength absorbing layer contains at least one of germanium atom or tin atom,
When using a long-wavelength light source such as a semiconductor laser,
Long-wavelength side light, which is hardly absorbed by the photosensitive layer, can be substantially completely absorbed by the layer, which prevents interference caused by reflection from the surface of the support 300. Is what you can do. The amount of germanium atom or tin atom contained in the layer for absorbing the surface 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 x 10
^It is desirable to set ² to 8 × 10 ⁵ atomic ppm.

Further, when the long-wavelength absorption layer is also a layer which also has a function as a charge injection blocking layer, a germanium atom or a tin atom, a group III atom or a group V atom, an oxygen atom, or a carbon atom is used. A layer formed of Non-Si (H, X) containing at least one selected from atoms and nitrogen atoms may be used.

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, before forming the ultra-thin film laminated structure, the inside of the deposition chamber 1 is sufficiently evacuated, and the mass flow controllers 221, 222, 223 and the inflow valves 241, 242, 243 are controlled by the microcomputer as shown in FIG. Was controlled and introduced into the deposition chamber 1. The flow rate change region in FIG. 7 is represented by the inflow valves 241, 2
The porosity of 42 was controlled 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 film laminated structure was controlled by maintaining the flow rate change pattern shown in FIG. 7 for a predetermined time.

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 deposition forming apparatus for forming.

The deposition film deposition apparatus is provided with a deposition chamber 50 capable of high vacuum.
1, substrate support 502, heating heater 504, conducting wire 505, gas supply cylinders 506, 507, 508, 509, gas introduction pipe 510, internal pressure sensor 511, thermal activation chamber 512, electric furnace 513, solid Si particles 51
4, compound introduction pipe 515 for active species (A), conduit 516 for active species (A), conduits 517, 524, 525 for active species (B), 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 the microcomputer to a predetermined flow rate as shown in FIG. Each raw material gas was controlled and introduced into each microwave activation chamber 523, 526.

The microwave activation chambers 523 and 526 activated the hydrogen gas, the first source gas, and the second source gas, and introduced each activated species into the deposition chamber 501. The total layer thickness of the ultra-thin layered structure was controlled by maintaining the flow rate change pattern shown in FIG. 8 for a predetermined time.

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

The deposited film forming apparatus includes 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-60.
4e, pressure gauges 601f to 604f, gas introduction pipes 609 and 610, substrate holder 612, substrate heating heater 613, substrate temperature monitoring thermocouple 616, substrate 618, vacuum exhaust valve 619, and deposition chamber 620.

For example, the ultrathin film laminated structure of the present invention was formed by the above-described apparatus as follows. 60% of the first source gas for ultra thin film formation
4, the second raw material gas was placed in 603, and the halogen-based oxidant that oxidizes with the respective raw material gases was placed in 601.

First, before forming the ultra-thin film laminated structure, the inside of the deposition chamber 620 is sufficiently exhausted, and the mass flow controllers 604b, 603b, 601b and the inflow valves 604d, 603d, 601d are controlled by a microcomputer as shown in FIG. The halogen-based oxidizing agent 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.

Examples 1 to 3 The layer formation shown in Table 1 was formed on the surface of a cylindrical Al substrate using the deposited film forming apparatus shown in FIG. 4 and according to the method for producing an ultra thin film laminated structure using the deposited film forming apparatus. Layer formation was performed under the conditions to obtain an electrophotographic light-receiving member having a layer structure shown in FIG. 3 (a).

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. A light source of tungsten lamp was used for irradiation of the light image, and a light amount 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 transferred on transfer paper with the corona charging of
A clear, high-density image having excellent resolution and good gradation reproducibility was obtained.

FIG. 10 shows the spectral sensitivity characteristics of the light receiving members obtained in each example. In addition, as a comparative example, under the conditions of Example 1, the electrophotographic light-receiving member when the constituent elements were not distributed between the respective ultrathin films and when the layers were formed under the layer forming conditions shown in Table 2 The spectral sensitivity characteristics are shown.

In the figure Indicates Example 2, Δ ... Δ indicates Example 3, ● ----,-Comparative example in which constituent elements are not distributed in Example 1, Shows comparative examples under the conditions of Table 2, respectively.

As is clear from FIG. 10, by stacking an ultra thin film composed of a-Si (O, C, N) (H, X) and an ultra thin film composed of a-Si (H, X) , The spectral sensitivity characteristics could be modulated to the short wavelength side.

Moreover, the sensitivity could be improved by continuously changing the constituent elements at the interface of the ultrathin film.

Example 4 Using a light-receiving member layer-formed under the layer-forming conditions shown in Table 1, electrification was performed, development was performed with a chargeable developer,
When images were formed in the same manner as in Example 1 except that the transfer was electrification, a clear high density image having excellent resolution and good gradation reproducibility was obtained.

Examples 5 to 10 A photoreceptive member for electrophotography was obtained in the same manner as in Example 1, except that the layer forming conditions were changed to those shown in Table 3.

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 11 An electrophotographic light-receiving member shown in FIG. 3 (g) was obtained in the same manner as in Example 1 except that the layer forming conditions were changed to those shown in Table 4.

An image formation of NP 9030 (manufactured by Canon Inc.) was performed 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. .

In addition, the sensitivity of the semiconductor laser (wavelength 788 nm) was improved by about 10% compared to the conventional photoreceptive member for electrophotography.

Example 12 An electrophotographic light-receiving member shown in FIG. 3 (e) was obtained in the same manner as in Example 1 except that the layer forming conditions were those shown in Table 5.

When the NP 9030 (manufactured by Canon Inc.) image formation was performed using the obtained light receiving member, excellent resolution was obtained.
A clear, high-density image with good gradation reproducibility was obtained.

In addition, the sensitivity of the semiconductor laser (wavelength 788 nm) was improved by about 7% as compared with the conventional light receiving member for electrophotography.

Example 13 The layer forming conditions were set as shown in Table 6 (base temperature: about 280 ° C., internal pressure during deposition: about 3 × 10 ⁻³ Torr), and the third layer was formed by using the deposited film forming apparatus shown in FIG. The electrophotographic light-receiving member shown in FIG. 3 (h) was obtained by microwave plasma discharge with the ultrathin film laminated structure of the present invention.

NP9030 (Canon Co., Ltd.)
(Manufacturing) image formation, a clear high density image having excellent resolution and good gradation reproducibility was obtained.

Example 14 A layer-forming condition was set as shown in Table 7 (base temperature: about 280 ° C., deposition chamber pressure: about 0.5 Torr), and a deposition film forming apparatus shown in FIG. 5 was used to obtain a photoreceptive member for electrophotography. It was The obtained light receiving member was attached to a cylinder having an outer diameter of 80 mm and a length of 358 mm.

NP9030 (Canon Co., Ltd.)
(Manufacturing) image formation, a clear high density image having excellent resolution and good gradation reproducibility was obtained.

Example 15 Layer forming conditions shown in Table 8 (base temperature of about 280 ° C., deposition chamber pressure of about 0.5 Torr, and using the deposited film forming apparatus of FIG. 6 were used to obtain an electrophotographic photograph shown in FIG. 3 (g). A light receiving member for use was obtained, which was attached to an Al cylinder having an outer diameter of 80 mm and a length of 358 mm.

NP9030 (Canon Co., Ltd.)
(Manufacturing) image formation, a clear high density image having excellent resolution and good gradation reproducibility was obtained.

〔The invention's effect〕

By continuously and smoothly changing at least one constituent element between the ultrathin films as in the ultrathin film laminated structure of the present invention, deterioration of the characteristics of the light receiving member with time is improved, and the sensitivity is improved. Further improvement is achieved.

[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 spectral sensitivity used in the examples of the present invention. FIG. 11 is an explanatory view of the ultrathin film laminated structure of the present invention.

 ─────────────────────────────────────────────────── ─── 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 (8)

[Claims] 1. A support and a layer thickness of 10Å to 150 on the support.
Å a first layer composed of a non-single crystalline material containing at least silicon atoms, at least a silicon atom having a layer thickness of 10 Å to 150 Å, and at least one selected from oxygen atom, carbon atom and nitrogen atom A second layer composed of a non-single crystalline material containing Al is 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 the first region. And a photoreceptive member having an ultrathin film laminated structure, comprising at least a photosensitive layer in which the concentration distribution of at least one atom of the constituent atoms of the second layer is continuously changed. 2. The light receiving member according to claim 1, wherein the first layer further contains a germanium atom or a tin atom. 3. A long-wavelength absorption layer composed of a non-single-crystal material containing silicon atoms and germanium atoms or tin atoms between the support and the photosensitive layer, according to claim 1. Light receiving member. 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. 6. The light receiving member according to claim 1, further comprising a charge injection blocking layer between the support and the photosensitive layer. 7. The non-single crystalline material in which the charge injection blocking layer contains silicon atoms and at least one atom selected from Group III or Group V of the periodic table, oxygen atoms, carbon atoms and nitrogen atoms. Claim 6 which is constituted by
Item 7. The light receiving member according to item. 8. The light receiving member according to claim 1, wherein the photosensitive layer further contains an atom belonging to Group III or Group V of the periodic table.