EP0211421B1 - Photorécepteur électrophotographique - Google Patents

Photorécepteur électrophotographique Download PDF

Info

Publication number
EP0211421B1
EP0211421B1 EP19860110686 EP86110686A EP0211421B1 EP 0211421 B1 EP0211421 B1 EP 0211421B1 EP 19860110686 EP19860110686 EP 19860110686 EP 86110686 A EP86110686 A EP 86110686A EP 0211421 B1 EP0211421 B1 EP 0211421B1
Authority
EP
European Patent Office
Prior art keywords
layer
electrophotographic photoreceptor
thickness
accordance
micron
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19860110686
Other languages
German (de)
English (en)
Other versions
EP0211421A1 (fr
Inventor
Eiichiro Tanaka
Yukimasa Kuramoto
Akio Takimoto
Koji Akiyama
Kyoko Onomichi
Masanori Watanabe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP17164785A external-priority patent/JPS6231862A/ja
Priority claimed from JP20344385A external-priority patent/JPS6263939A/ja
Priority claimed from JP60217061A external-priority patent/JPH0727246B2/ja
Priority claimed from JP60217050A external-priority patent/JPH0752301B2/ja
Priority claimed from JP1511886A external-priority patent/JPS62173474A/ja
Priority claimed from JP8744986A external-priority patent/JPS62242948A/ja
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Publication of EP0211421A1 publication Critical patent/EP0211421A1/fr
Application granted granted Critical
Publication of EP0211421B1 publication Critical patent/EP0211421B1/fr
Expired legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • G03G5/08214—Silicon-based
    • G03G5/08221—Silicon-based comprising one or two silicon based layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • G03G5/08285—Carbon-based
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • G03G5/08292—Germanium-based
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/142—Inert intermediate layers
    • G03G5/144—Inert intermediate layers comprising inorganic material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14704—Cover layers comprising inorganic material

Definitions

  • the present invention relates generally to an electrophotographic photoreceptor, and more particularly to a photoreceptor for an electrophotographic copy machine or a light beam printer.
  • Amorphous silicon (hereinafter is referred to as a-Si:H) which contains 10 to 40 atm % of hydrogen as modifying materials for reducing the concentration of localized states and has a high photosensitivity, does not give rise to environmental pollution and has a high hardness, is utilized as the photoconductive material of an electrophotographic photoreceptor.
  • a piled layer construction comprising such an a-Si:H layer has, however, in practice many drawbacks, like a too high corona charge current and a still not satisfactorily high sensitivity.
  • DE-A1-3304198 p.e. envisages two layers which separate the photoconductive layer from the substrate and both contain Si as an essential element.
  • the lower layer shall improve adhesiveness to the substrate whereas the upper layer shall have rectifying characteristics.
  • subclaims 2 to 5 of this prior art comprise an additional top layer which again contains silicon. It is obvious that such silicon comprising layers cannot act as carrier transport layer but are used according to the explanations given on page 26, lines 7 to 12, of this prior art as a stabilizing surface layer.
  • an electrophotographic photoreceptor having a piled layer constitution of a-Si:H and hydrogenerated amorphous germanium (hereinafrer is referred to as a-Ge:H) (the Japanese published unexamined patent application Sho 56-150753), a piled layer constitution of a-Si:H and hydrogenerated amorphous silicon germanium (hereinafter is referred to as a-Si 1-x Ge x :H(0 ⁇ x ⁇ 1)) (the Japanese published patent application Sho 57-115552), a single layer constitution of a-Si 1-x Ge x :H with addition of boron and oxygen (the Japanese published patent application Sho 57-172344), or the like is proposed.
  • the above-mentioned electrophotographic photoreceptorsmade from a-Si:H have many problems yet to be solved.
  • a first problems for example, is that the a-Si:H requires a very large corona charge current when its surface is charged, because the a-Si:H has a higher dielectric constant of about eleven, compared with a value of about three in an organic photosemiconductor, or about six in Se and a larger capacitance compared with other photoreceptor materials such as an organic photosemiconductor (hereinafter is referred to as OPC).
  • OPC organic photosemiconductor
  • a second problem is that the surface charge concentration of a-Si:H is higher and more light energies are required for light erase. Therefore, actual effective sensitivity is not sufficiently high.
  • a third problem is that a plasma chemical vapor deposition method (hereinafter referred to as a plasma CVD method) using silane gas (SiH4) and germane (GeH4) is generally adopted to form the a-Si:H and a-Si 1-x Ge x :H (0 ⁇ x ⁇ 1) layer, but the deposition rate of such layers is low and is less than 10 micron per hour. Furthermore reduction of manufacturing costs is difficult since silane gas and germane gas used therein is expensive.
  • a fourth problem is that the thickness of the actually used layer is less than 30 micron and the actual surface potential is less than 500 V and is lower than the surface potential of 800 V of a photoreceptor using Se. Therefore, there is still another problem in that a sufficient optical image concentration is not realized in a conventional two components development system.
  • a fifth problem is that pinholes are liable to be formed on the layer of a-Si:H, a-Si 1-x Ge x :H or a-Ge:H produced by the plasma CVD method, thereby presenting white stains.
  • a function-separated photoreceptor using an organic semiconductor material is disclosed in the Japanese published unexamined patent application Sho 56-116930, and a function-separated photoreceptor using an inorganic semiconductor material is also disclosed in the Japanese published unexamined patent application Sho 55-127561.
  • the corona charge potential increases due to reduction of the dielectric constant.
  • a long life photoreceptor such as a-Si:H layer which has higher hardness is not realized, since the organic semiconductor material has a low hardness.
  • An object of the present invention is to provide an electrophotographic photoreceptor which has a high sensitivity to visible light and a small corona charge current.
  • the electrophotographic photoreceptor in accordance with the present invention is based on the novel concept of combining an inorganic photoconductive layer for issuing movable carriers by light excitation and a carrier transport layer containing amorphous carbon as main component, whereby the above-mentioned carriers are efficiently injected into the amorphous carbon layer and can move effectively.
  • Amorphous carbon has a small dielectric constant and a high hardness.
  • the function-separated photoreceptor is formed by the amorphous carbon layer as a carrier transport layer and an a-Si:H layer as a photoconductive layer, the dielectric constant of the photoreceptor decreases by combination of both the layers, and the corona charge current decreases. As a result, surface charge concentration decrease and the sensitivity can be improved.
  • the electrophotographic photoreceptor comprises: a carrier transport layer containing amorphous carbon as main component and at least one element selected from the group consisting of hydrogen and halogen elements, the dielectric constant of said amorphous carbon layer being in the range of 2.3 - 6 and the thickness of said amorphous carbon layer being in the range of 5 to 50 ⁇ m, an inorganic photoconductive layer of 0.2 to 10 ⁇ m thickness for issuing movable carriers by light excitation, and a substrate for bearing said photoconductive layer and said carrier transport layer.
  • the amorphous carbon layer is containing hydrogen or halogen in a suitable concentration and thereby the carrier injection efficiency of the carriers generated in the inorganic photoconductive layer can be improved. Moreover, carrier injection from a substrate is prevented, and therefore a stable operation in the electrophotographic process is obtained.
  • the amorphous layer including 5--60 atm %, preferably 5--40 atm % of hydrogen has a small dielectric constant such as 2.3--6, and the carrier injection efficiency from the photoconductive layer is high.
  • an electrophotographic characteristic similar to the a-Si:H layer is realized by the layer of half or one third thickness compared to the photoreceptor which is formed only by the a-Si:H layer.
  • gases such as CH4, C2H4, C2H6, C2H2, C3H8 or C6H6 are usable as a base gas.
  • the fabrication costs of the photoreceptor are greatly reduced, since the above-mentioned gases are inexpensive in comparison with SiH4 gas which is used in the conventional process for forming the photoreceptor by a single layer of a-Si:H.
  • pinholes are not formed on the amorphous carbon layer which is formed by the plasma CVD method, and a fine printing without the white stains is achieved.
  • FIG.1 is a cross-sectional view of a first embodiment of an electrophotographic photoreceptor in accordance with the present invention.
  • FIG.2 is a cross-sectional view of a second embodiment of an electrophotographic photoreceptor in accordance with the present invention.
  • FIG.1 A cross-sectional view of a fundamental embodiment of an electrophotographic photoreceptor in accordance with the present invention is shown in FIG.1.
  • the electrophotographic photoreceptor has a carrier transport layer 2 of amorphous carbon including at least hydrogen or halogen (hereinafter referred to as a-C(:H:X), wherein X refers F, Cl, Br or I) and a photoconductive layer 3 including silicon, both formed on a substrate 1, the photoconductive layer 3 having a free surface 4.
  • a carrier transport layer 2 of amorphous carbon including at least hydrogen or halogen hereinafter referred to as a-C(:H:X), wherein X refers F, Cl, Br or I
  • a photoconductive layer 3 including silicon both formed on a substrate 1, the photoconductive layer 3 having a free surface 4.
  • the inorganic photoconductive layer 3 including at least one element of the group comprising hydrogen and halogen and at least one of the elements silicone and germanium as a main component is formed by a material selected from the following group: a single layer of a-Si(:H:X), a single layer of a-Ge(:H:X), a single layer of a-Si 1-x Ge x (:H:X), a multilayer of a-Si(:H:X) and a-Ge(:H:X), a multilayer of a-Ge(:H:X) and a-Si 1-x Ge x (:H:X), a multilayer of a-Si(:H:X) and a-Si 1-x Ge x (:H:X), a multilayer of a-Si(:H:X) and a-Si 1-x Ge x (:H:X), a multilayer of plural a-Si 1-x Ge x (:H:X) with
  • the photoconductive layer 3 including silicon in the present invention is formed by a single layer of a-Si(:H:X), a-Si 1-y C y (:H:X)(0 ⁇ y ⁇ 1), a-Si 1-y O y (:H:X)(O ⁇ y ⁇ 1) or a-Si 1-y N y (:H:X)(0 ⁇ y ⁇ 1), or by piled layers of the combination of the above-mentioned materials.
  • the suffix "y" in the above-mentioned representation can take various values between zero and one, and the elements with the suffix "y" are contained in the materials with the ratio shown by the value of "y". These various materials are also usable to form the photoconductive layer 3.
  • chalcogenide glass which is made of a material consisting of Se, Te or S, or two or more kinds thereof, which is added with Ge, for example, Ge-S, Ge-Se, Ge-Te, Ge-P-S, Ge-P-Se, Ge-P-Te, Ge-As-S, Ge-As-Se, Ge-As-Te, Ge-Sb-S, Ge-Sb-Se, Ge-Sb-Te, Ge-Si-As-Se, Ge-Si-As-Te, Ge-As-Te-Se, Ge-As-S-Te, K-Ca-Ge-S, and Ge-Te-Sb-S.
  • the thickness of the carrier transport layer 2 is 5--50 micron (micrometer) and preferably is 10--25 micron.
  • the thickness of the photoconductive layer 3 is 0.2--10 micron and preferably is 1--5 micron.
  • At least one element selected from oxygen, sulfur and nitrogen may be incorporated into the layer of a-C(:H:X) forming the carrier transport layer 2 in order to reduce defects in the layer of a-C(:H:X) and improve a change with the passage of time.
  • a barrier layer 10 is formed between the substrate 1 and the carrier transport layer 2 for effective interception of carriers which are injected from the substrate 1 into the carrier transport layer 2 in order to improve the characteristics of the electrophotography of the present invention as shown in FIG.2.
  • the barrier layer 10 is formed by metal oxides such as Al2O3 , BaO, BaO2 , BeO, Bi2O3 , CaO, CeO2 , Ce2O3, La2O3 , Dy2O3 , Lu2O3 , Cr2O3 ,CuO, Cu2O, FeO, PbO, MgO, SrO, Ta2O3 , ThO2 , ZrO2 , HfO2 , TiO2 , TiO, SiO2 , GeO2 , SiO, GeO or the like, metal nitrides such as TiN, AlN, SnN, NbN, TaN, GaN or the like, metal carbides such as WC, SnC, TiC or the like, insulators such as SiC, SiN, GeC, GeN, BC, BN or the like, or organic components such as polyethylene, polycarbonate, polyurethane, polyparaxylene or the like.
  • metal oxides such as Al2O3
  • a P-type semiconductor such as a-Si(:H:X), a-Si 1-x Ge x (:H:X), a-Ge(:H:X), a-C(:H:X), a-Si 1-x C x (:H:X) or a-Ge 1-x C x (:H:X), to which is added an element of group III of the periodic table, such as B, Al or Ga, is usable.
  • an N-type semiconductor as the barrier layer such as a-Si(:H:X), a-Si 1-x Ge x (:H:X), a-Ge(:H:X), a-C(:H:X), a-Si 1-x C x (:H:X) or a-Ge 1-x C x (:H:X), which is added an element such as N, P or As of V of the periodic table, is recommended to be used.
  • a surface covering layer may be formed on the free surface 4 in order to improve abrasion resistive characteristics and stable corona charging characteristics as shown in FIG.1 and FIG.2.
  • Suitable materials for the surface covering layer are inorganic materials such as Si x O 1-x , Si x C 1-x , Si x N 1-x , Ge x O 1-x , Ge x C 1-x , Ge x N 1-x , B x N 1-x , B x C 1-x , Al x N 1-x (0 ⁇ x ⁇ 1), or the like or plastics such as polyethyleneterephthalate, polycarbonate, polypropylene, polyamide, polytetrafluoroethylene, polytrifluoroethylene, polyvinylidenefluoride, polyurethane, or the like.
  • a reactive sputtering method in the gas atmosphere of Ar, H2 , F2 , Cl2 , C2H4 or C2H2 is also adopted by using a base gas comprising the element carbon, e.g.
  • a gas such as O2 , O3 , CO, CO2 , NO, NO2 , N2O , N2O3 , N2O4 , N2O5 , NO3 , or the like as a source of oxygen, a gas such as CS2 , H2S , S2O .
  • SO2 , SO3 or the like as a source of sulfur
  • a gas such as N2 , NH3 , H2NNH2 , HN3 , NH4N3 , F3N2 , F4N2 , NO, N2O, NO2, N2O3 , N2O4 , N2O5 , NO3 or the like as a source of nitrogen
  • these source gas is mixed with the gas of a-C(:H:X) in case of the plasma CVD method, and is mixed with a gas such as Ar, H2 , F2 , Cl2 , CH4 , C2H4 , C2H2 or the like in case of the reactive sputtering method.
  • the plasma CVD method using as base gas a silicon component such as SiH4 , Si2H6 , Si3H8 , SiF4 , SiCl4 , SiHF3 , SiH2F2 , SiH3F, SiHCl3 , SiH2Cl2 , SiH3Cl or the like is used to form a photoconductive layer comprising silicon represented by a-Si(:H:X), a-Si 1-y C y (:H:X)(0 ⁇ y ⁇ 1), a-Si 1-y O y (:H:X)(0 ⁇ y ⁇ 1) or a-Si 1-y N y (:H:X)(0 ⁇ y ⁇ 1).
  • the reactive sputtering method in the mixed gas atmosphere of Ar and H2 (F2 or Cl2 can be added to the mixed gas of Ar and H2.) is also adopted by using polycrystalline silicon as a target.
  • polycrystalline silicon as a target.
  • hydrocarbons such as CH4, C2H6 , C3H8 , C4H10 , C2H4 , C3H6 , C4H8 , C2H2 , C3H4 , C4H6 , C6H6 or the like, an allyl halide such as CH3F, CH3Cl, CH3I, C2H5Cl, C2H5Br or the like,a fluorine compound gas, such as CClF3 , CF
  • the conductivity of the layer can be controlled by addition of an impurity in the above-mentioned a-Si(:H:X), a-Si 1-y C y (:H:X) (0 ⁇ y ⁇ 1), a-Si 1-y O y (:H:X)(0 ⁇ y ⁇ 1), a-Si 1-y N y (:H:X)(0 ⁇ y ⁇ 1), or in the materials containing Ge, and in that way a preferable characteristic in the electrophotography is realized.
  • As p-type impurities for making p-type conductivity B Al, Ga, In or the like one in the group of IIb of the periodic table, are suitable and B, Al or Ga is preferable for use as the impurity.
  • As n-type impurities for n-type conductivity N P, As, Sb or the like one in the group of Vb of the periodic table is used, and among them P or As is preferable for use as the impurity.
  • the plasma CVD method is adopted for addition of these impurities, wherein one of the gases of B2H6 , B4H10 , B5H9 , B5H11 , B6H12 , B6H14 , BF3 , BCl3 , BBr3 , AlCl3 , (CH3)3Al, (C2H5)3Al, (iC4H9)3Al, (CH3)3Ga, (C2H5)3Ga, InCl3, (C2H5)3In or the like is added as a p-type impurity to the base gas comprising C or Si and one of the gases of PH3, P2H4, PH4I, PF3, PF5, PCl3, PCl5, PBr3, PBr5, PI3, AsH3, AsF3, AsCl3, AsBr3, SbH3, SbF3, SbF5, SbCl3, SbCl5 or the like is added as an n-type impurity to the base gas comprising
  • a mirror-finished aluminum substrate (1) was disposed in a capacitive coupling plasma CVD reactor wherein an electrode was 15.24 cm in diameter. After evacuation of air of the plasma CVD reactor to lower than 6.7 x 10 ⁇ 4Pa the substrate was heated to 150--300°C, preferably 200--250°C, and 10--80 sccm of C2H4 and 0.5--20 sccm of B2H6 , which were diluted to one percent with He, were introduced into the plasma CVD reactor. The pressure of the plasma CVD reactor was adjusted to 13.3 --133 Pa .
  • An a-C:H layer having a thickness of 25 micron into which was incorporated B was formed as the carrier transport layer 2 by a high frequency glow discharging of 20--150 W power and 13.56 MHz.
  • 10--40 sccm of SiH4 were injected in the reactor, and the pressure was adjusted to 16.7 - 133 Pa.
  • a non-doped a-Si:H layer having a thickness of 0.5--2 micron was formed as a photoconductive layer 3 by a high frequency glow discharging of 20--100 W power.
  • the electrophotographic photoreceptor When the electrophotographic photoreceptor was charged with a corona charge voltage of +6.3 KV, the surface potential reached to +3000 V and the residual potential was less than +30 V after exposure by white light. An exposure for half decay was less than 1 lux ⁇ sec and a high sensitivity was realized. When the electrophotographic layer was charged to +800 V and was exposed by the white light, the exposure for half decay was less than 0.3 lux ⁇ sec and a very high sensitivity was realized. The sensitivity was as large as twice that of the conventional electrophotographic photoreceptor wherein the a-Si:H layer having a thickness of 20 micron was charged by +400 V and was exposed with the same white light.
  • the sensitivity was improved to a value as large as two and half times of the conventional electrophotographic photoreceptor.
  • the corona charged potential of the former was as large as three times of that of the latter, and a higher sensitivity was realized by a small corona charge current.
  • a boron-added a-C:H layer acts as a carrier transport layer for holes and the dielectric constant of the electrophotographic photoreceptor decreases.
  • a mirror-finished aluminum drum was disposed in a cylindrical electrode of the capacitive coupling plasma CVD reactor wherein the size of the cylindrical electrode was of 45 cm length and of 16 cm inner diameter.
  • the aluminum drum was heated to 150--300°C, preferably 200--250°C. Then, 50--150 sccm of SiH4 and 50--150 sccm of B2H6 which was diluted with H2 and had a concentration of 400 ppm were introduced.
  • the pressure was adjusted to 16.7-133 Pa and a p-type a-Si:H layer having a thickness of 0.3--1.5 micron was formed as a barrier layer 10 on the substrate 1 by a high frequency glow discharging with a power of 100--250 W.
  • 50--150 sccm of SiH4 was introduced and the pressure was adjusted to 16.7 - 133 Pa and an un-doped a-Si:H layer 3 having a thickness of 5--1 micron was formed on the barrier layer.
  • 20--50 sccm of SiH4 were added together with CH4 and an a-Si 1-x C x layer having a thickness of 0.5--1 micron was formed.
  • the introduction of SiH4 was stopped and CH4 only was introduced, and a carrier transport layer having a thickness of 5--10 micron was formed.
  • the photoreceptor of this example was mounted in an optical printer wherein a LED having a wavelength of 670 nm was used as its light source. And when the surface voltage was a positive charge of +500--800 V, a clear print was obtained.
  • an a-Si:H(:F) layer was formed instead of the a-Si:H layer as the photoconductive layer or when an a-Si 1-x O x layer or a-Si 1-x N x layer was formed instead of the a-Si 1-x C x layer, an electrophotographic photoreceptor which was similar in its characteristics to the above-mentioned embodiment was realized.
  • the barrier layer 10 the two photoconductive layers 3 and the carrier transport layer 2 are formed on the substrate 1 in the named order as shown in FIG.2.
  • a surface covering layer 5 of a-Ge 1-x C x (0 ⁇ x ⁇ 1) having a thickness of 0.1--0.5 micron was formed on the surface of the electrophotographic photoreceptor which was made by the process of Example 2 by the plasma CVD method.
  • This photoreceptor was superior in heat and humidity resisting property. When it was mounted in the optical printer elucidated in the Example 2, the photoreceptor could print 800,000 sheets.
  • a polycarbonate resin layer having a dried thickness of 1 micron was coated on the electrophotographic photoreceptor which was made in the process of the example 2.
  • This electrophotographic photoreceptor was superior in humidity resisting property. When it was mounted in the optical printer elucidated in the Example 2, the photoreceptor could print 50,000 sheets.
  • An a-C:H layer having a thickness of 6 micron including 500--1000 atom ppm of P, an a-Si:H layer having a thickness of 0.5--2 micron including 0.5--50 atom ppm of P and a-Si 1-x N x :H layer having a thickness of 0.1--0.2 micron were piled in the named order on a substrate wherein Mo was deposited on the surface by the plasma CVD method.
  • the photoreceptor was charged by a corona charge voltage of -6.0 KV, the surface potential reached was -800 V. When it was exposed to white light, an exposure for half decay reached to 0.71 lux ⁇ sec and the residual potential was less than -15 V, and the sensitivity was higher.
  • the a-C:H layer containing P acts as a carrier transport layer of electrons.
  • An aluminum deposited glass substrate was disposed in a magnetron sputtering apparatus with a target having a diameter of 15.24 cm.
  • the substrate temperature was maintained in the range of 150--300°C, and a Dy2O3 layer having a thickness of 0.1--0.5 micron was formed in an atmosphere of Ar having a pressure of 0.4 - 2.7 Pa and O2 having a pressure of 1.3 - 5.3 Pa using a sinter of Dy2O3 as a target by a high frequency glow discharging of a power of 100--300 W.
  • an a-C:H layer having a thickness of 5 micron was formed in an atmosphere of Ar having a pressure of 0.13 - 1.3Pa and H2 having a pressure of 1.2 - 12 Pa, using graphite as a target by a high frequency glow discharging of a power of 100--600 W.
  • a photoconductive a-Si:H layer having a thickness of 0.5--2 micron was formed in an atmosphere of Ar having a pressure of 0.7 - 1.3Pa and H2 having a pressure of 0.04-0.5 Pa using polycrystal silicon as a target, by a high frequency glow discharging of a power of 200--800 W.
  • a-Si 1-x N x (0 ⁇ x ⁇ 1) layer having a thickness of 0.08--0.2 micron was formed as a surface covering layer by exchanging H2 to N2.
  • a non-doped a-C:H layer having an optical band gap of 1.7--1.9 eV, a layer thickness of 10--15 micron and a dielectric constant of 4--5 was formed on an aluminum substrate 1, by plasma CVD method using C2H2 gas.
  • an a-Si:H:F layer having a thickness of 1--3 micron was formed for the photoconductive layer in an atmosphere of a mixture of SiH4 and SiF4.
  • an a-Si 1-x N x (0 ⁇ x ⁇ 1) layer having a thickness of 0.08--0.2 micron was formed as a surface covering layer.
  • a corona charging process was applied to the electrophotographic photoreceptor which was obtained by the above-mentioned process under the corona charge voltage of -6.0 KV.
  • a higher surface voltage potential such as -1500 V was realized, and an exposure for half decay reached to 0.5 lux ⁇ sec using white light.
  • the above-mentioned result shows that the non-doped a-C:H layer acts as a carrier transport layer which has higher electron efficiency in the above-mentioned range of dielectric constant.
  • a mirror-finished aluminum drum was set in the capacitive coupling plasma CVD reactor. After evacuation of the air of the plasma CVD reactor to a pressure lower than 6.7x10 ⁇ 4 Pa, the aluminum drum was heated to 150--250°C. Then 5--30 sccm of GeH4 and 50--200 sccm of N2 were introduced. The pressure was adjusted to 13.3 - 133 Pa, and a Ge 1-x N x layer having a thickness of 0.1--2 micron was formed as a barrier layer by a high frequency glow discharging with a power of 100--400 W.
  • a Ge 1-x C x layer having a thickness of 0.1--0.8 micron was formed in a gas atmosphere of 5--10 sccm of GeH4 and 50--100 sccm of C2H4 under a pressure of 13.3 - 133 Pa by a high frequency glow discharging with a power of 100--500 W and the electrophotographic photoreceptor was made.
  • the photoreceptor of this example was mounted in a laser beam printer wherein a semiconductor laser source having a wavelength of 800 nm was used. A clear and fine printing without white stains was obtained in a negative charge. Furthermore, the photoreceptor could print 800,000 sheets and blurring of printing did not arise in a high humidity atmosphere (40°C, 90 Rh %). The photosensitivity of this photoreceptor was sensitive to white light.
  • a glass substrate wherein Al was deposited on the surface was set in a magnetron sputtering apparatus and was heated to 150°C--300°C.
  • a Dy2O3 layer having a thickness of 0.1--0.5 micron was formed in an atmosphere of Ar having a pressure of 0.4 -2.7 Pa and of O2 having a pressure of 1.3 - 5.3 Pa using a sinter of Dy2O3 as a target by a high frequency glow discharging of a power of 100--300 W.
  • an a-C:H layer having a thickness of 5 micron was formed in an atmosphere of Ar having a pressure of 0.13 - 5.3Pa and of H2 having a pressure of 1.2 - 12 Pa using graphite as the target by the high frequency glow discharging of a power of 100--600 W. Furthermore, an As-Se-Ge layer having a thickness of 1--2 micron was formed by vapour deposition, and an uniform polycarbonate layer having a dried thickness of 10 micron was formed on the As-Se-Ge layer as a surface covering layer. Thus the electrophotographic photoreceptor was made. After a corona charging process of the electrophotographic photoreceptor under the corona charge voltage of +6.3 KV, it was exposed to white light, a high charging potential and high sensitivity were achieved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)

Claims (11)

  1. Photorécepteur électrophotographique comprenant :
    une couche de transport de porteurs contenant du carbone amorphe comme composant principal et au moins un élément choisi dans le groupe constitué d'éléments d'hydrogène et d'halogène, la constante diélectrique de la couche de carbone amorphe étant comprise dans la plage de 2,3 à 6 et l'épaisseur de la couche de carbone amorphe se trouvant comprise dans la plage de 5 à 50 µm, une couche photoconductrice inorganique de 0,2 à 10 µm d'épaisseur, de préférence de 1 a 5 µm d'épaisseur, pour produire des porteurs mobiles par excitation lumineuse, et un substrat pour supporter la couche photoconductrice et la couche de transport de porteurs.
  2. Photorécepteur électrophotographique selon la revendication 1, conprenant en outre
       une couche de couverture de surface formée sur une surface libre du photorécepteur électrophotographique.
  3. Photorécepteur électrophotographique selon la revendication 1 ou 2, dans lequel
       la couche photoconductrice inorganique contient au moins un élément choisi dans le groupe constitué de silicium amorphe et du germanium.
  4. Photorécepteur électrophotographique selon la revendication 1 ou 2, dans lequel
       une couche de barrière est formée entre le substrat et la couche photoconductrice inorganique ou entre le substrat et la couche de transport de porteurs.
  5. Photorécepteur électrophotographique selon la revendication 1, 2 ou 3, dans lequel
       la couche photoconductrice inorganique contient au moins un élément choisi dans le groupe constitué d'éléments d'hydrogène et d'halogène.
  6. Photorécepteur électrophotographique selon la revendication 1 ou 2, dans lequel
       la couche de carbone amorphe contient au moins un élément choisi dans les groupes IIIB et Vb du tableau périodique des éléments.
  7. Photorécepteur électrophotographique selon la revendication 1 ou 2, dans lequel
       la couche photoconductrice inorganique contient au moins un élément choisi dans le groupe constitué des carbone, oxygène et azote.
  8. Photorécepteur électrophotographique selon la revendication 1 ou 2, dans lequel
       la couche de carbone amorphe contient au moins un élément choisi dans le groupe constitué des oxygène, soufre et azote.
  9. Photorécepteur électrophotographique selon la revendication 1 ou 2, dans lequel
       la couche photoconductrice inorganique contient au moins un élément choisi dans les groupes IIIb, et Vb du tableau périodique des éléments.
  10. Photorécepteur électrophotographique selon la revendication 1 ou 2, dans lequel
       la couche photoconductrice inorganique contient au moins un élément choisi dans le groupe VI du tableau périodique des éléments.
  11. Photorécepteur électrophotographique selon la revendication 1, 2 ou 10, dans lequel
       la couche photoconductrice inorganique contient des chalcogènes.
EP19860110686 1985-08-03 1986-08-01 Photorécepteur électrophotographique Expired EP0211421B1 (fr)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP17164785A JPS6231862A (ja) 1985-08-03 1985-08-03 電子写真感光体
JP171647/85 1985-08-03
JP203443/85 1985-09-17
JP20344385A JPS6263939A (ja) 1985-09-17 1985-09-17 電子写真感光体
JP60217061A JPH0727246B2 (ja) 1985-09-30 1985-09-30 電子写真感光体
JP60217050A JPH0752301B2 (ja) 1985-09-30 1985-09-30 電子写真感光体
JP217050/85 1985-09-30
JP217061/85 1985-09-30
JP15118/86 1986-01-27
JP1511886A JPS62173474A (ja) 1986-01-27 1986-01-27 電子写真感光体
JP8744986A JPS62242948A (ja) 1986-04-15 1986-04-15 電子写真感光体
JP87449/86 1986-04-15

Publications (2)

Publication Number Publication Date
EP0211421A1 EP0211421A1 (fr) 1987-02-25
EP0211421B1 true EP0211421B1 (fr) 1991-09-25

Family

ID=27548565

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19860110686 Expired EP0211421B1 (fr) 1985-08-03 1986-08-01 Photorécepteur électrophotographique

Country Status (2)

Country Link
EP (1) EP0211421B1 (fr)
DE (1) DE3681655D1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4863821A (en) * 1986-07-07 1989-09-05 Minolta Camera Kabushiki Kaisha Photosensitive member comprising charge generating layer and charge transporting layer having amorphous carbon

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5727263A (en) * 1980-07-28 1982-02-13 Hitachi Ltd Electrophotographic photosensitive film
US4394425A (en) * 1980-09-12 1983-07-19 Canon Kabushiki Kaisha Photoconductive member with α-Si(C) barrier layer
US4539283A (en) * 1981-01-16 1985-09-03 Canon Kabushiki Kaisha Amorphous silicon photoconductive member
US4430404A (en) * 1981-04-30 1984-02-07 Hitachi, Ltd. Electrophotographic photosensitive material having thin amorphous silicon protective layer
US4452874A (en) * 1982-02-08 1984-06-05 Canon Kabushiki Kaisha Photoconductive member with multiple amorphous Si layers
FR2524661B1 (fr) * 1982-03-31 1987-04-17 Canon Kk Element photoconducteur
US4510224A (en) * 1982-05-06 1985-04-09 Konishiroku Photo Industry Co., Ltd. Electrophotographic photoreceptors having amorphous silicon photoconductors

Also Published As

Publication number Publication date
EP0211421A1 (fr) 1987-02-25
DE3681655D1 (en) 1991-10-31

Similar Documents

Publication Publication Date Title
US4582770A (en) Printing member for electrostatic photocopying
CA1153238A (fr) Membre electrophotographique avec une couche de silicium amorphe renfermant de l'hydrogene
CA1181630A (fr) Constituant photoconducteur renfermant une couche non photoconductrice a base d'une matrice de silicium amorphe avec du carbone
US4409311A (en) Photosensitive member
EP0211421B1 (fr) Photorécepteur électrophotographique
US4943503A (en) Amorphous silicon photoreceptor
US5465137A (en) Printing member for electrostatic photocopying
EP0194874B1 (fr) Photorécepteur pour l'électrophotographie
US4889782A (en) Electrostatic photocopying machine
US4882252A (en) Electrophotographic sensitive member with amorphous silicon carbide
JPS6275536A (ja) 電子写真感光体
US4642278A (en) Photosensitive member with an insulating layer of amorphous silicon
JP2638511B2 (ja) 電子写真感光体の製造方法
US5103262A (en) Printing member for electrostatic photocopying
EP0290270A2 (fr) Elément photosensible électrophotographique, et son procédé de fabrication
JPS62173474A (ja) 電子写真感光体
JPH0823706B2 (ja) 電子写真感光体の製造方法
US4999270A (en) Printing member for electrostatic photocopying
JP2553558B2 (ja) 電子写真感光体
US5008171A (en) Printing member for electrostatic photocopying
JPS6263939A (ja) 電子写真感光体
JPS6275537A (ja) 電子写真感光体
EP0300807A2 (fr) Elément électrophotographique photosensible
US4971872A (en) Electrostatic photocopying machine
JPH0797226B2 (ja) 電子写真感光体及びその製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19870529

17Q First examination report despatched

Effective date: 19890118

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 3681655

Country of ref document: DE

Date of ref document: 19911031

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19940722

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19940809

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940816

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19950801

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19950801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19960430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST