JP2019164322A - Photoelectric conversion device, process cartridge, and image forming apparatus - Google Patents

Abstract

To provide a photoelectric conversion device that has characteristics hardly changed by external stimuli, such as temperature change, gas exposure, and humidity change, and is low cost and highly durable.SOLUTION: A photoelectric conversion device comprises: a support; a charge transport layer containing an organic charge transport material or a sensitizing coloring agent electrode layer containing an organic sensitizing coloring agent on the support; and a ceramic film on the charge transport layer or the sensitizing coloring agent electrode layer. Preferable is an aspect in which the ceramic film is a ceramic semiconductor film, and an aspect in which the ceramic semiconductor film includes delafossite.SELECTED DRAWING: Figure 5

Description

  The present invention relates to a photoelectric conversion device, a process cartridge, and an image forming apparatus.

  In recent years, photoelectric conversion devices including organic semiconductors have been developed and put on the market.

  Currently, photoelectric conversion devices such as electrophotographic photoreceptors that are widely used are mostly made of organic materials. When an electrophotographic photosensitive member made of such an organic material is used for repeated charging and static elimination, the organic material gradually changes in quality due to electrostatic hazards, and charge traps are generated in the layer. There is a problem in that the electrical characteristics of the electrophotographic photosensitive member are deteriorated due to the change in properties.

In addition, a dye-sensitized solar cell containing an organic sensitizing dye has been developed as an organic solar cell that is lower in cost than a silicon-based solar cell.
However, since the dye-sensitized solar cell contains an organic sensitizing dye, which is an organic material, the material used is altered by gas such as temperature, humidity, oxygen, ozone, NOx, ammonia, etc. Therefore, there is a problem that the function is easily deteriorated and inferior in terms of durability as compared with the silicon solar cell.

In display elements such as organic electroluminescence (EL) elements, light-emitting diode display elements, liquid crystal display elements, and electrophoretic ink display elements, display elements such as organic EL light-emitting layers sandwiched between an anode and a cathode are provided on a substrate. Laminated and formed. An organic EL display device has a wider viewing angle than a liquid crystal display device, has a high response speed, and is expected as a next-generation display device because of the variety of light-emitting properties of organic substances.
As a method for forming these organic EL elements, a coating type forming method is used in terms of productivity and cost. Further, the organic EL element is liable to be deteriorated by exposure to a gas such as heat, moisture or oxygen, and as a result, there is a problem that the life of the organic EL element is shortened.

As an electrophotographic photoreceptor excellent in wear resistance and stability of image characteristics, for example, an electrophotographic photoreceptor containing particulate ceramic as p-type semiconductor particles in a protective layer has been proposed (for example, Patent Document 1). reference).
In addition, an electrophotographic photosensitive member in which a charge generation layer composed of a metal oxide containing nitrogen is provided on a support having a conductive surface layer has high sensitivity to an exposure light source in a short wavelength region. Has been reported (for example, see Patent Document 2).

  In addition, a method for manufacturing a compound semiconductor thin film has been proposed, which includes a film forming step by an aerosol deposition method for forming a compound semiconductor thin film on a substrate (see, for example, Patent Document 3).

  It is an object of the present invention to provide a photoelectric conversion device that has a small change in characteristics with respect to external stimuli such as temperature change, gas exposure, and humidity change, and is low in cost and high in durability.

  The photoelectric conversion device of the present invention as a means for solving the problems includes a support, a charge transport layer containing an organic charge transport material on the support, or a sensitizing dye electrode layer containing an organic sensitizing dye. And a ceramic film on the charge transport layer or the sensitizing dye electrode layer.

  According to the present invention, it is possible to provide a photoelectric conversion device that is low in cost and highly durable with little change in characteristics even with respect to external stimuli such as temperature change, gas exposure, and humidity change.

FIG. 1 is a schematic configuration diagram showing an example of an image forming apparatus of the present invention. FIG. 2 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention. FIG. 3 is a schematic configuration diagram illustrating an example of an image forming unit for each color. FIG. 4 is a schematic diagram showing an example of the process cartridge of the present invention. FIG. 5 is a cross-sectional view showing an example of the photoelectric conversion device (electrophotographic photosensitive member) of the present invention. FIG. 6 is a cross-sectional view showing an example of the photoelectric conversion device (solar cell) of the present invention. FIG. 7 is a cross-sectional view showing an example of the photoelectric conversion device (organic EL element) of the present invention. FIG. 8 is a schematic configuration diagram showing an example of an aerosol deposition apparatus used when the ceramic film of the present invention is formed. FIG. 9 is a graph showing an example of the result of measuring the X-ray diffraction spectrum of copper aluminum oxide.

(Photoelectric conversion device)
The photoelectric conversion device of the present invention includes a support, a charge transport layer containing an organic charge transport material, or a sensitizing dye electrode layer containing an organic sensitizing dye on the support, and the charge transport layer or the sensitization. A ceramic film is provided on the dye electrode layer.
There is no restriction | limiting in particular as said photoelectric conversion device, According to the objective, it can select suitably, For example, an electrophotographic photoreceptor, a solar cell, an organic electroluminescent (EL) element, a transistor, an integrated circuit, a laser diode, light emission Examples of the device include a diode.

  The photoelectric conversion device of the present invention has found the following conventional problems, and has found that the photoelectric conversion device of the present invention can solve the above problems, and has been completed.

In the electrophotographic photosensitive member that is a photoelectric conversion device, attempts have been made to reduce image defects derived from the electrophotographic photosensitive member when used for a long period of time, and many developments relating to extending the life of the electrophotographic photosensitive member have been reported. Yes. In order to achieve a long life of the electrophotographic photosensitive member, it is necessary to improve durability against various hazards that the electrophotographic photosensitive member receives during image formation.
Here, the hazard is roughly classified into two types, a mechanical hazard and a chemical hazard.

  As an example of the chemical hazard, a hazard caused by an acidic gas, an alkaline gas, or the like generated when the surface of an electrophotographic photosensitive member is charged to give a charge is known. In the vicinity of the charger, acidic gases such as ozone and nitrogen oxides are generated (see, for example, J. Imaging Science Vol. 5, 205 (1988)), so that the electrophotographic photoreceptor is exposed to these acidic gases. In addition, charge transport materials such as hole transport materials and electron transport materials contained in an electrophotographic photosensitive member are deteriorated by an acid gas (for example, KONICA TECHNICICAL REPORT VOL. 13 (2000) “Nitrogen oxidation affecting the resolution of OPC The influence of the object "), the characteristics of the electrophotographic photoreceptor deteriorate. When using a short-life electrophotographic photosensitive member, deterioration due to acidic gas often occurs only on the outermost layer of the electrophotographic photosensitive member, and the degradation component remains small, but when using a long-life electrophotographic photosensitive member. However, there is a problem that deterioration due to acidic gas may reach the inside of the electrophotographic photosensitive member, resulting in a decrease in image density and background stains, and a high-quality image output cannot be maintained during long-term use.

  In order to solve the problem of chemical hazard, a technique has been proposed in which an antioxidant is added to the charge transport layer or the surface layer to suppress deterioration of the charge transport material due to the acid gas. In order to suppress the penetration of acidic gas into the charge transport layer and the surface layer, a technique for reducing the gas permeability of these layers has been proposed. In addition, a technique for suppressing the generation of discharge products (acidic gas) during the charging process has been proposed.

  However, even if these proposed techniques are used, the electrophotographic photosensitive member has a relatively large amount of components that are oxidatively deteriorated. There is a problem that high quality image output cannot be maintained.

The present invention is characterized by having a ceramic film on a charge transport layer or a sensitizing dye electrode layer containing an organic material, and changes in characteristics against external stimuli such as temperature change, gas exposure, and humidity change. Therefore, it is possible to provide a photoelectric conversion device that is low in cost and high in durability.
In the proposal of Patent Document 1 described in the background art, the protective layer contains ceramic as a p-type semiconductor, but the ceramic is not a film but a particulate semiconductor.
In the proposals in Patent Documents 2 and 3, the metal oxide film or the compound semiconductor thin film is not provided on the layer containing an organic material, and the object of the present invention cannot be achieved.

<Ceramic membrane>
The ceramic film is a film made of ceramic.
The ceramic is generally a metal compound obtained by firing a metal. There is no restriction | limiting in particular as said ceramic, According to the objective, it can select suitably, For example, metal oxides, such as a titanium oxide, a silica, an alumina, a zirconium oxide, a tin oxide, an indium oxide, etc. are mentioned.
The ceramic is preferably a ceramic semiconductor.
The ceramic film is preferably a ceramic semiconductor film.

<< Ceramic semiconductor >>
The ceramic semiconductor is a generic name for compounds that have a partial defect in the normal electron configuration due to oxygen deficiency or the like among ceramics, and exhibit conductivity under specific conditions due to the defect in the electron configuration.
The ceramic semiconductor film is a layer in which conductivity is developed under specific conditions due to defects in the electronic arrangement, and the ceramic semiconductor component is a densely arranged layer without any gap, and includes an organic compound. Define no layer. The ceramic semiconductor film preferably contains delafossite.
Furthermore, in the present invention, from the viewpoint of application to a photoelectric conversion device, it is preferable to have charge mobility of either holes or electrons.
The charge mobility of the ceramic semiconductor film at an electric field strength of 2 × 10 ⁵ V / cm is preferably 1 × 10 ⁻⁶ cm ² / Vsec or more. In the present invention, the higher the charge mobility, the better.
Here, the method for measuring the charge mobility is not particularly limited, and a general measurement method can be appropriately selected according to the purpose. For example, the procedure described in JP 2010-183072 A The method of sample preparation and measurement is mentioned.

Further, the bulk resistance including the thickness of the ceramic semiconductor film is preferably less than 1 × 10 ¹³ Ω.

-Delafosite-
The delafossite (hereinafter sometimes referred to as “p-type semiconductor” or “p-type metal compound semiconductor”) is not particularly limited as long as it has a function as a p-type semiconductor, and is appropriately selected according to the purpose. Examples thereof include p-type metal oxide semiconductors, p-type compound semiconductors containing monovalent copper, and other p-type metal compound semiconductors.
Examples of the p-type metal oxide semiconductor include CoO, NiO, FeO, Bi ₂ O ₃ , MoO ₂ , MoS ₂ , Cr ₂ O ₃ , SrCu ₂ O ₂ , and CaO—Al ₂ O ₃ .
The p-type compound semiconductor containing copper of the monovalent, for _{example, CuI, CuInSe 2, Cu 2} O, CuSCN, CuS, CuInS 2, CuAlO, CuAlO 2, CuAlSe 2, CuGaO 2, CuGaS 2, CuGaSe 2 and Can be mentioned.
Examples of the other p-type metal compound semiconductor include GaP, GaAs, Si, Ge, and SiC.

[Production of ceramic film]
The method for forming the ceramic film (film formation method) is not particularly limited, and a generally used film formation method for an inorganic material can be appropriately selected according to the purpose. For example, a vapor deposition method, Examples thereof include a liquid phase growth method and a solid phase growth method.
Examples of the vapor deposition method include physical vapor deposition (PVD) and chemical vapor deposition (CVD).
Examples of the physical vapor deposition method include vacuum deposition, electron beam deposition, laser ablation method, laser ablation MBE, MOMBE, reactive deposition, ion plating, cluster ion beam method, glow discharge sputtering, ion beam sputtering, Examples include reactive sputtering.
Examples of the chemical vapor deposition method include thermal CVD, MOCVD, RF plasma CVD, ECR plasma CVD, photo CVD, and laser CVD.
Examples of the liquid phase growth method include an LPE method, an electroplating method, an electroless plating method, and a coating method.
Examples of the solid phase growth method include SPE, recrystallization method, graphoepitaxy, LB method, sol-gel method, and aerosol deposition (AD) method.
Among these, the AD method is preferable in that it does not affect the formation of a uniform film in a relatively large area such as an electrophotographic photosensitive member or the characteristics of the electrophotographic photosensitive member.

-Aerosol deposition (AD) method-
The aerosol deposition (AD) method is a technique in which fine particles prepared in advance or ultra fine particles are mixed with a gas to form an aerosol, which is then sprayed onto a film-forming object (substrate) through a nozzle to form a film.
As a feature of the AD method, it is possible to form a film in a room temperature environment, and the film can be formed while maintaining the crystal structure of the raw material, so that the film is formed on a photoelectric conversion device (especially an electrophotographic photosensitive member). Suitable for

A method for forming a ceramic film by the aerosol deposition method will be described.
In this case, an aerosol deposition apparatus as shown in FIG. 8 is used. An inert gas for generating aerosol is stored in the gas cylinder 11 shown in FIG. The gas cylinder 11 is connected to an aerosol generator 13 via a pipe 12 a, and the pipe 12 a is drawn out to the inside of the aerosol generator 13. A certain amount of particles 20 made of a metal oxide or a compound semiconductor is introduced into the aerosol generator 13. Another pipe 12 b connected to the aerosol generator 13 is connected to the injection nozzle 15 inside the film forming chamber 14.

  Inside the film forming chamber 14, the substrate 16 is held by the substrate holder 17 so as to face the spray nozzle 15. Here, an aluminum foil (positive electrode current collector) is used as the substrate 16. An exhaust pump 18 for adjusting the degree of vacuum in the film forming chamber 14 is connected to the film forming chamber 14 via a pipe 12c.

  Although not shown, the film forming apparatus for forming the electrode according to the present embodiment moves the substrate holder 17 in the horizontal direction (the horizontal direction in the plane facing the injection nozzle 15 in the substrate holder 17), and causes the injection nozzle 15 to move. A mechanism for moving the substrate at a constant speed in the vertical direction (the vertical direction in the plane facing the injection nozzle 15 in the substrate holder 17) is provided. By performing film formation while moving the substrate holder 17 in the horizontal direction and the injection nozzle 15 in the vertical direction, a ceramic film having a desired area can be formed on the substrate 16.

  In the process of forming the ceramic film, first, the compressed air valve 19 is closed, and the vacuum from the film forming chamber 14 to the aerosol generator 13 is evacuated by the exhaust pump 18. Next, by opening the pneumatic valve 19, the gas in the gas cylinder 11 is introduced into the aerosol generator 13 through the pipe 12a, the particles 20 are sprinkled into the container, and the aerosol in which the particles 20 are dispersed in the gas is generated. Let The generated aerosol is jetted at high speed from the nozzle 15 toward the substrate 16 through the pipe 12b. When 0.5 seconds elapses with the pressure pneumatic valve 19 opened, the pressure pneumatic valve 19 is closed for the next 0.5 seconds. Thereafter, the pneumatic valve 19 is opened again, and the pneumatic valve 19 is repeatedly opened and closed with a period of 0.5 seconds. The gas flow rate from the gas cylinder 11 is 2 liters / minute, the film formation time is 7 hours, the degree of vacuum in the film formation chamber 14 when the pressure valve 19 is closed is about 10 Pa, and the pressure valve 19 is open. At this time, the degree of vacuum in the film forming chamber 14 is set to about 100 Pa.

  The spraying speed of the aerosol is controlled by the shape of the nozzle 15, the length and inner diameter of the pipe 12b, the gas internal pressure of the gas cylinder 11, the exhaust amount of the exhaust pump 18 (internal pressure of the film forming chamber 14), and the like. For example, when the internal pressure of the aerosol generator 13 is tens of thousands Pa, the internal pressure of the film forming chamber 14 is several hundred Pa, and the shape of the opening of the nozzle 15 is a circular shape having an inner diameter of 1 mm, the film is formed with the aerosol generator 13. Due to the difference in internal pressure with the chamber 14, the aerosol injection speed can be set to several hundred m / sec. If the internal pressure of the film forming chamber 14 is maintained at 5 Pa to 100 Pa and the internal pressure of the aerosol generator 13 is maintained at 50,000 Pa, a ceramic film having a porosity of 5% to 30% can be formed. It is preferable to adjust the average thickness of the ceramic film to 0.1 μm to 10 μm by adjusting the time for supplying the aerosol under these conditions.

  The particles 20 in the aerosol that have been accelerated to obtain kinetic energy collide with the substrate 16 and are finely crushed by the impact energy. Then, these crushed particles are bonded to the substrate 16 and the crushed particles are bonded to each other, whereby ceramic films are sequentially formed on the charge transport layer.

  The film is formed by a plurality of line patterns and rotation of the photosensitive drum. The positive electrode active material layer 21 having a desired area is formed while the drum holder 17 and the injection nozzle 15 are scanned in the vertical direction and the horizontal direction on the surface of the substrate 16 (current collector 23). As the method, first, the vertical direction is fixed, and the substrate holder 17 is scanned at a constant speed in the horizontal direction. When the scanning of one row is completed, the injection nozzle 15 is moved in the vertical direction in consideration of the overlap with the previous film formation area, and the substrate holder 17 is scanned in the horizontal direction. In this way, a desired film-forming area can be deposited by moving a plurality of times in the vertical direction until the desired vertical position is reached and repeating the scan in the horizontal direction.

[Electrophotographic photoconductor]
One embodiment of the photoelectric conversion device of the present invention is an electrophotographic photoreceptor.
The electrophotographic photoreceptor (hereinafter sometimes referred to as “photoreceptor”) includes a conductive support as a support, a charge transport layer containing an organic charge transport material on the conductive support, and the charge transport. The ceramic film is provided on the layer, a charge generation layer is further provided, and other layers such as an intermediate layer and a protective layer are further provided as necessary.
The above-mentioned matters can be applied as appropriate for the ceramic film.
A layer in which a charge generation layer and a charge transport layer are sequentially laminated may be referred to as a photosensitive layer.
The case where the photoelectric conversion device is an electrophotographic photosensitive member will be described below, but is not limited to the electrophotographic photosensitive member, and can be applied to other photoelectric conversion devices.

The configuration of the photoelectric conversion device 10A that is an electrophotographic photosensitive member will be described with reference to FIG. FIG. 5 is a cross-sectional view of an example of an electrophotographic photosensitive member.
FIG. 5 shows an embodiment of the electrophotographic photosensitive member. In the embodiment shown in FIG. 5, the electrophotographic photoreceptor 10 </ b> A has an intermediate layer 2, a charge generation layer 3, a charge transport layer 4, and a ceramic film 5 in this order on the conductive support 1.

<Support (conductive support)>
The conductive support is not particularly limited as long as it has a volume resistivity of 10 ¹⁰ Ω · cm or less, and can be appropriately selected according to the purpose. For example, aluminum, nickel, chromium , Nichrome, copper, silver, gold, platinum, iron, etc., or oxide such as tin oxide, indium oxide, etc. coated on film or cylindrical plastic, paper, etc. by vapor deposition or sputtering; aluminum, aluminum Alloy, nickel, stainless steel, etc .; these were subjected to surface treatment by cutting, superfinishing, polishing, etc. after making them into pipes by methods such as Drawing Ironing Method, Impact Ironing Method, Extracted Ironing Method, Extracted Drawing Method, Cutting Method, etc. Tube.

<Intermediate layer>
In the electrophotographic photoreceptor, an intermediate layer can be provided between the conductive support and the photosensitive layer. The intermediate layer is provided for the purpose of improving adhesiveness, preventing moire, improving coatability of the upper layer, and preventing charge injection from the conductive support.

The intermediate layer usually contains a resin as a main component. Since the photosensitive layer is coated on the intermediate layer, the resin used for the intermediate layer is preferably a thermosetting resin that is hardly soluble in an organic solvent. Among these, polyurethane, melamine resin, and alkyd-melamine resin are more preferable because many of them sufficiently satisfy the above purpose.
Examples of the organic solvent include tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, butanone, and the like. What diluted the said resin moderately using the said organic solvent can be used as a coating material.

  In addition, fine particles such as metal and metal oxide may be added to the intermediate layer in order to adjust conductivity and prevent moire. As the metal oxide, titanium oxide and zinc oxide are preferable. A dispersion obtained by dispersing the fine particles with a ball mill, an attritor, a sand mill or the like using the organic solvent and the resin component can be mixed to obtain a paint.

  As the method for forming the intermediate layer (film formation method), for example, a method of forming the paint on a conductive support by a dip coating method, a spray coating method, a bead coating method, or the like; For example, a method of heat-curing the film. In many cases, the average thickness of the intermediate layer is suitably about 2 μm to 20 μm. When the accumulation of the residual potential of the photoconductor becomes large, it should be less than 3 μm.

<Photosensitive layer>
The photosensitive layer of the photoreceptor is a laminated photosensitive layer in which a charge generation layer and a charge transport layer are sequentially laminated as a photosensitive layer.

<Charge generation layer>
The charge generation layer refers to a part of the laminated photosensitive layer and has a function of generating charges by exposure. The charge generation layer contains a charge generation material as a main component and, if necessary, a binder resin. Examples of the charge generation material include inorganic charge generation materials and organic charge generation materials.

  Examples of the inorganic charge generating material include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compound, and amorphous silicon. In amorphous silicon, dangling bonds that are terminated with hydrogen atoms or halogen atoms, or those that are doped with boron atoms, phosphorus atoms, or the like are preferably used.

  As the organic charge generating material, known materials can be used, for example, metal phthalocyanines such as titanyl phthalocyanine and chlorogallium phthalocyanine, metal-free phthalocyanines, azulenium salt pigments, squaric acid methine pigments, and symmetrical carbazole skeletons. Type or asymmetric azo pigments, symmetric or asymmetric azo pigments having a triphenylamine skeleton, symmetric or asymmetric azo pigments having a fluorenone skeleton, and perylene pigments. Among these, metal phthalocyanines, symmetric or asymmetric azo pigments having a fluorenone skeleton, symmetric or asymmetric azo pigments having a triphenylamine skeleton, and perylene pigments have high quantum efficiency of charge generation. Is preferable. These charge generation materials may be used alone or as a mixture of two or more.

Examples of the binder resin include polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, polyarylate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, and polyacrylamide. Can be mentioned.
Moreover, the polymeric charge transport material mentioned later can also be used. Of these, polyvinyl butyral is often used and is useful. These binder resins may be used alone or as a mixture of two or more.

[Method for producing charge generation layer]
The method for producing the charge generation layer is roughly classified into a vacuum thin film production method and a casting method from a solution dispersion system.
Examples of the vacuum thin film production method include a vacuum deposition method, a glow discharge decomposition method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD (chemical vapor deposition) method, and the like. It can be favorably applied to the production of a layer made of the organic charge generating material.

As a method for producing the charge generation layer by the casting method, the inorganic charge generation material or the organic charge generation material described above is dispersed by a ball mill, an attritor, a sand mill or the like using an organic solvent together with a binder resin as necessary. The dispersion may be applied after being diluted appropriately.
Examples of the organic solvent include tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, butanone, and the like. Among these, methyl ethyl ketone, tetrahydrofuran, and cyclohexanone are preferable because they have a lower environmental impact than chlorobenzene, dichloromethane, toluene, and xylene.
Application can be performed by dip coating, spray coating, bead coating, or the like.

The average thickness of the charge generation layer is preferably 0.01 μm to 5 μm.
When it is necessary to reduce the residual potential or to increase the sensitivity, these characteristics are often improved by increasing the thickness of the charge generation layer. On the other hand, the chargeability often deteriorates, such as charge charge retention and space charge formation. From these balances, the average thickness of the charge generation layer is more preferably 0.05 μm to 2 μm.

  If necessary, low-molecular compounds such as antioxidants, plasticizers, lubricants, ultraviolet absorbers and leveling agents may be added to the charge generation layer. These compounds can be used alone or as a mixture of two or more. When a low molecular weight compound and a leveling agent are used in combination, sensitivity deterioration often occurs. For this reason, the amount of these used is generally preferably 0.1 phr to 20 phr, more preferably 0.1 phr to 10 phr, and the amount of the leveling agent used is preferably 0.001 phr to 0.1 phr.

<Charge transport layer>
The charge transport layer refers to a part of the laminated photosensitive layer, and has a function of injecting and transporting the charge generated in the charge generation layer and neutralizing the surface charge of the photoreceptor provided by charging. The charge transport layer contains a charge transport material and a binder component for binding the charge transport material as main components.
The charge transport layer includes at least an organic charge transport material as a charge transport material, and further includes a low molecular weight electron transport material and a hole transport material as necessary.

  Examples of the low molecular electron transport material include electron accepting materials such as asymmetric diphenoquinone derivatives, fluorene derivatives, and naphthalimide derivatives. These electron transport materials may be used alone or as a mixture of two or more.

  As the hole transport material, an electron donating material is preferably used. For example, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, a triphenylamine derivative, a butadiene derivative, 9- (p-diethylaminostyrylanthracene), 1, 1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, Examples include thiophene derivatives. These hole transport materials may be used alone or as a mixture of two or more.

-Organic charge transport material-
Examples of the organic charge transport material (hereinafter sometimes referred to as “polymer charge transport material”) include a polymer having a carbazole ring such as poly-N-vinylcarbazole, a polymer having a hydrazone structure, and polysilylene. Examples thereof include polymers and aromatic polycarbonates. These organic charge transport materials can be used alone or as a mixture of two or more.

  When the organic charge transport material is laminated with a cross-linked surface layer on the charge transport layer, the organic charge transport material is less likely to ooze out components constituting the charge transport layer to the cross-linked surface layer. It is a material suitable for preventing poor curing of the crosslinked surface layer. In addition, since the charge transport material has a high molecular weight, it is advantageous in that it is less deteriorated by the heat of curing when the crosslinked surface layer is formed because of its excellent heat resistance.

Examples of the binder component include thermoplastics or thermosetting resins such as polystyrene, polyester, polyvinyl, polyarylate, polycarbonate, acrylic resin, silicone resin, fluorine resin, epoxy resin, melamine resin, urethane resin, phenol resin, alkyd resin, and the like. Resin etc. are mentioned. Among these, polystyrene, polyester, polyarylate, and polycarbonate are useful because many of them have good charge transfer characteristics when used as a binder component of a charge transport component. In addition, since the charge transport layer is preferably laminated with a cross-linked surface layer thereon, the charge transport layer is not required to have mechanical strength as compared with the conventional charge transport layer. For this reason, a material such as polystyrene, which has high transparency but a low mechanical strength, and which is difficult to apply in the prior art, can be effectively used as a binder component of the charge transport layer.
The binder component can be used alone or as a mixture of two or more kinds, or as a copolymer composed of two or more kinds of raw material monomers, and further copolymerized with a charge transport material.

In the modification of the charge transport layer, when an electrically inactive polymer compound is used, a cardo polymer type polyester having a bulky skeleton such as fluorene, a polyester such as polyethylene terephthalate or polyethylene naphthalate, a C type A polycarbonate in which the 3,3 ′ portion of the phenol component is alkyl-substituted with respect to a bisphenol-type polycarbonate such as a polycarbonate, a polycarbonate in which the geminal methyl group of bisphenol A is substituted with a long-chain alkyl group having 2 or more carbon atoms, Polycarbonate having a long-chain alkyl skeleton such as polycarbonate having a biphenyl or biphenyl ether skeleton, polycaprolactone, polycaprolactone (for example, described in JP-A-7-292095), acrylic resin, polystyrene, hydrogenation Butadiene is effective.
Here, the electrically inactive polymer compound refers to a polymer compound that does not include a chemical structure exhibiting photoconductivity such as a triarylamine structure. When these resins are used in combination with a binder resin as an additive, the content thereof is preferably 50% by mass or less with respect to the total solid content of the charge transporting layer due to restrictions on light attenuation sensitivity.

  When the low molecular charge transport material is used, the content is usually preferably 40 phr to 200 phr, more preferably 70 phr to 100 phr. When the polymer charge transporting material is used, a material obtained by copolymerizing the resin component in a proportion of 0 to 200 parts by weight, preferably about 80 to 150 parts by weight with respect to 100 parts by weight of the charge transporting component. Is preferably used.

  The content of the charge transport material is preferably 70 phr or more from the viewpoint of satisfying high sensitivity. In addition, α-phenyl stilbene compounds, benzidine compounds, butadiene compound monomers, dimers and polymer charge transport materials having these structures in the main chain or side chain are materials having high charge mobility. Many are useful.

The charge transport layer is formed by preparing a charge transport layer coating material by dissolving or dispersing a mixture or copolymer mainly composed of a charge transport component and a binder component in an appropriate solvent, and applying and drying the coating material. it can. As the coating method, a dipping method, a spray coating method, a ring coating method, a roll coater method, a gravure coating method, a nozzle coating method, a screen printing method, or the like is employed.
Examples of the dispersion solvent that can be used in preparing the charge transport layer coating material include ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ethers such as dioxane, tetrahydrofuran, and ethyl cellosolve; and aromatics such as toluene and xylene. Examples include: halogens such as chlorobenzene and dichloromethane; esters such as ethyl acetate and butyl acetate. Among these, methyl ethyl ketone, tetrahydrofuran, and cyclohexanone are preferable because they have a lower environmental impact than chlorobenzene, dichloromethane, toluene, and xylene. These solvents can be used alone or in combination.

  Since a cross-linked surface layer is usually laminated on the upper layer of the charge transport layer, the average thickness of the charge transport layer in this configuration is the thickness of the charge transport layer in consideration of film scraping in actual use. No design is required. The average thickness of the charge transport layer is preferably 10 μm to 40 μm, and more preferably 15 μm to 30 μm for practically ensuring the required sensitivity and charging ability.

  Further, if necessary, low-molecular compounds such as antioxidants, plasticizers, lubricants and ultraviolet absorbers and leveling agents described later can be added to the charge transport layer. These compounds can be used alone or as a mixture of two or more. When a low molecular weight compound and a leveling agent are used in combination, sensitivity deterioration often occurs. For this reason, the amount used is generally 0.1 phr to 20 phr, preferably 0.1 phr to 10 phr, and the amount used of the leveling agent is suitably about 0.001 phr to 0.1 phr.

<Ceramic membrane>
As the ceramic film in the electrophotographic photosensitive member and the manufacturing method thereof, the matters described in the ceramic film of the photoelectric conversion device of the present invention and the manufacturing method thereof can be appropriately selected and applied.

<Protective layer (surface layer)>
There is no restriction | limiting in particular as protective layers (surface layer) other than the said ceramic film | membrane, According to the objective, a well-known protective layer (surface layer) can be selected suitably.

(Image forming device)
The image forming apparatus of the present invention includes the electrophotographic photosensitive member (photoelectric conversion device), further includes an electrostatic latent image forming unit and a developing unit, and further includes other units as necessary.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.

<Electrostatic latent image forming means and electrostatic latent image forming step>
The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples thereof include at least a charging member that charges the surface of the electrostatic latent image carrier and an exposure member that exposes the surface of the electrostatic latent image carrier imagewise.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. After the surface of the electrostatic latent image carrier is charged, the imagewise exposure can be performed, and the electrostatic latent image forming unit can be used.

<< Charging member and charging >>
The charging member is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotron and scorotron.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.

<< Exposure member and exposure >>
The exposure member is not particularly limited and may be appropriately selected depending on the purpose, as long as the surface of the electrostatic latent image carrier charged by the charging member can be exposed like an image to be formed. Examples thereof include various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure member.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

<Developing means and developing process>
The developing unit is not particularly limited as long as it is a developing unit including toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image. Can be selected as appropriate.
The development step is not particularly limited as long as it is a step of developing the latent electrostatic image formed on the latent electrostatic image bearing member with toner to form a visible image. For example, it can be carried out by the developing means.

The developing means may be of a dry development type or a wet development type. Further, it may be a single color developing means or a multicolor developing means.
The developing means includes a stirrer for charging the toner by frictional stirring and a magnetic field generating means fixed inside, and a developer carrying that can carry and rotate the developer containing the toner on the surface. A developing device having a body is preferred.

<Other means and other processes>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a static elimination means, a recycling means, and a control means.
Examples of the other processes include a transfer process, a fixing process, a cleaning process, a static elimination process, a recycling process, and a control process.

Next, one mode for carrying out the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100A shown in FIG. 1 includes a photosensitive drum 10 as an electrostatic latent image carrier, a charging roller 20 as a charging unit, an exposure device (not shown) as an exposure unit, and development as a developing unit. And a cleaning device 6 having a cleaning blade as a cleaning means, and a static elimination lamp 70 as a static elimination means.
The intermediate transfer member 50 is an endless belt, is stretched by three rollers 51 arranged on the inner side thereof, and can move in the arrow direction. A part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50.
Further, a cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. Further, a transfer roller 80 serving as a transfer unit capable of applying a transfer bias for transferring (secondary transfer) the toner image to the recording paper 95 is disposed to face the intermediate transfer member 50.

Further, around the intermediate transfer member 50, a corona charger 52 for applying a charge to the toner image on the intermediate transfer member 50, a contact portion between the photosensitive drum 10 and the intermediate transfer member 50, and the intermediate transfer member 50 are provided. And the contact portion of the recording paper 95.
The developing device 45 for each color of black (K), yellow (Y), magenta (M), and cyan (C) includes a developer container 42 (K, Y, M, C), a developer supply roller 43, A developing roller 44 is provided.
In the image forming apparatus 100A, after the photosensitive drum 10 is uniformly charged by the charging roller 20, exposure light L is exposed on the photosensitive drum 10 imagewise by an exposure device (not shown), and an electrostatic latent image is obtained. Form. Next, the electrostatic latent image formed on the photosensitive drum 10 is developed by supplying a developer from the developing unit 45 to form a toner image, and then the toner image is transferred by a transfer bias applied from the roller 51. Is transferred (primary transfer) onto the intermediate transfer member 50. Further, the toner image on the intermediate transfer member 50 is given a charge by the corona charger 52 and then transferred (secondary transfer) onto the recording paper 95. The toner remaining on the photosensitive drum 10 is removed by the cleaning device 6, and the photosensitive drum 10 is once discharged by the discharging lamp 70.

FIG. 2 shows another example of the image forming apparatus of the present invention. The image forming apparatus 100B is a tandem color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can rotate in the direction of the arrow.
A cleaning device 17 for removing the toner remaining on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. Further, four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other on the intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 along the conveyance direction. A tandem developing device 120 is disposed.
As shown in FIG. 3, the image forming means 18 for each color includes a photosensitive drum 10, a charging roller 60 for uniformly charging the photosensitive drum 10, and a black electrostatic latent image formed on the photosensitive drum 10. (K), yellow (Y), magenta (M), and cyan (C) are developed with each color developer to form a toner image, and each color toner image is transferred onto the intermediate transfer member 50. A transfer roller 62, a photoreceptor cleaning device 63, and a charge removal lamp 64. In FIG. 3, symbol L indicates laser light.

In the image forming apparatus of FIG. 2, an exposure device (not shown) is disposed in the vicinity of the tandem developing device 120. The exposure apparatus exposes exposure light on the photosensitive drum 10 to form an electrostatic latent image.
Further, a secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. The secondary transfer device 22 includes a secondary transfer belt 24 that is an endless belt stretched between a pair of rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 can contact each other. It has become.
A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is arranged to be pressed against the fixing belt 26.
Further, in the vicinity of the secondary transfer device 22 and the fixing device 25, a reversing device 28 for reversing the recording paper in order to form images on both sides of the recording paper is disposed.

  Next, full color image formation (color copy) in the image forming apparatus 100B will be described. First, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 32 of the scanner 300. close. Next, when a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is placed on the contact glass 32. When set, the scanner 300 is immediately driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is emitted from the first traveling body 33, and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and received by the reading sensor 36 through the imaging lens 35. . Thus, a color original (color image) is read, and image information of each color of black, yellow, magenta, and cyan is obtained.

Furthermore, after an electrostatic latent image of each color is formed on the photosensitive drum 10 based on the obtained image information of each color by the exposure device, the electrostatic latent image of each color is supplied from the developing device of each color. Development is performed with a developer, and a toner image of each color is formed. The formed toner images of the respective colors are sequentially transferred (primary transfer) on the intermediate transfer member 50 that is rotated and moved by the support rollers 14, 15, and 16, thereby forming a composite toner image on the intermediate transfer member 50. .
In the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143 and separated one by one by the separation roller 145. Then, the sheet is fed to the sheet feeding path 146, conveyed by the conveying roller 147, guided to the sheet feeding path 148 in the copying apparatus main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the recording paper on the manual feed tray 54 is fed out, separated one by one by the separation roller 58, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the recording paper.

Then, the registration roller 49 is rotated in synchronization with the composite toner image formed on the intermediate transfer member 50, and the recording paper is sent between the intermediate transfer member 50 and the secondary transfer device 22, so that the composite toner image is transferred onto the recording paper. Transfer to (secondary transfer).
The recording sheet on which the composite toner image has been transferred is conveyed by the secondary transfer device 22 and sent out to the fixing device 25. In the fixing device 25, the composite toner image is fixed on the recording paper by being heated and pressed by the fixing belt 26 and the pressure roller 27. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55, reversed by the reversing device 28, guided again to the transfer position, formed on the back surface, discharged by the discharge roller 56, and stacked on the discharge tray 57.
The toner remaining on the intermediate transfer member 50 after the composite toner image is transferred is removed by the cleaning device 17.

(Process cartridge)
The process cartridge of the present invention has the electrophotographic photosensitive member (photoelectric conversion device), and further has developing means for developing the electrostatic latent image carried on the electrophotographic photosensitive member with toner to form a toner image. In addition, other means are provided as necessary.
The process cartridge is removably molded on various image forming apparatuses.

  The developing means includes at least a toner container that contains the toner and a toner carrier that carries and conveys the toner contained in the toner container. The developing unit may further include a regulating member or the like for regulating the thickness of the toner to be carried.

  FIG. 4 shows an example of a process cartridge according to the present invention. The process cartridge 110 includes the photosensitive drum 10, the corona charger 52, the developing device 40, the transfer roller 80, and the cleaning device 90. Reference numeral 95 in FIG. 4 indicates a recording sheet.

[Solar cell]
One embodiment of the photoelectric conversion device of the present invention is a solar cell.
The solar cell has a support, a sensitizing dye electrode layer containing an organic sensitizing dye, and the ceramic film on the sensitizing dye electrode layer, and further includes a first electrode, a hole blocking layer, And a second electrode and, if necessary, other members and the like.
Although the case where a photoelectric conversion device is a solar cell is demonstrated below, it is not limited only to a solar cell, It can apply also to another photoelectric conversion device.

  Hereinafter, a solar cell (photoelectric conversion device) according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like can be changed within a range that can be conceived by those skilled in the art, and any aspect is possible. As long as the functions and effects of the present invention are exhibited, the scope of the present invention is included.

The solar cell (photoelectric conversion device) includes a substrate as a support, a first electrode, a hole blocking layer, an electron transport layer, a sensitizing dye electrode layer, a ceramic semiconductor film as a ceramic film, And two electrodes.
The configuration of the photoelectric conversion device 10B that is a solar cell will be described with reference to FIG. FIG. 6 is a cross-sectional view of an example of a solar cell.
In the embodiment shown in FIG. 6, the first electrode 2 is formed on the substrate 1 as a support, the hole blocking layer 3 is formed on the first electrode 2, and the electron transport layer is formed on the hole blocking layer 3. An example of a configuration in which the photosensitizing material 5 is adsorbed to the electron transport material in the electron transport layer 4 and the ceramic semiconductor 6 is sandwiched between the first electrode 2 and the second electrode 7 facing the illustrated is illustrated. Has been. FIG. 6 shows an example of a configuration in which lead lines 8 and 9 are provided so that the first electrode 2 and the second electrode 7 are electrically connected.
Details will be described below.

<Support (substrate)>
The substrate 1 as the support is not particularly limited, and a known substrate can be used. The substrate 1 is preferably made of a transparent material, and examples thereof include glass, a transparent plastic plate, a transparent plastic film, and an inorganic transparent crystal.

<First electrode>
The first electrode 2 is not particularly limited as long as it is a conductive substance that is transparent to visible light, and a known one used for a normal photoelectric conversion element, a liquid crystal panel, or the like can be used.
Examples of the material for the first electrode include indium tin oxide (hereinafter referred to as ITO), fluorine-doped tin oxide (hereinafter referred to as FTO), antimony-doped tin oxide (hereinafter referred to as ATO), indium / tin oxide, and the like. Examples thereof include zinc oxide, niobium / titanium oxide, and graphene. These may be singly or plurally laminated.
The average thickness of the first electrode is preferably 5 nm to 10 μm, more preferably 50 nm to 1 μm.

The first electrode is preferably provided on the substrate 1 made of a material transparent to visible light in order to maintain a certain hardness. Examples of the substrate include glass, a transparent plastic plate, a transparent plastic film, and an inorganic transparent material. A crystal or the like is used.
For example, FTO-coated glass, ITO-coated glass, zinc oxide: aluminum-coated glass, FTO-coated transparent plastic film, ITO-coated transparent plastic film can be used. Etc.
In addition, a transparent electrode obtained by doping tin oxide or indium oxide with cations or anions having different valences, a metal electrode having a structure capable of transmitting light, such as a mesh shape or a stripe shape, on a substrate such as a glass substrate But you can.
These may be used singly or as a mixture of two or more or laminated ones.

Further, for the purpose of reducing the resistance, a metal lead wire or the like may be used in combination.
Examples of the material of the metal lead wire include metals such as aluminum, copper, silver, gold, platinum, and nickel. The metal lead wire can be formed by a method in which deposition is performed on the substrate by vapor deposition, sputtering, pressure bonding, or the like, and ITO or FTO is provided thereon.

<Hole blocking layer>
The material constituting the hole blocking layer 3 is not particularly limited as long as it is transparent to visible light and is an electron transport material, but titanium oxide is particularly preferable.
The hole blocking layer is provided in order to suppress a power decrease due to recombination (so-called reverse electron transfer) of holes in the electrolyte and electrons on the electrode surface when the electrolyte is in contact with the electrode. The effect of the hole blocking layer 3 is particularly remarkable in the solid dye-sensitized solar cell. Compared with a wet dye-sensitized solar cell using an electrolyte solution, a solid dye-sensitized solar cell using an organic hole transport material or the like recombines holes in the hole transport material and electrons on the electrode surface ( This is due to the high speed of reverse electron transfer.

  The film forming method of the hole blocking layer is not limited, but high internal resistance is required to suppress the loss current in room light, and the film forming method is also important. In general, a sol-gel method for forming a wet film can be mentioned, but there are cases where the film current is low and the loss current cannot be sufficiently suppressed. For this reason, dry film formation such as sputtering is more preferable, and the film density is sufficiently high and loss current can be suppressed.

  The hole blocking layer is also formed for the purpose of preventing electronic contact between the first electrode 2 and the hole transport layer 6. The average thickness of the hole blocking layer is not particularly limited, but is preferably 5 nm to 1 μm, more preferably 500 to 700 nm for wet film formation, and more preferably 10 to 30 nm for dry film formation.

<Electron transport layer>
In the solar cell, a porous electron transport layer 4 is formed on the hole blocking layer 3, and the electron transport layer may be a single layer or a multilayer.
The electron transport layer is composed of an electron transport material. Semiconductor particles are preferably used as the electron transport material.
In the case of multiple layers, a dispersion of semiconductor particles having different particle diameters can be applied in multiple layers, or different types of semiconductors, and application layers having different compositions of resins and additives can be applied in multiple layers. Multi-layer coating is an effective means when the average thickness is insufficient with a single coating.
In general, as the average thickness of the electron transport layer increases, the amount of supported photosensitizing material per unit projected area increases, so that the light capture rate increases. Loss due to coupling also increases. Therefore, the average thickness of the electron transport layer is preferably 100 nm to 100 μm.

The semiconductor is not particularly limited, and a known semiconductor can be used. Specifically, a single semiconductor such as silicon or germanium, a compound semiconductor typified by a metal chalcogenide, a compound having a perovskite structure, or the like can be given.
Examples of metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, or tantalum oxide, cadmium, zinc, lead, silver, Antimony, bismuth sulfide, cadmium, lead selenide, cadmium telluride and the like.
As other compound semiconductors, for example, phosphides such as zinc, gallium, indium, and cadmium, gallium arsenide, copper-indium-selenide, copper-indium-sulfide, and the like are preferable.
As the compound having a perovskite structure, strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium niobate and the like are preferable.

  Among these, an oxide semiconductor is preferable, and titanium oxide, zinc oxide, tin oxide, and niobium oxide are particularly preferable, and they may be used alone or in combination of two or more. The crystal type of these semiconductors is not particularly limited, and may be single crystal, polycrystal, or amorphous.

Although there is no restriction | limiting in particular as an average particle diameter of the primary particle of a semiconductor particle, 1 nm-100 nm are preferable and 5 nm-50 nm are more preferable.
In addition, the efficiency can be improved by mixing or laminating semiconductor particles having a larger average particle diameter to scatter incident light. In this case, the average particle size of the semiconductor is preferably 50 nm to 500 nm.

There is no restriction | limiting in particular as a preparation method of an electron carrying layer, The method of forming a thin film in vacuum, such as sputtering, and the wet film forming method are mentioned.
In consideration of the manufacturing cost and the like, a wet film forming method is particularly preferable, and a method of preparing a paste in which a powder or sol of semiconductor particles is dispersed and applying the paste onto an electron collector electrode substrate is preferable.
When this wet film-forming method is used, the coating method is not particularly limited and can be performed according to a known method. For example, dip method, spray method, wire bar method, spin coating method, roller coating method, blade coating method, gravure coating method, and wet printing methods such as relief printing, offset, gravure, intaglio printing, rubber printing, screen printing, etc. Can be used.

  When the semiconductor particle dispersion is produced by mechanical pulverization or using a mill, it is formed by dispersing at least semiconductor particles alone or a mixture of semiconductor particles and resin in water or an organic solvent. Examples of the resin used at this time include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, acrylic acid esters, and methacrylic acid esters, silicon resins, phenoxy resins, polysulfone resins, polyvinyl butyral resins, and polyvinyl resins. Formal resin, polyester resin, cellulose ester resin, cellulose ether resin, urethane resin, phenol resin, epoxy resin, polycarbonate resin, polyarylate resin, polyamide resin, polyimide resin and the like can be mentioned.

  Examples of the solvent for dispersing the semiconductor particles include alcohol solvents such as water, methanol, ethanol, isopropyl alcohol, and α-terpineol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl formate, ethyl acetate, and n acetate. Ester solvents such as butyl; ether solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane and dioxane; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Solvent: dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, -Halogenated hydrocarbon solvents such as chloronaphthalene; n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, Examples thereof include hydrocarbon solvents such as p-xylene, ethylbenzene and cumene. These can be used alone or as a mixed solvent of two or more.

Semiconductor particle dispersions or semiconductor particle pastes obtained by sol-gel method, etc. are used to prevent re-aggregation of particles, such as acids such as hydrochloric acid, nitric acid, acetic acid, polyoxyethylene (10) octylphenyl ether, etc. Surfactants, chelating agents such as acetylacetone, 2-aminoethanol, and ethylenediamine can be added.
It is also an effective means to add a thickener for the purpose of improving the film forming property. Examples of the thickener added at this time include polymers such as polyethylene glycol and polyvinyl alcohol, and thickeners such as ethyl cellulose.

  The semiconductor particles are preferably subjected to firing, microwave irradiation, electron beam irradiation, or laser beam irradiation in order to bring the particles into electronic contact with each other after coating and to improve film strength and adhesion to the substrate. . These processes may be performed alone or in combination of two or more.

  In the case of firing, the range of the firing temperature is not particularly limited, but if the temperature is raised too much, the resistance of the substrate may be increased or the substrate may be melted, so 30 ° C to 700 ° C is preferable, and 100 ° C to 600 ° C is preferable. Is more preferable. Moreover, although there is no restriction | limiting in particular in baking time, 10 minutes-10 hours are preferable.

The microwave irradiation may be performed from the electron transport layer forming side or from the back side. Although there is no restriction | limiting in particular in irradiation time, It is preferable to carry out within 1 hour.

  For the purpose of increasing the surface area of the semiconductor particles after firing and increasing the efficiency of electron injection from the photosensitizing material to the semiconductor particles, for example, chemical plating or trichloride using an aqueous solution of titanium tetrachloride or a mixed solution with an organic solvent. An electrochemical plating process using a titanium aqueous solution may be performed.

A film in which semiconductor particles having a diameter of several tens of nanometers are stacked by sintering or the like forms a porous state. This nanoporous structure has a very high surface area, which can be expressed using a roughness factor.
This roughness factor is a numerical value representing the actual area inside the porous body relative to the area of the semiconductor particles applied to the substrate. Accordingly, the roughness factor is preferably as large as possible, but it is also related to the average thickness of the electron transport layer, and is preferably 20 or more in the present invention.

<Sensitizing dye electrode layer>
The solar cell has a sensitizing dye electrode layer in which an organic sensitizing dye (photosensitizing material) is adsorbed on the surface of an electron transporting material that is the electron transporting layer 4 in order to further improve the conversion efficiency.

-Organic sensitizing dyes (photosensitizing materials)-
The photosensitizing material 5 as the organic sensitizing dye is not limited to the above as long as it is a compound that is photoexcited by the excitation light used, and specific examples thereof include the following compounds.
The metal complex compounds described in JP 7-500630 A, JP 10-233238 A, JP 2000-26487 A, JP 2000-323191 A, JP 2001-59062 A, etc. 10-93118, JP-A No. 2002-164089, JP-A No. 2004-95450, J. Pat. Phys. Chem. C, 7224, Vol. 111 (2007), etc., JP-A-2004-95450, Chem. Commun. , 4887 (2007), etc., JP-A No. 2003-264010, JP-A No. 2004-63274, JP-A No. 2004-115636, JP-A No. 2004-200068, JP-A No. 2004-235052. Gazette, J.A. Am. Chem. Soc. , 12218, Vol. 126 (2004), Chem. Commun. , 3036 (2003), Angew. Chem. Int. Ed. , 1923, Vol. 47 (2008), etc .; Am. Chem. Soc. 16701, Vol. 128 (2006), J.M. Am. Chem. Soc. , 14256, Vol. 128 (2006), JP-A-11-86916, JP-A-11-214730, JP-A-2000-106224, JP-A-2001-76773, JP-A-2003-7359. Described in JP-A-11-214731, JP-A-11-238905, JP-A-2001-52766, JP-A-2001-76775, JP-A-2003-7360, etc. Dyes, 9-arylxanthene compounds described in JP-A-10-92477, JP-A-11-273754, JP-A-11-273755, JP-A-2003-3273, etc., JP-A-10-93118 And triarylmethane compounds described in JP-A-2003-31273 JP-9-199744, JP-A No. 10-233238, JP-A No. 11-204821, JP-A No. 11-265738, JP-J. Phys. Chem. , 2342, Vol. 91 (1987), J. MoI. Phys. Chem. B, 6272, Vol. 97 (1993), Electroanaly. Chem. , 31, Vol. 537 (2002), JP-A-2006-032260, J. Pat. Porphyrins Phthalocyanines, 230, Vol. 3 (1999), Angew. Chem. Int. Ed. , 373, Vol. 46 (2007), Langmuir, 5436, Vol. 24 (2008) etc., and the phthalocyanine compound, porphyrin compound, etc. can be mentioned. Among these, it is particularly preferable to use metal complex compounds, coumarin compounds, polyene compounds, indoline compounds, and thiophene compounds.

More preferably, a compound represented by the following structural formula (3), a compound represented by the following structural formula (4), and a compound represented by the following structural formula (5) are available.

As a method for adsorbing the photosensitizing material 5 to the electron transport layer 4, a method of immersing an electron current collecting electrode containing semiconductor particles in the photosensitizing material solution or dispersion, the solution or dispersion is used as the electron transport layer. It is possible to use a method of applying to and adsorbing to the surface.
In the former case, an immersion method, a dip method, a roller method, an air knife method, or the like can be used.
In the latter case, a wire bar method, a slide hopper method, an extrusion method, a curtain method, a spin method, a spray method, or the like can be used.
Further, it may be adsorbed in a supercritical fluid using carbon dioxide or the like.

When adsorbing the photosensitizing material, a condensing agent may be used in combination.
The condensing agent has a catalytic action that seems to physically or chemically bind the photosensitizing material and the electron transport compound to the inorganic surface, or acts stoichiometrically, and advantageously shifts the chemical equilibrium. Any of them may be used. Furthermore, a thiol or a hydroxy compound may be added as a condensation aid.

  Examples of the solvent for dissolving or dispersing the photosensitizing material include alcohol solvents such as water, methanol, ethanol, and isopropyl alcohol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl formate, acetic acid Ester solvents such as ethyl or n-butyl acetate; ether solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or dioxane; N, N-dimethylformamide, N, N-dimethylacetamide, or N-methyl- Amide solvents such as 2-pyrrolidone; dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenze Halogenated hydrocarbon solvents such as bromobenzene, iodobenzene or 1-chloronaphthalene; n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene , Hydrocarbon solvents such as o-xylene, m-xylene, p-xylene, ethylbenzene, and cumene can be used, and these can be used alone or as a mixture of two or more.

Further, depending on the type of photosensitizing material, there are materials that work more effectively when the aggregation between the compounds is suppressed. Therefore, an aggregating and dissociating agent may be used in combination.
The aggregating / dissociating agent is preferably a steroid compound such as cholic acid or chenodeoxycholic acid, a long-chain alkyl carboxylic acid or a long-chain alkyl phosphonic acid, and is appropriately selected depending on the photosensitizing material to be used.
The addition amount of these aggregating and dissociating agents is preferably 0.01 to 500 parts by mass, more preferably 0.1 to 100 parts by mass with respect to 1 part by mass of the photosensitizing material.

  The temperature at which these are used to adsorb the photosensitizing material or the photosensitizing material and the aggregating / dissociating agent is preferably from −50 ° C. to 200 ° C. Moreover, this adsorption may be carried out while standing or stirring.

  Examples of the stirring method include, but are not limited to, a stirrer, a ball mill, a paint conditioner, a sand mill, an attritor, a disperser, and ultrasonic dispersion. The time required for adsorption is preferably from 5 seconds to 1,000 hours, more preferably from 10 seconds to 500 hours, and even more preferably from 1 minute to 150 hours. Adsorption is preferably performed in a dark place.

<Ceramic membrane>
As the ceramic film 6 in the solar cell and the manufacturing method thereof, the matters described in the ceramic film of the photoelectric conversion device of the present invention and the manufacturing method thereof can be appropriately selected and applied.

<Second electrode>
The second electrode is applied after the ceramic film is formed.
The second electrode can be usually the same as the first electrode described above, and the support is not necessarily required in a configuration in which the strength and sealability are sufficiently maintained.
Specific examples of the second electrode material include metals such as platinum, gold, silver, copper, and aluminum, carbon compounds such as graphite, fullerene, carbon nanotube, and graphene, and conductive metal oxides such as ITO, FTO, and ATO. , Conductive polymers such as polythiophene and polyaniline.
The average thickness of the second electrode layer is not particularly limited, and may be used alone or in combination of two or more.
The coating of the second electrode can be appropriately formed on the hole transport layer by a method such as coating, laminating, vapor deposition, CVD, or bonding depending on the type of material used and the type of hole transport layer.

In order to operate as a photoelectric conversion device (photoelectric conversion element), at least one of the first electrode and the second electrode must be substantially transparent.
In the photoelectric conversion device of the present invention, a method in which the first electrode side is transparent and sunlight is incident from the first electrode side is preferable. In this case, it is preferable to use a material that reflects light on the second electrode side, and glass, plastic, or metal thin film on which metal, conductive oxide is deposited is preferable.
It is also effective to provide an antireflection layer on the sunlight incident side.

  The photoelectric conversion element of the present invention can be applied to a solar cell and a power supply device provided with the solar cell. As an application example, any device can be used as long as it has conventionally used a solar cell or a power supply device using the solar cell. For example, although it may be used for an electronic desk calculator or a solar cell for a wristwatch, examples of utilizing the characteristics of the photoelectric conversion element of the present invention include power supply devices such as a mobile phone, an electronic notebook, and electronic paper. Moreover, it can also be used as an auxiliary power source for extending the continuous use time of a rechargeable or dry battery type electric appliance. Furthermore, it can be used as an alternative to a primary battery combined with a secondary battery as a self-supporting power source for sensors.

[Organic electroluminescence device]
One embodiment of the photoelectric conversion device of the present invention is an organic electroluminescence (EL) element.
The organic EL element includes a support, a charge transport layer containing an organic charge transport material on the conductive support, and the ceramic film on the charge transport layer. Electrode), a hole transport layer, a light-emitting layer, and a cathode (second electrode), and further include other layers such as a barrier film as necessary.
A layer having an anode (first electrode), a hole transport layer, a light emitting layer, an electron transport layer as the charge transport layer, and a cathode (second electrode) may be referred to as an “organic EL layer”.
Although the case where a photoelectric conversion device is an organic EL element is demonstrated below, it is not limited only to an organic EL element, It can apply also to another photoelectric conversion device.

FIG. 7 shows an organic EL element 10C which is an embodiment of the photoelectric conversion device of the present invention. An organic EL element having a ceramic film as the outermost layer of the organic EL layer is provided. The organic EL element 10 </ b> C includes a substrate 2 as a support, an organic EL layer 3, and a ceramic film 4.
The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like can be changed within a range that can be conceived by those skilled in the art, and any aspect is possible. As long as the functions and effects of the present invention are exhibited, the scope of the present invention is included.

<Support (substrate)>
The substrate 2 as the support is made of an insulating substrate. The substrate 2 may be a plastic or film substrate.

A barrier film may be disposed on the main surface 2 a of the substrate 2.
The barrier film can be, for example, a film made of silicon, oxygen, and carbon, or a film made of silicon, oxygen, carbon, and nitrogen. Examples of the material for the barrier film include silicon oxide, silicon nitride, and silicon oxynitride. The average thickness of the barrier film is preferably from 100 nm to 10 μm.

<Organic EL layer>
The organic EL layer 3 includes a light emitting layer, and is a functional part that contributes to light emission of the light emitting layer, such as carrier movement and carrier coupling, according to the voltage applied to the anode and the cathode. For example, an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are formed by being laminated in order from the support substrate 2 side. The organic EL layer 3 and the organic EL element 300 shown in FIG. 1 are of a top emission type that emits light to the side opposite to the substrate 2.
There is no restriction | limiting in particular as the organic EL layer 3, A well-known organic EL element can be selected suitably according to the objective.
A transparent electrode is laminated as the cathode.
The transparent electrode is formed using a conductive metal oxide such as SnO ₂ , In ₂ O ₃ , ITO, IZO, ZnO: Al. When using a transparent electrode as a cathode, it is desirable to increase the electron injection efficiency by using the uppermost layer of the organic EL layer as an electron injection layer. The transparent electrode preferably has a transmittance of 50% or more, more preferably 85% or more with respect to light having a wavelength of 400 nm to 800 nm. The average thickness of the transparent electrode is preferably 50 nm or more, more preferably 50 nm to 1 μm, and further preferably 100 nm to 300 nm.

<Ceramic membrane>
As the ceramic film 4 in the organic EL element and the manufacturing method thereof, the matters described in the ceramic film of the photoelectric conversion device of the present invention and the manufacturing method thereof can be appropriately selected and applied.
The ceramic film 4 is provided on the cathode so as to embed the organic EL layer 3. The ceramic film 4 is disposed on the side opposite to the substrate 2 in the organic EL layer 3. The ceramic film 4 has a gas barrier function, particularly a moisture barrier function.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited to a following example. In the following description, “part” means “part by mass”.

(Example 1)
-Example of production of electrophotographic photosensitive member-
As shown in FIG. 5, the electrophotographic photosensitive member of Example 1 having an intermediate layer, a charge generation layer, a charge transport layer, and a ceramic semiconductor film in this order on the conductive support was produced by the following procedure.
--Formation of intermediate layer--
The following intermediate layer coating solution was applied to an aluminum conductive support (outer diameter 60 mm) by a dipping method to form an intermediate layer. The average thickness of the intermediate layer after drying at 170 ° C. for 30 minutes was 5 μm.

(Intermediate layer coating solution)
-Zinc oxide particles (MZ-300, manufactured by Teika Co., Ltd.): 350 parts-3,5-di-t-butylsalicylic acid: 1.5 parts (TCI-D1947, manufactured by Tokyo Chemical Industry Co., Ltd.)
Blocked isocyanate: 60 parts (Sumijoule (registered trademark) 3175, solid content concentration 75% by mass, manufactured by Sumika Bayer Urethane Co., Ltd.)
-Dissolved solution obtained by dissolving 20% by mass of butyral resin with 2-butanone: 225 parts (BM-1, manufactured by Sekisui Chemical Co., Ltd.)
2-butanone: 365 parts

-Formation of charge generation layer-
On the obtained intermediate layer, the following charge generation layer coating solution was dip coated to form a charge generation layer. The average thickness of the charge generation layer was 0.2 μm.

(Coating solution for charge generation layer)
-Y-type titanyl phthalocyanine: 6 parts-Butyral resin (ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.): 4 parts-2-butanone (manufactured by Kanto Chemical Co., Inc.): 200 parts

--Formation of charge transport layer 1--
On the obtained charge generation layer, the following charge transport layer coating solution 1 was dip-coated to form a charge transport layer 1.
The average thickness of the charge transport layer after drying at 135 ° C. for 20 minutes was 22 μm.

(Coating liquid 1 for charge transport layer)
-Bisphenol Z-type polycarbonate: 10 parts (Panlite TS-2050, manufactured by Teijin Limited)
-Low molecular charge transport material of the following structural formula (6): 10 parts;
・ Tetrahydrofuran: 80 parts

--Formation of ceramic film 1--
(Delafosite)
-Copper oxide (I) (Wako Pure Chemical Industries, Ltd.): 40.014 g
・ Alumina (AA-03, manufactured by Sumitomo Chemical Co., Ltd.): 28.52g

The thin film (thickness 1 μm) of the above copper aluminum oxide was formed on quartz glass by the following method to obtain a sample.
Next, the obtained sample was attached to an X-ray diffractometer (MiniFlex 600, manufactured by Rigaku Corporation), and the X-ray diffraction spectrum of the copper aluminum oxide was measured. The X-ray diffractometer was measured with a detector D / te X Ultra2 attached. The result is shown in FIG.
As shown in FIG. 9, the diffraction angle 2θ of the X-ray diffraction spectrum in copper aluminum oxide is 31.5 ° or more and 32.5 ° or less, 35.5 ° or more and 37.5 ° or less, and 45.5 ° or more. It has a peak at any of 47.5 ° or less.
Furthermore, a thin film having an average film thickness of 1.7 μm was formed on ITO glass by using the copper aluminum oxide by the following method. This was provided with a gold counter electrode by a vacuum deposition method to produce a sandwich type cell.
This cell was attached to a time-of-flight measuring device (TOF-401, manufactured by Sumitomo Heavy Industries Mechatronics Co., Ltd.), and the hole mobility was measured. Specifically, the hole mobility is set such that the electric field strength in the sample is set to 2 × 10 ⁵ V / cm by setting a time-of-flight measuring apparatus so as to apply a voltage of 34 V to a sample having an average film thickness of 1.7 μm. Was 1 × 10 ⁻⁴ cm ² / Vsec.

Delafossite was prepared by the following procedure. Copper (I) oxide and alumina are weighed, transferred to a mayonnaise bin, and the mayonnaise bin is fixed to a sample table of a vibration shaker (VIBRAX-VXR Basic, manufactured by IKA) and vibrated at a vibration intensity of 1,500 rpm for 1 hour. The mixture was mixed and heated at 1,100 ° C. for 24 hours to obtain copper aluminate. Delafossite powder having a number average particle diameter of 1 μm obtained by pulverizing this in a mortar was used.
As a film forming chamber, a commercially available vapor deposition apparatus (VPC-400, manufactured by ULVAC) was used.
As an aerosol generator, a commercially available stirrer (TK AZ homomixer 2M-03 type, manufactured by Primix Co., Ltd.) was used. In addition, as an aerosol generator, you may use what installed the commercially available volume 1 liter pressurization bottle (RBN-S, the KSK company make) in the ultrasonic cleaner (SUS-103, the Shimadzu Corporation make).

  A pipe having an inner diameter of 4 mm was drawn from the aerosol generator into the film forming chamber, and an injection nozzle (YB1 / 8MSSP37, manufactured by Spraying System Japan) was attached to the tip of the pipe. A photoconductor was installed at a position 2 mm away from the spray nozzle. A movable type movable in the horizontal direction was used as the photosensitive member holder, and a movable type movable in the vertical direction was used as the ejection nozzle. By moving the photosensitive member holder and the ejection nozzle, the area for film formation can be determined. On the other hand, an aerosol generator and a gas cylinder filled with nitrogen were connected by a pipe having an inner diameter of 4 mm.

Using the apparatus, a ceramic film 1 having an average thickness of 1.0 μm was produced as follows.
40 g of delafossite having a number average particle diameter of 1 μm was charged into an aerosol generator. Next, a vacuum was drawn from the deposition chamber to the aerosol generator by an exhaust pump. Then, nitrogen gas was sent from the gas cylinder into the aerosol generator, stirring was started, and an aerosol in which particles were dispersed in the nitrogen gas was generated. The generated aerosol was ejected from the ejection nozzle toward the photoreceptor via a pipe. At this time, the flow rate of nitrogen gas was set to 13 L / min to 20 L / min. The film formation time was 20 minutes, and the degree of vacuum in the film formation chamber when the ceramic film 1 was formed was about 50 Pa to 150 Pa. A predetermined film forming area was formed by moving the substrate holder and the injection nozzle.
The number average particle diameter of delafossite was measured from image analysis obtained with a confocal microscope (OPTELICS H-1200, manufactured by Lasertec Corporation).

(Example 2)
In Example 1, instead of the ceramic film 1, the crosslinked surface layer 1 was formed according to the following procedure, and the ceramic film 1 was formed on the crosslinked surface layer 1 in the same manner as in Example 1, except that The electrophotographic photosensitive member of Example 2 was manufactured.

--Formation of crosslinked surface layer 1--
On the obtained charge transport layer, the following coating solution 1 for a cross-linked surface layer was spray-coated in a nitrogen stream and then left to stand in a nitrogen stream for 10 minutes to dry by touch.
Further, it was dried at 130 ° C. for 20 minutes. The average thickness of the surface layer of the crosslinked resin was 4.5 μm.
(Coating liquid 1 for crosslinked surface layer)
-Bisphenol Z polycarbonate: 75 parts (Panlite TS-2050, manufactured by Teijin Limited)
Aluminum oxide: 25 parts (Sumicorundum AA03, average particle size: 300 nm, manufactured by Sumitomo Chemical Co., Ltd.)
・ Surfactant (BYK-P104, manufactured by BYK-Chemie): 0.5 part ・ Tetrahydrofuran: 1,330 parts ・ Cyclohexanone: 570 parts

(Example 3)
In Example 1, instead of the ceramic film 1, the crosslinked surface layer 2 was formed by the following procedure, and the ceramic film 1 was formed on the crosslinked surface layer 2 in the same manner as in Example 1, except that An electrophotographic photosensitive member of Example 3 was produced.

--Formation of crosslinked surface layer 2--
On the obtained charge transport layer, the following coating solution 2 for a cross-linked surface layer was spray-coated in a nitrogen stream, then left in a nitrogen stream for 10 minutes and dried by touch. Thereafter, light irradiation was performed under the following conditions in a UV irradiation booth in which the inside of the booth was replaced with nitrogen gas so that the oxygen concentration was 2% or less.
Further, it was dried at 130 ° C. for 20 minutes. The average thickness of the surface layer of the crosslinked resin was 4.5 μm.
(Light irradiation conditions)
・ Metal halide lamp: 160 W / cm
・ Irradiation distance: 120mm
・ Irradiation intensity: 700 mW / cm ²
・ Irradiation time: 60 seconds

(Crosslinked surface layer coating solution 2)
Trimethylolpropane triacrylate: 5 parts (KAYARAD TMPTA, manufactured by Nippon Kayaku Co., Ltd., acrylic equivalent: 99, trifunctional or higher functional radical polymerizable compound having no charge transporting structure)
Dipentaerythritol caprolactone-modified hexaacrylate: 5 parts (KAYARAD DPCA-120, manufactured by Nippon Kayaku Co., Ltd., acrylic equivalent: 324)
-Radical polymerizable compound represented by the following structural formula (7): 10 parts (Radically polymerizable compound having a monofunctional charge transporting structure, acrylic equivalent 420)
1-hydroxy-cyclohexyl-phenyl-ketone: 1 part (Irgacure 184, manufactured by Ciba Specialty Chemicals, photopolymerization initiator)
・ Tetrahydrofuran: 100 parts

Example 4
In Example 1, the electrophotographic photosensitive member of Example 4 was produced in the same manner as in Example 1 except that the charge transport layer 1 was replaced with the charge transport layer 2 produced by the following procedure.

--Formation of charge transport layer 2--
(Coating liquid 2 for charge transport layer)
・ Delafossite with a number average particle diameter of 1 μm: 68.534 g
・ Silica (manufactured by ULVAC) 68.534g

As a film forming chamber, a commercially available vapor deposition apparatus (VPC-400, manufactured by ULVAC) was used.
As the aerosol generator, a commercially available stirrer (TK Adihomomixer 2M-03, manufactured by Primix Co., Ltd.) was used.

  A pipe having an inner diameter of 4 mm was drawn from the aerosol generator into the film forming chamber, and an injection nozzle (YB1 / 8MSSP37, manufactured by Spraying System Japan) was attached to the tip of the pipe. A photoconductor was installed at a position 2 mm away from the spray nozzle. A movable type movable in the horizontal direction was used as the photosensitive member holder, and a movable type movable in the vertical direction was used as the ejection nozzle. By moving the photosensitive member holder and the ejection nozzle, the area for film formation can be determined. On the other hand, an aerosol generator and a gas cylinder filled with nitrogen were connected by a pipe having an inner diameter of 4 mm.

Using the apparatus, a charge transport layer 2 having an average thickness of 1.0 μm was produced as follows.
The charge transport layer coating solution 2 was charged into an aerosol generator. Next, a vacuum was drawn from the deposition chamber to the aerosol generator by an exhaust pump. Then, nitrogen gas was sent from the gas cylinder into the aerosol generator, stirring was started, and an aerosol in which particles were dispersed in the nitrogen gas was generated. The generated aerosol was ejected from the ejection nozzle toward the photoreceptor via a pipe. At this time, the flow rate of nitrogen gas was set to 13 L / min to 20 L / min. The film formation time was 60 minutes, and the degree of vacuum in the film formation chamber when forming the charge transport layer was about 50 Pa to 150 Pa. A predetermined film forming area was formed by moving the substrate holder and the injection nozzle.

(Example 5)
In Example 1, the electrophotographic photosensitive member of Example 5 was manufactured in the same manner as in Example 1 except that the ceramic film 1 was replaced with the ceramic film 2 produced by the following procedure.

--Formation of ceramic film 2--
As the stratification chamber, a commercially available vapor deposition apparatus (VPC-400, manufactured by ULVAC) was used.
As the aerosol generator, a commercially available stirrer (TK Adihomomixer 2M-03, manufactured by Primix Co., Ltd.) was used.

  A pipe having an inner diameter of 4 mm was drawn into the stratification chamber from the aerosol generator, and an injection nozzle (YB1 / 8MSSP37, manufactured by Spraying System Japan) was attached to the tip of the pipe. A photoconductor was installed at a position 2 mm away from the spray nozzle. A movable type movable in the horizontal direction was used as the photosensitive member holder, and a movable type movable in the vertical direction was used as the ejection nozzle. By moving such a photosensitive member holder and a jet nozzle, the area to be stratified can be determined. On the other hand, an aerosol generator and a gas cylinder filled with nitrogen were connected by a pipe having an inner diameter of 4 mm.

Using the apparatus, a ceramic film 2 having an average thickness of 1.0 μm was produced as follows.
40 g of alumina powder (manufactured by Sumitomo Chemical Co., Ltd.) having a number average particle diameter of 1 μm was charged into the aerosol generator. Next, a vacuum was drawn from the deposition chamber to the aerosol generator by an exhaust pump. Then, nitrogen gas was sent from the gas cylinder into the aerosol generator, stirring was started, and an aerosol in which particles were dispersed in the nitrogen gas was generated. The generated aerosol was ejected from the ejection nozzle toward the photoreceptor via a pipe. At this time, the flow rate of nitrogen gas was set to 13 L / min to 20 L / min. The film formation time was 20 minutes, and the degree of vacuum in the film formation chamber when the ceramic film 2 was formed was about 50 Pa to 150 Pa. A predetermined film forming area was formed by moving the substrate holder and the injection nozzle.
The number average particle diameter of the alumina powder was measured from image analysis obtained with a confocal microscope (OPTELICS H-1200, manufactured by Lasertec Corporation).

(Comparative Example 1)
An electrophotographic photoreceptor of Example 5 was produced in the same manner as in Example 1 except that the ceramic film 1 was replaced with the crosslinked surface layer 2 in Example 1.

(Comparative Example 2)
In Example 1, an electrophotographic photosensitive member of Example 5 was produced in the same manner as in Example 1 except that the ceramic film 1 was replaced with a protective layer prepared by the following procedure.

--Formation of protective layer--
[Coating liquid for protective layer]
-Bisphenol Z polycarbonate: 100 parts (Panlite TS-2050, manufactured by Teijin Limited)
Aluminum (Al) -doped zinc oxide: 33.3 parts (Pazet CK, average particle size 34 nm, manufactured by Hakusui Tech Co., Ltd.)
Surfactant (polymer of low molecular weight unsaturated polycarboxylic acid): 1.7 parts (BYK-P105, manufactured by BYK Chemie)
・ Tetrahydrofuran: 2,667 parts ・ Cyclohexanone: 667 parts

The protective layer coating solution was prepared as follows.
First, in a 50 mL container charged with 110 g of zirconia beads (average particle size: 0.1 mm), Al-doped zinc oxide, a surfactant, and cyclohexanone are placed, and vibration dispersion is performed for 2 hours under a vibration condition of 1,500 rpm. Then, a dispersion liquid in which Al-doped zinc oxide was dispersed was prepared. Next, the dispersion was transferred to a 50 mL container charged with 60 g of sirconia beads (average particle size: 5 mm), and dispersed for 24 hours at a rotation speed of 200 rpm to prepare a mill base.
And the said mill base was added to the tetrahydrofuran solution which melt | dissolved the bisphenol Z polycarbonate, and the coating liquid for protective layers of the said composition was prepared.

<Evaluation of electrophotographic photoreceptor>
The following evaluation was carried out on the electrophotographic photoreceptors of Examples 1 to 5 and Comparative Examples 1 and 2 produced as described above. Table 1 shows the evaluation results for each electrophotographic photosensitive member.
<< NO ₂ image evaluation after exposure >>
First, the electrophotographic photosensitive member is allowed to stand in a NO ₂ atmosphere for a certain period of time, thereby adsorbing NO ₂ on the surface of the electrophotographic photosensitive member. As this exposure condition, as a result of examining the condition that NO ₂ adsorption is saturated at the adsorption site in the vicinity of the surface of the electrophotographic photosensitive member using various electrophotographic photosensitive members, 24 hours in a chamber controlled to a concentration of 40 ppm is obtained. Since it was found that exposure was preferable, the exposure conditions were an NO ₂ concentration of 40 ppm atmosphere and an exposure time of 24 hours.

In addition, Ricoh Pro C9110 (manufactured by Ricoh Co., Ltd.) modified to eliminate the initial idling process at the time of image output was used for image evaluation after NO ₂ exposure, Pro toner black C9100 was used, and A3 size paper was used. Image evaluation was performed using a copy paper (POD gloss coat, manufactured by Oji Paper Co., Ltd.).
As an output image, three halftone outputs are performed continuously at the timing when 0, 1,000, and 10,000 evaluation patterns are printed, and the dot reproduction state of the three output images is visually and microscopically displayed. And evaluated based on the following evaluation criteria.
〔Evaluation criteria〕
◎: No change in the dot reproduction status of the three output images, no problem 〇: There is a slight change in the dot reproduction status of the three output images, but there is no problem in actual use ×: There is a clear density change in the dot reproduction state

From the results in Table 1, it can be seen that the electrophotographic photoreceptors obtained in Examples 1 to 5 can obtain stable image quality even after exposure to NO ₂ . As a result, it has been found that the layer formed on the outermost surface of the electronic device of the present invention is a photoconductor that is suitable for photoconductor use and also has durability against chemical hazards.

(Example 6)
-Examples of solar cell production-
--- Production of titanium oxide semiconductor electrode--
A dense hole blocking layer 3 of titanium oxide was formed on the ITO glass substrate by reactive sputtering with oxygen gas using a target made of metallic titanium.
Next, 3 g of titanium oxide (P90, manufactured by Nippon Aerosil Co., Ltd.), 0.2 g of acetylacetone, 0.3 g of a surfactant (polyoxyethylene octylphenyl ether, manufactured by Wako Pure Chemical Industries, Ltd.), 5.5 g of water, and The bead mill process was performed for 12 hours with 1.0 g of ethanol.
1.2 g of polyethylene glycol (# 20,000) was added to the obtained dispersion to prepare a paste.
This paste was applied on the hole blocking layer so as to have an average thickness of 1.5 μm, dried at room temperature, and then baked at 500 ° C. for 30 minutes in the air to form a porous electron transport layer 4.

--- Production of dye-sensitized solar cell--
The titanium oxide semiconductor electrode was immersed in an acetonitrile / t-butanol solution (volume ratio 1: 1) with 0.5 mM of the compound represented by the structural formula (5) (manufactured by Mitsubishi Paper Industries Co., Ltd.) as an organic sensitizing dye. The sensitizing dye electrode layer was formed by allowing to stand in a dark place for 1 hour to adsorb the organic sensitizing dye.

--- Production of ceramic semiconductor film--
As a film forming chamber, a commercially available vapor deposition apparatus (VPC-400, manufactured by ULVAC) was used.
As the aerosol generator, a commercially available stirrer (TK Adihomomixer 2M-03, manufactured by Primix Co., Ltd.) was used.

  A pipe having an inner diameter of 4 mm was drawn from the aerosol generator into the film forming chamber, and an injection nozzle (YB1 / 8MSSP37, manufactured by Spraying System Japan) was attached to the tip of the pipe. A dye-sensitized solar cell was installed at a position 2 mm away from the spray nozzle. A movable type movable in the horizontal direction was used as the holder, and a movable type movable in the vertical direction was used as the injection nozzle. By moving the holder and the injection nozzle, the area for film formation can be determined. On the other hand, an aerosol generator and a gas cylinder filled with nitrogen were connected by a pipe having an inner diameter of 4 mm.

Using the apparatus, a ceramic semiconductor film having an average thickness of 1.0 μm was produced on a semiconductor electrode carrying an organic sensitizing dye as follows.
40 g of alumina powder (manufactured by Sumitomo Chemical Co., Ltd.) having a number average particle diameter of 1 μm was charged into the aerosol generator. Next, a vacuum was drawn from the deposition chamber to the aerosol generator by an exhaust pump. Then, nitrogen gas was sent from the gas cylinder into the aerosol generator, stirring was started, and an aerosol in which particles were dispersed in the nitrogen gas was generated. The generated aerosol was ejected from the ejection nozzle toward the photoreceptor via a pipe. At this time, the flow rate of nitrogen gas was set to 13 L / min to 20 L / min. The film formation time was 20 minutes, and the degree of vacuum in the film formation chamber when the ceramic semiconductor film was formed was about 50 Pa to 150 Pa. By moving the substrate holder and the injection nozzle, a ceramic semiconductor film was formed in a predetermined film formation area.
Silver was vacuum-deposited on the ceramic semiconductor film to a thickness of 100 nm to produce a second electrode, and a solar cell of Example 6 was produced.

(Comparative Example 3)
In Example 6, a solar cell of Comparative Example 3 was produced in the same manner as in Example 6 except that the following hole transport layer was produced instead of the production of the ceramic semiconductor film.
--- Fabrication of hole transport layer-
Organic hole transport material represented by the following structural formula (8) (compound name: 2,2 ′, 7,7′-tetrakis (N, N-di-p-methoxyphenylamino) -9,9′-spirobi Fluorene, product number: SHT-263, manufactured by Merck & Co., Inc.): 95 mmol (solid content: 14% by mass) was dissolved in a chlorobenzene solution. A hole transport layer was formed on the prepared solution by spin coating on a semiconductor electrode carrying an organic sensitizing dye.
Silver was vacuum deposited on the hole transport layer to a thickness of 100 nm to produce a second electrode, and a solar cell of Comparative Example 3 was produced.

<Evaluation of dye-sensitized solar cell>
About the dye-sensitized solar cell of Example 6 and Comparative Example 3 obtained as described above, in a 23 ° C. and 55% RH environment and under white LED irradiation after 24 hours (300 lux, 75 uW / cm ² ). The photoelectric conversion efficiency was measured. Next, it was stored in an environment of 30 ° C. and 90% RH for 1 month, and the photoelectric conversion efficiency was measured by the same method. The photoelectric conversion efficiency reduction rate x from 23 ° C. and 55% RH was determined by the following formula.
(formula)
(Conversion reduction rate x) = (Photoelectric conversion efficiency after storage at 30 ° C. and 90% RH) / (Photoelectric conversion efficiency at 23 ° C. and 55% RH)

  A desk lamp CDS-90α (Study Mode, manufactured by Cosmo Techno Co., Ltd.) was used as the white LED, and a solar cell evaluation system As-510-PV03 (manufactured by NF Circuit Design Block Co., Ltd.) was used as the evaluation device.

  As a result, the solar cell created in Example 6 had 23 ° C. and 55% RH conversion efficiency = 19.73% and the conversion efficiency reduction rate x = 10%, and the solar cell produced in Comparative Example 3 had 23 ° C. 55 % RH conversion efficiency = 20.11%, conversion efficiency reduction rate x = 25%.

(Example 7)
An organic EL device was produced according to Example 1 of JP-A-2003-007473.
Specifically, as an anode, an indium-tin oxide (ITO) film formed by sputtering on a glass substrate with a SiO ₂ layer as an undercoat layer and having a surface resistance of 15 Ω / □ is used. After sequentially washing with a cleaning agent and isopropyl alcohol, it was set in a vacuum deposition apparatus and evacuated to a vacuum of 1 × 10 ⁻⁴ Pa. The following compound HTM-1 is 40 nm as the hole transport layer, the following compound EM-1 is 15 nm as the light emitting layer, and the following compound No. 1 is used as the second electron transport layer. 1- 20 nm, 8-hydroxyquinolinol aluminum complex as a first electron transport layer was sequentially deposited by 30 nm. Further, a mask was set on the substrate, a cathode alloy of Mg: Ag = 10: 1 (deposition rate ratio) was formed to 200 nm, and an EL device having a light emission area of 2 mm × 2 mm square was produced. The substrate temperature during vapor deposition was room temperature.

--- Production of ceramic semiconductor film--
After forming the cathode, a ceramic semiconductor film was produced by the following method in a nitrogen atmosphere (inert atmosphere) without being exposed to the air.
As a film forming chamber, a commercially available vapor deposition apparatus (VPC-400, manufactured by ULVAC) was used.
As the aerosol generator, a commercially available stirrer (TK Adihomomixer 2M-03, manufactured by Primix Co., Ltd.) was used.

  A pipe having an inner diameter of 4 mm was drawn from the aerosol generator into the film forming chamber, and an injection nozzle (YB1 / 8MSSP37, manufactured by Spraying System Japan) was attached to the tip of the pipe. An organic EL element was installed at a position 2 mm away from the spray nozzle. A movable type movable in the horizontal direction was used as the holder, and a movable type movable in the vertical direction was used as the injection nozzle. By moving the holder and the injection nozzle, the area for film formation can be determined. On the other hand, an aerosol generator and a gas cylinder filled with nitrogen were connected by a pipe having an inner diameter of 4 mm.

Using the above apparatus, a ceramic semiconductor film having an average thickness of 1.0 μm was produced on the cathode as follows.
40 g of zinc oxide particles (MZ-300, manufactured by Teika Co., Ltd.) was charged into an aerosol generator. Next, a vacuum was drawn from the deposition chamber to the aerosol generator by an exhaust pump. Then, nitrogen gas was sent from the gas cylinder into the aerosol generator, stirring was started, and an aerosol in which particles were dispersed in the nitrogen gas was generated. The generated aerosol was ejected from the ejection nozzle toward the photoreceptor via a pipe. At this time, the flow rate of nitrogen gas was set to 13 L / min to 20 L / min. The film formation time was 20 minutes, and the degree of vacuum in the film formation chamber when the ceramic semiconductor film was formed was about 50 Pa to 150 Pa. By moving the substrate holder and the injection nozzle, a ceramic semiconductor film was formed in a predetermined film formation area.

(Comparative Example 4)
In Example 7, an organic EL layer in which an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode were laminated in this order on a substrate was formed without forming a ceramic semiconductor film. Except for this, an organic EL element of Comparative Example 4 was produced in the same manner as in Example 7.

<Evaluation of organic EL element>
The organic EL elements of Example 7 and Comparative Example 4 manufactured as described above were driven to measure the element lifetime.
The element lifetime was evaluated based on LT80 represented by the time from the start of driving until the luminance dropped to 80, assuming that the luminance at the start of driving was 100. The element lifetime was measured by driving the organic EL element with a constant current of 10 mA / cm ² . The driving voltage is a voltage when the organic EL element is driven with a constant current of 10 mA / cm ² . The current efficiency is a value when the luminance is 1000 cd / m ² (that is, 1000 nit).
As a result of the measurement, the element lifetime (LT80) of the organic EL element of Example 7 was 15 hours, and the element lifetime (LT80) of the organic EL element of Comparative Example 4 was 1 hour.

As an aspect of this invention, it is as follows, for example.
<1> a support;
On the support, a charge transport layer containing an organic charge transport material, or a sensitizing dye electrode layer containing an organic sensitizing dye,
A photoelectric conversion device comprising a ceramic film on the charge transport layer or the sensitizing dye electrode layer.
<2> The photoelectric conversion device according to <1>, wherein the ceramic film is a ceramic semiconductor film.
<3> The photoelectric conversion device according to <2>, wherein the charge mobility of the ceramic semiconductor film at an electric field strength of 2 × 10 ⁵ V / cm is 1 × 10 ⁻⁶ cm ² / Vsec or more.
<4> The photoelectric conversion device according to any one of <2> to <3>, wherein the ceramic semiconductor film includes delafossite.
<5> The diffraction angle 2θ of the X-ray diffraction spectrum in the ceramic semiconductor film is 31.5 ° to 32.5 °, 35.5 ° to 37.5 °, and 45.5 ° to 47.5 °. The photoelectric conversion device according to any one of <1> to <4>, which has a peak in any of the following.
<6> The photoelectric conversion device according to any one of <1> to <5>, which is an electrophotographic photosensitive member.
<7> A process cartridge comprising the photoelectric conversion device according to <6>.
<8> An image forming apparatus comprising the photoelectric conversion device according to <6>.
<9> The photoelectric conversion device according to any one of <1> to <5>, which is a solar battery.
<10> The photoelectric conversion device according to any one of <1> to <5>, wherein the photoelectric conversion device is an organic electroluminescence element.

  The photoelectric conversion device according to any one of <1> to <6> and <9> to <10>, the process cartridge according to <7>, and the image forming apparatus according to <8> are conventionally known. The above problems can be solved and the object of the present invention can be achieved.

Japanese Patent Laying-Open No. 2015-141269 JP 2008-180937 A JP 2011-1000087 A

10 Electrostatic latent image carrier (electrophotographic photoreceptor)
10B Solar cell 10C Organic electroluminescence element 100A Image forming apparatus 100B Image forming apparatus 110 Process cartridge

Claims (10)

A support;
On the support, a charge transport layer containing an organic charge transport material, or a sensitizing dye electrode layer containing an organic sensitizing dye,
A photoelectric conversion device comprising a ceramic film on the charge transport layer or the sensitizing dye electrode layer.   The photoelectric conversion device according to claim 1, wherein the ceramic film is a ceramic semiconductor film. The photoelectric conversion device according to claim 2, wherein the ceramic semiconductor film has a charge mobility of 1 × 10 ⁻⁶ cm ² / Vsec or more at an electric field strength of 2 × 10 ⁵ V / cm.   The photoelectric conversion device according to claim 2, wherein the ceramic semiconductor film includes delafossite.   The diffraction angle 2θ of the X-ray diffraction spectrum in the ceramic semiconductor film is any of 31.5 ° to 32.5 °, 35.5 ° to 37.5 °, and 45.5 ° to 47.5 °. The photoelectric conversion device according to claim 4 having a crab peak.   The photoelectric conversion device according to claim 1, which is an electrophotographic photosensitive member.   A process cartridge comprising the photoelectric conversion device according to claim 6.   An image forming apparatus comprising the photoelectric conversion device according to claim 6.   It is a solar cell, The photoelectric conversion device in any one of Claim 1 to 5.   The photoelectric conversion device according to claim 1, which is an organic electroluminescence element.