Metal oxide particles with p-type semiconductivity, electronic devices using them, methods for manufacturing electronic devices, and imaging devices.

Abstract

Metal oxide particles with p-type semiconductivity are provided. The metal oxide particles have a volume-based particle size distribution having a first local maxima and a second local maxima. The first local maxima is in the range of 0.1 μm or greater and less than 5 μm, and the second local maxima is in the range of 5 μm or greater and less than 50 μm. The ratio of the second local maxima to the first local maxima is 0.5 or greater and less than 2.0, and 99% or more of the volume of the metal oxide particles has a particle size in the range of 0.1–50 μm.

Description

Technical Field

[0001] This invention relates to metal oxide particles having p-type semiconductivity, electronic devices using the same, methods for manufacturing electronic devices, and imaging apparatus. Background Technology

[0002] In recent years, progress has been made in the development of optoelectronic conversion devices containing semiconductors formed from organic materials, and these devices have been launched into the market.

[0003] Currently, most photoelectric conversion devices, such as those used in electrophotographic photosensitive devices, are organic electronic devices formed from organic materials. However, organic electronic devices have a shorter lifespan than inorganic electronic devices. One reason is the poor gas barrier properties of the organic materials contained in organic electronic devices. The resin film of organic materials has more gaps than the dense film of inorganic materials. Therefore, food packaging materials such as polypropylene (PP) are laminated with aluminum to improve the weather resistance of the contents.

[0004] Compared to silicon-based solar cells, dye-sensitized solar cells containing organic sensitizing dyes have been developed as a low-cost organic solar cell.

[0005] However, since the dye-sensitized solar cells mentioned above are organic materials containing organic sensitizing dyes, the properties of the materials used are affected by gases such as temperature, humidity, oxygen, ozone, NOx and ammonia, which causes their function to deteriorate easily and their durability to be worse than that of silicon-based solar cells.

[0006] In display elements such as organic electroluminescent (EL) elements, light-emitting diode (LED) display elements, liquid crystal display elements, and electrophoretic ink display elements, an organic EL light-emitting layer sandwiched between an anode and a cathode is stacked on a substrate. Organic EL display devices offer wider viewing angles and faster response times than liquid crystal display devices, and due to the diversity of light emission from organic materials, they are highly anticipated as next-generation display devices. From a productivity and cost perspective, coating formation is used as a method for forming these organic EL elements. However, organic EL elements are prone to degradation when exposed to heat, moisture, or gases such as oxygen, resulting in a shortened lifespan.

[0007] Various attempts have been made to improve gas barrier properties in order to extend the lifespan of organic electronic devices such as electrophotographic photosensitive elements for printers, dye-sensitized solar cells, and organic EL elements. However, due to the large number of manufacturing processes and the adverse effects they have, there is room for further improvement in the balance between cost and durability.

[0008] Electrophotographic photosensitive materials with excellent wear resistance and image characteristic stability have been proposed, for example, to include p-type semiconductor particles treated with a surface treatment agent in the protective layer (see Patent Document 1).

[0009] In addition, as an organic EL device with long lifespan, high efficiency and low operating voltage, an organic EL device has been proposed, for example, by replacing the organic hole transport layer of the organic EL device with an inorganic p-type semiconductor (see Patent Document 2).

[0010] In addition, a laminated structure of a polycrystalline brittle material layer was proposed, which is formed by depositing ultrafine particle materials such as ceramic or metal materials with a particle size of less than 100 μm on a substrate through aerosol deposition. (See Patent Document 3).

[0011] In addition, a method for controlling the particle size distribution of zirconia particles and forming a white zirconia film by aerosol deposition was proposed (see Patent Document 4).

[0012] Wear resistance and gas barrier properties can be improved by applying a metal oxide with p-type semiconductivity to the surface. A specific viscoelasticity of the coating surface in a laminate in which a plastic substrate is coated with ceramic has been proposed (see Patent Document 5). However, simply applying a ceramic coating to the plastic substrate is insufficient to obtain precise semiconductor properties.

[0013] Citation List

[0014] Patent documents

[0015] [Patent Document 1] Japanese Patent No. 5664538

[0016] [Patent Document 2] Japanese Unexamined Patent Application Publication No. 2000-150166

[0017] [Patent Document 3] Japanese Unexamined Patent Application Publication No. 2008-201004

[0018] [Patent Document 4] Japanese Unexamined Patent Application Publication No. 2017-179421

[0019] [Patent Document 5] WO2018 / 194064 Summary of the Invention

[0020] Technical issues

[0021] The object of the present invention is to provide metal oxide particles that exhibit high gas barrier properties and p-type semiconductivity when metal oxide films are formed.

[0022] Solution to the problem

[0023] According to embodiments of the present invention, metal oxide particles having p-type semiconductivity are provided. The metal oxide particles have a volume-based particle size distribution having a first local maxima and a second local maxima. The first local maxima are in the range of 0.1 μm or greater and less than 5 μm, and the second local maxima are in the range of 5 μm or greater and less than 50 μm. The ratio of the second local maxima to the first local maxima is 0.5 or greater and less than 2.0, and 99% or more of the volume of the metal oxide particles has a particle size in the range of 0.1-50 μm.

[0024] Effects of the present invention

[0025] According to the present invention, metal oxide particles exhibiting p-type semiconductivity with high gas barrier properties can be provided during metal oxide film formation. Attached Figure Description

[0026] The accompanying drawings are intended to illustrate exemplary embodiments of the invention and should not be construed as limiting its scope. Unless explicitly stated otherwise, the drawings should not be considered to be drawn to scale. Furthermore, the same or similar reference numerals denote the same or similar components in several views.

[0027]

Figure 1

[0028] Figure 1 This is a perspective schematic diagram illustrating an example of an aerosol deposition apparatus used in forming the metal oxide film of the present invention.

[0029]

Figure 2

[0030] Figure 2 This is a cross-sectional view showing an example of the device (electrophotographic photosensitive device) of the present invention.

[0031]

Figure 3

[0032] Figure 3 This is a perspective schematic diagram illustrating an example of the imaging device of the present invention.

[0033]

Figure 4

[0034] Figure 4 This is a perspective schematic diagram illustrating another example of the imaging device of the present invention.

[0035]

Figure 5

[0036] Figure 5 This is a perspective schematic diagram illustrating an example of an imaging method in the imaging apparatus of the present invention.

[0037]

Figure 6

[0038] Figure 6 This is a perspective schematic diagram illustrating another example of the imaging device of the present invention.

[0039]

Figure 7

[0040] Figure 7 This is a perspective schematic diagram illustrating another example of the imaging device of the present invention.

[0041]

Figure 8

[0042] Figure 8 This is a cross-sectional view illustrating an example of the device (solar cell) of the present invention.

[0043]

Figure 9

[0044] Figure 9 This is a cross-sectional view illustrating an example of the device (organic EL element) of the present invention.

[0045]

Figure 10

[0046] Figure 10 This is a particle size distribution diagram of the metal oxide particles 1 with p-type semiconductivity of the present invention shown in the embodiment. Detailed Implementation

[0047] The terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the invention. The singular forms “a,” “an,” and “the” as used herein are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0048] However, the disclosure in this specification is not intended to be limited to the specific terms chosen, and should be understood to include all technical equivalents that have similar functions, operate in a similar manner, and achieve similar results.

[0049] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0050] electronic devices

[0051] The electronic device of the present invention (hereinafter also referred to as the "device") comprises, in sequence, a substrate, a charge transport layer containing a charge transport substance or a dye sensitized electrode layer containing a sensitized dye covering the substrate, a metal oxide film, wherein the metal oxide film comprises a metal oxide having p-type semiconductivity, and further comprises a silicon-containing layer and other components if necessary.

[0052] There are no particular restrictions on the electronic devices mentioned above, and appropriate selections can be made according to the purpose. Specific examples include, but are not limited to, electrophotographic photosensitive devices, solar cells, organic electroluminescent (EL) elements, transistors, integrated circuits, laser diodes, light-emitting diodes, and other devices.

[0053] silicon-containing layer

[0054] The device of the present invention preferably has a silicon-containing layer between the charge transport layer or dye-sensitized electrode layer and the metal oxide film. As the silicon-containing layer, any polysiloxane structure is acceptable, and there are no particular limitations; it can be appropriately selected according to the purpose.

[0055] By including the aforementioned silicon-containing layer with a polysiloxane structure, laminated structures of films formed from organic materials and films formed from metal oxides can be easily and inexpensively manufactured. The aforementioned silicon-containing layer has the effect of inhibiting substrate erosion during the formation of the metal oxide layer and preventing the peeling of the metal oxide layer.

[0056] The aforementioned silicon-containing layer is formed, for example, by crosslinking an organosilicon compound having any of the following: hydroxyl groups or hydrolyzable groups. If necessary, it may further include a catalyst, a crosslinking agent, an organosilicon sol, a silane coupling agent, and / or a polymer such as an acrylic polymer.

[0057] There are no particular limitations on the crosslinking method described above; it can be selected appropriately according to the purpose, with thermal crosslinking being preferred.

[0058] Examples of organosilicon compounds having either a hydroxyl group or a hydrolyzable group include, but are not limited to, compounds having an alkoxysilyl group, partially hydrolyzed condensates of compounds having an alkoxysilyl group, or mixtures thereof.

[0059] Specific examples of the compounds having an alkoxysilyl group include, but are not limited to, tetraalkoxysilanes such as tetraethoxysilane, alkyltrialkoxysilanes such as methyltriethoxysilane, and aryltrialkoxysilanes such as phenyltriethoxysilane. Additionally, compounds incorporating an epoxy group, methacrylyl group, or vinyl group may also be used.

[0060] The partially hydrolyzed condensates of the above-mentioned compounds containing alkoxysilyl groups can be produced by known methods such as adding a specified amount of water, a catalyst, etc. to the above-mentioned compounds containing alkoxysilyl groups to cause a reaction.

[0061] Commercially available products can be used as raw materials for the aforementioned silicon-containing layer. Specific examples include, but are not limited to, GR-COAT (manufactured by Daicel Chemical Industry Co., Ltd.), Glass Resin (manufactured by Owens Corning Co., Ltd.), Heatless Glass (manufactured by Ohashi Chemical Industry Co., Ltd.), NSC (manufactured by Nippon Seika Co., Ltd.), glass raw materials GO150SX and GO200CL (manufactured by Fine Glass Technology Co., Ltd.), and copolymers for copolymerizing acrylic resin or polyester resin with alkoxysilyl compounds, such as MKC silicate (manufactured by Mitsubishi Chemical Co., Ltd.), silicate / acrylic varnish XP-1030-1 (manufactured by Dai Nippon Color Materials Co., Ltd.), and NSC-5506 (manufactured by Nippon Seika Co., Ltd.).

[0062] The aforementioned silicon-containing layer may contain monoalkoxysilanes as constituent components.

[0063] Monoalkoxysilane

[0064] By including a certain amount of monoalkoxysilane in the composition of the silicon-containing layer, cracking of the silicon-containing layer can be prevented. This also contributes to the stability of device characteristics to changes in temperature and humidity.

[0065] Specific examples of monoalkoxysilanes include, but are not limited to, monoalkoxyalkylsilanes such as trimethylethoxysilane, trimethylmethoxysilane, tripropylethoxysilane, and trihexylethoxysilane. The number of carbon atoms as the alkoxy group can be 1 or more and 3 or less. The number of carbon atoms as the alkyl group can be 1 or more and 6 or less. Trimethylethoxysilane is particularly effective.

[0066] In addition, the aforementioned silicon-containing layer may contain at least one of the following as constituent components: a triphenylamine compound having hydroxyl groups, polymethylphenylsilane, and copper-iron oxide.

[0067] Triphenylamine compounds with hydroxyl groups

[0068] As the above-mentioned triphenylamine compound containing a hydroxyl group, any compound having a hydroxyl group, a nitrogen atom, and three aromatic groups bonded to the nitrogen atom is acceptable, without particular restrictions, and can be appropriately selected according to the purpose.

[0069] The above-mentioned triphenylamine compounds with hydroxyl groups, especially those shown in general formula (1), general formula (2), structural formula (3) and general formula (4), exhibit excellent reactivity with thermosetting resin monomers and good performance in terms of sensitivity characteristics, and are particularly useful.

[0070] [Chemical Formula 1]

[0071]

[0072] (In the formula, R1 and R2 each independently represent a substituted or unsubstituted aryl group. In addition, Ar1, Ar2 and Ar3 each independently represent an arylene group. As arylenes, divalent groups of the same aryl group as R1 and R2 can be listed.)

[0073] R1 and R2 each independently represent a substituted or unsubstituted aryl group. Specific examples include the following examples.

[0074] Examples of aromatic groups include phenyl, and examples of fused polycyclic aromatic groups include naphthyl, pyrene, 2-fluorenyl, 9,9-dimethyl-2-fluorenyl, azulel, anthracene, and triphenylene. 5H-dibenzo[a,d]cycloheptaphenyl, biphenyl, terphenyl, or groups represented by the following formula:

[0075] [Chemical Formula 2]

[0076]

[0077] (In the formula, W represents a divalent group such as -O-, -S-, -SO-, -SO2-, -CO- or lower. R) 106 This will be explained later.

[0078] [Chemical Formula 3]

[0079]

[0080] (In the formula, c represents an integer from 1 to 12. d represents an integer from 1 to 3. e represents an integer from 1 to 3. f represents an integer from 1 to 3. R) 107 and R 108 This will be explained later.

[0081] Examples of heterocyclic groups include, but are not limited to, thienyl, benzothienyl, furanyl, benzofuranyl, and carbazoyl.

[0082] The above-mentioned aryl and arylene groups may have the groups shown in (1) to (7) below as substituents.

[0083] Furthermore, these substituents serve as R in the above general formula. 106 R 107 and R 108 Specific examples are shown.

[0084] (1) Halogen atom, trifluoromethyl, cyano, nitro.

[0085] (2) As an alkyl group, preferably a straight-chain or branched alkyl group of C1 to C12, especially C1 to C8, more preferably C1 to C4, which may further contain a phenyl group substituted with a fluorine atom, hydroxyl group, cyano group, C1 to C4 alkoxy group, phenyl or halogen atom, C1 to C4 alkyl group or C1 to C4 alkoxy group. Specific examples include methyl, ethyl, n-propyl, isopropyl, tert-butyl, sec-butyl, n-butyl, isobutyl, trifluoromethyl, 2-hydroxyethyl, 2-cyanoethyl, 2-ethoxyethyl, 2-methoxyethyl, benzyl, 4-chlorobenzyl, 4-methylbenzyl, 4-methoxybenzyl and 4-phenylbenzyl.

[0086] (3) As alkoxy groups, examples include methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, n-butoxy, sec-butoxy, isobutoxy, 2-hydroxyethoxy, 2-cyanoethoxy, benzyloxy, 4-methylbenzyloxy, and trifluoromethoxy.

[0087] (4) As an aryloxy group, examples include those derived from aryl groups such as phenyl and naphthyl. It may also contain C1-C4 alkoxy, C1-C4 alkyl or halogen atoms as substituents. Specific examples include phenoxy, 1-naphthoxy, 2-naphthoxy, 4-methylphenoxy, 4-methoxyphenoxy, 4-chlorophenoxy, and 6-methyl-2-naphthoxy.

[0088] (5) As a substituted mercapto or aryl mercapto, specific examples include methylthio, ethylthio, phenylthio, and p-methylphenylthio.

[0089] (6) Groups represented by the following general formula:

[0090] [Chemical Formula 4]

[0091]

[0092] (where R is in the formula) 110 and R 111 Each can be represented independently as an alkyl or aryl group. Examples of aryl groups include phenyl, biphenyl, or naphthyl, which may contain a C1-C4 alkoxy, C1-C4 alkyl, or halogen atom as a substituent. They may also form a ring with the carbon atom on the aryl group. Specific examples include diethylamino, N-methyl-N-phenylamino, N,N-diphenylamino, N,N-di(p-tolyl)amino, dibenzylamino, piperidinyl, morpholinyl, and julolidyl group.

[0093] (7) Alkyldioxy and alkyldisulfide, such as methylenedioxy or methylenedisulfide.

[0094] Compounds of general formula (1) are readily soluble in solvents such as alcohols and cellosols. When using these solvents to form films, transparent and uniform films are easily formed.

[0095] [Chemical Formula 5]

[0096]

[0097] (In the formula, R3 and R4 each independently represent a substituted or unsubstituted aryl group. Additionally, Ar4, Ar5, and Ar6 each independently represent an arylene group, and divalent groups of the same aryl group as R3 and R4 can be listed as arylenes. Furthermore, m and n each independently represent a repeating number from 1 to 10.)

[0098] R3 and R4 represent the same substituents as R1 and R2 in general formula (1), respectively. In addition, Ar4, Ar5, and Ar6 also represent the same substituents as Ar1, Ar2, and Ar3 in general formula (1), respectively.

[0099] [Chemical Formula 6]

[0100]

[0101] [Chemical Formula 7]

[0102]

[0103] (In the formula, X represents -CH2-, -O-, -CH=CH-, or -CH2CH2-)

[0104] polymethylphenylsilane

[0105] There are no particular restrictions on the polymethylphenylsilanes mentioned above, and they can be selected appropriately according to the purpose.

[0106] The aforementioned polymethylphenylsilanes can be commercially available products. Examples of commercially available products include Ogsol SI-10-10 (polymethylphenylsilane, number average molecular weight Mn2100, weight average molecular weight Mw12700) manufactured by Osaka Gas Chemical Co., Ltd., and Ogsol SI-10-20 (polymethylphenylsilane, number average molecular weight Mn1100, weight average molecular weight Mw1800) manufactured by Osaka Gas Chemical Co., Ltd.

[0107] Copper-iron oxide

[0108] Examples of copper-iron oxides mentioned above include those described in the following description of the metal oxide film.

[0109] The average thickness of the silicon-containing layer is preferably 0.1 μm to 4.0 μm, and more preferably 0.3 μm to 1.5 μm.

[0110] The average thickness mentioned above can be obtained by measuring with an eddy current thickness gauge or by observing cross-sectional photographs using a scanning electron microscope. The average thickness is the arithmetic mean of the measurements taken at 20 points.

[0111] The following describes an example of a method for determining the average thickness of the silicon-containing layer in this invention.

[0112] First, 20 film thickness measurements were taken longitudinally at equal intervals on the substrate before silicon layer deposition using an eddy current thickness gauge (Fisherscope mms, manufactured by Fisher Instruments). Next, after silicon layer deposition, the film thickness was measured at the same locations as before, and the initial film thickness of the silicon layer was determined from the difference between the thicknesses before and after deposition.

[0113] Next, after forming a metal oxide film on the silicon-containing layer, a portion of the film is cut off. The cross-section of the cut sample is smoothed by ion milling or focused ion beam treatment, resulting in a sample with an observable cross-section. The sample is then observed using a scanning electron microscope, and the thickness of the silicon-containing layer is measured. Due to slight etching or metal oxide anchoring, the apparent film thickness of the silicon-containing layer after metal oxide film formation is less than the average film thickness measured by an eddy current thickness gauge. Therefore, image analysis of such cross-sectional images can be performed.

[0114] When a metal oxide film is embedded in a silicon-containing layer, the thickness of 10 peaks and 10 troughs at the interface is measured, and the average of these 20 points is taken as the average thickness. Furthermore, it is preferable to cut portions of the film at multiple locations for the same observation.

[0115] There are no particular limitations on the method for fabricating the silicon-containing layer described above, and it can be appropriately selected according to the purpose. Examples include coating the silicon-containing layer with a coating solution onto the charge transport layer or the dye-sensitized electrode layer, and then heating it.

[0116] There are no particular restrictions on the coating method; it can be selected appropriately according to the purpose. Examples include, but are not limited to, dip coating, spray coating, ring coating, roller coating, gravure coating, nozzle coating, and screen printing.

[0117] There are no particular restrictions on heating temperature and time; they can be selected appropriately according to the purpose.

[0118] The coating liquid for the silicon-containing layer mentioned above contains, for example, an organosilicon compound having either a hydroxyl group or a hydrolyzable group, preferably at least one of a triphenylamine compound having a hydroxyl group, polymethylphenylsilane, and a copper-iron oxide, and may also contain other components such as solvents if necessary.

[0119] Metal oxide film

[0120] As for the aforementioned metal oxide film, any film with P-type semiconductivity is acceptable, and there are no particular restrictions. It can be selected appropriately according to the purpose, but copper-iron oxide is preferred.

[0121] The electronic device having a metal oxide film formed by metal oxide particles related to the present invention is based on the understanding that it is sometimes impossible to obtain an electronic device with high density of metal oxide film in conventional devices.

[0122] In the previous aerosol deposition method, the particle size distribution of the p-type semiconducting metal oxide particles was not optimized during the film formation process. Therefore, there were problems with the adhesion to the substrate surface and the density of the film.

[0123] In this invention, when forming a metal oxide film containing a metal oxide with p-type semiconductivity on a charge transport layer or dye-sensitized electrode layer, p-type semiconducting metal oxide particles with an appropriate particle size distribution are used. This allows for the provision of electronic devices that achieve sufficient adhesion between the substrate surface and the metal oxide film, while simultaneously densifying the metal oxide film, exhibiting high gas barrier properties, and enabling fine photoelectric conversion.

[0124] Copper-iron oxide

[0125] As for the aforementioned copper-iron oxide (hereinafter also referred to as "p-type semiconductor" or "p-type metal compound semiconductor"), as long as it has the function of being a p-type semiconductor, there is no particular limitation. It can be appropriately selected according to the purpose. For example, p-type metal oxide semiconductors, p-type compound semiconductors containing monovalent copper, and other p-type metal compound semiconductors can be listed.

[0126] Specific examples of the aforementioned p-type metal oxide semiconductors include, but are not limited to, CoO, NiO, FeO, Bi2O3, MoO2, Cr2O3, SrCu2O2, and CaO-Al2O3.

[0127] Specific examples of p-type compound semiconductors containing monovalent copper include, but are not limited to, Cu2O, CuAlO, CuAlO2, and CuGaO2.

[0128] From the perspective of charge mobility and light transmittance, copper aluminum oxides such as CuAlO and CuAlO2 are preferred.

[0129] Metal oxide film thickness

[0130] The average thickness of the metal oxide film is preferably 0.3 μm to 5 μm, more preferably 0.3 μm to 5 μm, and the standard deviation of the film thickness is 0.07 μm or less.

[0131] When the average thickness of the aforementioned metal oxide film is 0.3 μm to 5 μm, it is beneficial to generate long-life and high-quality printed images with an excellent balance between abrasion resistance and electrostatic properties. Furthermore, when the standard deviation of the film thickness of the aforementioned metal oxide film is 0.07 μm or less, it is beneficial to generate printed images with excellent grayscale reproducibility that influences the visual impression of printed images such as human skin and landscapes.

[0132] The film thickness of the electrophotographic photoreceptor in one embodiment of the device of the present invention is measured as follows. First, for a cylindrical photoreceptor drum with a length of 380 mm and an outer diameter of 100 mm, the film thickness is measured at five points along the longitudinal direction of the photoreceptor drum, from 100 mm from the end of the drum at 50 mm intervals up to 300 mm. The film thickness is measured by image analysis of SEM cross-sectional photographs. Specifically, after cutting the drum with a saw, the cut sample is ion-milled to obtain a cross-section, and an SEM image is obtained. The film thickness is measured by analyzing the SEM image.

[0133] Manufacturing methods of electronic devices

[0134] The manufacturing method of the electronic device of the present invention is a method for manufacturing the above-described electronic device of the present invention.

[0135] The manufacturing method of the aforementioned electronic device includes the step of spraying the raw material of the aforementioned metal oxide film onto the aforementioned silicon-containing layer to form the aforementioned metal oxide film, and may include other steps if necessary.

[0136] The aforementioned raw material particles include the following metal oxide particles with p-type semiconductivity.

[0137] As a spraying method for the above-mentioned metal oxide film raw materials, the aerosol deposition method (AD method) can be cited.

[0138] Metal oxide particles with p-type semiconductivity

[0139] The metal oxide particles used as raw material particles for forming a metal oxide film by spraying the metal oxide particles of the present invention can be any particles with p-type semiconductivity, and there are no particular limitations. They can be appropriately selected according to the purpose. The copper-iron oxides described above are preferred. The particle size distribution based on volume has two local maxima: a first local maxima (0.1 μm or greater and less than 5 μm) and a second local maxima (5 μm or greater and less than 50 μm). The ratio of the second local maxima to the first local maxima is 0.5 or greater and less than 2.0.

[0140] However, the volumetric reference particle size of more than 99% of the particles must be in the range of 0.1 μm to 50 μm.

[0141] When the first local maximum value is less than 0.1 μm, particles tend to aggregate easily, making it difficult to form an aerosol. When the size is 5 μm or larger, the film is difficult to densify.

[0142] When the second local maximum value is less than 5 μm, the adhesion between the substrate surface and the metal oxide film deteriorates, making it prone to peeling. When it is 50 μm or larger, the substrate surface or the metal oxide film formed on the substrate surface will crack, and the metal oxide film cannot be formed.

[0143] In addition, when the ratio of the second local maximum value to the first local maximum value is less than 0.5, the film is easy to peel off due to the poor adhesion between the substrate surface and the metal oxide film. When the ratio is 2.0 or greater, the film is difficult to densify.

[0144] The metal oxide particles with p-type semiconductivity and the above-mentioned particle size distribution used in this invention can be obtained by using existing pulverizing mechanisms such as, but not limited to, planetary pulverizers, dry bead mills, jet mills, etc., from metal oxides manufactured by any method.

[0145] The particle size of the metal oxide particles was measured using a MICROTRAC MT3300EXII (manufactured by Microtrac Bell) at a pressure of 0.2 MPa for 10 seconds.

[0146] Furthermore, the preferred metal oxide particles with p-type semiconductivity are the aforementioned copper-iron oxides.

[0147] Aerosol deposition (AD) method

[0148] The aforementioned aerosol deposition (AD) method is a technique that mixes pre-prepared microparticles or ultraparticles with gas to form an aerosol, and then sprays it through a nozzle onto the object to be filmed (substrate) to form a film.

[0149] The AD method described above is characterized by the ability to form films at room temperature and while maintaining the crystal structure of the raw materials, making it suitable for forming films on devices (especially electrophotographic photosensitive devices).

[0150] The following describes an example of a method for forming metal oxide films using the aerosol deposition method described above.

[0151] In this case, use such Figure 1 An aerosol deposition apparatus as shown. Figure 1The gas cylinder 110 shown stores an inert gas for generating aerosols. The gas cylinder 110 is connected to an aerosol generator 130 via a pipe 120a, which extends into the interior of the aerosol generator 130. A certain amount of particles 200 made of metal oxides or compound semiconductors is introduced into the aerosol generator 130. Another pipe 120b, connected to the aerosol generator 130, is connected to a nozzle 150 within a film-forming chamber 140.

[0152] Metal oxide particles 200 with p-type semiconductivity are introduced into an aerosol generator 130 to generate an aerosol, which can be connected to a nozzle 150 via a piping 120b.

[0153] Inside the film-forming chamber 140, the substrate 160 is held in the substrate holder 170, facing the jet nozzle 150. Here, the substrate 160 can be a device such as a cylindrical conductive support, a photoreceptor, a solar cell, or an EL element. An exhaust pump 180 for adjusting the vacuum level inside the film-forming chamber 140 is connected to the film-forming chamber 140 via a piping 120c.

[0154] The film-forming apparatus for the electrode of this embodiment includes a mechanism that rotates the substrate holder 170 using a rotator 170a while laterally moving the spray nozzle 150 at a certain speed. By forming a film while laterally moving the spray nozzle 150, a metal oxide film with a desired area can be formed on the substrate 160.

[0155] In the process of forming a metal oxide film, firstly, the compressed air valve 190 is closed, and an exhaust pump 180 is used to evacuate the film-forming chamber 140 to the aerosol generator 130. Next, by opening the compressed air valve 190, gas from the gas cylinder 110 is introduced into the aerosol generator 130 through pipe 120a, spraying particles 200 into the container to generate an aerosol in which the particles 200 are dispersed. The generated aerosol is then sprayed at high speed from the nozzle 150 onto the substrate 160 through pipe 120b. If the compressed air valve 190 remains open for 0.5 seconds, it closes for the next 0.5 seconds. Afterward, the compressed air valve 190 is reopened, and this process repeats every 0.5 seconds. The gas flow rate from gas cylinder 110 is set to 2 liters / minute, the film formation time is 1 hour, the vacuum degree in film formation chamber 140 is about 10 Pa when compressed air valve 190 is closed, and the vacuum degree in film formation chamber 140 is about 100 Pa when compressed air valve 190 is open.

[0156] The aerosol injection rate is controlled by factors such as the shape of the nozzle 150, the length and inner diameter of the piping 120b, the internal gas pressure of the gas cylinder 110, and the exhaust volume of the exhaust pump 180 (internal pressure of the film-forming chamber 140). For example, when the internal pressure of the aerosol generator 130 is set to tens of thousands of Pascals, the internal pressure of the film-forming chamber 140 is several hundred Pascals, and the opening shape of the nozzle 150 is a circle with an inner diameter of 1 mm, the aerosol injection rate can reach several hundred meters per second due to the internal pressure difference between the aerosol generator 130 and the film-forming chamber 140. If the internal pressure of the film-forming chamber 140 is maintained at 5 Pa to 100 Pa and the internal pressure of the aerosol generator 130 is maintained at 50,000 Pa, a metal oxide film with a porosity of 5% to 30% can be formed. Preferably, the average thickness of the metal oxide film is adjusted to 0.1 μm to 10 μm by adjusting the aerosol supply time under these conditions.

[0157] The average thickness of the metal oxide film can be adjusted to an appropriate thickness for each device.

[0158] For the electrophotographic photosensitive element, which is one of the devices, the average thickness of the metal oxide film is preferably 1.2 μm to 1.8 μm, which is the optimal condition for obtaining device durability and print quality with high image quality.

[0159] Particles 200 in the aerosol, which are accelerated and gain kinetic energy, collide with the substrate 160 and are shattered into very small pieces due to the impact energy. Then, through the bonding of these shattered particles to the substrate 160 and the bonding of the shattered particles to each other, a metal oxide film is sequentially formed on the charge transport layer.

[0160] Film formation is achieved through multiple line patterns and rotation of the photoreceptor drum. This allows the jet nozzle 150 to form a metal oxide film of the desired area while scanning longitudinally and laterally across the surface of the substrate 160.

[0161] The following is an example of an embodiment of the device of the present invention.

[0162] 1: Electrophotographic photosensitive material and electrophotographic device

[0163] One embodiment of the electronic device of the present invention is an electrophotographic photosensitive device.

[0164] The aforementioned electrophotographic photoreceptor (hereinafter referred to as "photoreceptor") includes a conductive support as a support, a charge transport layer containing a charge transport substance on the conductive support, a silicon-containing layer on the charge transport layer, and the aforementioned metal oxide film on the silicon-containing layer. If necessary, it may also include other layers such as a charge generation layer, an intermediate layer, and a protective layer.

[0165] The aforementioned matters can be appropriately applied as the silicon-containing layer described above.

[0166] The above-mentioned matters can be appropriately applied as the aforementioned metal oxide film.

[0167] A layer consisting of a charge generation layer and a charge transport layer stacked sequentially can be called a photosensitive layer.

[0168] The following will describe the case where the device is an electrophotographic photosensitive device, but the device is not limited to electrophotographic photosensitive devices and can also be applied to other devices.

[0169] Reference Figure 2 The structure of device 10A, which is an electrophotographic photosensitive element, is explained. Figure 2 This is a cross-sectional view showing an example of an electrophotographic photoreceptor. For example... Figure 2 In the embodiment shown, the electrophotographic photoreceptor 10A has, in sequence, an intermediate layer 52, a charge generation layer 53, a charge transport layer 54, a silicon-containing layer 55, and a metal oxide film 56 on a conductive substrate 51. The intermediate layer 52 can be removed as needed.

[0170] Support (conductive support)

[0171] As the aforementioned conductive support, as long as the volume resistivity is 10... 10 Conductivity below Ω·cm is acceptable, with no particular restrictions. The appropriate material can be selected based on the purpose. Examples include coatings made by vapor deposition or sputtering of metals such as aluminum, nickel, chromium, nickel-chromium, copper, silver, gold, platinum, and iron, as well as oxides such as tin oxide and indium oxide, onto thin films or cylindrical plastics or paper. Other examples include tubes made by forming rough-machined tubes from aluminum, aluminum alloys, nickel, and stainless steel sheets through processes such as wire drawing, impact ironing, extrusion ironing, and cutting, followed by surface treatments such as cutting, ultra-precision machining, and grinding.

[0172] Intermediate layer

[0173] The aforementioned electrophotographic photoresist may have an intermediate layer disposed between the conductive support and the photosensitive layer. This intermediate layer is provided for purposes such as improving adhesion, preventing moiré patterns, improving the coatability of the upper layer, and preventing charge injection from the conductive support.

[0174] The aforementioned intermediate layer is typically composed mainly of resin. Since the photosensitive layer is coated onto the intermediate layer, a thermosetting resin that is poorly soluble in organic solvents is preferred as the resin used for the intermediate layer. Polyurethane, melamine resin, and alkyd melamine resin are preferred because they generally meet the aforementioned objectives.

[0175] Specific examples of the aforementioned organic solvents include, but are not limited to, tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, and butanone. Coatings can be obtained by appropriately diluting the aforementioned resin with these organic solvents.

[0176] Furthermore, to adjust conductivity and prevent moiré patterns, fine particles of metals, metal oxides, etc., can be added to the intermediate layer. Titanium oxide and zinc oxide are preferred as the metal oxides. The fine particles can be dispersed using the aforementioned organic solvent in a ball mill, ultrafine mill, sand mill, etc., and the resulting dispersion is mixed with the aforementioned resin components to form a coating.

[0177] Methods for fabricating the intermediate layer (film-forming method) include, for example, forming a film on a conductive support by dip coating, spraying, bead coating, etc., and, if necessary, heating and curing the resulting film. In most cases, an average thickness of 2 μm to 20 μm is suitable for the intermediate layer. When the accumulated residual potential of the photoreceptor increases, it is preferable to make it less than 3 μm.

[0178] Photosensitive layer

[0179] The photosensitive layer of the aforementioned electrophotographic photosensitive material is a stacked photosensitive layer consisting of a charge generation layer and a charge transport layer stacked sequentially.

[0180] Charge generation layer

[0181] The aforementioned charge-generating layer refers to a portion of the aforementioned laminated photosensitive layer, and has the function of generating charge through exposure. The aforementioned charge-generating layer contains a charge-generating substance as its main component, and may also contain an adhesive resin if necessary. Examples of the aforementioned charge-generating substance include inorganic charge-generating materials and organic charge-generating materials.

[0182] Specific examples of inorganic charge-generating materials include, but are not limited to, crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, and amorphous silicones. In amorphous silicones, dangling bonds terminated by hydrogen or halogen atoms, or dangling bonds doped with boron or phosphorus atoms, are preferred.

[0183] As the aforementioned organic charge-generating materials, known materials can be used, including metallic phthalocyanines such as titanium phthalocyanine and gallium chlorophthalocyanine, metal-free phthalocyanines, azulenium salt pigments, methylene squaric acid pigments, symmetrical or asymmetric azo pigments with a carbazole framework, symmetrical or asymmetric azo pigments with a triphenylamine framework, symmetrical or asymmetric azo pigments with a fluorenone framework, and perylene pigments. From the viewpoint of high overall quantum efficiency of charge generation, metallic phthalocyanines, symmetrical or asymmetric azo pigments with a fluorenone framework, symmetrical or asymmetric azo pigments with a triphenylamine framework, and perylene pigments are preferred. These charge-generating substances can be used alone or in combination of two or more.

[0184] Specific examples of the aforementioned adhesive resins include, but are not limited to, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, polyarylate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, and polyacrylamide.

[0185] Polyvinyl butyral is frequently used and is useful. These adhesive resins can be used alone or in mixtures of two or more.

[0186] Method for fabricating charge generation layer

[0187] Methods for fabricating the aforementioned charge-generating layer can be broadly categorized into vacuum thin-film fabrication and casting methods using solution dispersions.

[0188] Examples of vacuum thin film manufacturing methods include vacuum vapor deposition, glow discharge decomposition, ion plating, sputtering, reactive sputtering, and CVD (chemical vapor deposition), which are well applicable to the fabrication of layers formed from the aforementioned inorganic charge-generating materials and organic charge-generating materials.

[0189] As a method for producing a charge-generating layer by the above casting method, the inorganic or organic charge-generating material can be dispersed together with an adhesive resin using an organic solvent through a ball mill, grinder, sand mill, etc., and the dispersion can be appropriately diluted and coated.

[0190] Specific examples of the aforementioned organic solvents include, but are not limited to, tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, and butanone. From the perspective of low environmental impact, butanone, tetrahydrofuran, and cyclohexanone are preferred over chlorobenzene, dichloromethane, toluene, and xylene.

[0191] Coating can be carried out by dip coating, spray coating, bead coating, etc.

[0192] The average thickness of the charge-generating layer is preferably 0.01 μm to 5 μm.

[0193] Thickening the charge generation layer typically improves these properties when it is necessary to reduce residual potential or increase sensitivity. On the other hand, it often leads to deterioration of rechargeability, such as retention of charged charge and formation of space charge. The average thickness of the charge generation layer that balances the above issues is more preferably 0.05 μm to 2 μm.

[0194] Furthermore, if necessary, low-molecular-weight compounds such as antioxidants, plasticizers, lubricants, and UV absorbers, as well as leveling agents, can be added to the aforementioned charge-generating layer. These compounds can be used alone or in combination of two or more. In many cases, the combined use of low-molecular-weight compounds and leveling agents can lead to a decrease in sensitivity. Therefore, the amount used is generally preferably 0.1 phr to 20 phr, more preferably 0.1 phr to 10 phr, and the amount of leveling agent used is preferably 0.001 phr to 0.1 phr.

[0195] Charge transport layer

[0196] The aforementioned charge transport layer is a part of a laminated photosensitive layer, which has the function of injecting and transporting the charge generated by the aforementioned charge generation layer and neutralizing the surface charge of the photoreceptor due to charging. The aforementioned charge transport layer mainly comprises a charge transport material and an adhesive component for bonding them together.

[0197] The aforementioned charge transport materials include electron transport materials and hole transport materials.

[0198] Examples of electron transport substances include, but are not limited to, electron acceptor substances such as asymmetric biphenylquinone derivatives, fluorene derivatives, and naphthalimide derivatives. These electron transport substances can be used alone or in combination of two or more.

[0199] As the hole transport material mentioned above, an electron donor material is preferred. Examples include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, butadiene derivatives, 9-(p-diethylaminostyrylanthracene), 1,1-bis-(4-dibenzylaminophenyl)propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, α-phenylstyrene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. These hole transport materials can be used alone or in combination of two or more.

[0200] Examples of adhesive components include thermoplastic or thermosetting resins such as polystyrene, polyester, polyethylene, polyarylate, polycarbonate, acrylic resin, silicone resin, fluororesin, epoxy resin, melamine resin, polyurethane resin, phenolic resin, and alkyd resin. Among these, polystyrene, polyester, polyarylate, and polycarbonate are particularly useful as adhesive components for charge transport, due to their numerous materials exhibiting excellent charge transfer properties.

[0201] When using electroinert polymers in the modification of the charge transport layer, polyesters of Cardo-type polymers with a large volumetric backbone, such as fluorene, polyesters of polyethylene terephthalate, polyethylene naphthalate, etc., polycarbonates in which the 3,3' site of the phenolic portion of biphenyl-type polycarbonate such as C-type polycarbonate is replaced by an alkyl group, polycarbonates in which the twin methyl group of bisphenol A is replaced by a long-chain alkyl group having two or more carbon atoms, polycarbonates with bisphenol or a biphenyl ether backbone, polycaprolactone, polycarbonates with a long-chain alkyl backbone such as polycaprolactone, acrylic resins, polystyrene, hydrogenated butadiene, etc., are effective.

[0202] Here, electroinert polymers refer to polymers that do not contain chemical structures that exhibit photoconductivity, such as triarylamine structures. When these resins are used in combination with adhesive resins as additives, their content relative to the total solids content of the charge transport layer is preferably 50% by mass or less due to limitations in photoattenuation sensitivity.

[0203] When the above-mentioned charge-transporting material is used, its content is generally preferably 40 phr to 200 phr, more preferably 70 phr to 100 phr. In addition, the material is copolymerized with a resin component of 0 to 200 parts by mass relative to 100 parts by mass of the charge-transporting component, preferably 80 to 150 parts by mass.

[0204] The aforementioned charge transport layer can be formed by, for example, dissolving or dispersing a mixture or copolymer containing charge transport components and binder components as main components in a suitable solvent to prepare a coating for the charge transport layer, and then applying and drying the coating. As coating methods, dip coating, spray coating, ring coating, roller coating, gravure coating, nozzle coating, screen printing, etc., can be used. Examples of dispersants used in preparing the coating for the charge transport layer include ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ethers such as dioxane, tetrahydrofuran, and ethyl cellosolve; aromatics such as toluene and xylene; halogens such as chlorobenzene and dichloromethane; and esters such as ethyl acetate and butyl acetate. From the viewpoint of low environmental impact, methyl ethyl ketone, tetrahydrofuran, and cyclohexanone are preferred over chlorobenzene, dichloromethane, toluene, and xylene. These solvents can be used alone or in combination.

[0205] A cross-linked surface layer may sometimes be stacked on top of the aforementioned charge transport layer. In this structure, the average thickness of the charge transport layer does not need to be designed to increase its thickness to account for wear during actual use. Practically, to ensure necessary sensitivity and charging rate, the average thickness of the charge transport layer is preferably 10 μm to 40 μm, more preferably 15 μm to 30 μm.

[0206] In addition, if necessary, low-molecular-weight compounds such as antioxidants, plasticizers, lubricants, and UV absorbers, as well as leveling agents, can be added to the charge transport layer. These compounds can be used alone or in combination of two or more. In many cases, the combined use of low-molecular-weight compounds and leveling agents can lead to a decrease in sensitivity. Therefore, their usage is typically 0.1 phr to 20 phr, preferably 0.1 phr to 10 phr, and the leveling agent usage is 0.001 phr to 0.1 phr.

[0207] silicon-containing layer

[0208] As a silicon-containing layer in an electrophotographic photosensitive material, the silicon-containing layer of the device of the present invention may be appropriately selected and applied.

[0209] Metal oxide film

[0210] As for the metal oxide film in an electrophotographic photosensitive material and the method for its fabrication, the metal oxide film and the method for its fabrication in the device of the present invention can be appropriately selected and applied.

[0211] Imaging devices and imaging methods

[0212] The imaging apparatus of the present invention includes the above-described device. Examples of the above-described device include, for instance, the electrophotographic photosensitive element described above.

[0213] One embodiment of the imaging apparatus of the present invention includes the above-described electrophotographic photosensitive device, an electrostatic latent image forming apparatus and a developing apparatus, and may also include other apparatus if necessary.

[0214] The imaging method of the present invention uses the above-described device. Examples of the above-described device include, for instance, the electrophotographic photosensitive element described above.

[0215] One embodiment of the imaging method related to this invention includes at least an electrostatic latent image formation step and a development step, and may also include other steps if necessary.

[0216] The above imaging method can be performed appropriately by the above imaging device, the above electrostatic latent image formation process is preferably performed by the above electrostatic latent image formation device, the above developing process is preferably performed by the above developing device, and the above other processes are preferably performed by the above other devices.

[0217] Implementation form of imaging device

[0218] In the following text, an example of the configuration of the imaging device will be described with reference to the accompanying drawings.

[0219] Figure 3This illustrates an example of an imaging apparatus. The charging device 12 is used to uniformly charge the surface of the electrophotographic photoreceptor 11, employing known devices such as linear corona dischargers, grid-controlled corona dischargers, solid-state chargers, and charging rollers. From the viewpoint of reducing power consumption, the charging device 12 is preferably positioned in contact with or near the electrophotographic photoreceptor 11. Ideally, to prevent contamination of the charging device 12, it is positioned with an appropriate gap between the surfaces of the electrophotographic photoreceptor 11 and the charging device 12, and near the electrophotographic photoreceptor 11. The transfer apparatus 16 can generally use the aforementioned charger, and both transfer chargers and separate chargers are effective.

[0220] The electrophotographic photosensitive element 11 is driven by a driving device 1C, charged by a charging device 12, exposed and developed by an exposure device 13, transferred by a transfer device 16, exposed before cleaning by a pre-cleaning exposure device 1B, cleaned by a cleaning device 17, and de-energized by a de-energizing device 1A, and this process is repeated. The lubricant 3A, the coating brush 3B for applying the lubricant, and the coating blade 3C are positioned between the cleaning device 17 and the charging device 12, as shown in the figure, in the direction of movement relative to the electrophotographic photosensitive element 11.

[0221] exist Figure 3 In the process, light is irradiated from the support side of the electrophotographic photoreceptor 11 (at this time the support is transparent) before cleaning.

[0222] The above is an example of electrophotographic processing, for example, in Figure 3 The pre-cleaning exposure can be performed from the support side, but it can also be performed from the photosensitive layer side. Furthermore, image exposure and electrostatic irradiation can be performed from the support side. On the other hand, the light irradiation process includes image exposure, pre-cleaning exposure, and electrostatic irradiation, but it is also possible to set up pre-transfer exposure, pre-exposure of image exposure, and other known light irradiation processes to irradiate the electrophotographic photosensitive material.

[0223] The imaging device shown above can be fixed in a copier, fax machine, or printer for combined use, or it can be assembled into these devices as a processing cartridge. Processing cartridges come in a variety of shapes; as general examples, such as... Figure 4 The shape shown is that of a drum, but it can also be a sheet or a ring-shaped strip.

[0224] The processing cartridge includes at least an electrophotographic photosensitive element 11 carrying an electrostatic latent image, a developing apparatus 14 for developing the electrostatic latent image carried on the electrophotographic photosensitive element 11 with toner to form a visible image, and a lubricant supply apparatus 3 (3A, 3B, 3C) for supplying lubricant to the electrophotographic photosensitive element. If necessary, it may also include other apparatus appropriately selected from charging apparatus 12, exposure apparatus 13, transfer apparatus 16, cleaning apparatus 17, static removal apparatus 1A, etc. As a developing apparatus, it includes at least a developing container for containing toner and even developing agent, a developing carrier for carrying and transporting the toner or developing agent contained in the developing container, and may also include a layer thickness control member for controlling the thickness of the toner layer carried on the developing carrier. The processing cartridge can be detachably installed in various electrophotographic imaging devices, fax machines, and printers, and is particularly preferably detachably installed in the imaging device of the present invention.

[0225] Figure 5 Other examples of imaging apparatus are shown. In this imaging apparatus, a charging device 12, an exposure device 13, developing devices 14Bk, 14C, 14M, 14Y for each color (black (Bk), cyan (C), magenta (M), and yellow (Y), an intermediate transfer belt 1F serving as an intermediate transfer medium, and a cleaning device 17 are arranged sequentially around the electrophotographic photosensitive element 11.

[0226] like Figure 5 The (Bk, C, M, Y) markings shown correspond to the toner colors mentioned above and can be omitted if necessary. The developing devices 14Bk, 14C, 14M, and 14Y for each color can be controlled independently, and only the developing device for the color required for imaging can be driven. The toner image formed on the electrophotographic photoreceptor 11 is transferred to the intermediate transfer belt 1F via the first transfer device 1D located inside the intermediate transfer belt 1F.

[0227] The first transfer device 1D is configured to be contactable and separable from the electrophotographic photoreceptor 11, and the intermediate transfer belt 1F only contacts the electrophotographic photoreceptor 11 during the transfer operation. Color images are formed sequentially, and the toner image superimposed on the intermediate transfer belt 1F is transferred together with the second transfer device 1E onto the printing medium 18, and then fixed by the fixing device 19 to form the image.

[0228] The second transfer device 1E is also configured to be contactable and separable from the intermediate transfer belt 1F, and to contact the intermediate transfer belt 1F only during the transfer operation.

[0229] In transfer drum imaging devices, since the toner images of each color are sequentially transferred onto the printing medium that is electrostatically adsorbed onto the transfer drum, there is a limitation that printing on thick paper is not possible. On the other hand, in... Figure 5In the imaging apparatus of the intermediate transfer method shown, since the toner images of each color are superimposed on the intermediate transfer body 1F, it has the characteristic of being unrestricted by the printing medium. This intermediate transfer method is not only applicable to... Figure 5 The device shown can also be applied to devices as described above. Figure 3 , Figure 4 and the following Figure 6 , Figure 7 The imaging device shown. Lubricant 3A, coating brush 3B for applying lubricant and coating blade 3C are arranged between the cleaning device 17 and the charging device 12, with the rotation direction relative to the electrophotographic photoreceptor 11 as shown.

[0230] Figure 6 This describes a tandem imaging device, another example of an imaging apparatus. This device uses four colors—yellow (Y), magenta (M), cyan (C), and black (Bk)—as toners, and each color has a corresponding imaging unit. Furthermore, it includes electrophotographic sensors 11Y, 11M, 11C, and 11Bk corresponding to each color. Around each electrophotographic sensor 11Y, 11M, 11C, and 11Bk are charging devices 12Y, 12M, 12C, and 12Bk; exposure devices 13Y, 13M, 13C, and 13Bk; developing devices 14Y, 14M, 14C, and 14Bk; and cleaning devices 17Y, 17M, 17C, and 17Bk.

[0231] A transport transfer belt 1G, serving as a carrier of transfer material, is mounted by a drive unit 1C and is in contact with or separated from the transfer positions of the electrophotographic photosensitive bodies 11Y, 11M, 11C, and 11Bk, which are arranged in a straight line. Transfer devices 16Y, 16M, 16C, and 16Bk are installed at the transfer positions opposite to the electrophotographic photosensitive bodies 11Y, 11M, 11C, and 11Bk, separated by the transport transfer belt 1G.

[0232] like Figure 6 The illustrated tandem imaging apparatus has electrophotographic sensors 11Y, 11M, 11C, and 11Bk corresponding to each color. Because the toner image of each color is sequentially transferred onto the printing medium 18 carried on the transfer belt 1G, it can output full-color images faster compared to a full-color imaging apparatus with only one electrophotographic sensor. The toner image developed on the printing medium 18, which serves as the transfer material, is conveyed from the opposing positions of the electrophotographic sensor 11Bk and the transfer device 16Bk to the fixing device 19, where it is fixed onto the printing medium 18.

[0233] Furthermore, it can also be like this Figure 7 The structure of the embodiment shown. That is, as Figure 6 The direct transfer method shown using a 1G transfer belt is replaced with, as shown in the example Figure 7 The structure shown uses intermediate transfer belt 1F.

[0234] like Figure 7 In the example shown, electrophotographic photosensitive elements 11Y, 11M, 11C, and 11Bk, corresponding to each color, are used to form toner images of various colors. These images are then transferred sequentially and layered onto an intermediate transfer belt 1F, which is driven and supported by a roller 1C as a drive mechanism, and then transferred by a primary transfer device 1D, which is the first transfer device, to form a full-color image.

[0235] Next, the intermediate transfer belt 1F is further driven, so that the full-color image carried on the intermediate transfer belt 1F is conveyed to a position opposite to the secondary transfer device 1E, which is a second transfer device, and to a roller opposite to the secondary transfer device 1E. Then, it is transferred a second time to the transfer material 18 by the secondary transfer device 1E, forming the desired image on the transfer material.

[0236] 2: Solar cells

[0237] One embodiment of the device of the present invention is a solar cell.

[0238] The aforementioned solar cell includes a substrate, a dye-sensitized electrode layer containing a sensitized dye, a silicon-containing layer on the dye-sensitized electrode layer, and a metal oxide film on the silicon-containing layer. It also includes a first electrode, a hole-blocking layer, a second electrode, and other components if necessary.

[0239] The aforementioned matters can be appropriately applied as the silicon-containing layer described above.

[0240] The above-mentioned matters can be appropriately applied to the aforementioned metal oxide film.

[0241] The following description will focus on the case where the device is a solar cell, but the device described in this invention includes, but is not limited to, solar cells, and can also be applied to other devices.

[0242] In the following description, the solar cells related to the present invention will be illustrated with reference to the accompanying drawings. The present invention includes, but is not limited to, the embodiments shown below. Other embodiments may be formed by adding, modifying, and deleting elements. However, any modifications that can be made within the scope of what a person skilled in the art can conceive, and that can achieve the functions and effects of the present invention, are all included within the scope of the present invention.

[0243] The aforementioned solar cell includes a substrate as a base, a first electrode, a hole blocking layer, an electron transport layer, a dye-sensitized electrode layer, a silicon-containing layer, a ceramic semiconductor film as a metal oxide film, and a second electrode.

[0244] Reference Figure 8 The structure of device 10B, which is used as a solar cell, is explained. Figure 8A cross-sectional view showing an example of a solar cell.

[0245] exist Figure 8 In the embodiment shown, a first electrode 2 is formed on a substrate 1, which serves as a base. A hole-blocking layer 3 is formed on the first electrode 2, and a dye-sensitized electrode layer 5, formed of an electron transport substance 4 that adsorbs photosensitive material 4', is disposed on the hole-blocking layer 3. Figure 8 The image shows an example of a structure in which a silicon-containing layer 6 and a metal oxide film 7 are sandwiched between a dye-sensitized electrode layer 5 and a second electrode 8 opposite to the first electrode 2. Furthermore, in... Figure 8 The diagram shows an example of a structure in which leads 9 and 10 are provided to enable the first electrode 2 and the second electrode 8 to conduct to each other.

[0246] The materials of the metal oxide film 7 and the dye-sensitized electrode layer 5 can also be in a state of mutual permeation.

[0247] The following will explain in detail.

[0248] Substrate (base plate)

[0249] The substrate 1 used as the aforementioned base is not particularly limited, and any known substrate can be used. The substrate 1 is preferably made of a transparent material, such as glass, transparent plastic sheet, transparent plastic film, and inorganic transparent crystal.

[0250] First electrode

[0251] As the first electrode 2, any conductive material that is transparent to visible light can be used; there are no particular restrictions. Common photoelectric conversion elements or known electrodes used in liquid crystal panels, etc., can be used.

[0252] Materials used as the first electrode 2 include indium tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), indium zinc oxide, niobium titanium oxide, and graphene. These can be used individually or in stacks.

[0253] The average thickness of the first electrode is preferably 5 nm to 10 μm, more preferably 50 nm to 1 μm.

[0254] Furthermore, in order to maintain a certain hardness of the first electrode, it is preferable to place the first electrode on a substrate 1 made of a material that is transparent to visible light. Examples of substrates include glass, transparent plastic sheet, transparent plastic film, and inorganic transparent crystal.

[0255] Materials known to be integral with the first electrode 2 and the substrate 1 can be used, such as FTO coated glass, ITO coated glass, zinc oxide and aluminum coated glass, FTO coated transparent plastic film, ITO coated transparent film, etc.

[0256] Alternatively, a transparent electrode or a metal electrode with a light-transmitting structure, such as a mesh or strip, can be disposed on a substrate such as a glass substrate, in which tin oxide or indium oxide is doped with cations or anions of different valences.

[0257] They can be used individually, in combination, or layered.

[0258] Cavity barrier

[0259] As for the material constituting the hole blocking layer 3, it is not particularly limited as long as it is transparent to visible light and is an electron transport material, but titanium oxide is particularly preferred.

[0260] The hole-blocking layer 3 is incorporated to suppress the power loss caused by the recombination of holes in the electrolyte with electrons on the electrode surface due to contact between the electrolyte and the electrode (so-called reverse electron transfer). The effect of this hole-blocking layer 3 is particularly significant in solid-state dye-sensitized solar cells.

[0261] This is because, compared to wet dye-sensitized solar cells that use electrolytes, solid-state dye-sensitized solar cells, which use organic hole transport materials, etc., recombine holes in the hole transport material with electrons on the electrode surface more quickly (reverse electron transfer).

[0262] The method for forming the hole-blocking layer 3 is not limited, but a high internal resistance is required to suppress the loss current of indoor light, making the film formation method also important. Typically, the sol-gel method, a wet film formation process, can be used, but the film density may be low, failing to adequately suppress the loss current. Therefore, dry film formation methods such as sputtering are more preferred, as they provide a sufficiently high film density to suppress the loss current.

[0263] The hole blocking layer 3 is formed to prevent electronic contact between the first electrode 2 and the dye-sensitized electrode layer 5. The average thickness of the hole blocking layer is not particularly limited, but is preferably 5 nm to 1 μm; however, it is more preferably 500 to 700 nm for wet film deposition and more preferably 10 nm to 30 nm for dry film deposition.

[0264] Dye-sensitized electrode layer

[0265] The dye-sensitized electrode layer 5 is a layer that functions as an electrode by adsorbing sensitized dyes (photosensitive materials) 4' onto the surface of the electron transport material 4. By adsorbing the sensitized dyes 4' onto the electron transport material 4, the conversion efficiency of the aforementioned solar cell can be improved.

[0266] In the aforementioned solar cell, a porous electron transport layer is formed on the hole blocking layer 3. This electron transport layer can be a single layer or multiple layers.

[0267] The electron transport layer described above is composed of electron transport material 4. Semiconductor particles are preferably used as the electron transport material 4.

[0268] In multilayer coating, a dispersion of semiconductor particles with different particle sizes can be coated in multiple layers, or a coating layer composed of different types of semiconductors, resins, and additives with varying compositions can be coated in multiple layers. Multilayer coating is an effective method when the average thickness of a single coating layer is insufficient.

[0269] Generally, as the average thickness of the dye-sensitized electrode layer increases, the amount of photosensitizer material carried per unit projected area also increases, thus increasing the light capture rate. However, the diffusion distance of injected electrons also increases, leading to increased losses due to charge recombination. Therefore, the average thickness of the electron transport layer is preferably 100 nm to 100 μm.

[0270] There are no particular restrictions on the semiconductors used; any known semiconductor can be used. Specifically, examples include elemental semiconductors such as silicon and germanium, compound semiconductors represented by metal chalcogenides, and compounds with a perovskite structure.

[0271] 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, and cadmium telluride.

[0272] Other compound semiconductors include preferred zinc, gallium, indium, cadmium, phosphides, gallium arsenide, copper-indium-selenide, and copper-indium-sulfide.

[0273] Furthermore, strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium niobate, etc., are preferred as compounds with a perovskite structure.

[0274] Among them, oxide semiconductors are preferred, and titanium oxide, zinc oxide, tin oxide, and niobium oxide are particularly preferred. One type can be used alone, or two or more types can be used in combination. There are no particular restrictions on the crystal type of these semiconductors; they can be single crystal, polycrystalline, or amorphous.

[0275] The average particle size of the primary particles, which are semiconductor particles, is not particularly limited, but is preferably 1 nm to 100 nm, and more preferably 5 nm to 50 nm.

[0276] Furthermore, efficiency can be improved by mixing or laminating semiconductor particles with a larger average particle size to achieve incident light scattering. In this case, the average particle size of the semiconductor is preferably 50 nm to 500 nm.

[0277] There are no particular limitations on the method for fabricating electron transport layers. For example, methods such as sputtering to form thin films in a vacuum and wet film formation methods can be listed.

[0278] Considering manufacturing costs, a wet film-forming method is particularly preferred, and a method of preparing a paste containing dispersed semiconductor particles in powder or sol and coating it onto a current collector electrode substrate is preferred.

[0279] When using this wet film-forming method, there are no particular limitations on the coating method; any known method can be used. For example, dip coating, spray coating, wire rod coating, spin coating, roller coating, doctor blade coating, gravure coating, and various other wet printing methods such as letterpress, offset printing, gravure printing, gravure printing, rubber sheet printing, and screen printing can be used.

[0280] When a dispersion of semiconductor particles is manufactured using a mechanical pulverizer or grinder, it is formed by dispersing semiconductor particles, either alone or in a mixture of semiconductor particles and resin, in water or an organic solvent. Examples of resins used include polymers or copolymers of ethylene compounds such as styrene, vinyl acetate, acrylates, and methacrylates; silicone resins; phenoxy resins; polysulfone resins; polyvinyl butyral resins; polyvinyl formal resins; polyester resins; cellulose ester resins; cellulose ether resins; polyurethane resins; phenolic resins; epoxy resins; polycarbonate resins; polyarylate resins; polyamide resins; and polyimide resins.

[0281] Solvents for dispersing semiconductor particles include water, alcohol solvents such as methanol, ethanol, isopropanol, and α-terpineol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl formate, ethyl acetate, and n-butyl acetate; ether solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, and dioxane; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; halogenated hydrocarbon solvents such as dichloromethane, chloroform, bromoform, iodomethane, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, and 1-chloronaphthalene; and hydrocarbon solvents such as n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and cumene. These can be used individually or in combination of two or more.

[0282] To prevent particle re-aggregation, dispersions of semiconductor particles or pastes of semiconductor particles obtained through sol-gel methods can be supplemented with acids such as hydrochloric acid, nitric acid, or acetic acid; surfactants such as polyoxyethylene (10) octylphenyl ether; and chelating agents such as acetylacetone, 2-aminoethanol, and ethylenediamine. Furthermore, adding thickeners is also an effective method to improve film-forming properties. Examples of thickeners that can be added include polymers such as polyethylene glycol and polyvinyl alcohol, and thickeners such as ethyl cellulose.

[0283] After coating semiconductor particles, to ensure electrical contact between the particles and improve film strength and adhesion to the substrate, firing, microwave irradiation, electron beam irradiation, or laser irradiation are preferably performed. These processes can be performed individually or in combination.

[0284] During firing, the firing temperature range is not particularly limited, but if the temperature is too high, the substrate may have increased resistance or melt. Therefore, 30°C to 700°C is preferred, and 100°C to 600°C is more preferred. Furthermore, the firing time is not particularly limited, but 10 minutes to 10 hours is preferred.

[0285] The microwave irradiation described above can be performed from the side where the electron transport layer is formed or from the back side. There is no particular limitation on the irradiation time, but it is preferred to be within 1 hour.

[0286] After firing, in order to increase the surface area of ​​the semiconductor particles and improve the efficiency of electron injection from the photosensitive material into the semiconductor particles, chemical plating is performed, for example, using an aqueous solution of titanium tetrachloride or a mixed solution with an organic solvent, or electrochemical plating is performed using an aqueous solution of titanium trichloride.

[0287] A film formed by stacking semiconductor particles with diameters of tens of nanometers through processes such as sintering possesses a porous state. This nanoporous structure has a very large surface area, which can be represented by a roughness coefficient. This roughness coefficient represents the ratio of the actual area inside the porous material to the surface area of ​​the semiconductor particles coated on the substrate. Therefore, a larger roughness coefficient is better, but in this invention, considering its relationship with the average thickness of the electron transport layer, a roughness coefficient of 20 or higher is preferred.

[0288] Sensitized dyes (photosensitive materials)

[0289] As the photosensitive material 4' of the aforementioned sensitized dye, any compound that can be photoexcited by using excitation light is acceptable. This invention includes, but is not limited to, the aforementioned materials. Specifically, the following compounds can be listed. For example, phthalocyanine compounds, porphyrin compounds, etc., can be listed. Among these, metal complexes, coumarin compounds, polyene compounds, dihydroindole compounds, and thiophene compounds are particularly preferred.

[0290] As a method for adsorbing the photosensitive material 4' onto the electron transport material 4, one can use an impregnation method by immersing a current collector electrode containing semiconductor particles into a solution or dispersion of the photosensitive material, or a method by coating the solution or dispersion onto the electron transport layer and allowing adsorption. The former can utilize methods such as impregnation, dyeing, roller coating, and air knife coating. The latter can utilize methods such as wire rod coating, sliding hopper coating, extrusion, curtain coating, rotation coating, and spray coating. Alternatively, adsorption in supercritical fluids such as carbon dioxide can also be used.

[0291] When adsorbing photosensitive materials, condensing agents can be used in conjunction.

[0292] The aforementioned condensing agents act as physical or chemical catalysts to bind photosensitive materials and electron transport compounds to the surface of inorganic materials, or they can shift the chemical equilibrium in a favorable direction by altering its stoichiometry. Furthermore, thiols or hydroxyl compounds can be added as condensation aids.

[0293] Solvents used to dissolve or disperse photosensitive materials include: water, alcohols such as methanol, ethanol, or isopropanol; ketones such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; esters such as ethyl formate, ethyl acetate, or n-butyl acetate; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, or dioxane; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone; halogenated hydrocarbons such as dichloromethane, chloroform, bromoform, iodomethane, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, or 1-chloronaphthalene; and hydrocarbons such as n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and cumene. These can be used individually or in combination of two or more.

[0294] Furthermore, since different types of photosensitive materials exist, some materials may be more effective in inhibiting the aggregation between compounds, and therefore coagulation and dissociation agents can be used in conjunction with them. Examples of such coagulation and dissociation agents include steroidal compounds such as cholic acid and chenodeoxycholic acid, long-chain alkyl carboxylic acids, or long-chain alkylphosphonic acids, which can be appropriately selected according to the photosensitive material used. The amount of these coagulation and dissociation agents added relative to 1 part by weight of the photosensitive material is preferably 0.01 parts by weight to 500 parts by weight, more preferably 0.1 parts by weight to 100 parts by weight.

[0295] When using these methods, the preferred temperature for the adsorption photosensitive material or the photosensitive material and coagulation dissociation agent is -50°C to 200°C. Furthermore, the adsorption can be carried out under static or stirring conditions.

[0296] Examples of the above-mentioned stirring methods include, but are not limited to, agitators, ball mills, coating conditioners, sand mills, grinders, dispersers, and ultrasonic dispersers. The adsorption time is preferably 5 seconds to 1000 hours, more preferably 10 seconds to 500 hours, and even more preferably 1 minute to 150 hours. Furthermore, the adsorption is preferably carried out in the dark.

[0297] silicon-containing layer

[0298] As the silicon-containing layer and its fabrication method in the aforementioned solar cell, the method described in the silicon-containing layer and its fabrication method of the present invention can be appropriately selected and applied.

[0299] Metal oxide film

[0300] As for the metal oxide film 7 and its fabrication method in the above-mentioned solar cell, the method described in the metal oxide film and its fabrication method of the present invention can be appropriately selected and applied.

[0301] Second electrode

[0302] A second electrode is applied after the metal oxide film is formed. Furthermore, the same electrode as the first electrode described above can typically be used as the second electrode; a substrate is not necessarily required in a structure that adequately maintains strength and sealing.

[0303] Specific examples of second electrode materials include metals such as platinum, gold, silver, copper, and aluminum; carbon compounds such as graphite, fullerene, carbon nanotubes, and graphene; conductive metal oxides such as ITO, FTO, and ATO; and conductive polymers such as polythiophene and polyaniline.

[0304] There is no particular limitation on the average thickness of the second electrode layer; one type can be used alone, or two or more types can be used in combination.

[0305] Regarding the coating of the second electrode, it can be formed on the dye-sensitized electrode layer by appropriate methods such as coating, lamination, vapor deposition, CVD, and bonding, depending on the type of material used and the type of hole transport layer.

[0306] In order to function as a photoelectric conversion device (photoelectric conversion element), at least one of the first electrode and the second electrode must be substantially transparent.

[0307] In the device of the present invention, it is preferable that the first electrode is transparent, and that sunlight enters from the side of the first electrode. In this case, it is preferable to use a reflective material on the side of the second electrode, preferably a thin film of evaporated metal, conductive oxide glass, plastic, or metal.

[0308] Setting an anti-reflective layer on the side where sunlight is incident is also an effective method.

[0309] This photoelectric conversion element can be applied to solar cells and power supply devices equipped with such solar cells. As an example, any device that conventionally utilizes a solar cell or a power supply device using that solar cell can be used. For example, a solar cell can be used in an electronic desktop calculator or watch. As another example of utilizing the features of the photoelectric conversion element of this invention, power supply devices for mobile phones, electronic notebooks, or electronic paper devices can be listed. Furthermore, it can be used as an auxiliary power source to extend the continuous operating time of rechargeable or dry-cell battery-type electrical appliances. Moreover, it can be used as an independent power source for sensors and can be combined with a secondary battery to replace a primary battery.

[0310] 3: Organic electroluminescent elements

[0311] One embodiment of the device of the present invention is an organic electroluminescent (EL) element. Figure 9 This refers to an organic EL element 10C, which represents one of the device forms of the present invention.

[0312] In this invention, the inverse layer structure of organic EL, which is beneficial to durability, is regarded as a standard element structure, but the invention is not limited to this structure.

[0313] The aforementioned organic EL element reports a substrate 31, on which a stacked structure is formed by sequentially disposing of a cathode 32, an electron injection layer 33, an electron transport layer 34, a light-emitting layer 35, a hole transport layer 36, a silicon-containing layer 37, a metal oxide film 38, and an anode 39.

[0314] The following will explain in detail.

[0315] Substrate (base plate)

[0316] There are no particular limitations on the substrate 31 mentioned above, and any known substrate can be used. The substrate 31 is preferably made of a transparent material, and examples include glass, transparent plastic sheet, transparent plastic film, inorganic transparent crystal, etc.

[0317] cathode

[0318] Examples of materials that can be used for the cathode 32 include metal monomers or alloys thereof such as Li, Na, Mg, Ca, Sr, Al, Ag, In, Sn, Zn, and Zr. Furthermore, a protective electrode film such as LiF can be formed on the cathode 32 using the same method as for forming the cathode. ITO, IZO, FTO, and aluminum are also preferred. The average thickness of the cathode is preferably 10–500 nm, more preferably 100–200 nm. The thickness can be measured using an ellipsometer, a surface roughness meter, or microscopic image analysis.

[0319] Electron injection layer

[0320] An electron injection layer 33 can be provided to reduce the obstruction of electron injection from the cathode into the electron transport layer formed of an organic material with low electron affinity. Examples of materials used for the electron injection layer include metal oxides containing magnesium, aluminum, calcium, zirconium, silicon, titanium, and zinc, polyphenylene oxide, hydroxyquinoline, and naphthalimide derivatives.

[0321] The average thickness of the electron-injected layer is preferably 5–1000 nm, more preferably 10–30 nm. The average thickness of the electron-injected layer can be measured by an ellipsometry, a surface roughness meter, or microscopic image analysis.

[0322] Electron transport layer

[0323] Examples of low molecular weight compounds that can be used as materials for electron transport layer 34 include oxazole derivatives, oxadiazole derivatives, pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phenanthroline derivatives, triazine derivatives, triazole derivatives, imidazole derivatives, tetracarboxylic anhydride, various metal complexes represented by tris(8-hydroxyquinoline)aluminum (Alq3), thiophene derivatives, etc., and one or more of them can be used.

[0324] Among them, metal complexes such as Alq3 and pyridine derivatives are preferred.

[0325] The average thickness of the electron transport layer is preferably 10–200 nm, more preferably 40–100 nm. The thickness can be measured by an ellipsometry, a surface roughness meter, or microscopic image analysis.

[0326] Emissive layer

[0327] Examples of polymeric materials that form the luminescent layer 35 include poly(p-phenylenevinylene) compounds, polyfluorene compounds, and polycarbazole compounds.

[0328] Low molecular weight materials used to form the luminescent layer include, but are not limited to, tris(8-hydroxyquinoline)aluminum (Alq3), tris(4-methyl-8-quinoline)aluminum(III) (Almq3), zinc 8-hydroxyquinoline (Znq2), (1,10-phenanthroline)tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione]eupyramid(III) (Eu(TTA)3(phen)), metal complexes of 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin platinum(II), and bis[(2-o-hydroxybenzene)benzene]. Metal complexes of zinc(II) (ZnBTZ2), bis[2-(2-hydroxyphenyl)-pyridine]beryllium (Bepp2), metal complexes of tris[3-methyl-2-phenylpyridine]iridium(III) (Ir(mpy)3), stilbene derivatives, phenanthrene derivatives, perylene compounds, carbazole compounds, benzimidazole compounds, benzothiazole compounds, coumarin compounds, piperidinone compounds, oxadiazole compounds, quinacridone compounds, pyridine compounds, spirocyclic compounds, etc., and one or more of them may be used.

[0329] The average thickness of the light-emitting layer is not particularly limited, but is preferably 10–150 nm. More preferably, it is 20–100 nm. The thickness can be measured by an ellipsometry, a surface roughness meter, and microscopic image analysis.

[0330] Hole transport layer

[0331] Examples of materials used for hole transport layer 36 in the aforementioned organic EL include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, butadiene derivatives, 9-(p-diethylaminostyrylanthracene), 1,1-bis-(4-dibenzylaminophenyl)propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, lysine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. Other examples include polyarylamines, fluorene-arylamine copolymers, fluorene-dithiophene copolymers, poly(N-vinylcarbazole), polyvinylpyrene, polyvinylanthracene, polythiophene, polyalkylthiophene, polyhexylthiophene, poly(p-phenylenevinylene), polyvinylenevinylene, pyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin, or derivatives thereof. These hole transport substances can be used alone, in combination of two or more, or in combination with other compounds.

[0332] The average thickness of the hole transport layer is preferably 10–150 nm, more preferably 40–100 nm.

[0333] silicon-containing layer

[0334] As the silicon-containing layer 37 in the above-mentioned organic EL and the method thereof, the method described in the above-mentioned silicon-containing layer and the method thereof for fabrication of the device of the present invention can be appropriately selected and applied.

[0335] Metal oxide film

[0336] As for the metal oxide film 38 and its fabrication method in the above-mentioned organic EL, the method described in the metal oxide film and its fabrication method of the device of the present invention can be appropriately selected and applied.

[0337] anode

[0338] Gold, silver, aluminum, and ITO are preferred materials for anode 39. Thickness can be measured using an ellipsometry, surface roughness meter, or microscopic image analysis. When performing vacuum phase deposition, a crystal resonator thickness gauge can be used.

[0339] Example

[0340] The present invention will now be described in more detail with reference to embodiments, but the present invention includes, but is not limited to, the following embodiments. In the following description, "parts" refers to "parts by mass".

[0341] Preparation of copper aluminum oxides

[0342] Copper-aluminum oxide was prepared by the following steps: Equimolar amounts of cuprous oxide and aluminum oxide were weighed and transferred to a vial, and stirred with a TURBULA MIXER (T2C type, manufactured by Willy A. Bachofen AG Maschinenfabrik) to obtain a mixed powder. The resulting mixed powder was heated at 1100°C for 40 hours and sieved through a 100 μm sieve.

[0343] Mixed powder materials

[0344] • Cuprous oxide (NC-803, manufactured by NC Tech): 12kg

[0345] • Alumina (AA-03, manufactured by Sumitomo Chemical Co., Ltd.): 8.58 kg

[0346] The obtained copper-aluminum oxides were pulverized under arbitrary conditions using Drystar SDA1 (manufactured by Ashizawa Finetech Co., Ltd.) to obtain copper-aluminum oxide particles 1 to 10 with different particle size distributions, representing Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4. For reference, the particle size distribution of obtained copper-aluminum oxide particle 1 is shown below. Figure 10 Furthermore, Table 1 shows the particle size and frequency (%) of copper aluminum oxide particles at the first local maximum, the particle size and frequency (%) at the second local maximum, and the ratio of the second local maximum to the first local maximum.

[0347] The copper-aluminum oxide particles were vacuum dried at 100°C to adjust the water content of the copper-aluminum oxide particles to below 0.2% by mass.

[0348] The particle size of the copper aluminum oxide particles was determined using a MICROTRAC MT3300EXII (manufactured by Microtrac Bell) under conditions of 0.2 MPa pressure and a measurement time of 10 seconds.

[0349] Particle size distribution data were obtained by averaging five measurements of different samples.

[0350] The moisture content of the copper and aluminum oxide particles was determined using a trace moisture content measuring device (CA-200, manufactured by Mitsubishi Chemical Analysis Technology Co., Ltd.).

[0351] The elemental composition of the copper aluminum oxide was determined using a fluorescence X-ray analyzer (ZSX PrimuIV, manufactured by Rigaku Corporation), and the crystal structure was determined using an X-ray diffractometer (X'Pert PRO, manufactured by Spectris Corporation).

[0352] Furthermore, the volume-based particle size of the copper-aluminum oxide particles in Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4 is 99% or more in the range of 0.1 μm to 50 μm.

[0353] [Table 1]

[0354]

[0355] Example 2-1

[0356] Example of manufacturing an electrophotographic photosensitive element

[0357] The electrophotographic photosensitive material of Example 2-1, which is fabricated by means of an intermediate layer, a charge generation layer, a charge transport layer, a silicon-containing layer and a metal oxide film on a conductive substrate, is manufactured according to the following steps.

[0358] Formation of intermediate layer

[0359] An intermediate layer was formed by applying the following intermediate layer coating solution onto an aluminum conductive substrate (outer diameter 100 mm, thickness 1.5 mm) using an immersion method. After drying at 150°C for 30 minutes, the average thickness of the intermediate layer was 5 μm.

[0360] Intermediate layer coating liquid

[0361] • Zinc oxide particles (MZ-300, manufactured by TAYCA Co., Ltd.): 350 parts

[0362] ·3,5-Di-tert-butylsalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.): 1.5 parts

[0363] • Capped isocyanate: 60 parts

[0364] (Sumijuru (registered trademark) 3175, solids concentration 75% by mass, manufactured by Sumitomo Chemical Bayer urethane Co., Ltd.)

[0365] • 20% by weight of butyraldehyde resin dissolved in 2-butanone: 225 parts

[0366] (BM-1, manufactured by Sekisui Chemicals Co., Ltd.)

[0367] ·2-Butanone: 365 parts

[0368] Formation of charge generation layer

[0369] The obtained intermediate layer is impregnated and coated with the following charge generation layer coating solution to form a charge generation layer. The average thickness of the charge generation layer is 0.2 μm.

[0370] charge generation layer coating liquid

[0371] • Y-type titanoxyphthalocyanine: 6 parts

[0372] • Butyraldehyde resin (Eslek BX-1, manufactured by Sekisui Chemicals Co., Ltd.): 4 parts

[0373] ·2-Butanone (manufactured by Kanto Chemical Co., Ltd.): 200 parts

[0374] Formation of charge transport layer

[0375] The charge generation layer is impregnated and coated with the following charge transport layer coating liquid to form a charge transport layer.

[0376] After drying at 135°C for 20 minutes, the average thickness of the charge transport layer was 22 μm.

[0377] Coating liquid for charge transport layer

[0378] Bisphenol Z-type polycarbonate: 10 parts

[0379] (Panlight TS-2050, manufactured by Teijin Co., Ltd.)

[0380] • Low molecular weight charge transport materials with the following structural formula: 10 parts

[0381] [Chemical Formula 8]

[0382]

[0383] Tetrahydrofuran: 80 parts

[0384] Formation of silicon-containing layers

[0385] The following coating solution for silicon-containing layers is applied in a ring coating onto the obtained charge transport layer to form a silicon-containing layer.

[0386] After drying at 135°C for 20 minutes, the average thickness of the silicon-containing layer was 0.5 μm.

[0387] Silicon-containing coating liquid

[0388] • Silicone hard coating solution (NSC-5506, manufactured by Nippon Seika Co., Ltd.): 187 parts

[0389] • Trimethylethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.): 24 parts

[0390] • Charge transport material with the following structure (manufactured by Ricoh): 20 parts

[0391] [Chemical Formula 9]

[0392]

[0393] • Ethanol: 269 portions

[0394] Formation of metal oxide films

[0395] The film-forming chamber used was modified from a commercially available vapor deposition apparatus.

[0396] A commercially available agitator (TKAdihommixer 2M-03, manufactured by Primix Corporation) can be used as an aerosol generator. Alternatively, a device can be used that uses a commercially available 1-liter pump bottle (RBN-S, manufactured by KSK Corporation) as an aerosol generator, installed in an ultrasonic cleaner (SUS-103, manufactured by Shimadzu Corporation).

[0397] A 4mm inner diameter tube is pulled from the aerosol generator into the film-forming chamber, and a nozzle (YB1 / 8MSSP37, manufactured by Spraying System Japan) is installed at its front end. The photoreceptor is installed 50mm from the nozzle. The photoreceptor holder is equipped with a mechanism that allows the photoreceptor drum to rotate. The nozzle used is a laterally movable nozzle. The aerosol generator and the nitrogen cylinder are connected via a 4mm inner diameter pipe.

[0398] Using the above-described apparatus, a metal oxide film with a target average thickness of 1.5 μm was prepared as follows.

[0399] Copper and aluminum oxide particles 1 are loaded into an aerosol generator.

[0400] Next, a vacuum is drawn from the film-forming chamber to the aerosol generator using an exhaust pump. Then, nitrogen gas is introduced from the gas cylinder into the aerosol generator, and stirring begins to generate an aerosol with particles dispersed in the nitrogen gas. The generated aerosol is then sprayed onto the photoreceptor through a nozzle via a pipeline. At this time, the nitrogen flow rate is set to 13 L / min to 20 L / min. The film-forming time is 20 minutes, and the vacuum degree in the film-forming chamber during the formation of the metal oxide film is approximately 50 Pa to 150 Pa.

[0401] Example 2-2

[0402] Except that the copper-aluminum oxide particles 1 used to form the metal oxide film are replaced with copper-aluminum oxide particles 2, the electrophotographic photoreceptor is prepared in the same manner as in Example 2-1.

[0403] Example 2-3

[0404] Except that the copper-aluminum oxide particles 1 used to form the metal oxide film are replaced with copper-aluminum oxide particles 3, the electrophotographic photoreceptor is prepared in the same manner as in Example 2-1.

[0405] Examples 2-4

[0406] Except that the copper-aluminum oxide particles 1 used to form the metal oxide film are replaced with copper-aluminum oxide particles 4, the electrophotographic photoreceptor is prepared in the same manner as in Example 2-1.

[0407] Examples 2-5

[0408] Except that the copper-aluminum oxide particles 1 used to form the metal oxide film are replaced with copper-aluminum oxide particles 5, the electrophotographic photoreceptor is prepared in the same manner as in Example 2-1.

[0409] Examples 2-6

[0410] Except that the copper-aluminum oxide particles 1 used to form the metal oxide film are replaced with copper-aluminum oxide particles 6, the electrophotographic photoreceptor is prepared in the same manner as in Example 2-1.

[0411] Comparative Example 2-1

[0412] Except that the copper-aluminum oxide particles 1 used to form the metal oxide film are replaced with copper-aluminum oxide particles 7, the electrophotographic photoreceptor is prepared in the same manner as in Example 2-1.

[0413] Comparative Example 2-2

[0414] Except that the copper-aluminum oxide particles 1 used to form the metal oxide film are replaced with copper-aluminum oxide particles 8, the electrophotographic photosensitive material is prepared in the same manner as in Example 2-1.

[0415] Comparative Examples 2-3

[0416] Except that the copper-aluminum oxide particles 1 used to form the metal oxide film are replaced with copper-aluminum oxide particles 9, the electrophotographic photoreceptor is prepared in the same manner as in Example 2-1.

[0417] Comparative Examples 2-4

[0418] Except that the copper-aluminum oxide particles 1 used to form the metal oxide film are replaced with copper-aluminum oxide particles 10, the electrophotographic photoreceptor is prepared in the same manner as in Example 2-1.

[0419] Evaluation of electrophotographic photosensitive materials

[0420] The electrophotographic photosensitive materials of Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-4 prepared as described above were evaluated as follows. Table 1 shows the evaluation results of each electrophotographic photosensitive material.

[0421] Exposure to NO x Evaluation of front and back halftone image printing

[0422] Electrophotographic photoresist in NO xThe electron microscope was placed in an atmosphere for a certain period of time to allow NO2 to be adsorbed onto the surface of the electron microscope photoreceptor. The exposure conditions were an atmosphere with a NO2 concentration of 40 ppm and an NO concentration of 10 ppm, and the exposure time was 24 hours.

[0423] For exposure to NO x Image evaluation before and after exposure to NO was performed using a modified Ricoh Pro C9110 (manufactured by Ricoh) after initial idling processing at the time of image output was eliminated. x After printing 0, 1,000, and 10,000 copies of the image pattern respectively, an evaluation pattern was printed at a resolution of 600 dpi, alternating between white and black every 2 pixels vertically and horizontally. A3-size copy paper (POD glossy coating, manufactured by Oji Paper Co., Ltd.) was used for printing, and Pro Toner Black C9100 was used as the toner.

[0424] Visually select the most uniform area on the printed paper with the halftone image, and obtain a magnified image (4mm square, TIFF file format) using a microscope (MXMACROZVI, manufactured by Hirox).

[0425] The image data was obtained by using image analysis software (Image J, manufactured by the National Institutes of Health) to calculate the area of ​​all halftones except for the image edges, and the quality was evaluated based on the magnitude of its coefficient of variation (standard deviation divided by the mean).

[0426] Image evaluation

[0427] A: The coefficient of variation is less than 0.2.

[0428] B: The coefficient of variation is equal to or greater than 0.2 and less than 0.4.

[0429] C: Coefficient of variation equal to or greater than 0.4 and less than 0.5.

[0430] D: Coefficient of variation is 0.5 or higher, or halftone dots are not developed.

[0431] Table 2 shows the evaluation results of halftone image printing of the electrophotographic photoreceptors of Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-4.

[0432] [Table 2]

[0433]

[0434] In the past, even the p-type semiconductor metal oxide particles of Comparative Examples 2-1 to 2-4 were acceptable if the purpose was to form a metal oxide film. However, as explained in this invention, when used as a photoreceptor for obtaining high-resolution images over a long period of time, the metal oxide film needs to exhibit high gas barrier properties and excellent charge transport capabilities.

[0435] In contrast, the photoreceptors of Examples 2-1 to 2-6 are capable of precise photoelectric conversion, even when exposed to NO. x Subsequently, halftone image development can also be achieved without hindering practical use. To achieve such performance, the particle size distribution of the p-type semiconductor metal oxide particles must have two local maxima: a first local maxima (a range of 0.1 μm or larger and less than 5 μm) and a second local maxima (a range of 5 μm or larger and less than 50 μm), and it is necessary that the ratio of the second local maxima to the first local maxima is 0.5 or larger and less than 2.0.

[0436] The preferred embodiments described and implemented herein include the following (1) to (8):

[0437] (1) Metal oxide particles with p-type semiconductivity,

[0438] The metal oxide particles have a volume-based particle size distribution, which has a first local maxima and a second local maxima.

[0439] The first local maximum value is in the range of 0.1 μm or larger and less than 5 μm, and the second local maximum value is in the range of 5 μm or larger and less than 50 μm.

[0440] The ratio of the second local maximum to the first local maximum is 0.5 or greater and less than 2.0, and

[0441] 99% of the volume of the metal oxide particles or larger have a particle size in the range of 0.1-50 μm.

[0442] (2) The metal oxide particles as described in (1) above, wherein the metal oxide particles are copper-iron oxides.

[0443] (3) The metal oxide particles as described in (2) above, wherein the copper-iron oxide is a copper-aluminum oxide.

[0444] (4) An electronic device comprising:

[0445] Base;

[0446] A charge transport layer comprising a charge transport material, or a dye-sensitized electrode layer comprising a sensitized dye, wherein the charge transport layer or the dye-sensitized electrode layer covers the substrate; and

[0447] A metal oxide film comprising any one of (1) to (3) metal oxide particles, wherein the metal oxide film covers the charge transport layer or the dye sensitized electrode layer.

[0448] (5) The electronic device as described in (4) above further includes a silicon-containing layer between the charge transport layer or the dye-sensitized electrode layer and the metal oxide film.

[0449] (6) A method for manufacturing an electronic device, the method comprising:

[0450] Forming a charge transport layer containing a charge transport material or a dye-sensitized electrode layer containing a sensitized dye on a substrate; and

[0451] Metal oxide particles with p-type semiconductor properties are sprayed onto the charge transport layer or the dye-sensitized electrode layer to form a metal oxide film.

[0452] The metal oxide particles have a volume-based particle size distribution, which has a first local maxima and a second local maxima.

[0453] The first local maximum value is in the range of 0.1 μm or greater and less than 5 μm, and the second local maximum value is in the range of 5 μm or greater and less than 50 μm.

[0454] The ratio of the second local maximum to the first local maximum is 0.5 or greater and less than 2.0, and

[0455] The metal oxide particles have a particle size ranging from 0.1 to 50 μm, with 99% or more of their volume being the same.

[0456] (7) The method as described in (6) above, wherein the spraying method includes an aerosol deposition method for spraying the aerosol of the metal oxide particles.

[0457] (8) An imaging device comprising the electronic device described in (4) or (5).

[0458] According to the metal oxide particles with p-type semiconductor properties of (1) to (3) above, the electronic devices according to (4) and (5) above, the methods for manufacturing electronic devices according to (6) and (7) above, and the imaging device according to (8) above, the above-mentioned problems in the prior art can be solved and the above-mentioned objectives of the present invention can be achieved.

[0459] The above embodiments are illustrative and do not limit the invention. Therefore, many additional modifications and variations are possible based on the above teachings. For example, within the scope of the invention, elements and / or features of different illustrative embodiments can be combined with and / or substituted for each other.

[0460] This patent application is based on and claims priority to Japanese Patent Application No. 2020-087650, filed on May 19, 2020, with the Japan Patent Office, the entire disclosure of which is incorporated herein by reference.

[0461] List of reference numerals

[0462] (exist Figure 1-7 and Figure 9 )

[0463] 1A Electrostatic Discharge Device

[0464] 1B Pre-cleaning exposure device

[0465] 1C drive unit

[0466] 1D First Transfer Device, Initial Transfer Device

[0467] 1E Secondary Transfer Device, Secondary Transfer Device

[0468] 1F Intermediate Transfer Body, Intermediate Transfer Belt

[0469] 1G conveyor transfer belt

[0470] 2 First electrode

[0471] 3. Lubricant supply device

[0472] 3A Lubricant

[0473] 3B coating brush

[0474] 3C coating blade

[0475] 10A Electrostatic Latent Image Carrier (Electronic Photosensitive Material)

[0476] 10B Solar Cell

[0477] 10C Organic Electroluminescent Device

[0478] 11, 11Bk, 11C, 11M, 11Y Electrophotographic Photoresists

[0479] 12, 12Y, 12M, 12C, 12Bk charging devices

[0480] Exposure apparatus for 13, 13Y, 13M, 13C, and 13Bk

[0481] 14, 14Bk, 14C, 14M, 14Y developing apparatus

[0482] 15 Toners

[0483] 16, 16Y, 16M, 16C, 16Bk transfer devices

[0484] Cleaning devices 17, 17Y, 17M, 17C, 17Bk

[0485] 18. Transfer materials, printing media

[0486] 19 Fixing device

[0487] 31 Base

[0488] 32 Cathode

[0489] 33 Electron Injection Layer

[0490] 34 Electron Transport Layer

[0491] 35. Light-emitting layer

[0492] 36 Hole transport layer

[0493] 37 Silicon-containing layer

[0494] 38 Metal oxide films

[0495] 39 Anode

[0496] 51 Conductive substrate

[0497] 52 Intermediate Layer

[0498] 53 Charge Generation Layer

[0499] 54 Charge transport layer

[0500] 55 Silicon-containing layer

[0501] 56 Metal oxide films

[0502] 110 gas cylinder

[0503] 120a, 120b, 120c piping

[0504] 130 Aerosol Generator

[0505] 140 film-forming chamber

[0506] 150 nozzles

[0507] 160 substrate

[0508] 170 substrate frame

[0509] 170a Rotor

[0510] 180 exhaust pump

[0511] 190 Compressed Air Valve

[0512] 200 particles

[0513] (exist Figure 8 )

[0514] 1 substrate

[0515] 2 First electrode

[0516] 3. Cavity blocking layer

[0517] 4. Electron transport substances

[0518] 4' Photosensitive material

[0519] 5. Dye-sensitized electrode layer

[0520] 6. Silicon-containing layer

[0521] 7 Metal oxide films

[0522] 8 Second electrode

[0523] 9, 10 leads

Claims

1. An electronic device, comprising: Base; A charge transport layer containing a charge transport material, or a dye sensitized electrode layer containing a sensitized dye, wherein the charge transport layer or the dye sensitized electrode layer covers the substrate; as well as A metal oxide film comprising metal oxide particles having p-type semiconductivity, the metal oxide film covering the charge transport layer or the dye-sensitized electrode layer; and The silicon-containing layer between the charge transport layer or the dye-sensitized electrode layer and the metal oxide film. The metal oxide particles have a volume-based particle size distribution, which has a first local maxima and a second local maxima. The first local maximum value is in the range of 0.1 μm or greater and less than 5 μm, and the second local maximum value is in the range of 5 μm or greater and less than 50 μm. The ratio of the second local maximum to the first local maximum is 0.5 or greater and less than 2.0, and The metal oxide particles have a particle size in the range of 0.1-50 μm, with 99% or more of their volume being the same. The metal oxide particles comprise copper-iron oxides, and The copper-iron oxide type includes copper-aluminum oxide.

2. A method for manufacturing an electronic device, the method comprising: A charge transport layer containing a charge transport material or a dye sensitized electrode layer containing a sensitized dye is formed on a substrate. Metal oxide particles with p-type semiconductor properties are sprayed onto the charge transport layer or the dye-sensitized electrode layer to form a metal oxide film. A silicon-containing layer is formed between the charge transport layer or the dye-sensitized electrode layer and the metal oxide film. in, The metal oxide particles have a volume-based particle size distribution, which has a first local maxima and a second local maxima. The first local maximum value is in the range of 0.1 μm or greater and less than 5 μm, and the second local maximum value is in the range of 5 μm or greater and less than 50 μm. The ratio of the second local maximum to the first local maximum is 0.5 or greater and less than 2.

0. The metal oxide particles have a particle size in the range of 0.1-50 μm, with 99% or more of their volume being metal oxide particles. The metal oxide particles comprise copper-iron oxides, and The copper-iron oxide type includes copper-aluminum oxide.

3. The method as described in claim 2, wherein, The spraying method includes an aerosol deposition method for spraying aerosols of the metal oxide particles.

4. An imaging device comprising the electronic device of claim 1.

Images