Electronic device, method of manufacturing the same, imaging method, and imaging apparatus

Abstract

An electronic device comprising: a support; a charge transport layer comprising a charge transport material or a sensitizing dye electrode layer comprising a sensitizing dye, wherein the charge transport layer or sensitizing dye electrode layer is disposed on or over the support; a silicon-containing layer disposed on or over the charge transport layer or sensitizing dye electrode layer; and a metal oxide film disposed on or over the silicon-containing layer, wherein the ratio [Q(ACL) / Q(CTL)] is 10% or more, wherein Q(ACL) is the time integral of the transient photocurrent waveform of the electronic device (ACL) measured by the time-of-flight method, and Q(CTL) is the time integral of the transient photocurrent waveform of the electronic device (CTL) measured by the time-of-flight method.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to an electronic device and a method of producing the same, an imaging method, and an imaging apparatus. BACKGROUND

[0002] In recent years, photoelectric conversion devices in which organic semiconductors are used have been developed and have been on the market.

[0003] At present, widely available photoelectric conversion devices such as electrophotographic photoreceptors are mostly organic electronic devices formed of organic materials. However, organic electronic devices have a problem of shorter service life compared to inorganic electronic devices. One of the reasons for the shorter service life of organic electronic devices is poor gas barrier properties due to organic materials included in the organic electronic devices. Organic material resin films are porous compared to dense films of inorganic materials. Therefore, a food wrapping material such as polypropylene (PP) is laminated with aluminum to enhance the weather resistance of the wrapped contents.

[0004] As an inexpensive organic solar cell compared to silicon-based solar cells, a dye-sensitized solar cell including an organic sensitizing dye has been developed.

[0005] However, since the dye-sensitized solar cell includes an organic sensitizing dye which is an organic material, the applied material tends to deteriorate due to temperature, humidity, and gases (for example, oxygen, ozone, NOx, ammonia) compared to silicon-based solar cells, and thus the function of the dye-sensitized solar cell tends to degrade. Therefore, the dye-sensitized solar cell has a problem of poor durability compared to silicon-based solar cells.

[0006] In display elements such as organic electroluminescence (EL) elements, light emitting diode display elements, liquid crystal display elements, and electrophoretic ink display elements, a display element, such as an organic EL layer sandwiched between a positive electrode and a negative electrode, is disposed on a substrate. Organic EL display devices have a wide viewing angle and a high response speed compared to liquid crystal display devices, and thus are expected to become the next generation display device due to the light emission versatility of organic materials.

[0007] As a forming method of an organic EL element, a forming method using coating is adopted in view of productivity and cost. In addition, organic EL elements tend to deteriorate due to exposure to heat or gases such as moisture and oxygen. Therefore, there is a problem of a short service life of organic EL elements.

[0008] Various improvements have been made to improve gas barrier properties to extend the service life of organic electronic devices such as electrophotographic photoreceptors for printers, dye-sensitized solar cells, and organic EL elements. However, these improvements involve a large number of processes that are performed, which can adversely affect the organic electronic devices. Therefore, further improvements are needed to achieve a desired balance between cost and durability.

[0009] As an electrophotographic photoreceptor having superior wear resistance and stable image properties, for example, an electrophotographic photoreceptor including a protective layer including p-type semiconductor particles treated with a surface treatment agent is proposed (see, for example, PTL 1). As an organic EL element having a long service life, improved efficiency, and a low driving voltage, for example, an organic EL element in which an organic hole transport layer of the organic EL element is replaced with an inorganic p-type semiconductor is proposed (see, for example, PTL 2).

[0010] Further, a laminate is proposed in which a film of a particulate material (such as a ceramic material and a metallic material) of 100 micrometers or less is formed on a substrate by aerosol deposition to form a polycrystalline brittle material layer (see, for example, PTL 3).

[0011] By providing a p-type semiconductor metal oxide as a surface layer of an electronic device, wear resistance and gas barrier properties can be enhanced. A coating layer surface of a ceramic coating layer applied to an organic material is proposed to be defined in viscoelasticity (see, for example, PTL 4). However, simply applying a ceramic coating layer to a plastic base material is not sufficient to impart precise semiconductor properties.

[0012] Bibliographic List

[0013] Patent Literature

[0014] PTL 1: Japanese Patent No. 5664538

[0015] PTL 2: Japanese Unexamined Patent Application Publication No. 2000-150166

[0016] PTL 3: Japanese Unexamined Patent Application Publication No. 2008-201004

[0017] PTL 4: International Patent Publication No. WO2018 / 194064 SUMMARY

[0018] TECHNICAL PROBLEM

[0019] An object of the present disclosure is to provide an electronic device having a metal oxide film on its surface and achieving precise photoelectric conversion.

[0020] SOLUTION TO PROBLEM

[0021] According to one aspect of the present disclosure, an electronic device includes a support; a charge transport layer including a charge transport material or a sensitizing dye electrode layer including a sensitizing dye, wherein the charge transport layer or the sensitizing dye electrode layer is disposed on or over the support; a silicon-containing layer disposed on the charge transport layer or the sensitizing dye electrode layer, and a metal oxide film disposed on or over the silicon-containing layer. A ratio [Q(ACL) / Q(CTL)] is 10% or more, where Q(ACL) is a time integral of a transient photocurrent waveform of an electronic device (ACL) measured by a time-of-flight method, and Q(CTL) is a time integral of a transient photocurrent waveform of an electronic device (CTL) measured by the time-of-flight method. The electronic device (ACL) has the silicon-containing layer as an outermost layer, and is obtained by removing the metal oxide film from the electronic device. The electronic device (CTL) has the charge transport layer or the sensitizing dye electrode layer as an outermost layer, and is obtained by removing the metal oxide film and the silicon-containing layer from the electronic device.

[0022] Advantages of the Invention

[0023] The present disclosure can provide an electronic device having a metal oxide film on a surface thereof and achieving precise photoelectric conversion. BRIEF DESCRIPTION OF DRAWINGS

[0024] [ Figure 1 ] Figure 1 is a structural view illustrating an apparatus for removing a surface layer of an electronic device.

[0025] [ Figure 2A ] Figure 2A is a photograph illustrating one example of a ceramic in the form of a film.

[0026] [ Figure 2B ] Figure 2B is a photograph illustrating one example of a ceramic in the form of a film.

[0027] [ Figure 2C ] Figure 2C is a photograph illustrating one example of a ceramic in the form of a film.

[0028] [ Figure 3 ] Figure 3 is a schematic structural view illustrating one example of an aerosol deposition apparatus used when a metal oxide film of the present disclosure is formed.

[0029] [ Figure 4 ] Figure 4 is a cross-sectional view illustrating one example of an electronic device (electrophotographic photoreceptor) of the present disclosure.

[0030] [ Figure 5 ] Figure 5is a schematic structural view illustrating one example of an imaging device of the present disclosure.

[0031] [ Figure 6 ] Figure 6 is a schematic structural view illustrating another example of an imaging device of the present disclosure.

[0032] [ Figure 7 ] Figure 7 is a schematic structural view illustrating another example of an imaging device of the present disclosure.

[0033] [ Figure 8 ] Figure 8 is a schematic structural view illustrating another example of an imaging device of the present disclosure.

[0034] [ Figure 9 ] Figure 9 is a schematic structural view illustrating another example of an imaging device of the present disclosure.

[0035] [ Figure 10 ] Figure 10 is a cross-sectional view illustrating one example of an electronic device (solar cell) of the present disclosure.

[0036] [ Figure 11 ] Figure 11 is a cross-sectional view illustrating one example of an electronic device (organic EL element) of the present disclosure.

[0037] [ Figure 12 ] Figure 12 is a graph depicting an example of mobility measurement. DETAILED DESCRIPTION

[0038] <ELECTRONIC DEVICE>

[0039] The electronic device of the present disclosure includes a carrier, a charge transport layer or a sensitizing dye electrode layer, a silicon-containing layer, and a metal oxide film. As needed, the electronic device can further include other components.

[0040] The ratio [Q(ACL) / Q(CTL)] is 10% or more, where Q(ACL) is a time integral of a transient photocurrent waveform of the electronic device (ACL) measured by a time-of-flight method, and Q(CTL) is a time integral of a transient photocurrent waveform of the electronic device (CTL) measured by a time-of-flight method.

[0041] The electronic device (ACL) has a silicon-containing layer as the outermost layer, and is obtained by removing the metal oxide film from the electronic device of the present disclosure.

[0042] The electronic device (CTL) has a charge transport layer or a sensitizing dye electrode layer as the outermost layer, and is obtained by removing the metal oxide film and the silicon-containing layer from the electronic device of the present disclosure.

[0043] [Ratio [Q(ACL) / Q(CTL)]]

[0044] The ratio [Q(ACL) / Q(CTL)] is 10% or more. Since the ratio [Q(ACL) / Q(CTL)] is 10% or more, accurate photoelectric conversion can be achieved. When the ratio [Q(ACL) / Q(CTL)] is less than 10%, accurate photoelectric conversion cannot be achieved.

[0045] In order to achieve accurate photoelectric conversion (accurate development of a halftone image), the ratio [Q(ACL) / Q(CTL)] is preferably 12% or more, and more preferably 15% or more. The value of the ratio [Q(ACL) / Q(CTL)] is more preferred the larger it is. There is no specific limitation on the upper limit thereof and it can be appropriately selected depending on the intended purpose. Although a larger value of the ratio [Q(ACL) / Q(CTL)] is preferred, the effect thereof tends to level off as the value increases. Therefore, the upper limit thereof can be, for example, 30% or less, 25% or less, or 20% or less.

[0046] For example, the electronic device (ACL) having a silicon-containing layer as the outermost layer and obtained by removing the metal oxide film from the electronic device, and the electronic device (CTL) having a charge transport layer or a sensitizing dye electrode layer as the outermost layer and obtained by removing the metal oxide film and the silicon-containing layer from the electronic device can be produced in the following manner.

[0047] The individual metal oxide film, or the metal oxide film and the silicon-containing layer are removed by Figure 1 the device shown.

[0048] Figure 1 A device for removing the surface layer of an electronic device is shown. Figure 1 The device of the present disclosure is a photoreceptor reproduction device, but the device can also be used to remove the surface layer.

[0049] In Figure 1In the present embodiment, a cylindrical photosensitive body is described as an example, but the embodiment of the photosensitive body is not limited to the cylindrical photosensitive body. The photosensitive body 231 is attached to a driving motor (not shown), and the photosensitive body 231 rotates in the clockwise direction at a predetermined speed. The rotation speed of the photosensitive body 231 is controlled by a programmable logic controller (PLC). The rotation speed of the photosensitive body is adjusted according to the size of the outer diameter of the photosensitive body. The rotation speed is set to 50 rpm or faster but 500 rpm or slower. In order to prevent the rotation of the photosensitive body from jumping, a shaft can be inserted into the center of the photosensitive body to rotate, or a flywheel can be installed to rotate the photosensitive body.

[0050] A wrapping film 232 wound in a roll form on a feeding roller 239 is installed, and the end portion of the film is attached to a paper winding roller 240 by passing through paper feed rollers 238, 236, and a pressure roller 233. A brake unit can be provided on the feeding roller 239 to prevent the film from feeding backward. In addition, the film can be clamped between the paper feed roller 236 and a pinch roller 235 equipped with a load member 237 to prevent the film from shaking while feeding. As the load member, a member capable of applying a load such as a spring, a roller, or the like is used. Like the photosensitive body, the paper winding roller is rotated by a driving motor to wind the wrapping film.

[0051] The pressure roller 233 is pressed against the photosensitive body 231 on which the wrapping film 232 is present by adjusting the load member 234.

[0052] Friction is generated between the wrapping film 232 and the photosensitive body 231 due to the pressure applied by the pressure roller 233, and the surface of the photosensitive body is polished. When the load applied to the contact surface of the wrapping film and the contact surface of the photosensitive body is significantly uneven, the photosensitive body is polished unevenly. In order to polish the surface of the photosensitive body uniformly regardless of the polishing position, it is preferable to use a pressure roller having a JIS-A hardness (JIS K6301 A) of 40° or more but 80° or less and an outer diameter runout tolerance of 30 micrometers or less.

[0053] The jamming of the wrapping film 232 can be caused to some extent by the polishing powder generated from the polishing of the surface of the photosensitive body. Therefore, polishing defects can be prevented by feeding the wrapping film at a speed of about 1 m / hr or faster but about 3 m / hr or slower.

[0054] Once the metal oxide film is removed using the device of Figure 1 The silicon-containing layer is exposed once the metal oxide film is removed using the device of

[0055] Next, the silicon-containing layer is similarly removed by means of Figure 1 The amount of charge Q(CTL) is the time integral Q(CTL) of the transient photocurrent waveform of the electronic device (CTL) measured by the time-of-flight method.

[0056] The ratio of the amount of charge is determined from the amount of charge Q(ACL) and the amount of charge Q(CTL) according to the following formula.

[0057] [Equation 1]

[0058]

[0059] The amount of charge Q(ACL) is the time integral Q(ACL) of the transient photocurrent waveform of the electronic device (ACL) measured by the time-of-flight method.

[0060] The amount of charge Q(CTL) is the time integral Q(CTL) of the transient photocurrent waveform of the electronic device (CTL) measured by the time-of-flight method.

[0061] For example, the time integral is the area defined by the waveform of the graph and the horizontal axis in Figure 12

[0062] Figure 12 is a graph that depicts the results obtained by applying a bias of +500 V to the aluminum support of a photosensitive drum, irradiating the photosensitive drum with a pulsed laser of 782 nm from the electrode patch side, and displaying the state of the transport charge carriers photo-excited in the charge generation layer of the photosensitive body as a waveform of the photocurrent transient with respect to time with an oscilloscope. The time-of-flight measurement device (TOF-401) used in the measurement of the present disclosure can continuously display the transient photocurrent waveforms measured a set number of times on the oscilloscope within the device. From the observation of the waveforms, it can be confirmed that the waveforms match each other and there is no variation in the waveforms. Furthermore, the average of the waveform data of all the measurements is recorded as the measurement result. Since it is possible to make the peak curve of the waveform sharp, it is possible to calculate a reproducible amount of charge. Figure 12 A waveform is depicted that is the average of 32 transient photocurrent waveforms obtained by 32 measurements.

[0063] In the present disclosure, several measurements of Q(ACL) and Q(CTL) can be performed at several points, but Q(ACL) and Q(CTL) can each be measured at a predetermined one point. In the example of the present disclosure described later, the measurement is performed at one position on the center of the measurement target.

[0064] The electronic device is not particularly limited and can be appropriately selected according to the intended purpose. Examples of the electronic device include devices such as electrophotographic photoreceptors, solar cells, organic electroluminescence (EL) elements, transistors, integrated circuits, laser diodes, and light-emitting diodes.​

[0065] <silicon-containing layer>

[0066] The silicon-containing layer is not particularly limited and can be appropriately selected depending on the intended purpose, as long as the silicon-containing layer has a polysiloxane structure.

[0067] Since the silicon-containing layer has a polysiloxane structure, when a metal oxide film is formed, the silicon-containing layer, which is a laminate structure including an organic material film and a metal oxide film that are easily and inexpensively formed, can suppress corrosion of the underlying layer, or can prevent separation of the metal oxide film.

[0068] For example, the silicon-containing layer is formed by cross-linking an organosilicon compound having a hydroxyl group or a hydrolysable group. As needed, the silicon-containing layer can further include a catalyst, a cross-linking agent, an organosilica sol, a silane coupling agent, or a polymer such as an acrylic polymer.

[0069] The cross-linking is not particularly limited and can be appropriately selected depending on the intended purpose. The cross-linking is preferably thermal cross-linking.

[0070] Examples of the organosilicon compound having a hydroxyl group or a hydrolysable group include a compound having an alkoxysilyl group, a partially hydrolyzed condensate of the compound having an alkoxysilyl group, and a mixture thereof.

[0071] Examples of the compound having an alkoxysilyl group include tetraalkoxysilane such as tetraethoxysilane, alkyltrialkoxysilane such as methyltriethoxysilane, and aryltrialkoxysilane such as phenyltriethoxysilane.

[0072] Note that an epoxy group, a methacryl group, or a vinyl group can be introduced into any of the compounds listed above.

[0073] The partially hydrolyzed condensate of the compound having an alkoxysilyl group can be produced by any method known in the art, for example, by reacting a mixture by adding a predetermined amount of water, a catalyst, or the like to the compound having an alkoxysilyl group.

[0074] As a raw material of the silicon-containing layer, a commercial product can be used. Specific examples thereof include GR-COAT (available from Daicel Corporation), Glass Resin (available from OWENS CORNING JAPAN LLC.), Non-thermal glass (available from OHA SHI CHEMICAL INDUSTRIES LTD.), NSC (available from NIPPON FINE CHEMICAL CO., LTD.), glass stock solution GO150SX and GO200CL (available from Fine Glass Technologies Co., Ltd.), and MKC silicate (available from Mitsubishi Chemical Corporation) as a copolymer between an alkoxysilyl compound and an acrylic resin or a polyester resin, silicate / acrylic varnish XP-1030-1 (available from Dainippon Shikizai Kogyo Co., Ltd.), and NSC-5506 (available from NIPPON FINE CHEMICAL CO., LTD.).

[0075] <<Monoalkoxysilane>>

[0076] The silicon-containing layer preferably contains a monoalkoxysilane as a constituent component.

[0077] Since a predetermined amount of a monoalkoxysilane is contained in the constituent component of the silicon-containing layer, formation of a crack of the silicon-containing layer can be prevented. In addition, properties of the electronic device are stable to temperature fluctuations.

[0078] Examples of the monoalkoxysilane include monoalkoxyalkylsilanes such as trimethylethoxysilane, trimethylmethoxysilane, tripropylethoxysilane, and trihexylethoxysilane. For example, the number of carbon atoms of the alkoxy group is 1 or more but 3 or less. For example, the number of carbon atoms of the alkyl group is 1 or more but 6 or less. Trimethylethoxysilane is particularly effective.

[0079] The amount of the monoalkoxysilane in the constituent component of the silicon-containing layer is preferably 5% by mass or more but 50% by mass or less, and more preferably 10% by mass or more but 30% by mass or less.

[0080] The silicon-containing layer preferably contains at least one selected from a triphenylamine compound having a hydroxyl group, a polymethylphenylsilane, and a chalcocite oxide as a constituent component, because the ratio [Q(ACL) / Q(CTL)] can be easily adjusted to 10% or more.

[0081] The above component can exist as a reaction product obtained by reacting with another component constituting the silicon-containing layer, or can also exist as it is without undergoing any reaction.

[0082] The amount of the combination of the triphenylamine compound and the delafossite oxide in the constituent components of the silicon-containing layer is not particularly limited and can be appropriately selected depending on the intended purpose. The amount of the combination is preferably 10 mass% or more but 40 mass% or less with respect to the total amount of all the constituent components of the silicon-containing layer, since the ratio [Q(ACL) / Q(CTL)] can be easily adjusted to 10% or more, imparting a desired adhesion on both sides of the silicon-containing layer, preventing cracking of the silicon-containing layer, and preventing excessive etching when a metal oxide film is formed.

[0083] <<Triphenylamine Compound Containing Hydroxyl Group>>

[0084] The triphenylamine compound having a hydroxyl group is not particularly limited and can be appropriately selected depending on the intended purpose, as long as the triphenylamine compound is a compound having a hydroxyl group, a nitrogen atom, and 3 aromatic groups bonded to the nitrogen atom.

[0085] As the triphenylamine compound having a hydroxyl group, the following compounds represented by General Formula (1), General Formula (2), Structural Formula (3), and General Formula (4) are particularly effective because such compounds generally have excellent reactivity with thermosetting resin monomers and have excellent sensitivity.

[0086] [Chemistry 1]

[0087]

[0088] R1and R2are each a substituted or unsubstituted aryl group. R1and R2may be the same or different.

[0089] Ar1, Ar2, and Ar3are each an arylene group. Examples of the arylene group include divalent groups of the same aryl groups as those listed for R1and R2. Ar1, Ar2, and Ar3may be the same or different.

[0090] Specific examples of R1and R2as the substituted or unsubstituted aryl group include the following groups. R1and R2may be the same or different.

[0091] Listed as the aromatic hydrocarbon groups are phenyl, fused polycyclic groups (e.g., naphthyl, pyrenyl, 2-fluorenyl, 9,9-dimethyl-2-fluorenyl, azulenyl, anthryl, triphenylenyl, phenyl, fluorenylidenylphenyl, and 5H-dibenzo[a,d]cycloheptenylidenephenyl group, and non-fused polycyclic groups (e.g., biphenyl, terphenyl, and the following groups):

[0092] [Chemistry 2]

[0093]

[0094] (Provided that W is -O-, -S-, -SO-, -SO2-, -CO- or any of the following divalent groups, and R 106 will be described later)

[0095] [Chemical 3]

[0096]

[0097] (Provided that c is an integer of 1 to 12, d is an integer of 1 to 3, e is an integer of 1 to 3, f is an integer of 1 to 3, and R 107 and R 108 will be described later).

[0098] As the heterocyclic group, thienyl group, benzothienyl group, furanyl group, benzofuranyl group and carbozolyl group are listed.

[0099] The above-mentioned aryl group and arylene group can include the following groups as the substituent.

[0100] Further, the following substituents are also specific examples of R 106 , R 107 and R 108 of the above-mentioned general formula.

[0101] (1) halogen atom, trifluoromethyl group, cyano group and nitro group.

[0102] (2) alkyl group, which is preferably C1to C 12 , specifically preferably C1to C 18 , more preferably C1to C4straight chain or branched alkyl group, and can further include fluorine atom, hydroxyl group, cyano group, C1to C4alkoxy group, phenyl group or phenyl group substituted with halogen atom, C1to C4alkyl group or C1to C4alkoxy group. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, sec-butyl group, n-butyl group, isobutyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group and 4-phenylbenzyl group.

[0103] (3) As the alkoxy group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, t-butoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, 2-hydroxyethoxy group, 2-cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group and trifluoromethoxy group are specifically listed.

[0104] (4) As the aryloxy group, there are listed aryl groups such as phenyl and naphthyl, which can include a C1to C4alkoxy group, a C1to C4alkyl group or a halogen atom as a substituent. Specific examples thereof include phenoxy, 1-naphthoxy, 2-naphthoxy, 4-methylphenoxy, 4-methoxyphenoxy, 4-chlorophenoxy and 6-methyl-2-naphthoxy.

[0105] (5) As the substituted mercapto group or arylmercapto group, there are specifically listed methylmercapto, ethylmercapto, phenylmercapto and p-methylphenylmercapto.

[0106] (6) A group represented by the following general formula:

[0107] [Chemical 4]

[0108]

[0109] In the above formula, R 110 and R 111 each independently is an alkyl group or an aryl group. Examples of the aryl group include phenyl, biphenyl and naphthyl, which can include a C1to C4alkoxy group, a C1to C4alkyl group or a halogen atom as a substituent. Alternatively, a ring can be formed together with a carbon atom on the aryl group. Specific examples thereof include diethylamino, N-methyl-N-phenylamino, N,N-diphenylamino, N,N-di(p-tolyl)amino, dibenzylamino, piperidyl, morpholino and julolidyl groups.

[0110] (7) There are listed an alkylidene dioxy group such as methylenedioxy and an alkylidene dithio group such as methylenedithio.

[0111] The compound represented by the general formula (1) is easily dissolved in a solvent such as an alcohol and a cellulose solvent. When a film is formed using such a solvent, a clear and uniform film is easily formed.

[0112] [Chemical 5]

[0113]

[0114] R3and R4each are a substituted or unsubstituted aryl group. R3and R4may be the same or different.

[0115] Further, Ar4, Ar5and Ar6each are an arylene group. Examples of the arylene group include divalent groups identical to the aryl groups of R3and R4. Ar4, Ar5and Ar6may be the same or different. Further, m and n each are a repeating number of 1 to 10.

[0116] R3and R4are each the same substituent as R1and R2of General Formula (1), respectively. In addition, Ar4, Ar5, and Ar6are each the same substituent as Ar1, Ar2, and Ar3of General Formula (1), respectively.

[0117] [Chemistry 6]

[0118]

[0119] [Chemistry 7]

[0120]

[0121] (In the above formula, X is -CH2-, -0-, -CH=CH-, or -CH2CH2-.)

[0122] <<Polymethylphenylsilane>>

[0123] The polymethylphenylsilane is not particularly limited and can be appropriately selected depending on the intended purpose.

[0124] The polymethylphenylsilane can be selected from commercial products. Examples of the commercial products include OGSOL SI-10-10 (polymethylphenylsilane, number average molecular weight (Mn): 2,100, weight average molecular weight (Mw): 12,700) available from Osaka Gas Chemicals Co., Ltd., and OGSOL SI-10-20 (polymethylphenylsilane, number average molecular weight (Mn): 1,100, weight average molecular weight (Mw): 1,800) available from Osaka Gas Chemicals Co., Ltd.

[0125] <<Chalcocite oxide>>

[0126] Examples of the chalcocite oxide include the chalcocite oxides listed in the description of the metal oxide film described later.

[0127] The average thickness of the silicon-containing layer is preferably 0.1 micrometers or more but 4.0 micrometers or less, and more preferably 0.3 micrometers or more but 1.5 micrometers or less.

[0128] The average thickness can be measured by using an eddy current film thickness meter or observing a cross-sectional photograph taken by a scanning electron microscope. The average thickness is an arithmetic average of values measured from 20 points.

[0129] One example of a method for determining the average thickness of the silicon-containing layer of the present disclosure will be described. First, the film thickness of the coated target material before the silicon-containing layer is coated is measured at 20 points at the same intervals along the longitudinal direction of the coated target material by means of an eddy current film thickness gauge (FISCHERSCOPE mms, available from FISCHER INSTRUMENTS K.K.). Next, the film thickness of the target material after the silicon-containing layer is formed thereon is measured at the same points, and the initial film thickness of the silicon-containing layer is determined from the difference in the film thickness of the target material before and after the silicon-containing layer is formed.

[0130] Next, a metal oxide film is formed on the silicon-containing layer. Thereafter, a portion of the resultant is cut out, and the cut piece is processed by ion milling or focused ion beam processing to prepare a sample from which a smooth cross section of the formed film can be obtained. The sample is observed under a scanning electron microscope to measure the thickness of the silicon-containing layer. Due to slight etching or embedding (anchoring) of the metal oxide, the apparent film thickness of the silicon-containing layer after the metal oxide film is formed can be smaller than the average film thickness determined by the eddy current film gauge. Therefore, image analysis using a cross section photograph is additionally performed.

[0131] When the metal oxide is embedded in the silicon-containing layer, the thickness of the silicon-containing layer is measured at 10 points on the peak of the interface and 10 points on the valley of the interface, and the average of the measured values at the total of 20 points is determined as the average thickness. Furthermore, the sample can also be partially cut at several other positions, and preferably similar observation is performed on each of the resulting cut pieces.

[0132] The method of forming the silicon-containing layer is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include a method in which a silicon-containing layer coating liquid is applied on a charge transport layer or a sensitizing dye electrode layer, and then heated.

[0133] The coating method is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include dip coating, spray coating, ring coating, roll coating, gravure coating, nozzle coating, and screen printing.

[0134] The temperature and duration of heating are not particularly limited and can be appropriately selected depending on the intended purpose.

[0135] The silicon-containing layer coating liquid includes, for example, an organosilicon compound having a hydroxyl group or a hydrolysable group. The silicon-containing layer coating liquid preferably contains at least one selected from triphenylamine compounds having a hydroxyl group, polymethylphenylsilane, and copper-iron ore oxides. The silicon-containing layer coating liquid can further contain a solvent as needed.

[0136] <metal oxide film>

[0137] The metal oxide film is not particularly limited and can be appropriately selected depending on the intended purpose.

[0138] The metal oxide film includes a metal oxide, and preferably further includes silicon dioxide.

[0139] The metal oxide is preferably a p-type semiconductor.

[0140] The metal oxide is preferably a chalcocite oxide.

[0141] According to one aspect of the present disclosure, the electronic device of the present disclosure is accomplished based on the insight that the electronic device known in the art can not be able to realize a metal oxide film of a high degree of uniformity (less variation in film thickness) in which film formation unevenness of the metal oxide film is suppressed.

[0142] According to film formation of the metal oxide including a p-type semiconductor by the aerosol deposition known in the art, when the flowability of the raw material powder is poor, the formation of the metal oxide tends to be uneven, and the process capability is insufficient, and thus it is not realizable as a mass production of industrial products.

[0143] According to one aspect of the present disclosure, a metal oxide film is provided on a silicon-containing layer, in which the metal oxide film includes a metal oxide including a p-type semiconductor and silicon dioxide. Thus, film formation unevenness of the metal oxide film can be suppressed, and an electronic device in which the metal oxide film thickness has a high degree of uniformity and film formation unevenness is suppressed can be provided.

[0144] In the proposal of Japanese Patent No. 5664538, the protective layer includes a ceramic as a p-type semiconductor, but the ceramic is not in a film form but in a granular semiconductor form. The proposal of Japanese Patent No. 5664538 Figure 1 A conceptual diagram showing that the granular semiconductor is dispersed in the protective layer is shown. The film form here indicates Figure 2A 、 2B and the embodiment of the whitest surface layer seen in FIGS. 1C and 2C.

[0145] Japanese Unexamined Patent Application Publication No. 2000-150166 discloses the use of a hole transport layer including an inorganic p-type semiconductor, but it does not disclose that the hole transport layer includes silicon dioxide.

[0146] Japanese Unexamined Patent Application Publication No. 2008-201004 discloses the formation of a dense polycrystalline brittle material layer formed of particles, but it does not disclose that the particles include silicon dioxide.

[0147] <<Chalcocite Oxide>>

[0148] The chalcogenide oxide of copper and iron (hereinafter, can be referred to as "p-type semiconductor" or "p-type metal compound semiconductor") is not particularly limited and can be appropriately selected depending on the intended purpose, as long as the chalcogenide oxide has a function as a p-type semiconductor. Examples of the chalcogenide oxide of copper and iron include a p-type metal oxide semiconductor, a p-type metal compound semiconductor including monovalent copper, and other p-type metal compound semiconductors.

[0149] Examples of the p-type metal oxide semiconductor include CoO, NiO, FeO, Bi2O3, M0O2, Cr2O3, SrCu2O2, and CaO-Al2O3.

[0150] Examples of the p-type metal compound semiconductor including monovalent copper include Cu2O, CuAlO, CuAlO2, and CuGaO2.

[0151] Among the examples listed above, copper aluminum oxides such as CuAlO and CuAlO2 are preferable in view of charge mobility and light transmittance.

[0152] <silicon dioxide>

[0153] The silicon dioxide included in the metal oxide film can be appropriately synthesized for use, or can be selected from commercial products. Examples of the commercial products include REOLOSIL ZD-30S (available from Tokuyama Corporation), HDK H-2000 (available from Wacker Asahikasei Silicone Co., Ltd.), and AEROSIL R976 and AEROSIL RA200HS (available from NIPPON AEROSIL CO., LTD.).

[0154] The amount of the silicon dioxide included in the metal oxide film is preferably 0.5% by mass or more but 1.5% by mass or less with respect to the metal oxide film, more preferably 0.7% by mass or more but 1.3% by mass or less. When the amount of the silicon dioxide is within the above range, film formation unevenness of the metal oxide film can be suppressed, and an electronic device in which the film thickness of the metal oxide film has a high uniformity can be obtained.

[0155] <film thickness of the metal oxide film>

[0156] The average thickness of the metal oxide film is preferably 0.3 micrometers or more but 1.8 micrometers or less. More preferably, the average thickness of the metal oxide film is 0.3 micrometers or more but 5 micrometers or less, and the standard deviation of the film thickness is 0.07 micrometers or less.

[0157] In the case of an electrophotographic photoreceptor that is one embodiment of the electronic device of the present disclosure, for example, the film thickness is measured at five points arranged at 50 mm intervals over a distance of 100 mm to 300 mm from the edge of the photoreceptor drum in the longitudinal direction of the photoreceptor drum, where the photoreceptor drum is a cylindrical photoreceptor drum having a length of 380 mm and an outer diameter of 100 mm. The film thickness is determined by image analysis of SEM cross-sectional photographs. Specifically, the drum is cut with a saw to obtain a sample, the cross section of the sample is exposed by ion milling, and an SEM image of the cross section is obtained. The film thickness is measured by analyzing the SEM image.

[0158] When the average thickness of the metal oxide film is 0.3 micrometers or more but 5 micrometers or less, it is advantageous because a high-quality printed image with a superior balance between abrasion resistance and static electricity and a long service life can be formed. Furthermore, when the standard deviation of the film thickness of the metal oxide film is 0.07 micrometers or less, it is advantageous because the printed image has superior gradation reproducibility, which affects the appearance of a printed image of human skin or a landscape.

[0159] <Method of producing an electronic device>

[0160] The method of producing an electronic device of the present disclosure is a production method of the electronic device of the present disclosure. The method of producing an electronic device includes spraying a raw material of a metal oxide film onto a silicon-containing layer to form a metal oxide film. As necessary, the method can further include other steps.

[0161] Examples of the raw material include a metal oxide and silicon dioxide.

[0162] The method of spraying the raw material of the metal oxide film is not particularly limited and can be appropriately selected from general inorganic material film formation methods according to the intended purpose. Examples thereof include a vapor deposition method, a liquid phase growth method, and a solid phase growth method.

[0163] The vapor deposition method is classified into, for example, a physical vapor deposition method (PVD) and a chemical vapor deposition method (CVD).

[0164] Examples of the physical vapor deposition method include vacuum vapor deposition, electron beam vapor deposition, laser milling, laser milling MBE, MOMBE, reactive vapor deposition, ion plating, cluster ion beam, glow discharge sputtering, ion beam sputtering, and reactive sputtering.

[0165] Examples of the chemical vapor deposition method include thermal CVD, MOCVD, RF plasma CVD, ECR plasma CVD, photo CVD, and laser CVD.

[0166] Examples of liquid phase growth methods include LPE, electroplating, electroless plating, and coating.

[0167] Examples of solid-phase growth methods include SPE, recrystallization, graphoepitaxy, LB method, sol-gel method, and aerosol deposition (AD).

[0168] In the examples listed above, aerosol deposition (AD) is preferred because it does not adversely affect the uniformity of film formation over a relatively large area, such as in electrophotographic photosensitive materials, or the properties of the electrophotographic photosensitive material. In other words, the preferred method for spraying metal oxide film raw materials is to spray the raw material particles of the metal oxide film onto the silicon-containing layer via aerosol deposition.

[0169] Examples of raw material particles include metal oxide particles and silicon dioxide particles.

[0170] <Aerosol Deposition (AD)>

[0171] Aerosol deposition (AD) is a technique that mixes pre-prepared particles or microparticles with gas to form an aerosol, and then sprays the aerosol through a nozzle onto a film-forming target (substrate) to form a film.

[0172] As a characteristic of aluminosilicate (AD) deposition, film formation can be carried out at room temperature, and the film formation can be performed while maintaining essentially the same crystal structure of the raw materials. Therefore, AD is suitable for film formation in electronic devices (especially electrophotographic photosensitive devices).

[0173] An example of a method for forming metal oxide films by aerosol deposition will be described.

[0174] In this method, the following is used Figure 3 The aerosol deposition apparatus shown in the figure. Figure 3 The gas cylinder 110 shown stores an inert gas for generating aerosols. The gas cylinder 110 is connected to an aerosol generator 130 via a conduit 120a, which is guided inside the aerosol generator 130. A certain amount of particles 200 formed from metal oxides or semiconductor compounds is placed inside the aerosol generator 130. Another conduit 120b, connected to the aerosol generator 130, is connected to a spray nozzle 150 within a film-forming chamber 140.

[0175] The particles 200 formed of the p-type semiconductor metal oxide and the silicon dioxide are introduced into the aerosol generator 130 and generate an aerosol, and the generated aerosol is guided to the jet nozzle 150 through the pipe 120b. Alternatively, the aerosol of the p-type semiconductor metal oxide is generated by an aerosol generator (not shown) in which the p-type semiconductor metal oxide is included, and the aerosol of the silicon dioxide is generated by an aerosol generator (not shown) in which the silicon dioxide is included, and the generated aerosols are transmitted through pipes and are jetted at high speed from 2 nozzles toward the substrate, respectively.

[0176] Inside the film forming chamber 140, the substrate 160 is held by the substrate holder 170 to face the jet nozzle 150. As the substrate 160, a cylindrical conductive carrier or an electronic device such as a photoreceptor, a solar cell, and an EL element can be used. An exhaust pump 180 for adjusting the degree of vacuum inside the film forming chamber 140 is connected to the film forming chamber 140 through the pipe 120c.

[0177] Although not shown, the film forming apparatus for forming an electrode of the present embodiment includes a system configured to move the jet nozzle 150 laterally at high speed while rotating the substrate holder 170 by the rotation unit 170a. By performing film formation by moving the jet nozzle 150 laterally, a metal oxide film of a desired area can be formed on the substrate 160.

[0178] In the process of forming the metal oxide film, first, the compression valve 190 is closed to form a vacuum inside the film forming chamber 140 from the atmosphere of the film forming chamber 140 to the aerosol generator 130 by the exhaust pump 180. Next, the compression valve 190 is opened to introduce the gas inside the gas cylinder 110 into the aerosol generator 130 through the pipe 120a to disperse the particles 200 inside the container. Thereby, an aerosol in a state in which the particles 200 are dispersed in the gas is generated. The generated aerosol is jetted at high speed toward the substrate 160 by the jet nozzle 150 through the pipe 120b. When 0.5 seconds elapse in the state in which the compression valve 190 is opened, then the compression valve 190 is closed for the next 0.5 seconds. Thereafter, the compression valve 190 is opened again, and the opening and closing of the compression valve 190 are repeatedly performed every 0.5 seconds. The flow rate of the gas from the gas cylinder 110 is 2 L / min, the film forming duration is 1 hour, the degree of vacuum inside the film forming chamber 140 when the compression valve 190 is closed is about 10 Pa, and the degree of vacuum inside the film forming chamber 140 when the compression valve 190 is opened is about 100 Pa.

[0179] The ejection speed of the aerosol is controlled by the shape of the ejection nozzle 150, the length or inner diameter of the pipe 120b, the internal gas pressure of the gas cylinder 110, or the amount of gas exhausted by the exhaust pump 180 (the internal pressure of the film formation chamber 140). When the internal pressure of the aerosol generator 130 is several tens of thousands of Pa, the internal pressure of the film formation chamber 140 is several hundreds of Pa, and the shape of the opening of the ejection nozzle 150 is a circular shape having an inner diameter of 1 mm, the ejection speed of the aerosol can be set to several hundreds of meters per second, for example, by the internal pressure difference between the aerosol generator 130 and the film formation chamber 140. When the internal pressure of the film formation chamber 140 is maintained to a range of 5 Pa or more but 100 Pa or less and the internal pressure of the aerosol generator 130 is maintained to 50,000 Pa, a metal oxide layer having a porosity of 5% or more but 30% or less can be formed. The average thickness of the metal oxide film is preferably adjusted to a range of 0.1 micrometers or more but 10 micrometers or less by adjusting the duration of supplying the aerosol under the above conditions.

[0180] The average thickness of the metal oxide film can be adjusted to a suitable thickness with respect to each electronic device.

[0181] In the case of an electrophotographic photoreceptor as an example of an electronic device, the preferred average thickness of the metal oxide film is 1.2 micrometers or more but 1.8 micrometers or less as a condition for obtaining durability and high print quality of the electronic device as an optimal mode.

[0182] The particles 200 in the aerosol that reach kinetic energy by acceleration are crushed into the substrate 160, and the particles 200 are finely pulverized by collision energy. When the pulverized particles are combined to the substrate 160 and the pulverized particles are combined to each other, the metal oxide film is sequentially formed on the charge transport layer.

[0183] The film formation is performed together with the patterning by several times of use of a line pattern or the rotation of a photosensitive drum. By scanning the substrate holder 170 or the ejection nozzle 150 in the longitudinal direction and the lateral direction on the substrate 160, a metal oxide film of a desired area is formed.

[0184] Examples of embodiments of the electronic device of the present disclosure will be listed below.

[0185] <1: Electrophotographic Photoreceptor and Electrophotographic Apparatus>

[0186] One embodiment of the electronic device of the present disclosure is an electrophotographic photoreceptor.

[0187] An electrophotographic photoreceptor (hereinafter can be referred to as "photoreceptor") includes a conductive support as a support; a charge transport layer including a charge transport material, wherein the charge transport layer is disposed on or over the conductive support; a silicon-containing layer disposed on or over the charge transport layer, and a metal oxide film disposed on or over the silicon-containing layer. The electrophotographic photoreceptor can further include other layers, such as a charge generating layer, an intermediate layer, and a protective layer, as necessary.

[0188] The silicon-containing layer is as described above.

[0189] The metal oxide film is as described above.

[0190] Note that a layer obtained by sequentially laminating the charge generating layer and the charge transport layer can be referred to as a photosensitive layer.

[0191] Hereinafter, an example in which the electronic device is an electrophotographic photoreceptor will be described, but the electronic device is not limited to the electrophotographic photoreceptor, and can be applied to other embodiments of the electronic device.

[0192] Reference will be made to Figure 4 The structure of the electronic device as the electrophotographic photoreceptor 10A will be described. Figure 4 is a cross-sectional view illustrating one example of an electrophotographic photoreceptor. Figure 4 One embodiment of an electrophotographic photoreceptor is depicted in Figure 4 In one embodiment of the electrophotographic photoreceptor 10A, the electrophotographic photoreceptor 10A includes an intermediate layer 52, a charge generating layer 53, a charge transport layer 54, a silicon-containing layer 55, and a metal oxide film 56 on a conductive support 51 in this order. The intermediate layer 52 can be appropriately omitted.

[0193] <<Support (Conductive Support)>>

[0194] The conductive support is not particularly limited and can be appropriately selected depending on the intended purpose, as long as the conductive support exhibits electrical conductivity with a volume resistivity of 10 10 ohm-cm or less. Examples thereof include: a film or a cylindrical plastic or paper coated with a metal (e.g., aluminum, nickel, chromium, nickel-chromium alloy, copper, silver, gold, platinum, and iron) or an oxide (e.g., tin oxide and indium oxide) by vapor deposition or sputtering; and a tube obtained by changing a sheet material of aluminum, an aluminum alloy, nickel, stainless steel, or the like into a tube by a method such as drawing ironing, impact ironing, extruded ironing, extruded drawing, and machining, and then performing surface treatment such as machining, superfinishing, and polishing.

[0195] <Intermediate Layer>

[0196] The electrophotographic photoreceptor can include an intermediate layer provided between the conductive support and the photosensitive layer. The intermediate layer is provided for the purpose of improving adhesion, preventing moire, improving the coatability of the upper layer, and preventing injection of charges from the conductive support.

[0197] The intermediate layer generally includes a resin as a main component. Since the photosensitive layer is applied on the intermediate layer, the resin used in the intermediate layer is preferably a thermosetting resin that is hardly soluble in an organic solvent. Among the thermosetting resins, polyurethane, melamine resin, and alkyd-melamine resin are more preferable as the resin for the intermediate layer because a plurality of the resins listed above achieve the above-mentioned purposes.

[0198] Examples of the organic solvent include tetrahydrofuran, cyclohexanone, di alkyl, dichloroethane, and butanone. The coating material of the intermediate layer can be prepared by appropriately diluting the resin with the organic solvent.

[0199] Further, for the purpose of adjusting the electrical conductivity or preventing moire, particles of a metal, a metal oxide, or the like can be added to the intermediate layer. The metal oxide is preferably titanium oxide or zinc oxide. The coating material of the intermediate layer can be prepared by dispersing the particles in an organic solvent by means of a ball mill, an attritor, a sand mill, or the like to prepare a dispersion liquid, and mixing the dispersion liquid and a resin component.

[0200] Examples of the production method (film formation method) of the intermediate layer include a method of applying the coating material on the conductive support to form a film by dip coating, spray coating, bead coating, or the like, and a method of optionally heating the resulting film to cure. The average thickness of the intermediate layer is generally appropriately about 2 micrometers or more but about 20 micrometers or less. When the residual potential of the photoreceptor is excessively accumulated, the average thickness of the intermediate layer can be less than 3 micrometers.

[0201] <Photosensitive Layer>

[0202] The photosensitive layer of the electrophotographic photoreceptor is a laminated photosensitive layer in which a charge generation layer and a charge transport layer are laminated in this order.

[0203] <Charge Generation Layer>

[0204] The charge generation layer is a part of the laminated photosensitive layer. The charge generation layer having a function of generating charges due to exposure includes a charge generation material as a main component, and can further include a binder resin as necessary. Examples of the charge generation material include inorganic charge generation materials and organic charge generation materials.

[0205] Examples of the inorganic charge generating material include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, and amorphous silicon. As the amorphous silicon, it is preferable to use amorphous silicon in which dangling bonds are terminated with hydrogen atoms or halogen atoms, and amorphous silicon doped with boron atoms, phosphorus atoms, or the like.

[0206] As the organic charge generating material, known materials can be used. Examples thereof include: metal phthalocyanines such as titanium oxyphthalocyanine and chlorogallium phthalocyanine; metal-free phthalocyanines; azulene salt pigments; squarylium methine pigments; symmetrical or asymmetrical azo pigments having a carbazole skeleton; symmetrical or asymmetrical azo pigments having a triphenylamine skeleton; symmetrical or asymmetrical azo pigments having a fluorenone skeleton; and perylene pigments. Among the above-listed examples, metal phthalocyanines, symmetrical or asymmetrical azo pigments having a fluorenone skeleton, symmetrical or asymmetrical azo pigments having a triphenylamine skeleton, and perylene pigments are preferable because the quantum efficiency of charge generation is extremely high. The above-listed charge generating materials can be used alone or in combination.

[0207] Examples of the binder resin include polyamides, polyurethanes, epoxy resins, polyketones, polycarbonates, polyacrylates, silicone resins, acrylic resins, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, and polyacrylamide.

[0208] Among the above-listed examples, polyvinyl butyral is generally used and is effective. The above-listed binder resins can be used alone or in combination.

[0209] <Method for producing a charge generating layer>

[0210] For example, the method for producing a charge generating layer is roughly classified into a vacuum thin film forming method and a casting method of a solution dispersion system.

[0211] Examples of the vacuum thin film forming method include vacuum vapor deposition, glow discharge decomposition, ion plating, sputtering, reactive sputtering, and chemical vapor deposition (CVD). The above-listed methods are suitable for producing a layer formed of an inorganic charge generating material or an organic charge generating material.

[0212] As the method for producing a charge generating layer by a casting method, for example, an inorganic charge generating material or an organic charge generating material is dispersed in an organic solvent with the aid of a ball mill, an attritor, a sand mill, or the like, optionally together with a binder resin, to prepare a dispersion liquid, the dispersion liquid is appropriately diluted, and the resultant is coated.

[0213] Examples of the organic solvent include tetrahydrofuran, cyclohexanone, di alkyl, dichloroethane, and butanone. Among the above listed examples, methyl ethyl ketone, tetrahydrofuran, and cyclohexanone are preferred because the above solvents have a low environmental load compared to chlorobenzene, dichloromethane, toluene, and xylene.

[0214] The coating can be performed by dip coating, spray coating, bead coating, or the like.

[0215] The average thickness of the charge generation layer is preferably 0.01 micrometers or more but 5 micrometers or less.

[0216] When the reduction of residual potential and high sensitivity are important, an increase in the thickness of the charge generation layer can generally improve the above properties. On the other hand, a thick charge generation layer can generally result in the deterioration of the charging property such as charge retention or space charge formation. To balance the above advantages and the above disadvantages, the average thickness of the charge generation layer is more preferably 0.05 micrometers or more but 2 micrometers or less.

[0217] In addition, a low molecular compound such as an antioxidant, a plasticizer, a lubricant, and a UV absorber, and a leveling agent can be optionally added to the charge generation layer. The above listed compounds can be used alone or in combination. When a low molecular compound and a leveling agent are used in combination with other components of the charge generation layer, the sensitivity can generally deteriorate. Therefore, the amount of the low molecular compound and the leveling agent is generally preferably 0.1 phr or more but 20 phr or less, more preferably 0.1 phr or more but 10 phr or less. The use amount of the leveling agent is preferably 0.001 phr or more but 0.1 phr or less.

[0218] <Charge transport layer>

[0219] The charge transport layer is a part of the laminated photosensitive layer, and has a function of injecting and transporting the charge generated in the charge generation layer to neutralize the surface charge of the charged photoreceptor. The charge transport layer includes a charge transport material and a binder component that binds the charge transport material as main components.

[0220] The charge transport material includes an electron transport material and a hole transport material.

[0221] Examples of the electron transport material include electron-accepting materials such as asymmetric diphenylquinone derivatives, fluorene derivatives, and naphthalimide derivatives. The above listed electron transport materials can be used alone or in combination.

[0222] As the hole transport material, an electron-donating material is preferably used. Examples thereof include oxazole derivatives, Oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, butadiene derivatives, 9-(p-diethylaminostyryl anthracene), 1,1-bis-(4-dibenzylaminophenyl)propane, styrylanthracene, styrylpyrazoline, phenylhydrazone, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, fenadine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. The above-listed hole-transporting materials can be used alone or in combination.

[0223] Examples of the binder component include thermoplastic or thermosetting resins such as polystyrene, polyester, polyethylene, polyacrylate, polycarbonate, acrylic resin, silicone resin, fluorine resin, epoxy resin, melamine resin, urethane resin, phenol resin, and alkyd resin. Among the above-listed examples, polystyrene, polyester, polyacrylate, and polycarbonate are effectively used as the binder component of the charge-transporting component because many of them exhibit superior charge-transporting properties.

[0224] When an electrically inert polymer compound is used for the modification of the charge-transporting layer, cardo polymer-type polyesters having a large skeleton such as fluorene, polyesters (e.g., polyethylene terephthalate and polyethylene naphthalate), polycarbonates in which the 3,3' position of the phenol component of bisphenol polycarbonate such as C-type polycarbonate is substituted with an alkyl group, polycarbonates in which the geminal methyl group of bisphenol A is substituted with a long-chain alkyl group having 2 or more carbon atoms, polycarbonates having a biphenyl or biphenyl ether skeleton, polycaprolactone, polycarbonates having a long-chain alkyl skeleton such as polycaprolactone, acrylic resins, polystyrene, hydrogenated butadiene, and the like are effective.

[0225] In the present specification, the term "electrically inert polymer compound" means a polymer compound that does not have a chemical structure such as a triarylamine structure that exhibits photosensitivity. When such a resin is used as an additive together with a binder resin, its amount is preferably 50 mass% or less relative to the total solid content of the charge-transporting layer in view of the limitation related to the light decay sensitivity.

[0226] When a charge-transporting material is used, the amount of the charge-transporting material is generally preferably 40 phr or more but 200 phr or less, more preferably 70 phr or more but 100 phr or less. A copolymer in which the resin component is copolymerized in an amount of 0 mass parts or more but 200 mass parts or less, preferably about 80 mass parts or more but about 150 mass parts or less, relative to 100 mass parts of the charge-transporting component is preferably used.

[0227] The charge transport layer can be formed, for example, by dissolving or dispersing a mixture or copolymer comprising charge transport components and binder components as main components in a suitable solvent to prepare a charge transport layer coating material, and then applying and drying the coating material. As coating methods, dip coating, spray coating, ring coating, roll coater coating, gravure coating, nozzle coating, screen printing, etc., can be employed.

[0228] Examples of dispersing solvents used in preparing charge transport layer coating materials include: ketones, such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ethers, such as diethyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; and ethers, such as diethyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone. Alkanes, tetrahydrofurans, and ethyl cellosolves; aromatics such as toluene and xylene; halogens such as chlorobenzene and dichloromethane; and esters such as ethyl acetate and butyl acetate. Among the examples listed above, methyl ethyl ketone, tetrahydrofuran, and cyclohexanone are preferred because these solvents have lower environmental impacts compared to chlorobenzene, dichloromethane, toluene, and xylene. The solvents listed above can be used alone or in combination.

[0229] A cross-linked surface layer can be disposed above the charge transport layer. With this structure, it is not necessary to ensure the average thickness of the charge transport layer, taking into account wear that occurs during use. To ensure the required sensitivity and chargeability for practical use, the average thickness of the charge transport layer is preferably 10 micrometers or more but less than 40 micrometers, more preferably 15 micrometers or more but less than 30 micrometers.

[0230] In addition, low-molecular-weight compounds, such as antioxidants, plasticizers, lubricants, and UV absorbers, as well as leveling agents, may optionally be added to the charge transport layer. Sensitivity can generally be degraded when low-molecular-weight compounds and leveling agents are used in combination with other components of the charge transport layer. Therefore, the amounts of the compounds listed above are generally 0.1 phr or greater but less than 20 phr, preferably 0.1 phr or greater but less than 10 phr. The amount of leveling agent is suitably about 0.001 phr or greater but about 0.1 phr or less.

[0231] <Silicon-containing layer>

[0232] The silicon-containing layer of the electrophotographic photosensitive element is suitably selected from the description of the silicon-containing layer of the electronic device of this disclosure.

[0233] <Metal Oxide Films>

[0234] The metal oxide film of the electrophotographic photoreceptor and the method for producing the same are suitably selected from the detailed description of the metal oxide film of the electronic device of the present disclosure and the method for producing the same.

[0235] Imaging Equipment and Imaging Methods

[0236] The imaging apparatus disclosed herein includes electronic devices. For example, the electronic device is an electrophotographic photosensitive device.

[0237] Embodiments of the imaging apparatus disclosed herein include an electrophotographic photosensitive element (electronic device). The imaging apparatus further includes an electrostatic latent image forming unit and a developing unit, and may further include other units as needed.

[0238] The imaging method disclosed herein uses an electronic device. For example, the electronic device is an electrophotographic photoreceptor.

[0239] The imaging method of this disclosure includes at least an electrostatic latent image formation step and a development step, and may further include other steps as needed.

[0240] The imaging method is performed appropriately by an imaging device, the electrostatic latent image formation step is performed appropriately by an electrostatic latent image formation unit, the developing step is performed appropriately by a developing unit, and the other steps mentioned above are performed appropriately by the other units mentioned above.

[0241] <Implementation Methods of Imaging Equipment>

[0242] The following section will describe a structural example of the imaging device with reference to the accompanying drawings.

[0243] Figure 5 An example of an imaging apparatus is shown. The charging device 12 is a unit configured to uniformly charge the surface of the electrophotographic photoreceptor 11. Any known unit, such as a corotron, scorotron, solid-state charger, or charging roller, can be used as the charging device 12. For reduced power consumption, the charging device 12 is preferably arranged in contact with or adjacent to the electrophotographic photoreceptor 11. To prevent contamination of the charging device 12, the charging system is preferably positioned adjacent to the electrophotographic photoreceptor 11, with an appropriate gap between the surfaces of the electrophotographic photoreceptor 11 and the charging device 12. Generally, the aforementioned charger can be used as a transfer device 16. As a transfer device 16, a combination of a transfer charger and a separate charger is effective.

[0244] The electrophotographic photosensitive element 11 is driven by the drive unit 1C. Charging via the charging device 12, image exposure via the exposure device 13, development and transfer via the transfer device 16, pre-cleaning exposure via the pre-cleaning exposure device 1B, cleaning via the cleaning device 17, and charge removal via the charge removal device 1A are repeatedly performed. Lubricant 3A, a coating brush 3B for applying the lubricant, and a coating blade 3C are disposed between the cleaning device 17 and the charging device 12 along the travel direction of the electrophotographic photosensitive element 11. Figure 5 As shown.

[0245] In Figure 5 , light for a pre-cleaning exposure is applied from the carrier side of the electrophotographic photoreceptor 11 (in this case, the carrier is light-transmissive).

[0246] The above-mentioned photoelectric process is one example. For example, the pre-cleaning exposure is performed from Figure 5 the carrier side in, but the pre-cleaning exposure can also be performed from the photosensitive layer side. Furthermore, the application of light for the image exposure and the charge erasing can be performed from the carrier side. Meanwhile, the light for the image exposure, the light for the pre-cleaning exposure, and the light for the charge erasing are shown as light irradiation steps. However, in addition to the light irradiation steps, a transfer pre-exposure, a pre-exposure for the image exposure, and other light irradiation steps known in the art can be performed to perform light irradiation to the electrophotographic photoreceptor.

[0247] Furthermore, the above-mentioned image forming unit can be fixed and integrated with a copier, a facsimile, or a printer. Alternatively, the image forming unit can be integrated with any of the above-mentioned devices in the form of a process cartridge. Various examples of the shape of the process cartridge can be listed, but as a general example, Figure 6 the shape shown in is listed. The electrophotographic photoreceptor 11 has a drum shape, but the electrophotographic photoreceptor 11 can be in the shape of a sheet or a looped belt.

[0248] The process cartridge at least includes an electrophotographic photoreceptor on which an electrostatic latent image is carried, a developing unit configured to develop the electrostatic latent image carried on the electrophotographic photoreceptor with toner to form a visible image, and a lubricant supply unit configured to supply a lubricant to the electrophotographic photoreceptor. The process cartridge can further include other units as appropriate, such as a charging unit, an exposure unit, a transfer unit, a cleaning unit, and a charge erasing unit. The developing unit at least includes a developer container configured to store toner or a developer thereon, and a developer carrier configured to carry and transport the toner or the developer stored in the developer container. The developing unit can further include a layer thickness adjusting member configured to adjust the thickness of a toner layer carried on the developer carrier. The process cartridge can be detachably installed in various electrophotographic image forming apparatuses, facsimiles, and printers, and is particularly preferably detachably installed in the image forming apparatus of the present disclosure.

[0249] Figure 7 Another example of an image forming apparatus is shown. In the image forming apparatus, the charging device 12, the exposure device 13, the black (Bk), cyan (C), magenta (M), and yellow (Y) developing devices 14Bk, 14C, 14M, and 14Y, the intermediate transfer belt 1F as an intermediate transfer member, and the cleaning device 17 are disposed in this order on the outer periphery of the electrophotographic photoreceptor 11.

[0250] Note that,Figure 7 The letters (Bk, C, M, and Y) depicted in the middle indicate the colors of the toner, and are appropriately omitted if necessary. Each color of the developing devices 14Bk, 14C, 14M, 14Y can be independently controlled, and only the developing device for the color used for imaging is driven. The toner image formed on the electrophotographic photoreceptor 11 is transferred to the intermediate transfer belt IF by the first transfer device ID provided inside the intermediate transfer belt IF.

[0251] The first transfer device ID is provided so that the first transfer device ID can be in contact with the electrophotographic photoreceptor 11, and the intermediate transfer belt IF is in contact with the electrophotographic photoreceptor 11 only during the transfer operation. Imaging of each color is performed, and the toner images superimposed on the intermediate transfer belt IF are collectively transferred onto the print medium 18 by the second transfer device IE, and then fixed by the fixing device 19 to form an image. The second transfer device IE is also provided so that the second transfer device IE can be in contact with the intermediate transfer belt IF, and is in contact with the intermediate transfer belt IF only during the transfer operation.

[0252] In an image forming apparatus of a transfer drum system, toner images of different colors electrostatically attracted to a transfer drum are sequentially transferred to a print medium, and thus there is a limitation that the image forming apparatus of the transfer drum system cannot perform printing on thick paper. Meanwhile, in an image forming apparatus of an intermediate transfer system, as shown in Figure 7 , toner images of different colors are superimposed on an intermediate transfer belt IF. Thus, there is no limitation on the print medium used. The above-described intermediate transfer system can be applied not only to the apparatus shown in Figure 7 , but also to the image forming apparatuses shown in Figure 5 , 6 , 8, and 9.

[0253] The lubricant 3A and the coating brush 3B and the coating doctor blade 3C for coating the lubricant are provided between the cleaning device 17 and the charging device 12 with respect to the rotation direction of the electrophotographic photoreceptor 11, as shown in Figure 7 .

[0254] Figure 8 Another example of an image forming apparatus is shown. The image forming apparatus uses 4 colors of toner, i.e., yellow (Y), magenta (M), cyan (C), and black (Bk), and imaging units of each color are provided in the image forming apparatus. Further, electrophotographic photoreceptors 11Y, 11M, 11C, and 11Bk for 4 colors are provided. At the outer periphery of each of the electrophotographic photoreceptors 11Y, 11M, 11C, or 11Bk, a charging device 12Y, 12M, 12C, or 12Bk, an exposure device 13Y, 13M, 13C, or 13Bk, a developing device 14Y, 14M, 14C, or 14Bk, a cleaning device 17Y, 17M, 17C, or 17Bk, and the like are provided.

[0255] Further, the transfer belt 1G, which is a transfer material carrier, is held by the driving unit 1C, which enters and exits each transfer position of the electrophotographic photoreceptors 11Y, 11M, 11C, and 11Bk arranged in a straight line. The transfer devices 16Y, 16M, 16C, and 16Bk are arranged at the transfer positions, respectively facing the electrophotographic photoreceptors 11Y, 11M, 11C, and 11Bk via the transfer belt 1G.

[0256] Figure 8 The serial system imaging apparatus illustrated in FIG. 1 includes the electrophotographic photoreceptors 11Y, 11M, 11C, or 11Bk of each color, and the toner images of all colors are sequentially transferred to the print medium held on the transfer belt 1G. Thus, compared with the full-color imaging apparatus including only one electrophotographic photoreceptor, the serial system imaging apparatus can output a full-color image at a significantly high speed. The toner image developed on the print medium 18 serving as a transfer material is transported from the positions at which the electrophotographic photoreceptor 11Bk and the transfer device 16Bk face each other to the fixing device 19, and the toner image is fixed on the print medium 18 by the fixing device 19.

[0257] Further, the imaging apparatus can have Figure 9 The structure in the embodiment is illustrated. Specifically, it is possible to employ Figure 9 The structure illustrated in FIG. 1 using the intermediate transfer belt 1F is used instead of the direct transfer system using the transfer belt 1G illustrated in FIG. 1. Figure 8

[0258] In the example illustrated in FIG. 1, the imaging apparatus includes the electrophotographic photoreceptors 11Y, 11M, 11C, or 11Bk of each color, and the toner images of all colors formed by the electrophotographic photoreceptors are sequentially transferred and laminated on the intermediate transfer belt 1F by the primary transfer unit 1D as a first transfer unit, which is driven and supported by the driving unit 1C including a roller, thereby forming a full-color image. Figure 9 Next, the intermediate transfer belt 1F is further driven, and the full-color image carried thereon is transported to the position of the secondary transfer unit 1E as a second transfer device and the roller arranged to face the secondary transfer unit 1E. Then, the full-color image is secondary-transferred onto the print medium 18 by the secondary transfer unit 1E, thereby forming a desired image on the transfer material.

[0259] <2: Solar Cell>

[0260] One embodiment of the electronic device of the present disclosure is a solar cell.

[0261]

[0262] ​​The solar cell includes a support, a sensitizing dye electrode layer including a sensitizing dye, a silicon-containing layer disposed on or above the sensitizing dye electrode layer, and a metal oxide film disposed on or above the silicon-containing layer. The solar cell further includes a first electrode, a hole-blocking layer, and a second electrode, and can further include other components as needed.

[0263] The silicon-containing layer is as described above.

[0264] The metal oxide film is as described above.

[0265] Hereinafter, an example in which the electronic device is a solar cell will be described, but the electronic device is not limited to the solar cell, and other embodiments as the electronic device can be applied.

[0266] A solar cell of the present disclosure will be described below with reference to the drawings. Note that the present disclosure is not limited to the embodiments described below. The embodiments described below can be changed. For example, another embodiment can be practiced, or the embodiments described below can be added, corrected, or omitted within a range that can be implemented by those skilled in the art. Any of the above-described embodiments is included in the scope of the present disclosure as long as the functions and effects of the present disclosure are exhibited.

[0267] The solar cell includes a substrate serving as a support, a first electrode, a hole-blocking layer, an electron transport layer, a sensitizing dye electrode layer, a silicon-containing layer, a ceramic semiconductor film serving as a metal oxide film, and a second electrode.

[0268] The structure of the electronic device 10B, which is a solar cell, will be described with reference to Figure 10 Figure 10 is a cross-sectional view illustrating one example of a solar cell.

[0269] In Figure 10 In the illustrated embodiment, a first electrode 2 is formed on a substrate 1 serving as a support, a hole-blocking layer 3 is formed on the first electrode 2, and a sensitizing dye electrode 5 in which a light-sensitizing material 4' is adsorbed on an electron transport material 4 is disposed on the hole-blocking layer 3. The illustrated example has a structure in which a silicon-containing layer 6 and a metal oxide film 7 are sandwiched between the first electrode 2 and a second electrode 8 facing the first electrode 2. In addition, in Figure 10 In the illustrated embodiment, a first electrode 2 is formed on a substrate 1 serving as a support, a hole-blocking layer 3 is formed on the first electrode 2, and a sensitizing dye electrode 5 in which a light-sensitizing material 4' is adsorbed on an electron transport material 4 is disposed on the hole-blocking layer 3. The illustrated example has a structure in which a silicon-containing layer 6 and a metal oxide film 7 are sandwiched between the first electrode 2 and a second electrode 8 facing the first electrode 2. In addition, in

[0270] The material of the metal oxide film 7 can be incorporated into the sensitizing dye electrode layer, and the material of the sensitizing dye electrode layer can be incorporated into the metal oxide film 7.

[0271] Details will be described below.

[0272] <Support (Substrate)> ​

[0273] The substrate 1 serving as a carrier is not particularly limited and can be selected from substrates known in the art. The substrate 1 is preferably a transparent material. Examples thereof include glass, a transparent plastic plate, a transparent plastic film, and an inorganic transparent crystal.

[0274] <First electrode>

[0275] The first electrode 2 is not particularly limited as long as the first electrode 2 is a conductive material that is transparent to visible light. As the first electrode 2, electrodes known in the art, such as general photoelectric conversion elements and liquid crystal panels, can be used.

[0276] Examples of the material of the first electrode include indium tin oxide (hereinafter referred to as ITO), fluorine-doped tin oxide (hereinafter referred to as FTO), antimony-doped tin oxide (hereinafter referred to as ATO), indium zinc oxide, niobium titanium oxide, and graphene. The above-listed materials can be used alone or in combination as a laminate.

[0277] The average thickness of the first electrode is preferably 5 nm or more but 10 micrometers or less, more preferably 50 nm or more but 1 micrometer or less.

[0278] In addition, to maintain a certain hardness, the first electrode is preferably provided on a substrate 1 formed of a material that is transparent to visible light. As the substrate, for example, glass, a transparent plastic plate, a transparent plastic film, an inorganic transparent crystal, and the like are used.

[0279] A first electrode integrated with a substrate known in the art can be used. Examples thereof include FTO-coated glass, ITO-coated glass, zinc oxide: aluminum-coated glass, FTO-coated transparent plastic film, and ITO-coated transparent plastic film.

[0280] In addition, the first electrode can be a transparent electrode prepared by doping tin oxide or indium oxide with cations or anions having different valence states, and a metal electrode having a structure, such as a mesh or a strip, that is transparent to light provided on a substrate, such as a glass substrate.

[0281] The above-listed examples can be used alone, as a mixture, or as a laminate.

[0282] In addition, for the purpose of reducing resistance, a metal lead or the like can be used in combination.

[0283] Examples of the material of the metal lead include metals, such as aluminum, copper, silver, gold, platinum, and nickel. The metal lead is provided on a substrate by vapor deposition, sputtering, press bonding, or the like, and ITO or FTO is provided thereon.

[0284] <<Hole blocking layer>>

[0285] The material constituting the hole-blocking layer 3 is not particularly limited, as long as the material is transparent to visible light and is an electron-transporting material. The material is particularly preferably titanium oxide.

[0286] The hole-blocking layer is provided to suppress the decrease in electric power caused by recombination between holes in the electrolyte and electrons present on the surface of the electrode (i.e., reverse electron transport) when the electrode contacts the electrolyte hole-blocking layer. The above-described effect of the hole-blocking layer 3 is particularly significant in a solid dye-sensitized solar cell. This is because a solid dye-sensitized solar cell using an organic hole-transporting material or the like has a high recombination (reverse electron transport) rate between holes in the hole-transporting material and electrons present on the surface of the electrode, compared with a wet dye-sensitized solar cell using an electrolyte solution.

[0287] The method of forming the hole-blocking layer is not particularly limited, but it is important to have a high internal resistance for preventing current loss due to indoor light. Therefore, the method of forming the hole-blocking layer is also important. Examples thereof generally include a sol-gel method as a wet film formation. The sol-gel method can not sufficiently prevent current loss. Therefore, the method thereof is more preferably dry film formation, such as sputtering, and the dry film formation can give a sufficiently high film density, and can prevent current loss.

[0288] The hole-blocking layer is formed for the purpose of preventing electron contact between the first electrode and the hole-transporting layer. The average thickness of the hole-blocking layer is not particularly limited. The average thickness of the hole-blocking layer is preferably 5 nm to 1 micrometer. In wet film formation, the average thickness thereof is more preferably 500 nm to 700 nm. In dry film formation, the average thickness thereof is more preferably 10 nm to 30 nm.

[0289] <Sensitizing dye layer>

[0290] The solar cell includes a porous electron-transporting layer provided on the hole-blocking layer 3. The electron-transporting layer can be a single layer or multiple layers.

[0291] The electron-transporting layer is formed of an electron-transporting material. As the electron-transporting material, a semiconductor particle is preferably used.

[0292] In the case of multiple layers, a dispersion liquid each including semiconductor particles of different particle sizes can be applied to form multiple layers, or a coating layer each including a different type of semiconductor particle or each having a different resin or additive composition can be provided to form multiple layers. Multiple layer coating is effective when one coating layer cannot provide a sufficient average thickness.

[0293] As the average thickness of the sensitizing dye layer increases, in general, the amount of photo- sensitive material carried per unit of projected area increases, and thus the light capture rate increases. However, the diffusion length of the injected electrons increases, and thus the charge loss due to recombination also increases. Therefore, the average thickness of the electron transport layer is preferably 100 nm or more but 100 micrometers or less.

[0294] The semiconductor is not particularly limited, and any semiconductor known in the art can be used as the semiconductor. Specific examples thereof include: elemental semiconductors such as silicon and germanium; compound semiconductors such as metal chalcogenides; and compounds having a perovskite structure.

[0295] Examples of the metal chalcogenide include: oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, and tantalum; sulfides of cadmium, zinc, lead, silver, antimony, and bismuth; selenides of cadmium and lead; and telluride of cadmium.

[0296] Examples of other compound semiconductors include: phosphides of zinc, gallium, indium, and cadmium; gallium arsenide; copper indium selenide; and copper indium sulfide.

[0297] Further, the compound having a perovskite structure is preferably strontium titanate, calcium titanate, sodium titanate, barium titanate, or potassium niobate.

[0298] Among the examples listed above, the oxide semiconductor is preferred, and titanium oxide, zinc oxide, tin oxide, and niobium oxide are particularly preferred. The examples listed above can be used alone or in combination as a mixture. The crystal type of the semiconductors listed above is not particularly limited. The crystal type thereof can be single crystal, polycrystal, or amorphous.

[0299] The average particle diameter of the primary particles of the semiconductor particles is not particularly limited. The average particle diameter thereof is preferably 1 nm or more but 100 nm or less, more preferably 5 nm or more but 50 nm or less.

[0300] Further, the efficiency can be improved by mixing or laminating semiconductor particles having a larger average particle diameter due to the effect of scattering incident light. In this case, the average particle diameter of the semiconductor is preferably 50 nm or more but 500 nm or less.

[0301] The production method of the electron transport layer is not particularly limited. The production method thereof includes methods of forming a thin film in a vacuum, such as sputtering and wet film formation.

[0302] In view of the production cost, the wet film formation is particularly preferred. A method in which a paste in which semiconductor particle powder or sol is dispersed is prepared, and the paste is applied to a electron-collecting electrode substrate is preferred.

[0303] When a wet film formation method is employed, the coating method is not particularly limited, and the coating can be performed according to any method known in the art. The coating can be performed according to various methods, such as dip coating, spray coating, wire bar coating, spin coating, roll coating, blade coating, gravure coating, and wet printing methods (e.g., relief printing, offset printing, gravure printing, intaglio printing, rubber plate printing, and screen printing).

[0304] When the dispersion liquid of the semiconductor particles is formed by mechanical pulverization or with a grinder, the dispersion liquid is formed by dispersing at least the semiconductor particles alone or a mixture including the semiconductor particles and a resin in water or an organic solvent. Examples of the resin used include the following: vinyl compounds such as polymers or copolymers of styrene, vinyl acetate, acrylate, and methacrylate; silicone resins; phenoxy resins; polysulfone resins; polyvinyl butyral resins; polyvinyl formal resins; polyester resins; cellulose ester resins; cellulose ether resins; urethane resins; phenolic resins; epoxy resins; polycarbonate resins; polyacrylate resins; polyamide resins; and polyimide resins.

[0305] Examples of the solvent used for dispersing the semiconductor particles include: water; alcohol-based solvents such as methanol, ethanol, isopropanol, and a-methylcedenol; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester-based solvents such as ethyl formate, ethyl acetate, and n-butyl acetate; ether-based solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, and dioxane; amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; halogenated hydrocarbon-based solvents such as dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, and 1-chloronaphthalene; and hydrocarbon-based 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. The above-listed examples can be used alone or in combination.

[0306] The dispersion liquid of the semiconductor particles or the paste of the semiconductor particles obtained by a sol-gel method or the like can include an acid (e.g., hydrochloric acid, nitric acid, and acetic acid), an interfacial activator (e.g., polyoxyethylene (10) octylphenyl ether), and a chelating agent (e.g., acetylacetone, 2-aminoethanol, and ethylenediamine) to prevent re-aggregation of the particles.

[0307] Furthermore, it is also effective to add a thickening agent for the purpose of improving film formability. Examples of the thickening agent include: polymers such as polyethylene glycol and polyvinyl alcohol; and ethyl cellulose.​

[0308] After the semiconductor particles are applied, the particles are brought into electrical contact with each other, and preferably firing, microwave irradiation, electron beam irradiation, or laser irradiation is performed to improve the film strength or adhesion to the substrate. The above-listed examples can be implemented alone or in combination.

[0309] When firing is performed, the firing temperature is not particularly limited. When the temperature is too high, the resistance of the substrate can be too high or the substrate can melt. Therefore, the fixed temperature is preferably 30°C or higher but 700°C or lower, more preferably 100°C or higher but 600°C or lower. Furthermore, the firing duration is not particularly limited, but the firing duration is preferably 10 minutes or longer but 10 hours or shorter.

[0310] For microwave irradiation, microwaves can be applied from the electron transport layer side or the back side. The irradiation duration is not particularly limited, but the microwave irradiation is preferably performed for 1 hour or less.

[0311] After firing, chemical plating using a mixed solution of a titanium tetrachloride aqueous solution and an organic solvent, or electrochemical plating using a titanium tetrachloride aqueous solution, which increases the surface area of the semiconductor particles, or increases the electron injection efficiency from the photo-sensitizing material to the semiconductor particles, can be performed.

[0312] A film formed by laminating semiconductor particles having a diameter of several tens of nanometers by firing forms a porous state. The nanoporous structure has a very large surface area, and the surface area can be represented by a roughness factor.

[0313] The roughness factor is a numerical value representing the actual area of the inside of the pores relative to the area of the semiconductor particles applied to the substrate. Therefore, a larger roughness factor is more preferable. The roughness factor is related to the average thickness of the electron transport layer. In the present disclosure, the roughness factor is preferably 20 or greater.

[0314] The solar cell includes a sensitized dye electrode layer 5 to further improve the conversion efficiency. The sensitized dye electrode layer 5 is a layer in which a sensitized dye (photo-sensitizing material) is adsorbed on the surface of the electron transport material 4 that is an electron transport layer.

[0315] - Sensitized dye (photo-sensitizing material) -

[0316] The light-sensitizing material that functions as a sensitizing dye is not limited as long as the light-sensitizing material is a compound that is photo-excited by the excitation light used. Specific examples thereof include: metal complex compounds disclosed in Japanese translation of PCT international application publication No. JP-T-07-500630, Japanese unexamined patent application publication Nos. 10-233238, 2000-26487, 2000-323191, and 2001-59062; coumarin compounds disclosed in Japanese unexamined patent application publication Nos. 10-93118, 2002-164089, and 2004-95450 and J. Phys. Chem. C, 7224, Vol. 111 (2007); polyene compounds disclosed in Japanese unexamined patent application publication No. 2004-95450 and Chem. Commun., 4887 (2007); dihydroindolizine compounds disclosed in Japanese unexamined patent application publication Nos. 2003-264010, 2004-63274, 2004-115636, 2004-200068, and 2004-235052, J. Am. Chem. Soc, 12218, Vol. 126 (2004), Chem. Commun., 3036 (2003), and Angew. Chem. Int. Ed., 1923, Vol. 47 (2008); thiophene compounds disclosed in J. Am. Chem. Soc, 16701, Vol. 128 (2006) and J. Am. Chem. Soc, 14256, Vol. 128 (2006); cyanine dyes disclosed in Japanese unexamined patent application publication Nos. 11-86916, 11-214730, 2000-106224, 2001-76773, and 2003-7359; merocyanine dyes disclosed in Japanese unexamined patent application publication Nos. 11-214731, 11-238905, 2001-52766, 2001-76775, and 2003-7360; 9-aryl xanthene compounds disclosed in Japanese unexamined patent application publication Nos. 10-92477, 11-273754, 11-273755, and 2003-31273; triarylmethane compounds disclosed in Japanese unexamined patent application publication Nos. 10-93118 and 2003-31273; and metal complexes disclosed in Japanese unexamined patent application publication Nos. 09-199744, 10-233238, 11-204821, 11-265738, J. Phys. Chem., 2342, Vol. 91 (1987), J. Phys. Chem. B, 6272, Vol. 97 (1993), Electroanal. Chem., 31, Vol. 537 (2002), Japanese unexamined patent application publication No. 2006-032260, J.phthalocyanine compounds and coumarin compounds disclosed in Porphyrins Phthalocyanines, 230, Vol. 3 (1999), Angew. Chem. Int. Ed., 373, Vol. 46 (2007), and Langmuir, 5436, Vol. 24 (2008). Among the above-listed examples, metal complex compounds, coumarin compounds, polyene compounds, indoline compounds, and thiophene compounds are particularly preferably used.

[0317] As a method of adsorbing the photo-sensitizing material 4 onto the electron-transporting material 4, a method of dipping an electron-collecting electrode including semiconductor particles in a photo-sensitizing material solution or dispersion, or a method of applying a solution or dispersion to an electron-transporting layer so that semiconductor particles are adsorbed thereon can be employed.

[0318] In the case of the former method, dipping, dip coating, roll coating, air-knife coating, or the like can be employed.

[0319] In the case of the latter method, wire bar coating, slide hopper coating, extrusion, curtain coating, spin coating, spray coating, or the like can be employed.

[0320] Further, adsorption of the semiconductor particles can be performed in a supercritical fluid using carbon dioxide or the like.

[0321] When the photo-sensitizing material is adsorbed, a condensing agent can be used in combination.

[0322] The condensing agent can be a reagent having a catalytic function to physically or chemically bind the photo-sensitizing material and the electron-transporting compound to the surface of the inorganic material, or a reagent that stoichiometrically acts to favorably change the chemical equilibrium. Further, a mercaptan or a hydroxyl compound can be added as a condensing aid.

[0323] Examples of the solvent used to dissolve or disperse the photo-sensitizing material include water; alcohol-based solvents such as methanol, ethanol, and isopropanol; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester-based solvents such as ethyl formate, ethyl acetate, and n-butyl acetate; ether-based solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, and dioxane; amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; halogenated hydrocarbon-based solvents such as dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, and 1-chloronaphthalene; and hydrocarbon-based 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. The above-listed examples can be used alone or in combination. alkane; amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; halogenated hydrocarbon-based solvents such as dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, and 1-chloronaphthalene; and hydrocarbon-based 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. The above-listed examples can be used alone or in combination.

[0324] Further, there are photosensitive materials that function more effectively when aggregation between compound molecules is inhibited depending on the type of the photosensitive material. Therefore, the aggregation dissociating agent can be used in combination.

[0325] The aggregation dissociating agent is preferably a steroid compound (e.g., cholic acid and chenodeoxycholic acid), a long-chain alkyl carboxylic acid, or a long-chain alkyl phosphonic acid. The aggregation dissociating agent can be appropriately selected depending on the photosensitive material used.

[0326] The aggregation dissociating agent is preferably 0.01 parts by mass or more but 500 parts by mass or less, more preferably 0.1 parts by mass or more but 100 parts by mass or less, with respect to 1 part by mass of the photosensitive material.

[0327] The adsorption temperature of the photosensitive material or the combination of the photosensitive material and the aggregation dissociating agent is preferably -50°C or higher but 200°C or lower. Further, the adsorption can be performed with standing or stirring.

[0328] Examples of the stirring method include stirring with a stirrer, a ball mill, a paint conditioner, a sand mill, a mortar mill, and a disperser, and ultrasonic dispersion, but the method is not limited to the examples listed above. The time required for the adsorption is preferably 5 seconds or longer but 1000 hours or shorter, more preferably 10 seconds or longer but 500 hours or shorter, more preferably 1 minute or longer but 150 hours or shorter. Further, the adsorption is preferably performed in the dark.

[0329] <silicon-containing layer>

[0330] The silicon-containing layer of the solar cell and the method for producing the same can be appropriately selected from the description of the silicon-containing layer of the electronic device of the present disclosure and the method for producing the same.

[0331] <metal oxide film>

[0332] The metal oxide film 7 of the solar cell and the method for producing the same can be appropriately selected from the description of the metal oxide film of the electronic device of the present disclosure and the method for producing the same.

[0333] <second electrode>

[0334] The second electrode is provided after the metal oxide film is formed.

[0335] Further, the same electrode as the first electrode can generally be used as the second electrode. The carrier does not necessarily need to be provided in a structure in which the strength and the air tightness are sufficiently maintained.

[0336] Specific examples of the material of the second electrode include: metals such as platinum, gold, silver, copper, and aluminum; carbon-based compounds such as graphite, fullerene, carbon nanotube, and graphene; conductive metal oxides such as ITO, FTO, and ATO; and conductive polymers such as polythiophene and polyaniline.

[0337] The average thickness of the second electrode is not particularly limited. Furthermore, the above-listed materials can be used alone or in combination.

[0338] The second electrode can be appropriately formed on the hole transport layer by a method such as coating, lamination, vapor deposition, CVD, and adhesion, depending on the material used or the type of the hole transport layer.

[0339] In order for the electronic device to function as a photoelectric conversion device (photoelectric conversion element), the first electrode or the second electrode or both are substantially transparent.

[0340] In the electronic device of the present disclosure, the side on which the first electrode is provided is transparent, and preferably, sunlight is applied from the side of the first electrode. In this case, a material that reflects light is preferably used on the side of the second electrode, and the material is preferably glass or plastic coated with a metal or a conductive oxide by vapor deposition, or a metal film.

[0341] Furthermore, it is also effective to provide an antireflection layer on the side on which sunlight is applied.

[0342] The photoelectric conversion element can be applied to a solar cell and a power source including the solar cell. An application example can be any device that utilizes a solar cell or a power source that utilizes a solar cell. For example, the photoelectric conversion element can be used for a solar cell of a desktop electronic calculator or a wristwatch. Examples of devices that utilize the properties of the photoelectric conversion element of the present disclosure include power sources for mobile phones, electronic organizers, electronic paper, and the like. Furthermore, the photoelectric conversion element can be used as an auxiliary power source to extend the continuous use time of a rechargeable or dry battery type electric appliance. Furthermore, the photoelectric conversion element can be used as a primary battery substitute in combination with a secondary battery, as a self-sufficient power source for a sensor.

[0343] <3: Organic electroluminescent element>

[0344] An embodiment of the electronic device of the present disclosure is an organic electroluminescent (EL) element.

[0345] Figure 11 An organic EL element 10C, which is an embodiment of the electronic device of the present disclosure, is shown.

[0346] In the present disclosure, a standard element structure is a reverse layer structure of an organic EL element, which is advantageous for the durability of the element, but the structure of the organic EL element is not limited to the reverse layer structure.

[0347] The organic EL element has a laminated structure including a support 31 and 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 placed in this order on the support.

[0348] Details are described hereinafter.

[0349] <Support (Substrate)>

[0350] The support 31 is not particularly limited and can be selected from supports known in the art. It is preferable to use a transparent material as the substrate 1. Examples thereof include glass, a transparent plastic plate, a transparent plastic film, and a transparent inorganic crystal.

[0351] <Cathode>

[0352] Examples of the cathode material include single metal elements such as Li, Na, Mg, Ca, Sr, Al, Ag, In, Sn, Zn, and Zr, and alloys thereof. In addition, LiF or the like can also be formed on the cathode in the same manner as the formation of the cathode, as an electrode protection film. In addition to the materials listed above, ITO, IZO, FTO, and aluminum are preferable. The average thickness of the cathode is preferably 10 nm to 500 nm, more preferably 100 nm to 200 nm. The thickness thereof can be measured by spectroscopic ellipsometry, using a surface roughness meter, or microscopic image analysis.

[0353] <Electron Injection Layer>

[0354] The electron injection layer 33 is provided as a layer for reducing the barrier for electron injection from the cathode into the electron transport layer formed of an organic material having a small electron affinity. Examples of the material for the electron injection layer include metal oxides including magnesium, aluminum, calcium, zirconium, silicon, titanium, or zinc, polyphenylene vinylene, hydroxyquinoline, and naphthaylimide derivatives.

[0355] The average thickness of the electron injection layer is preferably 5 nm to 1000 nm, more preferably 10 nm to 30 nm. The average thickness of the electron injection / electron transport layer can be measured by spectroscopic ellipsometry, using a surface roughness meter, or microscopic image analysis.

[0356] <Electron Transport Layer>

[0357] Examples of low molecular weight compounds that can be used as the electron transport layer material include oxazole derivatives, Oxadiazole derivatives, pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phenanthroline derivatives, triazine derivatives, triazole derivatives, imidazole derivatives, tetracarboxylic anhydrides, various metal complexes such as tris(8-hydroxyquinoline)aluminum (Alq3), and thioxyl derivatives. The above examples can be used alone or in combination.

[0358] Among the above examples, metal complexes such as Alq3and pyridine derivatives are preferred.

[0359] The average thickness of the electron transport layer is preferably 10 nm to 200 nm, more preferably 40 nm to 100 nm. The thickness thereof can be measured by spectroscopic ellipsometry, using a surface roughness meter, or microscopic image analysis.

[0360] <Light-emitting layer>

[0361] Examples of the polymer material used to form the light-emitting layer 35 include polyparaphenylene vinylene-based compounds, polyfluorene-based compounds, and polycarbazole-based compounds.

[0362] Examples of the low-molecular-weight material used to form the light-emitting layer include metal complexes such as tris(8-hydroxyquinoline)aluminum (Alq3), aluminum(III)tris(4-methyl-8-quinolinolato) (Almq3), zinc(II)8-hydroxyquinolinate (Znq2), (1,10-phenanthroline)-tris-(4,4,4-trifluorotricarboxylic acid)-1-(2-thiophene)-butane-1,3-dione) europium(III) (Eu(TTA)3(phen)), platinum(II)2,3,7,8,12,13,17,18-octylethyl-21H,23H-porphyrin, zinc(II)bis[2-(o-hydroxyphenylbenzothiazole] (ZnBTZ2), beryllium(II)bis[2-(2-hydroxyphenyl)-pyridine] (Bepp2), and iridium(III)tris[3-methyl-2-phenylpyridine] (Ir(mpy)3), distyrylbenzene derivatives, phenanthrene derivatives, perylene-based compounds, carbazole-based compounds, benzimidazole-based compounds, benzothiazole-based compounds, coumarin-based compounds, pyrenone-based compounds, oxadiazole-based compounds, quinacridone-based compounds, pyridine-based compounds, and spiro compounds. The above-listed examples can be used alone or in combination.

[0363] The average thickness of the light-emitting layer is not particularly limited. The average thickness thereof is preferably 10 nm to 150 nm, more preferably 20 nm to 100 nm.

[0364] The film thickness can be measured by spectroscopic ellipsometry, a surface roughness meter, or microscopic image analysis.

[0365] <hole transport layer>

[0366] Examples of the material for the hole transport layer 36 of the organic EL element include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, butadiene derivatives, 9-(p-diethylaminostyryl anthracene), 1,1-bis-(4-dibenzylaminophenyl)propane, styrylanthracene, styrylpyrazoline, phenylhydrazone, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, fenadine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. Other examples thereof include polyarylamines, fluorene-arylamines copolymers, fluorene-dithiophene copolymers, poly(N-vinylcarbazole), polyvinylpyrene, polyvinylanthracene, polythiophene, polyalkylthiophene, polyhexylthiophene, poly(p-phenylene vinylene), poly(thinylene vinylene), pyrenecarboxaldehyde resin, ethylcarbazolecarboxaldehyde resin, and derivatives thereof. The above hole transport materials can be used alone or in combination, or as a mixture with other compounds.

[0367] The average thickness of the hole transport layer is preferably 10 nm to 150 nm, more preferably 40 nm to 100 nm.

[0368] The above hole transport materials can be used alone or in combination.

[0369] <silicon-containing layer>

[0370] The silicon-containing layer 37 of the organic EL element and the method for producing the same are appropriately selected from the description of the silicon-containing layer of the electronic device of the present disclosure and the method for producing the same.

[0371] <metal oxide film>

[0372] The metal oxide film 38 of the organic EL element and the method for producing the same are appropriately selected from the description of the metal oxide film of the electronic device of the present disclosure and the method for producing the same.

[0373] <positive electrode>

[0374] The material of the positive electrode 39 is preferably gold, silver, copper, aluminum, or ITO. The film thickness can be measured by spectroscopic ellipsometry, using a surface roughness meter or microscopic image analysis. In the case where the film is formed by vacuum vapor deposition, the film thickness can be measured with a quartz crystal oscillator film thickness tester.

[0375] Embodiments

[0376] Embodiments of the present disclosure will be described hereinafter. However, the present disclosure should not be construed as being limited to these embodiments. In the following embodiments, "parts" means "mass parts" unless otherwise specified.

[0377] (Production Example 1)

[0378] -Preparation of copper-aluminum oxide-

[0379] The copper-aluminum oxide was prepared in the following manner. The cuprous oxide and the aluminum oxide presented below were taken in equimolar amounts. The collected cuprous oxide and the aluminum oxide were transferred into a mayonnaise bottle, and the mixture therein was stirred by means of a tubular mixer (T2C type, available from Willy A. Bachofen AG Maschinenfabrik) to obtain a powder mixture. The obtained powder mixture was heated at 1,100°C for 40 hours, and the resultant was passed through a screen having a 100-micron pore diameter.

[0380] (Powder mixture material)

[0381] Cuprous oxide (NC-803, available from NC TECH Co., Ltd.): 12 kg

[0382] Aluminum oxide (AA-03, available from SUMITOMO CHEMICAL COMPANY, LIMITED): 8.58 kg

[0383] The obtained copper-aluminum oxide was pulverized by means of a DRYSTAR SDA1 (available from Ashizawa Finetech Ltd.) to obtain a copper-aluminum oxide powder having a particle size of 10% (D10), 50% (D50), and 90% (D90) of 0.7 ± 0.1 microns, 5.0 ± 0.5 microns, and 26 ± 3 microns, respectively. The powder of the copper-aluminum oxide was vacuum-dried at 100°C to adjust the moisture content of the aluminum copper oxide to 0.2 mass% or less.

[0384] The particle size of the copper-aluminum oxide was a value measured by means of a MICROTRAC MT3300 (MicrotracBEL Corp.) using a 0.2% aqueous sodium hexametaphosphate solution as a dispersion medium with a measurement duration of 10 seconds.

[0385] As for the moisture content measurement of the copper-aluminum oxide, a Karl Fischer moisture meter (CA-200, available from Mitsubishi Chemical Analytech Co., Ltd.) was used.

[0386] The elemental composition ratio of the copper aluminum oxide was determined by an X-ray fluorescence spectrometer (ZSX Primus IV, available from Rigaku Corporation), and the crystal structure was measured by means of an X-ray diffractometer (X'Pert PRO, available from Spectris Co., Ltd.).

[0387] <Example 1>

[0388] -Production Example of Electrophotographic Photophoretic-

[0389] Each of the 20 electrophotographic photophoretic of Example 1 was produced in the following manner. Each of the electrophotographic photophoretic of Example 1 included an intermediate layer, a charge generation layer, a charge transport layer, a silicon-containing layer, and a metal oxide film disposed on a conductive support in the following order.

[0390] -Formation of Intermediate Layer-

[0391] The following intermediate layer coating liquid was applied to an aluminum conductive support (outer diameter: 100 mm, thickness: 1.5 mm) by dip coating to form an intermediate layer. After drying at 150°C for 30 minutes, the average thickness of the intermediate layer was 5 micrometers.

[0392] (Intermediate Layer Coating Liquid)

[0393] Zinc oxide particles (MZ-300, available from TAYCA CORPORATION): 350 parts

[0394] 3,5-di-tert-butylsalicylic acid (available from Tokyo Chemical Industry Co., Ltd.): 1.5 parts

[0395] Blocked isocyanate (Sumidur (registered trademark) 3175, solid content: 75 mass%, available from Sumika Bayer Urethane Co., Ltd.): 60 parts

[0396] A solution obtained by dissolving a butyral resin (20 mass%) in 2-butanone (BM-1, available from SEKISUI CHEMICAL CO., LTD.): 225 parts

[0397] 2-Butanone: 365 parts

[0398] -Formation of Charge Generation Layer-

[0399] The following charge generation layer coating liquid was applied to the obtained intermediate layer by dip coating to form a charge generation layer. The average thickness of the charge generation layer was 0.2 micrometers.

[0400] (Charge Generation Layer Coating Liquid)

[0401] Y-type titanyl phthalocyanine: 6 parts

[0402] Butyral resin (S-LEC BX-1, available from SEKISUI CHEMICAL CO., LTD.): 4 parts

[0403] 2-butanone (available from KANTO CHEMICAL CO., INC.): 200 parts

[0404] - forming a charge transport layer -

[0405] The following charge transport layer coating liquid was applied to the obtained charge generation layer by dip coating to form a charge transport layer.

[0406] After drying at 135°C for 20 minutes, the average thickness of the charge transport layer was 22 micrometers.

[0407] (charge transport layer coating liquid)

[0408] Bisphenol Z polycarbonate (PANLITE TS-2050, available from TEIJIN LIMITED): 10 parts

[0409] Low molecular charge transport material having the following structural formula: 10 parts

[0410] [Chemical 8]

[0411]

[0412] Tetrahydrofuran: 80 parts

[0413] - forming a silicon-containing layer -

[0414] The following silicon-containing layer coating liquid was applied to the obtained charge transport layer by spin coating to form a silicon-containing layer. After drying at 120°C for 20 minutes, the average thickness of the silicon-containing layer was 0.5 micrometers.

[0415] (silicon-containing layer coating liquid)

[0416] Silicone hard coating liquid (NSC-5506, available from NIPPON FINE CHEMICAL CO., LTD.): 210 parts

[0417] Trimethylethoxysilane (available from Tokyo Chemical Industry Co., Ltd.): 27 parts

[0418] Charge transport material having the following structure (available from Ricoh Company, Limited): 10 parts

[0419] [Chemical 9]

[0420]

[0421] Ethanol: 253 parts

[0422] - Formation of Metal Oxide Film -

[0423] As a film forming chamber, a chamber obtained by modifying a commercially available vapor deposition device was used.

[0424] A commercially available agitator (T.K. AGI HOMO MIXER 2M-03, available from PRIMIX Corporation) was used as an aerosol generator. Note that, as the aerosol generator, an ultrasonic cleaner (SUS-103, available from Shimadzu Corporation) in which a commercially available pressure supply bottle (RBN-S, available from Kato Stainless Kagaku Co.) having a volume of 1 L was provided can be used.

[0425] A pipe having an inner diameter of 4 mm was led from the aerosol generator to the film forming chamber, and a spray nozzle (YB1 / 8MSSP37, available from Spraying Systems Co.) was attached to the edge of the pipe. A photosensitive body was provided at a position 50 mm from the spray nozzle. As a photosensitive body holder, a mechanism that can rotate the photosensitive drum was provided. As the spray nozzle, a spray nozzle that can be moved laterally was used. The aerosol generator and a gas cylinder filled with nitrogen were connected with a pipe having an inner diameter of 4 mm.

[0426] With the above device, a target metal oxide film having an average thickness of 0.5 micrometers was produced in the following manner.

[0427] A powder mixture including copper aluminum oxide and silica particles (Reolosil ZD-30S, available from Tokuyama Corporation) obtained in Production Example 1 (99% (copper aluminum oxide): 1% (silica particles) mass ratio) in which the silica particles had been surface-treated with dimethyldichlorosilane and hexamethyldisilazane, had a BET surface area of 190 ± 25 m2 / g and a carbon content of 2.9 mass%, was charged into the aerosol generator. 2

[0428] ​Next, evacuation was performed from the film formation chamber to the aerosol generator by using an exhaust pump. Then, nitrogen was sent from a gas cylinder into the aerosol generator, and stirring was started to generate an aerosol in which particles were dispersed in nitrogen. The generated aerosol was sprayed from a spray nozzle toward the photosensitive body through a pipe. The flow rate of the nitrogen was 13 L / min to 20 L / min. In addition, the film formation duration was 20 minutes, and the degree of vacuum inside the film formation chamber during the formation of the metal oxide layer was about 50 Pa to about 150 Pa. The amount of the silicon dioxide particles included at the photosensitive body surface (metal oxide film) after the formation of the film was determined by an X-ray fluorescence spectrometer (ZSX Primus IV, available from Rigaku Corporation). Silicon dioxide particles were included in the photosensitive body in the same amount as the loading amount.

[0429] (Example 2)

[0430] An electrophotographic photosensitive body was produced in the same manner as in Example 1, except that the silicon-containing layer coating liquid was changed as follows.

[0431] (Silicon-containing layer coating liquid)

[0432] Organic silicon hard coating liquid (NSC-5506, available from NIPPON FINE CHEMICAL CO., LTD.): 187 parts

[0433] Trimethylethoxysilane (available from Tokyo Chemical Industry Co., Ltd.): 24 parts

[0434] Charge transport material having the following structure (available from Ricoh Company, Limited): 20 parts

[0435] [Chemical 10]

[0436]

[0437] Ethanol: 269 parts

[0438] (Example 3)

[0439] An electrophotographic photosensitive body was produced in the same manner as in Example 1, except that the silicon-containing layer coating liquid was changed as follows.

[0440] (Silicon-containing layer coating liquid)

[0441] Organic silicon hard coating liquid (NSC-5506, available from NIPPON FINE CHEMICAL CO., LTD.): 140 parts

[0442] Trimethylethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.): 18 parts

[0443] A charge transport material having the following structure (available from Ricoh Company, Limited) : 40 parts

[0444] [Chemistry 11]

[0445]

[0446] Ethanol: 302 parts

[0447] (Example 4)

[0448] An electrophotographic photoreceptor was produced in the same manner as in Example 1, except that the silicon-containing layer coating liquid was changed as follows.

[0449] (Silicon-containing layer coating liquid)

[0450] Silicone hard coating liquid (NSC-5506, available from NIPPON FINE CHEMICAL CO., LTD.): 210 parts

[0451] Trimethylethoxysilane (available from Tokyo Chemical Industry Co., Ltd.): 27 parts

[0452] Polysilane (OGSOL SI-10-10, available from Osaka Gas Chemicals Co., Ltd.): 10 parts

[0453] Tetrahydrofuran: 253 parts

[0454] (Example 5)

[0455] An electrophotographic photoreceptor was produced in the same manner as in Example 1, except that the silicon-containing layer coating liquid was changed as follows.

[0456] (Silicon-containing layer coating liquid)

[0457] Silicone hard coating liquid (NSC-5506, available from NIPPON FINE CHEMICAL CO., LTD.): 187 parts

[0458] Trimethylethoxysilane (available from Tokyo Chemical Industry Co., Ltd.): 24 parts

[0459] Polysilane (OGSOL SI-10-10, Osaka Gas Chemicals Co., Ltd.): 20 parts

[0460] Tetrahydrofuran: 269 parts

[0461] (Example 6)

[0462] An electrophotographic photoreceptor was produced in the same manner as in Example 1, except that the silicon-containing layer coating liquid was changed as follows.

[0463] (Silicon-containing layer coating liquid)

[0464] Organosilicon hard coating liquid (NSC-5506, available from NIPPON FINE CHEMICAL CO., LTD.): 140 parts

[0465] Trimethylethoxysilane (available from Tokyo Chemical Industry Co., Ltd.): 18 parts

[0466] Polysilane (OGSOL SI-10-10, available from Osaka Gas Chemicals Co., Ltd.): 40 parts

[0467] Tetrahydrofuran: 302 parts

[0468] (Example 7)

[0469] An electrophotographic photoreceptor was produced in the same manner as in Example 1, except that the silicon-containing layer coating liquid was changed as follows.

[0470] (Silicon-containing layer coating liquid)

[0471] Organosilicon hard coating liquid (NSC-5506, available from NIPPON FINE CHEMICAL CO., LTD.): 187 parts

[0472] Trimethylethoxysilane (available from Tokyo Chemical Industry Co., Ltd.): 24 parts

[0473] Charge transport material having the following structure (available from Ricoh Company, Limited): 20 parts

[0474] [Chemical 12]

[0475]

[0476] Acid catalyst (p-toluenesulfonic acid, available from Tokyo Chemical Industry Co., Ltd.): 0.008 parts

[0477] Tetrahydrofuran: 269 parts

[0478] (Production Example 2)

[0479] The uncomminuted copper aluminum oxide produced in Production Example 1 was comminuted with a DRYSTAR SDA1 (available from Ashizawa Finetech Ltd.) to obtain a copper aluminum oxide powder having a cumulative particle size distribution 10% (D10) of 0.5 ± 0.1 micrometers, a cumulative particle size distribution 50% (D50) of 1.6 ± 0.2 micrometers, and a cumulative particle size distribution 90% (D90) of 7.2 ± 0.7 micrometers.

[0480] A 50 mL glass sample bottle was charged with 100 g of each of YTZ balls having a diameter of 2 mm, 0.18 g of a wet dispersing additive (BYK-P105, available from BYK), 9.945 g of cyclopentanone, and 9 g of the comminuted copper aluminum oxide. The sample bottle was rotated at a speed of 150 rpm for 24 hours to perform a dispersion treatment of the copper aluminate. Subsequently, the dispersion liquid was passed through stainless steel screens having a mesh size of 400 mesh and 1,000 mesh to remove coarse particles. The solid content of the filtrate was adjusted to 30 mass% with ethanol. The resultant was provided as a metal oxide dispersion liquid.

[0481] (Production Example 8)

[0482] A silicon-containing layer coating liquid was prepared using the metal oxide dispersion liquid obtained in Production Example 2.

[0483] An electrophotographic photoreceptor was produced in the same manner as in Example 1, except that the silicon-containing layer coating liquid was replaced with the following silicon-containing layer coating liquid.

[0484] (Silicon-containing layer coating liquid)

[0485] Organosilicon hard coating liquid (NSC-5506, available from NIPPON FINE CHEMICAL CO., LTD.): 210 parts

[0486] Trimethylethoxysilane (available from Tokyo Chemical Industry Co., Ltd.): 27 parts

[0487] Metal oxide dispersion liquid of Production Example 2: 33 parts

[0488] Ethanol: 230 parts

[0489] (Example 9)

[0490] An electrophotographic photoreceptor was produced in the same manner as in Example 8, except that the silicon-containing layer coating liquid was replaced with the following silicon-containing layer coating liquid.

[0491] (Silicon-containing layer coating liquid)

[0492] Silicone hard coating liquid (NSC-5506, available from NIPPON FINE CHEMICAL CO., LTD.): 187 parts

[0493] Trimethylethoxysilane (available from Tokyo Chemical Industry Co., Ltd.): 24 parts

[0494] Metal oxide dispersion liquid of Production Example 2: 67 parts

[0495] Ethanol: 222 parts

[0496] (Example 10)

[0497] An electrophotographic photoreceptor was produced in the same manner as in Example 8, except that the silicon-containing layer coating liquid was replaced with the following silicon-containing layer coating liquid.

[0498] (Silicon-containing layer coating liquid)

[0499] Silicone hard coating liquid (NSC-5506, available from NIPPON FINE CHEMICAL CO., LTD.): 140 parts

[0500] Trimethylethoxysilane (available from Tokyo Chemical Industry Co., Ltd.): 18 parts

[0501] Metal oxide dispersion liquid of Production Example 2: 133 parts

[0502] Ethanol: 309 parts

[0503] (Comparative Example 1)

[0504] An electrophotographic photoreceptor was produced in the same manner as in Example 1, except that the silicon-containing layer coating liquid was changed as follows.

[0505] (Silicon-containing layer coating liquid)

[0506] Silicone hard coating liquid (NSC-5506, available from NIPPON FINE CHEMICAL CO., LTD.): 233 parts

[0507] Trimethylethoxysilane (available from Tokyo Chemical Industry Co., Ltd.): 30 parts

[0508] Ethanol: 237 parts

[0509] <Removal of silicon-containing layer and metal oxide film>

[0510] The silicon-containing layer and the metal oxide film were removed in the following manner. Specifically, the photoreceptor drum was installed in aFigure 1 The photosensitive body reproducing device shown removes the silicon-containing layer and the metal oxide film under the removal conditions presented in Table 1 below. The completion of the removal of the silicon-containing layer or the metal oxide film can be judged by observing the point of discontinuous change in the torque measurement value of the photosensitive drum installed in the device and the change in the appearance of the photosensitive drum.

[0511] If the removal is continued after the discontinuous change in the torque measurement value is observed, the film thickness of the underlayer is reduced. In order to perform reproducible tests, it is desirable to terminate the removal process within 30 seconds after the discontinuous change is observed.

[0512] <Removal conditions for the silicon-containing layer and the metal oxide film>

[0513] [Table 1]

[0514]

[0515] <Evaluation of electrophotographic photosensitive bodies>

[0516] For each of the electrophotographic photosensitive bodies of Examples 1 to 10 and Comparative Example 1 produced in the above-described manner, it was a cylindrical photosensitive drum having a length of 380 mm and an outer diameter of 100 mm to which a gold electrode patch was adhered, the gold electrode patch including a silver wire having a diameter of 0.1 mm as a lead wire. The gold electrode patch was adhered at a position 190 mm from the edge of the drum along a predetermined circumferential direction and a longitudinal direction of the photosensitive drum. In addition, a colorless transparent polyester fiber adhesive tape (available from NITTO DENKO CORPORATION) having a thickness of 60 micrometers was adhered thereon, the size being large enough to sufficiently cover the gold electrode patch. The gold electrode patch was obtained by vacuum vapor deposition of a 25-nm gold electrode (electrode area: 50 mm 2 ) on a polywrap (available from UBE FILM, LTD.). A carbon tape (available from Nisshin EM Co, Ltd.) was used to adhere between the gold electrode and the lead wire.

[0517] The photosensitive drum obtained in the above-described manner was provided to a time-of-flight measuring device (TOF-401, available from Sumitomo Heavy Industries, Ltd.). The measurement environment was a dark room, the temperature and humidity of which were maintained at 23 degrees Celsius and 55% RH.

[0518] A sub-nanometer dye laser KEC-160 attached to the device was used to irradiate the photosensitive drum with a pulsed excitation light. As a laser dye for the light source, a DMSO solution (0.25 M) of DOTC (3,3'-dimethyl oxatricarbocyanine iodide, available from Optron Science, Inc.) was prepared. A quartz cell for the device filled with the DMSO solution was set in the middle of the light path of the nitrogen pulsed laser emitted from the device to change the wavelength of the pulsed laser. In the time-of-flight measurement, a pulsed laser having a wavelength of 782 nm was used. The diameter of the exposed area of the photosensitive surface was 0.5 mm.

[0519] A bias (+500 V) was applied to the aluminum support of the photosensitive drum to emit a pulsed laser having a wavelength of 782 nm from the surface thereof on which the electrode patch was provided, the transport state of the charge carriers photoexcited in the charge generation layer of the photosensitive drum was drawn, and the waveform indicating the change in the photocurrent with time was observed using an oscilloscope. Figure 12 Examples of the measurement results are shown.

[0520] In the present disclosure, the area defined by the waveform of the Figure 12 The area defined by the waveform of the

[0521] In order to compare the charge amounts between the samples, the measurement conditions of all the transient photocurrents were fixed. Specifically, the load resistance RL of the time-of-flight measurement device was fixed at 1 kΩ, the signal gain was fixed at 50 times, the ND filter through which the pulsed laser passed was fixed at 10%, and the number of integrations of the transient photocurrent measurement was fixed at 32 times. Since the transient photocurrent waveforms of the 32 measurements did not significantly change, it was assumed that the irradiance of the pulsed laser was substantially constant.

[0522] <Ratio of charge amounts>

[0523] Once the metal oxide film is removed using the device of Figure 1 The silicon-containing layer is exposed once the metal oxide film is removed using the device of

[0524] Next, by means of the Figure 1The device of the present application similarly removes the silicon-containing layer. As described above, in the same manner, the amount of charge Q(CTL) is calculated from the measurement of the transient photocurrent waveform of the electronic device in this state.

[0525] The ratio of the amount of charge is determined from the amount of charge Q(ACL) and the amount of charge Q(CTL) according to the following formula.

[0526] [Equation 2]

[0527]

[0528] <Evaluation of halftone image printing>

[0529] Each of the photoreceptors obtained in the examples and comparative examples was assembled to be mounted, and a halftone image was printed by means of Ricoh Pro C9110 (available from Ricoh Company, Limited). As the halftone image, an image pattern in which white and black were arranged alternately every 2 pixels in the longitudinal direction and the lateral direction was printed at an image resolution of 600 dpi. As the printing paper, A3-sized copy paper (POD Gloss Coat, available from Oji Paper Co., Ltd.) and Protoner Black C9100 were used as toner.

[0530] The most uniform area on the printed halftone image of the printing paper was selected based on visual observation, and a magnified photographic image (tif file format) of the selected area of 4 square millimeters in size was taken by means of a microscope (MXMACROZVI, available from HIROX CO., LTD.).

[0531] The area of all points in the obtained image except for the image edges was determined using image analysis software (ImageJ, available from The National Institute of Health, U.S.A.), and the result was evaluated based on the value of the coefficient of variation (the value obtained by dividing the standard deviation by the average value).

[0532] (Image level)

[0533] Level 5: Coefficient of variation is less than 0.2.

[0534] Level 4: Coefficient of variation is 0.2 or more but less than 0.3.

[0535] Level 3: Coefficient of variation is 0.3 or more but less than 0.4.

[0536] Level 2: Coefficient of variation is 0.4 or more but less than 0.5.

[0537] Level 1: Coefficient of variation is 0.5 or more, or non-developable point.

[0538] The evaluation results of the ratio of the amount of charge of the electronic devices of Examples 1 to 10 and Comparative Example 1 and halftone image printing are shown in Table 2.

[0539] [Table 2]

[0540]

[0541] Conventionally, when the silicone hard coating material of Comparative Example 1 is used, the light attenuation property or the charging property of the photoreceptor is not problematic. However, in the case where such a photoreceptor is used as a photoreceptor for generating a high-precision image, it is clear in the present disclosure that a large amount of charge is required as the amount of charge that contributes to charge transport.

[0542] The photoreceptor of which the ratio of the amount of charge is 10% or more of Examples 1 to 10 is capable of precise photoelectric conversion and can develop a halftone image that is not problematic in practice. In order to increase the ratio of the amount of charge to 10% or more, it is effective to add a p-type semiconductor material in the silicon-containing layer. For example, triphenylamine derivatives or metal oxide particles of delafossite used in Examples 1 to 10 are effective.

[0543] For example, the embodiments of the present disclosure are as follows.

[0544] <1> An electronic device comprising:

[0545] a carrier;

[0546] a charge transport layer containing a charge transport material or a sensitizing dye electrode layer containing a sensitizing dye, wherein the charge transport layer or the sensitizing dye electrode layer is disposed on or over the carrier;

[0547] a silicon-containing layer disposed on or over the charge transport layer or the sensitizing dye electrode layer; and

[0548] a metal oxide film disposed on or over the silicon-containing layer,

[0549] wherein the ratio [Q(ACL) / Q(CTL)] is 10% or more, wherein Q(ACL) is a time integral of a transient photocurrent waveform of an electronic device (ACL) measured by a time-of-flight method, and Q(CTL) is a time integral of a transient photocurrent waveform of an electronic device (CTL) measured by a time-of-flight method,

[0550] wherein the electronic device (ACL) has the silicon-containing layer as an outermost layer, and is obtained by removing the metal oxide film from the electronic device, and

[0551] wherein the electronic device (CTL) has the charge transport layer or the sensitizing dye electrode layer as an outermost layer, and is obtained by removing the metal oxide film and the silicon-containing layer from the electronic device.

[0552] <2> The electronic device according to <1>,

[0553] wherein the silicon-containing layer contains at least one selected from a triphenylamine compound having a hydroxyl group, polymethylphenylsilane, and a delafossite oxide as a constituent component.

[0554] <3> The electronic device according to <2>,

[0555] wherein the amount of the combination of the triphenylamine compound and the delafossite oxide is 10 mass% or more but 40 mass% or less with respect to the total amount of all the constituent components of the silicon-containing layer.

[0556] <4> The electronic device according to any one of <1> to <3>,

[0557] wherein the silicon-containing layer contains a monoalkoxysilane as a constituent component.

[0558] <5> The electronic device according to any one of <1> to <4>,

[0559] wherein the metal oxide film includes a delafossite oxide.

[0560] <6> The electronic device according to <5>,

[0561] wherein the delafossite oxide is a copper aluminum oxide.

[0562] <7> The electronic device according to any one of <1> to <6>,

[0563] wherein the metal oxide film includes silicon dioxide.

[0564] <8> A method of producing an electronic device, the method including spraying a metal oxide film raw material onto a silicon-containing layer to form the metal oxide film,

[0565] wherein the electronic device is the electronic device according to any one of <1> to <7>, and the metal oxide film and the silicon-containing layer are the metal oxide film and the silicon-containing layer of the electronic device.

[0566] <9> The method according to <8>,

[0567] wherein the spraying is spraying particles of the metal oxide film raw material onto the silicon-containing layer by aerosol deposition.

[0568] <10> An imaging method comprising

[0569] forming an image using the electronic device according to any one of <1> to <7>.

[0570] <11> An imaging apparatus comprising

[0571] the electronic device according to any one of <1> to <7>.

[0572] The electronic device according to any one of <1> to <7>, the method of producing an electronic device according to <8> or <9>, the imaging method according to <10>, and the imaging apparatus according to <11> can solve the above-described various problems existing in the related art, and can achieve the objects of the present disclosure.

[0573] Reference mark list

[0574] 1A: charge removing device

[0575] 1B: pre-cleaning exposure device

[0576] 1C: driving unit

[0577] 1D: first transfer device

[0578] 1E: second transfer device

[0579] 1F: intermediate transfer belt

[0580] 1G: conveyance transfer belt

[0581] 3A: lubricant

[0582] 3B: coating brush

[0583] 3C: coating doctor blade

[0584] 3D: pressure spring

[0585] 10A: electrophotographic photoreceptor

[0586] 10B: electronic device

[0587] 10C: organic EL element

[0588] 11, 11Y, 11M, 11C, 11Bk: electrophotographic photoreceptor

[0589] 12, 12Y, 12M, 12C, 12Bk: charging device

[0590] 13, 13Y, 13M, 13C, 13Bk: exposure device

[0591] 14, 14Y, 14M, 14C, 14Bk: developing device

[0592] 16, 16Y, 16M, 16C, 16Bk: transfer device

[0593] 17, 17Y, 17M, 17C, 17Bk: cleaning device

[0594] 18: print medium

[0595] 19: fixing device

[0596] 231: photoreceptor

[0597] 232: wrapping film

[0598] 233: pressure roller

[0599] 234: load member

[0600] 235: pinch roller

[0601] 236: paper feed roller

[0602] 237: load member

[0603] 238: paper feed roller

[0604] 239: feed roller

[0605] 240: take-up roller

[0606] 241: photoreceptor torque meter

Claims

1.An electronic device comprising: a support; a charge transport layer comprising a charge transport material or a sensitizing dye electrode layer comprising a sensitizing dye, wherein the charge transport layer or the sensitizing dye electrode layer is disposed on or over the support; a silicon-containing layer disposed on or over the charge transport layer or the sensitizing dye electrode layer; and a metal oxide film disposed on or over the silicon-containing layer, wherein a ratio [Q (ACL) / Q (CTL) ] is 10% or more, wherein Q (ACL) is a time integral of a transient photocurrent waveform of an electronic device (ACL) measured by a time-of-flight method, and Q (CTL) is a time integral of a transient photocurrent waveform of an electronic device (CTL) measured by a time-of-flight method, wherein the electronic device (ACL) has the silicon-containing layer as an outermost layer, and is obtained by removing the metal oxide film from the electronic device, and wherein the electronic device (CTL) has the charge transport layer or the sensitizing dye electrode layer as an outermost layer, and is obtained by removing the metal oxide film and the silicon-containing layer from the electronic device, wherein the metal oxide film comprises a delafossite oxide and a silicon dioxide. 2.The electronic device according to claim 1, wherein the silicon-containing layer contains at least one selected from a triphenylamine compound having a hydroxyl group, a polymethylphenylsilane, and a delafossite oxide as a constituent component. 3.The electronic device according to claim 2, wherein a combined amount of the triphenylamine compound and the delafossite oxide is 10 mass% or more but 40 mass% or less with respect to a total amount of all constituent components of the silicon-containing layer. 4.The electronic device according to any one of claims 1 to 3, wherein the silicon-containing layer contains a monoalkoxysilane as a constituent component. 5.The electronic device according to claim 1, wherein the delafossite oxide is a copper aluminum oxide. 6.A method of producing an electronic device, the method comprising spray coating a metal oxide film raw material onto a silicon-containing layer to form the metal oxide film, wherein the electronic device is the electronic device according to any one of claims 1 to 5, and the metal oxide film and the silicon-containing layer are the metal oxide film and the silicon-containing layer of the electronic device. 7.The method according to claim 6, wherein the spray coating is spray coating of particles of the metal oxide film raw material onto the silicon-containing layer by aerosol deposition. 8.An imaging method comprising forming an image using the electronic device according to any one of claims 1 to 5. 9.An imaging apparatus comprising the electronic device according to any one of claims 1 to 5. ​

Images