TW202114261A - Electronic device and method for producing the same, image forming method, and image forming apparatus - Google Patents

Abstract

Provided is an electronic device including: a support; a charge-transporting layer including a charge-transporting material, or a sensitizing-dye electrode layer including a sensitizing dye, where the charge-transporting layer or the sensitizing dye electrode layer is disposed on or above the support; and a metal oxide layer disposed on or above the charge-transporting layer or the sensitizing-dye electrode layer, wherein the metal oxide layer includes p-type semiconductor metal oxide and silica or metal oxide particles, and wherein an amount of the silica or metal oxide particles included in the metal oxide layer is 0.5% by mass or greater but 1.5% by mass or less relative to the metal oxide layer.

Description

Electronic device and its manufacturing method, image forming method and image forming equipment

The invention relates to an electronic device, a method of manufacturing the electronic device, an image forming method, and an image forming equipment.

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

Currently, widely used photoelectric conversion devices, such as electrophotographic photoreceptors, are mainly organic electronic devices formed of organic materials. However, compared with inorganic electronic devices, organic electronic devices have the problem of shorter service life. One of the reasons for the shorter service life is that the organic material contained in the organic electronic device has poor gas barrier properties. Compared with dense films of inorganic materials, resin films of organic materials have many gaps. Therefore, food packaging materials, such as polypropylene (PP), are laminated with an aluminum layer to enhance the weather resistance of the contents.

As an organic solar cell that is low-cost compared to silicon-based solar cells, dye-sensitized solar cells including organic sensitizing dyes have been developed.

Since dye-sensitized solar cells include organic sensitizing dyes as organic materials, the materials used are prone to deterioration due to temperature, humidity, and gases (for example, oxygen, ozone, nitrogen oxide, ammonia) compared with silicon-based solar cells , So the function of dye-sensitized solar cells tends to deteriorate. Therefore, compared with silicon-based solar cells, the problem of dye-sensitized solar cells is their poor durability.

Among display elements such as organic electroluminescence (EL) elements, light-emitting diode display elements, liquid crystal display elements, and electrophoretic ink display elements, such as an organic EL layer sandwiched between the positive electrode and the negative electrode, etc. The display element is laminated on the substrate. Compared with liquid crystal display devices, organic EL The display device has a wide viewing angle and a high response rate. Therefore, due to the diversity of organic light-emitting materials, it is expected to become the next-generation display device.

As a method of forming an organic EL element, a forming method using coating is used in consideration of productivity and cost. In addition, organic EL elements tend to deteriorate due to exposure to heat or gases such as moisture and oxygen. As a result, the organic EL element has the problem of short service life.

Attempts have been made to enhance gas barrier properties to extend the service life of organic electronic devices such as electrophotographic photoreceptors used in printers, dye-sensitized solar cells, and organic EL elements. However, the large number of manufacturing processes has an adverse effect on organic electronic devices. Therefore, there is room for improvement in the balance between cost and durability.

As an electrophotographic photoreceptor having excellent abrasion resistance and stability of image characteristics, for example, an electrophotographic photoreceptor having a protective layer including p-type semiconductor particles treated with a surface treatment agent (for example, See Patent Document 1).

As an organic EL element with long service life, improved efficiency, and low driving voltage, for example, an organic EL element has been proposed in which the organic hole transport layer of the organic EL element is replaced by an inorganic p-type semiconductor (for example, see Patent Document 2) .

In addition, a laminate has been proposed in which particulate materials such as ceramic materials and metal materials, such as ceramic materials and metallic materials, are deposited on a substrate to form a film to form a polycrystalline brittle material layer (for example, see Patent Document 3. ).

By providing a metal oxide having a p-type semiconductor as the surface layer, gas barrier properties can be improved. As a method of forming a metal oxide film, aerosol deposition with excellent mass productivity is suitable. When the fluidity of the raw material powder is poor, the film formation of the metal oxide tends to be uneven, and the process capability is insufficient, so it may not be able to be mass-produced as an industrial product.

Reference list

Patent literature

Patent Document 1: Japanese Patent No. 5664538;

Patent Document 2: Japanese Unexamined Patent Application Publication No. 2000-150166;

Patent Document 3: Japanese Unexamined Patent Application Publication No. 2008-201004.

The object of the present invention is to provide an electronic device that can suppress unevenness in the film formation of a metal oxide layer and has high uniformity in the thickness of the metal oxide layer.

According to one aspect of the present invention, an electronic device includes: a supporting member; 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 The electrode layer is arranged on or above the supporting member; and a metal oxide layer is arranged on or above the charge transport layer or the sensitizing dye electrode layer, wherein the metal oxide layer includes a p-type semiconductor metal oxide And silicon dioxide or metal oxide particles, and relative to the metal oxide layer, the content of silicon dioxide or metal oxide particles contained in the metal oxide layer is 0.5% by mass or more but 1.5% by mass or less .

The present invention can provide an electronic device that can suppress unevenness in the film formation of a metal oxide layer and has high uniformity in the thickness of the metal oxide layer.

1: substrate

1A: Charge elimination device

1B: Pre-clean exposure device

1C: drive unit

1D: First transfer device

1E: Second transfer device

1F: Intermediate transfer belt, intermediate transfer member

1G: transfer transfer belt

2: The first electrode

3: Hole barrier layer

3A: Lubricant

3B: Coating brush

3C: Coating blade

4: electron transport layer

5: Sensitized material

6: Metal oxide

7: second electrode

8,9: Lead

10A: Electronic device, electrophotographic photoreceptor

10B: Solar cell

10C: Organic electroluminescence element

11, 11Bk, 11C, 11M, 11Y: Electrophotographic photoreceptor

12, 12Y, 12M, 12C, 12Bk: charging device

13,13Y,13M,13C,13Bk: Exposure device

14,14Bk, 14C, 14M, 14Y: developing device

16,16Y,16M,16C,16Bk: transfer device

17,17Y,17M,17C,17Bk: cleaning device

18: Printed media

19: Fixing device

20: substrate

20a: Main surface

30: Organic EL layer

40: metal oxide layer

51: Conductive support parts

52: middle layer

53: charge generation layer

54: charge transport layer

55: Silicon hard coating

56: metal oxide layer

110: Cylinder

120a, 120b, 120c: pipe

130: Aerosol Generator

140: Film forming chamber

150: nozzle

160: substrate

170: substrate holder

170a: Rotating unit

180: Exhaust pump

190: Compression valve

200: particles

FIG. 1 is a schematic configuration diagram illustrating an example of the image forming apparatus of the present invention.

Fig. 2 is a schematic configuration diagram illustrating another example of the image forming apparatus of the present invention.

Fig. 3 is a schematic configuration diagram illustrating an example of an image forming unit in the image forming apparatus of the present invention.

Fig. 4 is a schematic configuration diagram illustrating another example of the image forming apparatus of the present invention.

Fig. 5 is a schematic configuration diagram illustrating another example of the image forming apparatus of the present invention.

Fig. 6 is a cross-sectional view illustrating an example of the electronic device (electrophotographic photoreceptor) of the present invention.

Fig. 7 is a cross-sectional view illustrating an example of the electronic device (solar cell) of the present invention.

Fig. 8 is a cross-sectional view illustrating an example of the electronic device (organic EL element) of the present invention.

FIG. 9 is a schematic structural diagram illustrating an example of an aerosol deposition apparatus for forming the metal oxide layer of the present invention.

Fig. 10A is a picture depicting an example of film-forming ceramics.

Fig. 10B is a picture depicting an example of film-forming ceramics.

Fig. 10C is a picture depicting an example of film-forming ceramics.

<Electronic Device>

The electronic device of the present invention includes a supporting member; a charge transport layer containing a charge transport material, or a sensitizing dye electrode layer containing a sensitizing dye; and a metal oxide layer, wherein the charge transport layer or the sensitizing dye electrode layer is provided on the supporting member On or above, the metal oxide layer is disposed on or above the charge transport layer or the sensitizing dye electrode layer. The metal oxide layer includes p-type semiconductor metal oxide and silicon dioxide or metal oxide particles. The content of silicon dioxide or metal oxide particles contained in the metal oxide layer is 0.5% by mass or more but 1.5% by mass or less with respect to the metal oxide layer.

There is no particular limitation on the electronic device, and the electronic device can be appropriately selected according to the desired purpose. Examples of electronic devices include devices such as electrophotographic photoreceptors, solar cells, organic electroluminescence (EL) elements, transistors, integrated circuits, laser diodes, and light emitting diodes.

In addition, the electronic device of the present invention has been completed based on the following findings. That is to say, there may be a situation in which the thickness of the metal oxide layer of the electronic device in the prior art may not have high uniformity (the thickness of the metal oxide layer is not uniform when the unevenness in the film formation of the metal oxide layer is suppressed). The change is small).

According to the formation of metal oxides containing p-type semiconductors using aerosol deposition methods known in the art, the formation of metal oxides tends to be non-uniform when the fluidity of the raw material powder is poor, and the process capability is insufficient, so it may not be possible to achieve It is mass produced as an industrial product.

The present invention includes a metal oxide layer on the charge transport layer or the sensitizing dye electrode layer, wherein the metal oxide layer includes a metal oxide including a p-type semiconductor and silicon dioxide or metal oxide particles. Therefore, it is possible to suppress the unevenness of the film formation of the metal oxide layer, and it is possible to provide an electronic device having a metal oxide layer with a high uniform thickness and which can suppress unevenness in the film formation.

In Patent Document 1 (Japanese Patent No. 5664538), the protective layer includes ceramic as a p-type semiconductor, but the ceramic is not a film shape but a granular semiconductor. FIG. 1 of Patent Document 1 illustrates a conceptual diagram in which particulate semiconductors are dispersed in a protective layer. The film shape here refers to the whitest example of the surface layer seen in FIGS. 10A, 10B, and 10C.

Patent Document 2 (Japanese Unexamined Patent Application Publication No. 2000-150166) does not disclose the use of a hole transport layer containing an inorganic p-type semiconductor, but Patent Document 2 does not disclose that the hole transport layer includes silicon dioxide.

In Patent Document 3 (Japanese Patent Application Laid-Open No. 2008-201004), a dense polycrystalline brittle material layer formed of particles is formed, but Patent Document 3 does not disclose that silicon dioxide is contained in these particles.

<Metal Oxide Layer>

The metal oxide layer includes p-type semiconductor metal oxide and silicon dioxide or metal oxide particles. In the present invention, the p-type semiconductor metal oxide is preferably cupronite oxide.

<<Copper iron oxide>>

There is no particular restriction on the copper-iron ore oxide (hereinafter may be referred to as "p-type semiconductor" or "p-type metal compound semiconductor"), and the copper-iron ore oxide can be appropriately selected according to the desired purpose, as long as the copper-iron ore The oxide functions as a p-type semiconductor. Examples of the copper-ironite oxide include p-type metal oxide semiconductors, p-type metal compound semiconductors containing monovalent copper, and other p-type metal compound semiconductors.

Examples of p-type metal oxide semiconductors include CoO, NiO, FeO, Bi ₂ O ₃ , MoO ₂ , MoS ₂ , Cr ₂ O ₃ , SrCu ₂ O ₂ , and CaO-Al ₂ O ₃ .

Examples of p-type metal compound semiconductor containing monovalent copper include _{CuI, CuInSe 2, Cu 2 O} , CuSCN, CuS, CuInS 2, CuAlO, CuAlO 2 ,, CuAlSe 2, CuGaO 2, CuGaS 2, and CuGaSe _2.

Examples of other p-type metal compound semiconductors include GaP, GaAs, Si, Ge, and SiC.

Among the above examples, in consideration of charge mobility and light transmittance, copper aluminum oxides such as CuAlO and CuAlO _{2 are} preferred.

<<Silica Dioxide>>

The silicon dioxide contained in the metal oxide layer of the present invention may be appropriately synthesized for use, or may be selected from commercially available products. Examples of commercially available products include REOLOSIL ZD-30S (available from Tokuyama Co., Ltd.), HDK H-2000 (available from Wacker Asahikasei Silicone Co., Ltd.), and AEROSIL R976 and AEROSIL RA200HS (available from NIPPON AEROSIL CO.,LTD.).

The silicon dioxide is preferably in the form of particles. The volume average particle diameter of the silica particles is preferably 1 micrometer or more but 50 micrometers or less.

The average particle size of the silica particles can be measured using a particle size distribution analyzer MT3300EX, etc., available from MicrotracBEL Corp..

The content of silicon dioxide contained in the metal oxide layer is 0.5% by mass or more but 1.5% by mass or less, and preferably 0.7% by mass or more but 1.3% by mass or less with respect to the metal oxide layer. When the amount of silicon dioxide is within the above range, the unevenness of the film formation of the metal oxide layer can be suppressed, and an electronic device having a metal oxide layer with a highly uniform thickness can be obtained.

<<Metal Oxide Particles>>

Examples of metal oxide particles contained in the metal oxide layer of the present invention include aluminum oxide, barium titanate, chromium oxide, copper oxide, iron oxide, magnesium oxide, manganese oxide, strontium titanate, tin oxide, titanium oxide, Zinc oxide, and zirconium oxide.

The metal oxide particles may be appropriately synthesized for use, or may be selected from commercially available products. Examples of commercially available products include alumina AKP-50 (available from Sumitomo Chemical Co., Ltd.), alumina AKP-20 (available from Sumitomo Chemical Co., Ltd.), and alumina TM-DAR (available from Daming Chemical Co., Ltd.) ), and zinc oxide SF-10 (available from Sakai Chemical Industry Co., Ltd.).

The volume average particle diameter of the metal oxide particles is preferably 1/100 to 1/10 of the size of the metal oxide particles (base particles) having a p-type semiconductor, and more preferably 1 micrometer or more but 3 micrometers or less.

The method for measuring the volume average particle size of the metal oxide particles may be the same as the method for measuring the silica particles.

The content of the metal oxide particles contained in the metal oxide layer is 0.5% by mass or more but 1.5% by mass or less, and preferably 0.7% by mass or more but 1.3% by mass or less with respect to the metal oxide layer. When the content of the metal oxide particles is within the above range, the unevenness of the film formation of the metal oxide layer can be suppressed, and an electronic device having a metal oxide layer with a highly uniform thickness can be obtained.

<<Thickness of metal oxide layer>>

In the present invention, the average thickness of the metal oxide layer is preferably 1.2 μm or more but 1.8 μm or less. More preferably, the average thickness of the metal oxide layer is 1.2 micrometers or more but 1.8 micrometers or less, and the standard deviation of the thickness of the metal oxide layer is 0.07 micrometers or less.

In the case of an electrophotographic photoreceptor as an embodiment of the electronic device of the present invention, for example, the thickness of the photoreceptor is measured at 5 points of a cylindrical photoconductor drum with a length of 380 mm and an outer diameter of 100 mm, where, Take 5 points in the length direction at an interval of 50 mm from a position 100 mm from the edge of the photoconductor drum to a position 300 mm from the edge of the photoconductor drum. The aforementioned thickness measurement was performed on 20 photoconductor drums to obtain a total of 100 points of thickness data. The measurement of the thickness is performed by using a method of light interference according to Japanese Patent No. 5521607. Determine the standard deviation, and determine the thickness from the average of the obtained data.

When the average thickness of the metal oxide layer is 1.2 micrometers or more but 1.8 micrometers or less, it has an advantage because it can form a high-quality printed image, which has an excellent balance between abrasion resistance and electrostatic properties , And long service life. In addition, when the standard deviation of the thickness of the metal oxide layer is 0.07 μm or less, it is advantageous because the printed image can include excellent gray-scale reproducibility, which affects the appearance of human skin or landscape in the printed image.

<<Process Capability>>

In addition, the process capability index Cpk is calculated from the obtained thickness average value and standard deviation according to the following equations (1) to (3). The process capability index is a value that evaluates the degree of deviation of the arithmetic mean value X of the thickness from the standard median value. The larger the Cpk, the higher the ability to produce electronic devices with stable quality.

Cpk=Cp(1- K ) (1)

In the above equation, USL is the upper limit of the standard, LSL is the lower limit of the standard, X is the arithmetic mean of the thickness, and σ is the standard deviation. In addition, Cp is the comparison between 6 σ indicating variation in the film forming process and the standard width.

<Production of Metal Oxide Layer>

The manufacturing method (film formation method) of the metal oxide layer is not particularly limited, and it can be appropriately selected from commonly used inorganic material film formation methods. Examples thereof include a vapor deposition method, a liquid phase growth method, and a solid phase growth method.

Vapor deposition methods are classified, for example, into physical vapor deposition (PVD) and chemical vapor deposition (CVD).

Examples of physical vapor deposition methods include vacuum deposition, electron beam evaporation, laser abrasion, laser abrasion molecular beam epitaxy (laser abrasion MBE), metal organic molecular beam epitaxy (MOMBE), reactive vapor deposition, ionization Plating, cluster ion beam, glow discharge sputtering, ion beam sputtering, and reactive sputtering.

Examples of chemical vapor deposition methods include thermal chemical vapor deposition (thcrmal CVD), metal organic chemical vapor deposition (MOCVD), radio frequency plasma chemical vapor deposition (RF plasma CVD), electron cyclotron resonance plasma chemical vapor deposition (ECR plasma CVD), light-irradiated chemical vapor deposition (photo CVD), and laser chemical vapor deposition (laser CVD).

Examples of liquid phase growth methods include liquid phase epitaxy (LPE), electroplating, electroless plating, and coating.

Examples of solid phase growth methods include solid phase extraction (SPE), recrystallization, graphite epitaxy, LB method, sol-gel method, and aerosol deposition (AD).

Among the examples listed above, aerosol deposition (AD) is preferable because aerosol deposition (AD) does not affect the uniform film formation of a large area film such as an electrophotographic photoreceptor or the performance of an electrophotographic photoreceptor. Cause adverse effects.

<<Aerosol Deposition (AD)>>

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

As the characteristics of AD, film formation can be performed in a room temperature environment, and film formation can be performed in a state where the crystal structure of the raw material is basically maintained. Therefore, AD is suitable for film formation on electronic devices (especially electrophotographic photoreceptors).

A method of forming a metal oxide layer according to aerosol deposition will be described.

In this method, an aerosol deposition apparatus as shown in FIG. 9 is used. The gas cylinder 110 shown in FIG. 9 stores inert gas for generating aerosol. The gas cylinder 110 is connected to the aerosol generator 130 through a pipe 120a, and the pipe 120a is guided to the inside of the aerosol generator 130. A certain amount of particles 200 formed of metal oxide or compound semiconductor are placed inside the aerosol generator 130. Another pipe 120 b connected to the aerosol generator 130 is coupled with the nozzle 150 inside the film forming chamber 140.

In the present invention, particles 200 formed of p-type semiconductor metal oxide and silicon dioxide are introduced into the aerosol generator 130 to generate aerosol, and the generated aerosol is guided to the nozzle 150 through the pipe 120b. Alternatively, the aerosol of p-type semiconductor metal oxide and silicon dioxide is produced by an aerosol generator (not shown in the figure) containing p-type semiconductor metal oxide and silicon dioxide, and the aerosol of silicon dioxide is produced therein An aerosol generator (not shown in the figure) containing silicon dioxide is produced, and the produced aerosol is transported through a pipe and ejected from two nozzles toward the substrate at a high speed.

Inside the film forming chamber 140, the substrate 160 is sandwiched by the substrate holder 170 to face the nozzle 150. As the substrate 160, a cylindrical conductive support member, or an electronic device such as a photoreceptor, a solar cell, or 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 via a pipe 120c.

Although not shown in the figure, the film forming apparatus for forming the electrode of the present embodiment includes a system configured to move the nozzle 150 laterally at high speed when the substrate holder 170 is rotated by the rotating unit 170a. By The film formation is performed while the nozzle 150 is moved laterally, and a metal oxide layer having a desired area can be formed on the substrate 160.

In the process of forming the metal oxide layer, first, the compression valve 190 is closed to use the exhaust pump 180 to vacuum the internal atmosphere from the film forming chamber 140 to the aerosol generator 130. Next, the compression valve 190 is opened to introduce the gas inside the gas cylinder 110 into the aerosol generator 130 via the pipe 120a to disperse the particles 200 inside the container. As a result, an aerosol is generated in a state where the particles 200 are dispersed in the gas. The generated aerosol is sprayed to the substrate 160 at a high speed by the nozzle 150 through the pipe 120b. After 0.5 seconds have passed with the compression valve 190 opened, the compression valve 190 is closed within the next 0.5 seconds. After that, the compression valve 190 is opened again, and the opening and closing of the compression valve 190 are repeated in a cycle of 0.5 seconds. The flow rate of the gas from the gas cylinder 110 is 5L/min, and the film formation time is 1 hour. When the compression valve 190 is closed, the vacuum degree inside the film formation chamber 140 is about 10 Pa, and when the compression valve 190 is opened, the film formation chamber The vacuum degree inside 140 is about 100Pa.

The spraying speed of the aerosol is controlled by the shape of the nozzle 150, the length or inner diameter of the pipe 120b, the internal air pressure of the gas cylinder 110, or the amount of gas discharged by the exhaust pump 180 (the internal pressure of the film forming chamber 140). When the internal pressure of the aerosol generator 130 is tens of thousands of Pa, the internal pressure of the film forming chamber 140 is tens of Pa to hundreds of Pa, and the opening shape of the nozzle 150 is a circle with an inner diameter of 1.0 mm, for example, The internal pressure difference between the aerosol generator 130 and the film forming chamber 140 can set the aerosol jet speed to several hundreds of meters per second. When the internal pressure of the film forming chamber 140 is maintained in the range of 5 Pa to 100 Pa and the internal pressure of the aerosol generator 130 is maintained at 50,000 Pa, a metal oxide layer with a porosity of 5% to 30% may be formed. By adjusting the continuous supply time of the aerosol under the above conditions, preferably, the average thickness of the metal oxide layer is adjusted to a range of 0.1 micrometers to 10 micrometers.

The average thickness of the metal oxide layer can be adjusted to an appropriate thickness for each electronic device.

In the case of an electrophotographic photoreceptor as an example of an electronic device, as a condition for obtaining the best mode of durability and high printing quality of the electronic device, the preferable average thickness of the metal oxide layer is 1.2 micrometers to 1.8 micrometers .

The particles 200 that have obtained kinetic energy through acceleration in the aerosol are crushed and pressed into the substrate 160, and the particles 200 are crushed into powder through the collision energy. When the powder particles are combined with the substrate 160 and the powder particles are combined with each other, a metal oxide layer is sequentially formed on the charge transport layer.

Use linear patterns for patterning several times, or rotate the photoconductor drum to form a film. By scanning the substrate (drum) holder 170 or the nozzle 150 along the longitudinal and lateral directions of the substrate 160, a metal oxide layer including a desired area is formed.

<Electrophotographic Photoreceptor>

An embodiment of the electronic device of the present invention is an electrophotographic photoreceptor.

The electrophotographic photoreceptor (hereinafter may be referred to as the "photoreceptor") includes: a conductive support member used as a support member; a charge transport layer containing a charge transport material, wherein the charge transport layer is provided on or over the conductive support member; and The metal oxide layer is arranged on or above the charge transport layer. The electrophotographic photoreceptor further includes a charge generation layer, and may further include other layers, such as an intermediate layer and a protective layer, as necessary.

The above-mentioned metal oxide layer can be suitably used as the metal oxide layer.

Note that a layer obtained by sequentially stacking a charge generation layer and a charge transport layer may be referred to as a photosensitive layer.

The electronic device will be described below as an example of the electrophotographic photoreceptor, but the example of the electronic device is not limited to the electrophotographic photoreceptor, and the present invention can also be applied to other electronic devices.

The structure of the electronic device 10A as an electrophotographic photoreceptor will be described with reference to FIG. 6. Fig. 6 is a cross-sectional view illustrating an example of an electrophotographic photoreceptor.

Fig. 6 shows an example of an electrophotographic photoreceptor. In the embodiment of FIG. 6, the electrophotographic photoreceptor 10A includes an intermediate layer 52, a charge generation layer 53, a charge transport layer 54, a silicon hard coat layer 55, and a metal oxide provided on the conductive support member 51 in the following order Layer 56. The intermediate layer 52 and the silicon hard coat 55 can be omitted arbitrarily.

<<Support member (conductive support member)>>

There is no particular limitation on the conductive support member, and the conductive support member can be appropriately selected according to the desired purpose, as long as the conductive support member exhibits a volume resistance value of 10 10 ohm. The conductivity below cm is sufficient. Examples of conductive support members include: metal (e.g., aluminum, nickel, chromium, nichrome, copper, silver, gold, platinum, and iron) or oxides (e.g., tin oxide and iron) coated by vapor deposition or sputtering Indium oxide) film or cylindrical plastic or paper; and through methods such as stretching and shrinking, impact shrinking, extrusion shrinking, extrusion stretching and processing, and then processing, super finishing and grinding The surface treatment of aluminum, aluminum alloy, nickel, stainless steel and other plates are cut into pipes to obtain pipe fittings.

<<Middle layer>>

The electrophotographic photoreceptor may include an intermediate layer disposed between the conductive support member and the photosensitive layer. The purpose of providing the intermediate layer is to improve adhesion, prevent ripples, improve the coatability of the upper layer, and prevent charge injection from the conductive support member.

The intermediate layer usually includes 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 organic solvents. Among the thermosetting resins, polyurethane, melamine resin, and alkyd melamine resin are more preferable as the resin for the intermediate layer, because many of the resins listed above achieve the above-mentioned purpose.

Examples of organic solvents include tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, and butanone. An organic solvent can be used to appropriately dilute the resin to prepare a coating for the intermediate layer.

In addition, in order to adjust conductivity or prevent ripples, particles of metal, metal oxide, etc. may be added to the intermediate layer. The metal oxide is preferably titanium oxide or zinc oxide. The coating for the intermediate layer can be prepared by dispersing particles in an organic solvent by using a ball mill, attritor, sand mill, etc. to prepare a dispersion liquid, and mixing the dispersion liquid and the resin component.

Examples of the manufacturing method (film forming method) of the intermediate layer include: a method of forming a film by coating a paint on a conductive support member through dip coating, spray coating, bead coating, etc.; and selectively heating the obtained film to cure Methods. Generally, the average thickness of the intermediate layer is suitably about 2 micrometers to about 20 micrometers. When the remaining potential of the photoreceptor is excessively accumulated, the average thickness of the intermediate layer may be less than 3 microns.

<<Photosensitive layer>>

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

<<Charge Generation Layer>>

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 may further include a binder resin as necessary. Examples of charge generating materials include inorganic charge generating materials and organic charge generating materials.

Examples of inorganic charge generating materials include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compound, 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, and the like.

As the organic charge generating material, known materials can be used. Examples of organic charge generating materials include: metal phthalocyanines such as titanyl phthalocyanine and chlorogallium phthalocyanine; metal-free phthalocyanine; azulenium (azulenium) salt pigment; methine squarate pigment; symmetry with a carbazole skeleton Or asymmetric azo pigments; symmetric or asymmetric azo pigments with a triphenylamine skeleton; symmetric or asymmetric azo pigments with a ketone skeleton; and perylene-based pigments. Among the above examples, preferred are metal phthalocyanines, symmetric or asymmetric azo pigments having a ketone skeleton, symmetric or asymmetric azo pigments having a triphenylamine skeleton, and perylene Base pigment, because the quantum efficiency of charge generation is extremely high. The charge generating materials listed above can be used alone or in combination.

Examples of binder resins include polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, polyacrylate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, Polystyrene, poly-N-vinylcarbazole, and polypropylene amide.

In the examples listed above, polyvinyl butyral is often used and it is effective. The binder resins listed above can be used alone or in combination.

<<Method of manufacturing charge generation layer>>

The manufacturing method of the charge generation layer is roughly classified into a vacuum thin film forming method and a casting method of a solution dispersion system.

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 methods listed above are suitable for producing layers formed of inorganic charge generating materials or organic charge generating materials.

As a method of manufacturing the charge generating layer by the casting method, an inorganic charge generating material or an organic charge generating material is selectively dispersed together with a binder resin in an organic solvent through a ball mill, attritor, sand mill, etc., to prepare the dispersion Liquid, appropriately dilute the dispersion, and apply the product.

Examples of organic solvents include tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, and butanone. Among the above examples, methyl ethyl ketone, tetrahydrofuran, and cyclohexanone are preferable because the above solvents have a lower environmental load than chlorobenzene, methylene chloride, toluene, and xylene.

It can be coated by dipping, spraying, bead coating and other methods.

The average thickness of the charge generation layer is preferably 0.01 μm to 5 μm.

When reducing the residual potential and high sensitivity become important, increasing the thickness of the charge generation layer can generally improve the above-mentioned properties. On the other hand, a thicker charge generation layer may often deteriorate the charge rate such as charge retention or space charge formation. In order to strike a balance between the above advantages and the above disadvantages, the average thickness of the charge generation layer is more preferably 0.05 μm to 2 μm.

In addition, low molecular compounds such as antioxidants, plasticizers, lubricants, and ultraviolet absorbers and leveling agents may be optionally added to the charge generation layer. The compounds listed above 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 may often become poor. Therefore, the amount of the low-molecular compound and the leveling agent is generally preferably 0.1 phr to 20 phr, and more preferably 0.1 phr to 10 phr. The use amount of the leveling agent is preferably 0.001 phr to 0.1 phr.

<<Charge Transport Layer>>

The charge transport layer is a part of the laminated photosensitive layer, and has a function of injecting and transporting charges 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.

Charge transport materials include electron transport materials and hole transport materials.

Examples of electron transport materials include electron-accepting materials such as asymmetric diphenoquinone derivatives, fluorene derivatives, and naphthalenedimethimide derivatives. The electron transport materials listed above can be used alone or in combination.

As the hole transport material, an electron supply material is preferably used. Examples of electronic supply materials include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, butadiene derivatives, 9-(p-diethylaminostyrylanthracene), 1,1 -Bis-(4-dibenzylaminophenyl)propane, styrylanthracene, styrylpyrazoline, phenylhydrazone, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, Phenidine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. The hole transport materials listed above can be used alone or in combination.

Examples of binder components include thermoplastic or thermosetting resins such as polystyrene, polyester, polyethylene, polyacrylate, polycarbonate, acrylic resin, silicone resin, fluororesin, epoxy resin, melamine resin, polyurethane resin, phenolic resin Resin, and alkyd resin. In the examples listed above, polystyrene, polyester, polyacrylate, and polycarbonate are effectively used as the binder component of the charge transport component because many of them exhibit excellent charge transport properties.

When an electrically inert polymer compound is used for the modification of the charge transport layer, it is effective: Cardo polymer type polyester with a huge skeleton, such as fluorene, polyester (for example, polyethylene terephthalate) Glycol ester and polyethylene naphthalate); wherein the 3,3' position of the phenol component of the bisphenol polycarbonate such as C-type polycarbonate is substituted with an alkyl group; wherein the twin of bisphenol A Polycarbonate in which the methyl group is substituted by a long-chain alkyl group with more than 2 carbon atoms; polycarbonate with a biphenyl or diphenyl ether skeleton; polycaprolactone; a polycarbonate with a long-chain alkyl skeleton, such as Polycaprolactone (for example, disclosed in Japanese Unexamined Patent Application Publication No. 07-292095); acrylic resin; polystyrene; hydrogenated butadiene, etc.

In this specification, the term "electrically inert polymer compound" refers to a polymer compound that does not exhibit a chemical structure such as a triarylamine structure that exhibits photoconductivity. When this resin is used together with a binder resin as an additive, considering the limitation related to matting sensitivity, the amount thereof is preferably 50% by mass or less relative to the total solid content of the charge transport layer.

When a charge transport material is used, generally the content of the charge transport material is preferably 40 phr to 200 phr, and more preferably 70 phr to 100 phr. It is preferable to use a copolymer in which the resin component is copolymerized at 0 to 200 parts by mass relative to 100 parts by mass of the charge transport component, preferably about 80 to about 150 parts by mass.

The charge transport layer can be formed by dissolving or dispersing a mixture or copolymer containing a charge transport component and a binder component as main components in an appropriate solvent to prepare a charge transport layer coating, and coating and drying the coating. As the coating method, dip coating, spray coating, ring coating, roll coater coating, gravure coating, nozzle coating, screen printing, etc. can be used.

Examples of the dispersion solvent used when preparing the charge transport layer coating material include: ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ethers such as dioxane, tetrahydrofuran, and ethyl cyrus; aromatics , Such as toluene and xylene; halogens such as chlorobenzene and dichloromethane; and esters such as ethyl acetate and butyl acetate. Among the above examples, methyl ethyl ketone, tetrahydrofuran, and cyclohexanone are preferable because the above solvents have a lower environmental load than chlorobenzene, methylene chloride, toluene, and xylene. The solvents listed above can be used alone or in combination.

In order to ensure the required sensitivity and charge rate in practice, the average thickness of the charge transport layer is preferably 10 to 40 microns, and more preferably 15 to 30 microns.

In addition, low-molecular compounds such as antioxidants, plasticizers, lubricants, and ultraviolet absorbers and a leveling agent described later may be optionally added to the charge transport layer. When low-molecular compounds and leveling agents are used in combination with other components of the charge transport layer, sensitivity may often become poor. Therefore, the amount of the aforementioned compound is usually 0.1 phr to 20 phr, and more preferably 0.1 phr to 10 phr. The amount of a suitable leveling agent is about 0.001 phr to about 0.1 phr.

<<Silicon Hard Coating>>

The organosilicon hard coat is formed by cross-linking organosilicon compounds having hydroxyl groups or hydrolyzable groups. The organosilicon hard coat layer may further include a catalyst, a crosslinking agent, an organosilica sol, a silane coupling agent, or a polymer such as an acrylic polymer as needed.

There is no particular restriction on crosslinking, and it can be appropriately selected according to the desired purpose. The crosslinking is preferably thermal crosslinking.

Examples of the organosilicon compound having a hydroxyl group or a hydrolyzable group include: a compound having an alkoxysilyl group; a partial hydrolysis condensate of a compound having an alkoxysilyl group; and mixtures thereof.

Examples of the compound having an alkoxysilyl group include: tetraalkoxysilane, such as tetraethoxysilane; alkyltrialkoxysilane, such as methyltriethoxysilane; and aryltrialkoxysilane Silanes, such as phenyltriethoxysilane.

Note that an epoxy group, a methacryloyl group, or a vinyl group can be introduced into any of the above-mentioned compounds.

The partially hydrolyzed condensate of a compound having an alkoxysilyl group can be prepared by any method known in the art, for example, by adding a predetermined amount of water, a catalyst, etc. to the compound having an alkoxysilyl group to make The mixture reacts.

As the raw material of the organic silicon hard coat layer, commercially available products can be used. Specific examples of raw materials for the organic silicon hard coat layer include GR-COAT (available from Daicel Co., Ltd.), glass resin (available from OWENS CORNING JAPAN LLC.), and non-thermal glass (available from Ohashi Chemical Industry Co., Ltd.) , NSC (available from Nippon Seika Co., Ltd.), glass raw material liquid GO150SX and GO200CL (available from Fine Glass Technologies Co., Ltd.), and as a combination of alkoxysilyl compound and acrylic resin or polyester resin Inter-copolymer MKC silicate (available from Mitsubishi Chemical Co., Ltd.), and silicate/acrylic varnish XP-1030-1 (available from Dai Nippon Color Material Industry Co., Ltd.).

The thickness of the organic silicon hard coat layer is preferably 0.1 μm or more but 4.0 μm or less, and more preferably 0.3 μm or more but 1.5 μm or less.

<<<Metal Oxide Layer>>

The metal oxide layer of the electrophotographic photoreceptor and the manufacturing method thereof can be appropriately selected from the description of the metal oxide layer of the electronic device of the present invention and the manufacturing method thereof.

<Method of Manufacturing Electronic Device>

The method for manufacturing an electronic device of the present invention is a method of manufacturing an electronic device, the electronic device comprising: a supporting member; 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 arranged on or above the supporting member; and the metal oxide layer is arranged on or above the charge transport layer or the sensitizing dye electrode layer. The method includes spraying p-type semiconductor metal oxide and silicon dioxide or metal oxide particles to form a metal oxide layer.

The method of spraying p-type semiconductor metal oxide and silicon dioxide or metal oxide particles is not particularly limited, and can be appropriately selected according to the desired purpose. The preferred method is aerosol deposition.

<Image forming apparatus and image forming method>

The image forming apparatus of the present invention includes an electronic device (electrophotographic photoreceptor). The image forming apparatus further includes an electrostatic latent image forming unit and a developing unit, and may also include other units as needed.

The image forming method associated with the present invention includes at least an electrostatic latent image forming step and a developing step, and may further include other steps as needed.

The image forming method is adapted to be performed by an image forming device, the electrostatic latent image forming step is adapted to be performed by an electrostatic latent image forming unit, the developing step is adapted to be performed by a developing unit, and the above-mentioned other steps are adapted to be performed by the above-mentioned other units.

<Examples of Image Forming Apparatus>

Hereinafter, an example of the structure of an image forming apparatus will be described with reference to the drawings.

Fig. 1 is an example of an image forming apparatus. The charging device 12 is a unit configured to uniformly charge the surface of the electrophotographic photoreceptor 11. As the charging device 12, any known unit can be used, such as a corotron, a scorotron, a solid-state charger, and a charging roller. In view of reducing power consumption, the charging device 12 is preferably used to be arranged in contact with or adjacent to the electrophotographic photoreceptor 11. In order to prevent contamination of the charging device 12, it is preferable to arrange the charging system adjacent to the electrophotographic photoreceptor 11 with an appropriate gap between the surface of the electrophotographic photoreceptor 11 and the charging device 12. Generally, the above-mentioned charger can be used as the transfer device 16. As the transfer device 16, a combination of a transfer charger and a separation charger is effective.

The electrophotographic photoreceptor 11 is driven by the drive unit 1C. Repeat the following steps: charging by the charging device 12; image exposure by the exposure device 13; development and transfer by the transfer device 16; pre-cleaning exposure of the pre-cleaning exposure device 1B; cleaning by the cleaning device 17; The charge of the elimination device 1A is eliminated. As shown in FIG. 1, the lubricant 3A, the coating brush 3B for coating the lubricant, and the coating blade 3C are provided between the cleaning device 17 and the charging device 12 in the traveling direction of the electrophotographic photoreceptor 11.

In FIG. 1, light for pre-cleaning exposure is applied from one side of the supporting member of the electrophotographic photoreceptor 11 (in this case, the supporting member is light-transmissive).

The above optoelectronic process is an example. For example, the pre-cleaning exposure is performed from the side of the support member in FIG. 1, but the pre-cleaning exposure can also be performed from the side of the photosensitive layer. In addition, the application of image exposure light and charge elimination light can also be performed from one side of the supporting member. At the same time, image exposure lighting, pre-cleaning exposure lighting and charge elimination lighting are shown as lighting steps. However, in addition to the lighting step In addition, transfer pre-exposure, image exposure pre-exposure, and other lighting steps known in the art can be performed to irradiate the electrophotographic photoreceptor with light.

In addition, the above-mentioned image forming unit may be fixed and integrated with a photocopier, facsimile machine or printer. Alternatively, the image forming unit may be integrated with any of the above-mentioned devices in the form of a process cartridge. Many examples of processing cassette shapes can be listed, but the shape shown in FIG. 2 is cited as a typical example. The electrophotographic photoreceptor 11 is in the shape of a drum, but the electrophotographic photoreceptor 11 may be in the shape of a sheet or an endless belt.

The processing cartridge includes at least: an electrophotographic photoreceptor carrying an electrostatic latent image; 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, It is configured to supply lubricant onto the electrophotographic photoreceptor. The processing cassette may further include appropriately selected other units as required, such as a charging unit, an exposure unit, a transfer unit, a cleaning unit, and a neutralization unit. The developing unit includes at least: a developer container configured to store toner or developer thereon; and a developer carrier configured to carry and transport the toner or developer stored in the developer container. The developing unit may further include a layer thickness adjusting member configured to adjust the thickness of the toner layer carried on the developer carrier. The process cassette can be detachably installed in various electrophotographic image forming apparatuses, facsimile machines, and printers, and is particularly preferably detachably installed in the image forming apparatus of the present invention.

Fig. 3 is another example of an image forming apparatus. In this image forming apparatus, the charging device 12, the exposure device 13, the black (Bk) developing device 14Bk, the cyan (C) developing device 14C, the magenta (M) developing device 14M, and the yellow (Y) developing device 14Y are in the middle The intermediate transfer belt 1F of the transfer member and the cleaning device 17 are sequentially arranged around the electrophotographic photoreceptor 11.

Note that the letters (Bk, C, M, and Y) shown in FIG. 3 indicate the color of the toner, and are appropriately omitted when necessary. Each color of the developing devices 14Bk, 14C, 14M, and 14Y can be independently controlled, and only the developing devices for the colors used for image formation will be driven. The toner image formed on the electrophotographic photoreceptor 11 is transferred to the intermediate transfer belt 1F by the first transfer device 1D provided inside the intermediate transfer belt 1F.

The first transfer device 1D is provided in such a way that the first transfer device 1D can contact the electrophotographic photoreceptor 11, and the intermediate transfer belt 1F contacts the electrophotographic photoreceptor 11 only during the transfer operation. Image formation of each color is performed, and the toner image superimposed on the intermediate transfer belt 1F is collectively transferred to the printing medium 18 through the second transfer device 1E, and then fixed by the fixing device 19 to form image. The second transfer device 1E is also provided in such a way that the second transfer device 1E can be in contact with the intermediate transfer belt 1F, and the second transfer device 1E is in contact with the intermediate transfer belt 1F only during the transfer operation.

In the image forming equipment of the transfer drum system, the toner images of different colors that are electrostatically attracted to the transfer drum are sequentially transferred to the printing medium, so the image forming equipment of the transfer drum system cannot be used on thick paper. print. At the same time, as shown in FIG. 3, in the image forming apparatus of the intermediate transfer system, toner images of different colors are overlapped on the intermediate transfer member 1F. Therefore, there are no restrictions on the printing media used. The above-mentioned intermediate transfer system can be applied not only to the apparatus shown in FIG. 3, but also to the image forming apparatuses shown in FIGS. 1, 2, 4, and 5.

As shown in FIG. 3, the lubricant 3A, the coating brush 3B for coating the lubricant, and the coating blade 3C are provided between the cleaning device 17 and the charging device 12 with respect to the rotation direction of the electrophotographic photoreceptor 11.

Fig. 4 is another example of an image forming apparatus. The image forming device uses four colors of toner, namely yellow (Y), magenta (M), cyan (C), and black (Bk), and the image forming unit for each color is provided in the image forming device . In addition, electrophotographic photoreceptors 11Y, 11M, 11C, and 11Bk for four colors are provided. Around each electrophotographic photoreceptor 11Y, 11M, 11C, or 11Bk, a charging device 12Y, 12M, 12C, or 12Bk, an exposure device 13Y, 13M, 13C, or 13Bk, and a developing device 14Y, 14M, 14C, or 14Bk are provided for cleaning Device 17Y, 17M, 17C or 17Bk, etc.

In addition, a transport transfer belt 1G as a transfer material carrier is held by a drive unit 1C, and the transport transfer belt 1G is brought in and out of each of the electrophotographic photoreceptors 11Y, 11M, 11C, and 11Bk arranged in a straight line. Transfer position. The transfer devices 16Y, 16M, 16C, and 16Bk are respectively provided at transfer positions facing the electrophotographic photoreceptors 11Y, 11M, 11C, and 11Bk via the conveying transfer belt 1G.

The tandem system image forming apparatus shown in FIG. 4 includes an electrophotographic photoreceptor 11Y, 11M, 11C, or 11Bk for each color, and sequentially transfers toner images of all colors to the transfer belt On the printed media on 1G. Therefore, compared with a full-color image forming apparatus that includes only one electrophotographic photoreceptor, a tandem system image forming device can output a full-color image at a relatively high speed. The toner image developed on the printing medium 18 as a transfer material is transferred from the position where the electrophotographic photoreceptor 11Bk and the transfer device 16Bk are opposed to each other to the fixing device 19, and the toner image is fixed on the printing medium through the fixing device 19 18 on.

In addition, the image forming apparatus may have the structure in the embodiment shown in FIG. 5. Specifically, the structure of the intermediate transfer belt 1F shown in FIG. 5 may be used instead of the direct transfer system using the conveying transfer belt 1G shown in FIG. 4.

In the example shown in FIG. 5, the image forming apparatus includes an electrophotographic photoreceptor 11Y, 11M, 11C, or 11Bk for each color. Through the main transfer unit 1D as the first transfer unit, the electrophotographic photoreceptor The formed toner images of all colors are sequentially transferred and laminated onto an intermediate transfer belt 1F driven and supported by a driving unit including a roller 1C, thereby forming a full-color image.

Next, the intermediate transfer belt 1F is further driven, and the full-color image carried thereon is transferred to the secondary transfer unit 1E as the secondary transfer device and the rollers provided to face the secondary transfer unit 1E. position. Then, the full-color image is secondarily transferred to the transfer material 18 through the secondary transfer unit 1E to form a desired image on the transfer material.

<Solar Cell>

One embodiment of the electronic device of the present invention is a solar cell.

The solar cell includes: a support member; a sensitizing dye electrode layer including a sensitizing dye; and a metal oxide layer provided on or above the sensitizing dye electrode layer. The solar cell further includes a first electrode; a hole blocking layer; and a second electrode, and may further include other members as necessary.

Hereinafter, an example in which the electronic device is a solar battery will be described, but the electronic device is not limited to the solar battery and can be applied to other electronic devices.

Hereinafter, the solar cell (electronic device) of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiments described below. The following embodiments can be changed, for example, another embodiment can be used, or within the range that can be achieved by a person with ordinary knowledge in the art, additions, corrections, or omissions can be made in the following embodiments, and as long as the present invention is shown The functions and effects of the invention, any of the above-mentioned embodiments are included in the scope of the present invention.

The solar cell (electronic device) includes: a substrate serving as a supporting member; a first electrode; a hole blocking layer; an electron transport layer; a sensitizing dye electrode layer; a ceramic semiconductor film serving as a metal oxide layer; and a second electrode.

The structure of the electronic device 10B as a solar cell will be described with reference to FIG. 7. Fig. 7 is a cross-sectional view illustrating an example of a solar cell.

In the embodiment shown in FIG. 7, the first electrode 2 is formed on the substrate 1 used as the supporting member, the hole blocking layer 3 is formed on the first electrode 2, and the charge transport layer is formed on the hole blocking layer 3. Sensitizing material 5 is sucked Attached to the charge transport material of the electron transport layer 4, and the metal oxide 6 is provided between the first electrode 2 and the second electrode 7 facing the first electrode 2. In addition, in FIG. 7, an example of a structure in which leads 8 and 9 are provided to electrically connect the first electrode 2 and the second electrode 7 is shown.

The metal oxide and the electron transport layer 4 can penetrate each other and thus partially penetrate each other.

The details are described below.

<<Supporting parts (substrate)>>

The substrate 1 used as the supporting member is not particularly limited, and may be selected from substrates known in the art. The substrate 1 is preferably a transparent material. Examples of substrates include glass, transparent plastic plates, transparent plastic films, and inorganic transparent crystals.

<First electrode>

The first electrode 2 is not particularly limited, as long as the first electrode 2 is a conductive material transparent to visible light. As the first electrode 2, an electrode known in the art such as a general photoelectric conversion element and a liquid crystal panel can be used.

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 materials listed above can be used alone or in combination as a laminated structure.

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

In addition, in order to maintain a certain hardness, the first electrode is preferably provided on the substrate 1 formed of a material transparent to visible light. As the substrate, for example, glass, transparent plastic plate, transparent plastic film, inorganic transparent crystal, etc. are used.

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

In addition, the first electrode may be a transparent electrode prepared by doping tin oxide or indium oxide with cations or anions having different valences, and a metal electrode having a light-transmissive structure (such as mesh or stripes) may be arranged on For example, on a glass substrate.

The examples listed above can be used alone, in combination, or stacked.

In addition, in order to reduce electrical resistance, metal leads or the like can be used in combination.

Examples of the material of the metal lead include metals such as aluminum, copper, silver, gold, platinum, and nickel. The metal lead is arranged on the substrate through vapor deposition, sputtering, pressure bonding, etc., and ITO or FTO is arranged on the metal lead.

<<Hole barrier layer>>

There is no particular limitation on the material constituting the hole barrier layer 3, as long as the material is transparent to visible light and is an electron transport material. The material of the hole barrier layer is particularly preferably titanium oxide.

The hole blocking layer is provided to suppress a decrease in power caused by recombination (ie, reverse electron transfer) between holes in the electrolyte and electrons existing on the surface of the electrode when the electrode is in contact with the electrolyte hole blocking layer. The solid-state dye-sensitized solar cell particularly clearly shows the above-mentioned effect of the hole blocking layer 3. This is because compared with wet dye-sensitized solar cells using an electrolyte solution, solid-state dye-sensitized solar cells using organic hole transport materials and the like have a difference between the holes in the hole transport material and the electrons present on the electrode surface. High recombination (reverse electron transport) speed between.

The method for forming the hole barrier layer is not particularly limited, but having high internal resistance is important to prevent current loss due to indoor light. Therefore, the method used to form the hole barrier layer is also very important. Examples of the hole barrier layer generally include a sol-gel method that is a wet film formation. The sol-gel method may not be able to fully exhibit the loss current. Therefore, the method of forming the hole barrier layer is more preferably dry film formation, such as sputtering, and the dry film formation can provide a sufficiently high film density and can prevent current loss.

The hole blocking layer is formed to prevent electronic contact between the first electrode 2 and the hole transport layer 6. The average thickness of the hole barrier layer is not particularly limited. The average thickness of the hole barrier layer is preferably 5 nanometers to 1 micrometer. In wet film formation, the average thickness is more preferably 500 nm to 700 nm. In dry film formation, the average thickness is more preferably 10 nm to 30 nm.

<<Electron Transport Layer>>

The solar cell includes a porous electron transport layer 4 provided on the hole blocking layer 3. The electron transport layer may be a single layer or multiple layers.

The electron transport layer is formed of an electron transport material. As the electron transport material, it is preferable to use semiconductor particles.

In the case of multiple layers, dispersion liquids each containing semiconductor particles of different particle sizes may be applied to form multiple layers, or it may be provided that each contains semiconductor particles of different types or each has a different resin. Or a coating composed of additives to form multiple layers. Multi-layer coatings are effective when one layer of coating cannot provide a sufficient average thickness.

Generally, as the average thickness of the electron transport layer increases, the carrying capacity of the photosensitive material per unit projected area increases, and therefore the light capture rate also increases. However, the diffusion length of the injected electrons increases, so the charge loss due to recombination also increases. Therefore, the average thickness of the electron transport layer is preferably 100 nanometers to 100 micrometers.

No particular limitation is placed on the semiconductor, and any semiconductor known in the art can be used as the semiconductor. Specific examples of semiconductors include: a single type of semiconductor, such as silicon and germanium; compound semiconductors, such as metal chalcogenides; and compounds having a perovskite structure.

Examples of metal chalcogenides include: oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, and tantalum; cadmium, zinc, lead, silver, antimony And bismuth sulfides; cadmium and lead selenides; and cadmium tellurides.

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

In addition, the compound having a perovskite structure is preferably strontium titanate, calcium titanate, sodium titanate, barium titanate, or potassium niobate.

Among the examples listed above, oxide semiconductors are 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. There is no particular limitation on the crystal types of the semiconductors listed above. The crystal type can be single crystal, polycrystalline or amorphous.

The average particle diameter of the original particles of the semiconductor particles is not particularly limited. The average particle size is preferably 1 nanometer to 100 nanometers, and more preferably 5 nanometers to 50 nanometers.

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

The manufacturing method of the electron transport layer is not particularly limited. The production method of the electron transport layer includes a method of forming a thin film in a vacuum, such as sputtering and a wet film forming method.

Considering the production cost, the wet film forming method is particularly preferred. Preferred is a method of preparing a paste of powder or sol in which semiconductor particles are dispersed, and applying the paste to an electron collector substrate.

When a wet film forming method is used, the coating method is not particularly limited, and the coating can be performed according to any method known in the art. Can be coated according to various methods, such as dipping, spraying, wire Bar coating, spin coating, roll coating, knife coating, gravure coating, and wet printing methods (for example, relief printing, offset printing, gravure printing, rubber plate printing, and screen printing).

When forming a dispersion of semiconductor particles by mechanical pulverization or using a grinder, the dispersion is formed by dispersing at least individual semiconductor particles or a mixture containing semiconductor particles and resin in water or an organic solvent. Examples of resins used include: polymers or copolymers of vinyl compounds such as styrene, vinyl acetate, acrylate and methacrylate; silicone resins; phenoxy resins; polyvinyl butyral resins Resin; Polyvinyl formal resin; Polyester resin; Cellulose ester resin; Cellulose ether resin; Polyurethane resin; Phenolic resin; Epoxy resin; Polycarbonate resin; Polyacrylate resin; Polyamide resin; Amide resin.

Examples of solvents used to disperse semiconductor particles include: water; alcohol-based solvents such as methanol, ethanol, isopropanol, and α-terpineol; 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, meta-xylene, p-xylene, ethylbenzene and cumene. The examples listed above can be used alone or in combination.

The dispersion liquid of semiconductor particles or the paste of semiconductor particles obtained by the sol-gel method or the like may include acids (for example, hydrochloric acid, nitric acid, and acetic acid), surfactants (for example, polyoxyethylene (10) octyl phenyl ether). ) And chelating agents (e.g., acetone, 2-aminoethanol, and ethylenediamine) to prevent particles from re-aggregating.

In addition, in order to improve film-forming properties, it is also effective to add a thickener. Examples of thickeners include: polymers such as polyethylene glycol and polyvinyl alcohol; and ethyl fiber.

After the semiconductor particles are applied, the particles are brought into electrical contact with each other, and it is preferable to perform firing, microwave irradiation, electron beam irradiation, or laser irradiation to improve film strength or adhesion to the substrate. The examples listed above can be used alone or in combination.

When firing, the range of the firing temperature is not particularly limited. When the temperature is too high, the resistance of the substrate may be too high or the substrate may melt. Therefore, the fixing temperature is preferably 30 degrees Celsius to Celsius 700 degrees, and more preferably 100 degrees to 600 degrees Celsius. In addition, the firing time is not particularly limited, but is preferably 10 minutes to 10 hours.

For microwave irradiation, microwaves can be applied from the side or back of the electron transport layer. The irradiation time is not particularly limited, but the progress of the microwave irradiation is preferably within 1 hour.

After firing, a mixed solution of titanium tetrachloride aqueous solution and organic solvent can be used for electroless plating, or titanium tetrachloride aqueous solution can be used for electrochemical plating to increase the surface area of semiconductor particles, or to increase the surface area of semiconductor particles from photosensitive materials to semiconductor particles. Electron injection efficiency.

A porous state is formed by firing a film formed by laminating semiconductor particles having a diameter of several tens of nanometers. The nanoporous structure has a very high surface area, and this surface area can be represented by a roughness factor.

The roughness factor is a value representing the actual area of the inner area of the hole relative to the area of the semiconductor particles applied to the substrate. Therefore, a larger roughness factor is better. The roughness factor is related to the average thickness of the electron transport layer. In the present invention, the roughness factor is preferably 20 or more.

<<Sensitizing Dye Electrode Layer>>

The solar cell includes a sensitized dye electrode layer to further improve the conversion efficiency. The sensitizing dye electrode layer is a layer in which a sensitizing dye (photosensitive material) is adsorbed on the surface of the electron transport material as the electron transport layer 4.

-Sensitizing dyes (photosensitive materials)-

The photosensitive material 5 used as the sensitizing dye is not limited, as long as the photosensitive material 5 is a compound that is photoexcited by excitation light and used.

Specific examples of sensitizing dyes include: Japanese translation disclosed in PCT International Application Publication No. JP-T-07-500630, Japanese Unexamined Patent Application Publication Nos. 10-233238, 2000-26487, 2000-323191, and 2001-59062 Metal complexes in Japanese Unexamined Patent Application Publication Nos. 10-93118, 2002-164089 and 2004-95450 and J. Phys. Chem. C, 7224, Vol. 111 (2007) Compound; disclosed in Japanese Unexamined Patent Application Publication No. 2004-95450 and Chem. Commun., 4887 (2007) in polyene compounds; disclosed in Japanese Unexamined Patent Application Publication No. 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) indoline compounds; disclosed in J. Am. Chem. Soc., 16701, Vol. 128 (2006) and J. Am. Chem. Soc., 14256, Vol. Thiophene in 128 (2006) Compounds; Cyanine dyes disclosed in Japanese Unexamined Patent Application Publication Nos. 11-86916, 11-214730, 2000-106224, 2001-76773, and 2003-7359; Japanese Unexamined Patent Application Publication Nos. 11-214731, The merocyanine dyes in Nos. 11-238905, 2001-52766, 2001-76775, and 2003-7360; 9 disclosed in Japanese Unexamined Patent Publication Nos. 10-92477, 11-273754, 11-273755, and 2003-31273 Aryl dibenzopyran compounds; triarylmethane compounds disclosed in Japanese Unexamined Patent Application Publication Nos. 10-93118 and 2003-31273; and 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. Porphyrins Phthalocyanines, 230, Vol. 3 (1999), Angew. Chem. Int. Ed., 373, Vol. 46 (2007) And the phthalocyanine compound in Langmuir, 5436, Vol. 24 (2008). Among the above examples, it is particularly preferable to use metal complexes, coumarin compounds, polyene compounds, indoline compounds, and thiophene compounds.

As a method of allowing the photosensitive material 5 to be adsorbed on the electron transport layer 4, a method of immersing an electron collector including semiconductor particles in a photosensitive material solution or dispersion may be used, or a solution or dispersion applied to the electron transport layer may be used. In order to make the semiconductor particles adsorbed on it.

In the case of the former method, dipping, dip coating, roll coating, air knife coating, etc. can be used.

In the case of the latter method, wire bar coating, sliding hopper coating, extrusion, curtain coating, spin coating, spray coating, etc. can be used.

In addition, the adsorption of semiconductor particles can be performed in a supercritical fluid using carbon dioxide or the like.

When the photosensitive material is adsorbed, a condensing agent may be used in combination.

The condensing agent may be a reagent that has a catalytic function to physically or chemically bond the photosensitive material and the electron transport compound to the surface of the inorganic material, or a stoichiometric function to favorably change the chemical balance. In addition, mercaptans or hydroxyl compounds can be added as co-condensing agents.

Examples of solvents used to dissolve or disperse photosensitive materials 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 formic acid Ethyl, 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-dimethyl Formamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; halogenated hydrocarbon-based solvents, such as dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane Alkane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromine Benzene, 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 examples listed above can be used alone or in combination.

In addition, when the aggregation function between compound molecules is suppressed according to the type of the photosensitive material, there is a more effective photosensitive material. Therefore, depolymerization agents can be used in combination.

The depolymerizing agent is preferably a steroid compound (for example, cholic acid and chenodeoxycholic acid), a long-chain alkyl carboxylic acid, or a long-chain alkyl phosphonic acid. The depolymerizing agent is appropriately selected depending on the photosensitive material used.

Relative to 1 part by mass of the photosensitive material, the amount of the depolymerization agent is preferably 0.01 parts by mass to 500 parts by mass, and more preferably 0.1 parts by mass to 100 parts by mass.

The adsorption temperature of the photosensitive material or the combination of the photosensitive material and the depolymerization agent is preferably minus 50°C or higher but 200°C or lower. In addition, the adsorption can be carried out under standing or stirring.

Examples of the method of stirring include stirring using a stirrer, a ball mill, a paint blender, a sand mill, an attritor, and a disperser, and ultrasonic dispersion, but the method is not limited to the examples listed above. The time required for adsorption is preferably 5 seconds or more but 1000 hours or less, more preferably 10 seconds or more but 500 hours or less, and still more preferably 1 minute or more but 150 hours or less. In addition, adsorption is preferably performed in the dark.

<<<Metal Oxide Layer>>

The metal oxide layer 6 in the solar cell and the manufacturing method thereof can be appropriately selected from the description of the metal oxide layer and the manufacturing method of the electronic device of the present invention.

<<Second electrode>>

After forming the metal oxide layer, a second electrode is provided.

In addition, generally the same electrode as the first electrode can be used as the second electrode. It is not necessary to provide the supporting member in a structure that sufficiently maintains strength and airtightness.

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 nanotubes and graphene; conductive metal oxides such as ITO, FTO and ATO; and conductive polymers such as polythiophene and polyaniline.

The average thickness of the second electrode is not particularly limited. In addition, the materials listed above can be used alone or in combination.

Depending on the material used or the type of the hole transport layer, the second electrode may be appropriately formed on the hole transport layer through methods such as coating, lamination, vapor deposition, CVD, and bonding.

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.

In the electronic device of the present invention, the side where the first electrode is provided is transparent, and it is preferable to apply sunlight from the side of the first electrode. In this case, it is preferable to use a reflective material on one side of the second electrode, and the material is preferably glass or plastic coated with metal or conductive oxide by vapor deposition, or a metal film.

In addition, it is also effective to provide an anti-reflection layer on the side where sunlight is applied.

The photoelectric conversion element of the present invention can be applied to solar cells and power sources including solar cells. Application examples can be any device that has used solar cells, or power supplies that use solar cells. For example, the photoelectric conversion element can be used in the solar cell of a desktop electronic calculator or a watch. Examples of using the characteristics of the photoelectric conversion element of the present invention include power sources for mobile phones, electronic notebooks, electronic paper, and the like. In addition, the photoelectric conversion element can be used as an auxiliary power source to extend the continuous use time of rechargeable or dry battery electrical equipment. In addition, the photoelectric conversion element can be used in combination with a secondary battery as a substitute for the main battery and used as a self-sufficient power source for the sensor.

<Organic Electroluminescence Element>

An embodiment of the electronic device of the present invention is an organic electroluminescence (EL) element.

The organic EL element includes: a support member; a charge transport layer containing a charge transport material, provided on or above the support member; and a metal oxide layer, provided on or above the charge transport layer. The organic EL element further includes a positive electrode (first electrode), a hole transport layer, a light emitting layer, and a negative electrode (second electrode), and may also include other layers, such as a barrier film.

Note that a layer including a positive electrode (first electrode), a hole transport layer, a light-emitting layer, an electron transport layer as a charge transport layer, and a negative electrode (second electrode) may be referred to as an "organic EL layer."

Hereinafter, an example in which the electronic device is an organic EL element will be described, but the electronic device is not limited to the organic EL element and can be applied to other embodiments of the electronic device.

FIG. 8 shows an organic EL element 10C, which is an embodiment of the electronic device of the present invention. An organic EL element 10C having a metal oxide layer is provided, and the metal oxide layer is located on the outermost surface of the organic EL layer. The organic EL element 10C includes a substrate 20 as a supporting member, an organic EL layer 30, and a metal oxide layer 40.

Note that the present invention is not limited to the embodiments described below. The following embodiments can be changed, for example, another embodiment can be used, or within the range that can be achieved by a person with ordinary knowledge in the field, Additions, corrections, or omissions are made in the following embodiments, and as long as the functions and effects of the present invention are exhibited, any of the above-mentioned embodiments are included in the scope of the present invention.

<<Supporting parts (substrate)>>

The substrate 20 serving as a supporting member is an insulating substrate. The substrate 20 may be a plastic or film substrate.

The barrier film may be provided on the main surface 20 a of the substrate 20.

The barrier film is, for example, a film formed of silicon, oxygen, and carbon, or a film formed of silicon dioxide, oxygen, carbon, and nitrogen. Examples of the material of the barrier film include silicon oxide, silicon nitride, and silicon oxynitride. The average thickness of the barrier film is preferably 100 nanometers or more but 10 micrometers or less.

<<Organic EL layer>>

The organic EL layer 30 includes a light-emitting layer, and is a functional part for contributing to the light emission of the light-emitting layer, for example, promoting carrier mobility or carrier recombination according to a voltage applied between the anode and the anode. For example, the organic EL layer is formed by sequentially stacking a positive electrode, a hole transport layer, a light emitting layer, an electron transport layer, and a negative electrode from one side of the support substrate 20.

The organic EL layer 30 is not particularly limited, and can be appropriately selected from organic EL elements known in the art according to the desired purpose.

The transparent electrode is laminated as a negative electrode.

The transparent electrode is formed by using conductive metal oxides such as SnO ₂ , In ₂ O ₃ , ITO, IZO, and ZnO:Al. When a transparent electrode is used as a negative electrode, it is ideal to provide the electron injection layer as the uppermost layer of the organic EL layer to improve electron injection efficiency. The transmittance of the transparent electrode to light with a wavelength of 400 nm to 800 nm is preferably 50% or more, more preferably 85% or more. The average thickness of the transparent electrode is preferably 50 nanometers or more, more preferably 50 nanometers to 1 micrometer, and still more preferably 100 nanometers to 300 nanometers.

<<<Metal Oxide Layer>>

The metal oxide layer 40 of the organic EL element and the manufacturing method thereof can be appropriately selected from the description of the metal oxide layer and the manufacturing method of the electronic device of the present invention.

The metal oxide layer 40 is provided on the negative electrode to bury the organic EL layer 30 therein. The metal oxide layer 40 is provided on the organic EL layer 30 opposite to the side where the substrate 20 is provided. The metal oxide layer 40 has a gas barrier function, especially a moisture barrier function.

Example

The present invention will be described in more detail with examples and comparative examples. The present invention should not be interpreted as being limited to these examples. In the following description, "parts" means "parts by mass".

-Preparation of copper aluminum oxide-

The copper aluminum oxide is prepared in the following manner. The weights of cuprous oxide and aluminum oxide are prepared so that their molar numbers are equal. The collected cuprous oxide and aluminum oxide were transferred to a mayonnaise bottle, and the mixture therein was stirred with a cylindrical mixer (T2C type, available from Willy A. Bachofen AG Maschinenfabrik) to obtain a powder mixture. The obtained powder mixture was heated at 1100 degrees Celsius for 40 hours, and then the product was passed through a sieve with an aperture of 100 microns.

<Powder Mix Material>

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

Alumina (AA-03, available from Sumitomo Chemical Co., Ltd.): 8.58 kg

Use DRYSTAR SDA1 (available from Ashizawa Finetech Ltd.) to pulverize the obtained copper-aluminum oxides to obtain a cumulative number of 10% (D10), 50% (D50), and 90% (D90) of 0.7±0.1 Micron, 5.0 ± 0.5 microns, 26 ± 3 microns of copper and aluminum oxide powder. The powder of the copper aluminum oxide was vacuum dried at 100 degrees Celsius to adjust the water content of the copper aluminum oxide to 0.2% by mass or less.

A 0.2% sodium hexametaphosphate aqueous solution was used as a dispersion medium and measured with MICROTRAC MT3300 (MicrotracBEL Corp.) to obtain the particle size value of the copper aluminum oxide. The measurement time was 10 seconds.

As for the determination of the moisture content of copper and aluminum oxide, a Karl Fischer moisture analyzer (CA-200, available from Mitsubishi Chemical Analytical Technology Co., Ltd.) was used.

An X-ray fluorescence spectrometer (ZSX Primus IV, available from Rigaku Corporation) was used to determine the composition ratio of the elements of copper aluminum oxide, and an X-ray diffractometer (X'Pert PRO, available from Spectris Co., Ltd.) was used. Measure the crystal structure.

<Example 1>

-Example of manufacturing electrophotographic photoreceptor-

The 20 electrophotographic photoreceptors in Example 1 were each manufactured in the following manner. Each electrophotographic photoreceptor of Example 1 includes an intermediate layer, a charge generation layer, a charge transport layer, a silicon hard coat layer, and a metal oxide layer provided on the conductive support member in the following order.

-Formation of the middle layer-

The following intermediate layer coating liquid was coated on the aluminum conductive support member (outer diameter: 100 mm, thickness: 1.5 mm) through dip coating to form an intermediate layer. After drying at 150 degrees Celsius for 30 minutes, the average thickness of the intermediate layer was 5 microns.

<Intermediate layer coating liquid>

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

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

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

Solution obtained by dissolving butyral resin (20% by mass) in 2-butanone (BM-1, available from Sekisui Chemical Co., Ltd.): 225 parts

2-Butanone: 365 parts

--Formation of charge generation layer--

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 is 0.2 micrometers.

<Charge Generation Layer Coating Liquid>

Y-type titanyl phthalocyanine: 6 parts

Butyral resin (S-LEC BX-1, available from Sekisui Chemical Co., Ltd.): 4 parts

2-Butanone (available from Kanto Chemical Co., Ltd.): 200 copies

--Formation of charge transport layer--

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

After drying at 135 degrees Celsius for 20 minutes, the average thickness of the charge transport layer was 22 microns.

<Charge Transport Layer Coating Liquid>

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

Low molecular charge transport material with the following structural formula: 10 parts

Tetrahydrofuran: 80 parts

-Formation of silicon hard coat-

The following silicon hard coat coating liquid was applied to the obtained charge transport layer by ring coating to form a silicon hard coat.

After drying at 135 degrees Celsius for 20 minutes, the average thickness of the silicon hard coating was 0.5 microns.

(Silicon hard coat coating liquid)

Silicon hard coat liquid: (NSC-5506, available from Nippon Seiki Co., Ltd.): 80 parts

Tetrahydrofuran: 20 parts

--Formation of metal oxide layer--

As the film forming chamber, a chamber obtained by modifying a commercially available vapor deposition apparatus was used.

A commercially available stirrer (TKAGI HOMO MIXER 2M-03, available from PRIMIX Corporation) is used for the aerosol generator. Note that as the aerosol generator, an ultrasonic cleaner (SUS-103, available from Shimadzu Corporation) can be used, and a commercially available pressure supply bottle (RBN-S, available from Kato Stainless Steel Chemical Co., Ltd.) can be used. It has a volume of 1L.

A pipe with an inner diameter of 4 mm was drawn from the aerosol generator to the film forming chamber, and a nozzle (YB1/8MSSP37, available from Spraying Systems Co.) was attached to the edge of the pipe. The photoconductor is arranged at a distance of 50 mm from the nozzle. As the photoreceptor holder, a mechanism that can rotate the photoreceptor drum is provided. As the nozzle, a nozzle that can move laterally is used. Connect the aerosol generator to the gas cylinder filled with nitrogen using a pipe with an inner diameter of 4 mm.

Using the above-mentioned device, the target metal oxide layer with an average thickness of 1.5 micrometers was produced in the following manner.

The aerosol generator is filled with a powder mixture containing copper aluminum oxide and silicon dioxide particles. The copper aluminum oxide is obtained in the above manner. The silicon dioxide particles (Reolosil ZD-30S, available from Tokuyama Co., Ltd.) have been Surface treatment with dimethyldichlorosilane and hexamethyldisilazane, the BET surface area is 190±25m ² /g, the carbon content is 2.9% by mass, and the mass ratio of copper aluminum oxide and silicon dioxide particles 99.5%: 0.5%.

Next, vacuum exhaust is performed from the film forming chamber to the aerosol generator through an exhaust pump. Then, the nitrogen gas is fed into the aerosol generator from the gas cylinder, and stirring is started to generate the aerosol, in which the particles are dispersed in the nitrogen gas. The generated aerosol is ejected from the nozzle toward the photoreceptor through the pipe. The flow rate of nitrogen is 13L/min to 20L/min. In addition, the film formation time was 20 minutes, and the vacuum degree inside the film formation chamber during the formation of the metal oxide layer was about 50 Pa to about 150 Pa.

An X-ray fluorescence spectrometer (ZSX Primus IV, available from Rigaku Corporation) was used to determine the amount of silica particles contained on the surface of the photoreceptor. The amount of silicon dioxide particles contained in the photoreceptor is the same as the amount of charge.

<Example 2>

Except that the amount of silicon dioxide particles in the powder mixture containing copper aluminum oxide and silicon dioxide particles for forming metal oxides was changed to 1.0% by mass, 20 electrophotographic photosensitive materials were manufactured in the same manner as in Example 1. body.

<Example 3>

Except that the amount of silicon dioxide particles in the powder mixture containing copper aluminum oxide and silicon dioxide particles for forming the metal oxide was changed to 1.5% by mass, 20 electrophotographic photosensitive materials were manufactured in the same manner as in Example 1. body.

<Example 4>

In addition to changing the silicon dioxide particles in the powder mixture containing copper aluminum oxide and silicon dioxide particles used to form metal oxides into silicon dioxide particles that have been surface-treated with dimethyldichlorosilane, its BET Except that the specific surface area is 200±25m ² /g, and the carbon content is 2.8% by mass (HDK H-2000, available from Wacker Asahikasei Silicone Co., Ltd.), 20 electrophotographic sensitizers were manufactured in the same manner as in Example 2 body.

<Example 5>

In addition to changing the silica particles in the powder mixture containing copper aluminum oxide and silica particles used to form metal oxides to Aerosil R976 (available from NIPPON AEROSIL CO., LTD.), with a BET specific surface area of 250±25 m ² /g and a carbon content of 1.8% by mass, 20 electrophotographic photoreceptors were manufactured in the same manner as in Example 2.

<Example 6>

In addition to changing the silicon dioxide particles in the powder mixture containing copper aluminum oxide and silicon dioxide particles used to form metal oxides to Aerosil RA200HS that has been surface-treated with trimethylsilyl groups and amino groups. Available from NIPPON AEROSIL CO., LTD.) with a BET specific surface area of 140±25 m ² /g and a carbon content of 1.8% by mass, 20 electrophotographic photoreceptors were manufactured in the same manner as in Example 2.

<Comparative Example 1>

Except that silicon dioxide particles were added to the powder mixture containing copper aluminum oxide and silicon dioxide particles for forming the metal oxide layer, 20 electrophotographic photoreceptors were manufactured in the same manner as in Example 1.

<Comparative Example 2>

Except that the amount of silicon dioxide particles in the powder mixture containing copper aluminum oxide and silicon dioxide particles used to form the metal oxide was changed to 0.3% by mass, 20 electrophotographic photosensitive materials were manufactured in the same manner as in Example 1. body.

<Comparative Example 3>

Except that the amount of silica particles in the powder mixture containing copper aluminum oxide and silica particles used to form the metal oxide was changed to 2.0% by mass, 20 electrophotographic photosensitive materials were manufactured in the same manner as in Example 1. body.

<Example 7>

In addition to using a powder mixture containing copper aluminum oxide and aluminum oxide particles to form the metal oxide layer, the volume average particle size of these aluminum oxide particles (AKP-50, available from Sumitomo Chemical Co., Ltd.) is 0.20 microns, and the BET ratio The surface area was 10.3 m ² /g, and the mass ratio of copper aluminum oxide and alumina particles was 99.5%: 0.5%, and 20 electrophotographic photoreceptors were manufactured in the same manner as in Example 1.

<Example 8>

Except that the amount of metal oxide particles in the powder mixture containing copper aluminum oxide and metal oxide particles used to form the metal oxide was changed to 1.0% by mass, 20 electrophotographic photosensitive materials were manufactured in the same manner as in Example 7. body.

<Example 9>

Except that the amount of metal oxide particles in the powder mixture containing copper aluminum oxide and metal oxide particles used to form the metal oxide was changed to 1.5% by mass, 20 electrophotographic photosensitive materials were manufactured in the same manner as in Example 7. body.

<Example 10>

In addition to changing the metal oxide particles in the powder mixture containing copper aluminum oxide and metal oxide particles used to form the metal oxide to alumina (AKP-20, available from Sumitomo Chemical Co., Ltd.), the volume average particle size Except that the diameter was 0.46 μm and the BET specific surface area was 4.3 m ² /g, 20 electrophotographic photoreceptors were manufactured in the same manner as in Example 8.

<Example 11>

In addition to changing the metal oxide particles in the powder mixture containing copper aluminum oxide and metal oxide particles used to form the metal oxide layer to TM-DAR (available from Daming Chemical Industry Co., Ltd.), the volume average particle size Except for 0.10 micrometers and a BET specific surface area of 14.5 m ² /g, 20 electrophotographic photoreceptors were manufactured in the same manner as in Example 8.

<Example 12>

Except that the metal oxide particles in the powder mixture containing copper aluminum oxide and metal oxide particles used to form the metal oxide layer were changed to SF-10 (available from Sakai Chemical Industry Co., Ltd.), the particle size was 0.28 Except for micrometers and a BET specific surface area of 11.0 m ² /g, 20 electrophotographic photoreceptors were manufactured in the same manner as in Example 8.

<Comparative Example 4>

Except that the amount of metal oxide particles in the powder mixture containing copper aluminum oxide and metal oxide particles used to form the metal oxide was changed to 0.3% by mass, 20 electrophotographic photosensitive materials were manufactured in the same manner as in Example 7. body.

<Comparative Example 5>

Except that the amount of metal oxide particles in the powder mixture containing copper aluminum oxide and metal oxide particles used to form the metal oxide was changed to 2.0% by mass, 20 electrophotographic photosensitive materials were manufactured in the same manner as in Example 7. body.

<Evaluation of Electrophotographic Photoreceptor>

In each of the electrophotographic photoreceptors produced in the above-mentioned method in Examples 1 to 12 and Comparative Examples 1 to 5, the thickness of a cylindrical photoconductor drum with a length of 380 mm and an outer diameter of 100 mm was 100 mm from the drum edge. The measurement was performed at five points in the longitudinal direction at an interval of 50 mm between positions 300 mm from the edge of the drum. The thickness measurement was performed on 20 photoconductor drums to obtain a total of 100 points of thickness data. The thickness measurement is performed according to the method of Japanese Patent No. 5521607 using light interference. In addition to determining the thickness from the average value of the obtained data, the standard deviation was also determined.

Based on the average value and standard deviation of the obtained thickness, the process capability index (Cpk) is calculated according to the following equations (1) to (3). The results are shown in Table 1. The process capability index is a value obtained by evaluating the degree of deviation of the arithmetic mean value X of the thickness from the standard median value. The larger the Cpk, the higher the ability to manufacture electronic devices with stable quality.

Cpk=Cp(1- K ) (1)

In the above equation, USL is the upper limit of the standard, LSL is the lower limit of the standard, X is the arithmetic mean of the thickness, and σ is the standard deviation. In addition, Cp is the comparison between 6 σ, which indicates variation in the film forming process, and the standard width.

Since a large number of photoreceptors cannot be measured when judging the influence of process capability on products on the market, a total of 100 points of thickness measurement values can be obtained for evaluation by narrowing the measurement interval.

Table 1

From the results of Table 1, it was found that the metal oxide layer of each electrophotographic photoreceptor obtained in Examples 1 to 12 had less unevenness in its thickness.

It was found that when the content of silicon dioxide particles in the powder mixture containing copper aluminum oxide and silicon dioxide particles used for the metal oxide layer was changed from 0.5% by mass in Example 1 to 1.5% by mass in Example 3, it was obtained A high Cpk (process capability index).

In addition, it was found that when the content of the metal oxide particles in the powder mixture containing copper aluminum oxide and metal oxide particles used for the metal oxide layer was changed from 0.5% by mass in Example 7 to 1.5% by mass in Example 9 At that time, a high Cpk (process capability index) was obtained.

For example, the embodiment of the present invention is as follows:

<1> An electronic device, including:

A supporting part;

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 above the supporting member; and

A metal oxide layer disposed on or above the charge transport layer or the sensitizing dye electrode layer,

Wherein, the metal oxide layer includes p-type semiconductor metal oxide and silicon dioxide or metal oxide particles, and

Wherein, relative to the metal oxide layer, the content of the silicon dioxide or metal oxide particles contained in the metal oxide layer is 0.5% by mass or more but 1.5% by mass or less.

<2> The electronic device according to <1>, wherein the average thickness of the metal oxide layer is 1.2 μm or more but 1.8 μm or less, and the standard deviation of the thickness of the metal oxide layer is 0.07 μm or less.

<3> The electronic device according to <1>, wherein the p-type semiconductor metal oxide is cupronite oxide.

<4> The electronic device according to <3>, wherein the copper-iron ore oxide is copper-aluminum oxide.

<5> A method of manufacturing an electronic device, the method comprising:

Spraying p-type semiconductor metal oxide and silicon dioxide or metal oxide particles to form a metal oxide layer,

Wherein, the electronic device includes:

A supporting part;

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 above the supporting member; and

The metal oxide layer is arranged on or above the charge transport layer or the sensitizing dye electrode layer.

<6> The method of manufacturing an electronic device according to <5>, wherein the spraying is aerosol deposition.

<7> An image forming method, comprising: forming an image using the electronic device according to any one of <1> to <4>.

<8> An image forming apparatus, comprising: the electronic device according to any one of <1> to <4>.

The electronic device according to any one of <1> to <4>, the method of manufacturing an electronic device according to <5> or <6>, the image forming method according to <7>, and the image forming according to <8> The device can solve the above-mentioned various problems in the field and can achieve the purpose of the present invention.

10A: Electronic device, electrophotographic photoreceptor

51: Conductive support parts

52: middle layer

53: charge generation layer

54: charge transport layer

55: Silicon hard coating

56: metal oxide layer

Claims (8)

An electronic device, including: A supporting part; 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 above the supporting member; and A metal oxide layer disposed on or above the charge transport layer or the sensitizing dye electrode layer, Wherein, the metal oxide layer includes p-type semiconductor metal oxide and silicon dioxide or metal oxide particles, and Wherein, relative to the metal oxide layer, the content of the silicon dioxide or metal oxide particles contained in the metal oxide layer is 0.5% by mass or more but 1.5% by mass or less. The electronic device according to claim 1, wherein the average thickness of the metal oxide layer is 1.2 micrometers or more but 1.8 micrometers or less, and the standard deviation of the thickness of the metal oxide layer is 0.07 micrometers or less. The electronic device according to claim 1, wherein the p-type semiconductor metal oxide is cupronite oxide. The electronic device according to claim 3, wherein the copper-iron ore oxide is copper-aluminum oxide. A method of manufacturing an electronic device, the method comprising: Spraying p-type semiconductor metal oxide and silicon dioxide or metal oxide particles to form a metal oxide layer, Wherein, the electronic device includes: A supporting part; 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 above the supporting member; and The metal oxide layer is arranged on or above the charge transport layer or the sensitizing dye electrode layer. The method of manufacturing an electronic device according to claim 5, wherein the spraying is aerosol deposition. An image forming method includes: forming an image using the electronic device according to any one of claims 1 to 4. An image forming equipment comprising: the electronic device according to any one of claims 1 to 4.

Images