JP2004221496A - Photoelectric conversion device, its manufacturing method, and electronic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a photoelectric conversion device of superior design and to provide the photoelectric conversion device of superior design and a photoelectric apparatus equipped with the same. <P>SOLUTION: The method of manufacturing the photoelectric conversion device comprises processes of forming a first electrode 3 on a substrate 2, forming a dense layer (dense electron transport layer) 41 on the first electrode 3, providing a porous layer (porous electron transport layer) 42 coming into contact with the dense layer 41, depositing a colorant layer D coming into contact with the porous layer 42, forming a hole transport layer 5 coming into contact with the colorant layer D, and providing a second electrode 6 on the hole transport layer 5. At least, one of the first electrode 3, the dense layer 41, the porous layer 42, the colorant layer D, the hole transport layer 5, and the second electrode 6 is so shaped as to have a displaying form X (a part indicating prescribed information or a part forming a prescribed design) by an ink jet method. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for manufacturing a photoelectric conversion element, a photoelectric conversion element, and an electronic device.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, solar cells (photoelectric conversion elements) have attracted attention as environmentally friendly power supplies, and single-crystal silicon-type solar cells used for power supplies for artificial satellites and the like, and solar cells using polycrystalline silicon and amorphous silicon Is widely used for industry and home use. Recently, as a solar cell that can be manufactured at low cost without using a large-scale facility using inexpensive materials, a wet dye-sensitized solar cell (see Patent Document 1) and a dry dye-sensitized solar cell have been proposed. 2. Description of the Related Art A sensitive solar cell (see Patent Document 2) has been proposed.
[0003]
In general, these conventional solar cells cannot be freely designed, and may restrict the design of various devices on which the solar cells are mounted.
That is, conventional solar cells using silicon and dry dye-sensitized solar cells are all limited in shape to a square or the like, and there is no design freedom, and wet dye-sensitized solar cells are Since it has a structure for sealing the electrolyte, it cannot be formed into an arbitrary shape.
[0004]
Further, it is necessary to arrange a solar cell at a position where sunlight can be received for power generation, and to secure a light receiving area capable of securing a required power generation amount. For this reason, in a device equipped with a solar cell, the solar cell must be arranged in a relatively large area at a prominent position on the front surface, which greatly restricts the design of the device equipped with the solar cell. was there. Such a restriction is remarkable in a small device which cannot secure a large installation area for installing a solar cell.
[0005]
[Patent Document 1]
JP-A-2002-252040
[Patent Document 2]
JP-A-2002-314107
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for manufacturing a photoelectric conversion element capable of obtaining a photoelectric conversion element having an excellent design, a photoelectric conversion element having an excellent design, and an electronic device including the photoelectric conversion element.
[0007]
[Means for Solving the Problems]
Such an object is achieved by the present invention described below.
The method for manufacturing a photoelectric conversion element of the present invention includes the steps of: forming a first electrode on a substrate;
Forming at least a partly porous electron transport layer on the first electrode;
Forming a dye layer to contact the electron transport layer;
Forming a hole transport layer to contact the dye layer,
Forming a second electrode on the hole transport layer, the method comprising the steps of:
At least one of the first electrode, the electron transport layer, the dye layer, the hole transport layer, and the second electrode is formed by using a printing method to display predetermined information or a predetermined portion. It is characterized in that it is formed in a shape having a part constituting a design.
Thereby, a photoelectric conversion element excellent in design can be obtained.
[0008]
In the method for manufacturing a photoelectric conversion element according to the aspect of the invention, the dye layer and at least one of the second electrode, the electron transport layer, the hole transport layer, and the first electrode may include the predetermined information. Is preferably formed in a shape having a portion for displaying a symbol or a portion constituting a predetermined design.
Thereby, a photoelectric conversion element having more excellent design properties can be obtained.
[0009]
The method for manufacturing a photoelectric conversion element of the present invention includes the steps of: forming a first electrode on a substrate;
Forming a dense electron transport layer on the first electrode;
Forming a porous electron transport layer to contact the dense electron transport layer;
Forming a dye layer to be in contact with the porous electron transport layer;
Forming a hole transport layer to contact the dye layer,
Forming a second electrode on the hole transport layer, the method comprising the steps of:
At least one of the first electrode, the dense electron transport layer, the porous electron transport layer, the dye layer, the hole transport layer, and the second electrode is formed using a printing method. And a portion having a portion for displaying predetermined information or a portion constituting a predetermined design.
Thereby, a photoelectric conversion element excellent in design can be obtained.
[0010]
In the method for manufacturing a photoelectric conversion element of the present invention, the dye layer, the first electrode, the dense electron transport layer, the porous electron transport layer, the hole transport layer, and the second electrode At least one of them is preferably formed in a shape having a portion for displaying the predetermined information or a portion constituting a predetermined design.
Thereby, a photoelectric conversion element having more excellent design properties can be obtained.
[0011]
In the method for manufacturing a photoelectric conversion element of the present invention, it is preferable that the mask used in the printing method is formed of a metal plate, a resin nonwoven fabric, or a resin film.
[0012]
In the method for manufacturing a photoelectric conversion element according to the aspect of the invention, it is preferable that the mask is fixed with a pressure-sensitive adhesive.
This makes it possible to sharpen the outline of a portion displaying predetermined information or a portion constituting a predetermined design, and to easily install and remove a mask.
[0013]
In the method for manufacturing a photoelectric conversion element according to the aspect of the invention, it is preferable that the predetermined information is a character, a number, a symbol, a graphic, or a segment forming a part thereof.
[0014]
In the method for manufacturing a photoelectric conversion element according to the present invention, after the step of forming the second electrode, a portion for displaying the predetermined information or a predetermined design is formed on a side of the substrate opposite to the first electrode. It is preferable to include a step of forming a decorative portion that borders the contour of the portion to be formed.
Thereby, the outline of a portion displaying predetermined information or a portion forming a predetermined design can be made clearer.
[0015]
The photoelectric conversion element of the present invention is characterized by being manufactured by the method for manufacturing a photoelectric conversion element of the present invention.
Thereby, a photoelectric conversion element excellent in design can be obtained.
[0016]
An electronic device according to the present invention includes the photoelectric conversion element according to the present invention.
Thereby, an electronic device having excellent design properties can be obtained.
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, a method for manufacturing a photoelectric conversion element, a photoelectric conversion element, and an electronic device of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
FIG. 1 is a perspective view showing an embodiment of the photoelectric conversion device of the present invention, FIG. 2 is a sectional view taken along line AA in FIG. 1, and FIGS. 3 and 4 show the photoelectric conversion device shown in FIG. It is the figure seen from the lower side. In the following description, the upper side of the paper in FIGS. 1 and 2 is referred to as “upper” or “upper”, the lower side is referred to as “lower” or “lower”, and the upper side of each layer (each member) is referred to. The “upper surface” and the lower surface are referred to as “lower surface”.
[0018]
The photoelectric conversion element 1 shown in FIG. 1 does not require an electrolyte solution, and is a so-called dry photoelectric conversion element. The photoelectric conversion element 1 includes a substrate 2, a first electrode 3, a dense layer (a dense electron transport layer) 41, a porous layer (a porous electron transport layer) 42, and a dye layer D. , The hole transport layer 5 and the second electrode 6 are stacked in this order. Hereinafter, the configuration of each layer (each part) will be described.
The substrate 2 supports each layer of the first electrode 3, the dense layer 41, the porous layer 42, the dye layer D, the hole transport layer 5, and the second electrode 6, and has a flat (or layered) shape. Of members.
[0019]
In the photoelectric conversion element 1 of the present embodiment, as shown in FIGS. 1 and 2, for example, light such as sunlight (hereinafter, simply referred to as “light”) from the substrate 2 and a first electrode 3 described later. ) Is incident (irradiated). Therefore, each of the substrate 2 and the first electrode 3 is preferably substantially transparent (colorless transparent, colored transparent or translucent). Thereby, light can efficiently reach the dye layer D described later.
Examples of the constituent material of the substrate 2 include various glass materials, various ceramic materials, and various resin materials such as polycarbonate (PC) and polyethylene terephthalate (PET). Further, the substrate 2 may be formed of a single layer or a multilayer of a plurality of layers.
[0020]
The average thickness of the substrate 2 is appropriately set depending on the material, the use, and the like, and is not particularly limited. For example, the average thickness can be as follows.
When the substrate 2 is hard, the average thickness is preferably about 0.1 to 1.5 mm, and more preferably about 0.8 to 1.2 mm. When the substrate 2 has flexibility (flexibility), the average thickness is preferably about 0.5 to 150 μm, and more preferably about 10 to 75 μm.
Note that, for example, when the photoelectric conversion element 1 is mounted on various electronic devices, the components of the electronic device can be used as the substrate 2 of the photoelectric conversion element 1.
[0021]
On the upper surface of the substrate 2, a layered first electrode 3 is provided.
The constituent material of the first electrode 3 is, for example, indium tin oxide (ITO), tin oxide (FTO) doped with fluorine, indium oxide (IO), tin oxide (SnO).₂), Various metal materials such as aluminum, nickel, cobalt, platinum, silver, gold, copper, molybdenum, titanium, tantalum or alloys containing these, and graphite. Various carbon materials and the like, and one or more of them can be used in combination.
[0022]
The average thickness of the first electrode 3 is appropriately set depending on the material, application, and the like, and is not particularly limited. For example, the following can be used.
When the first electrode 3 is made of various metal oxides, the average thickness is preferably about 0.05 to 5 μm, and more preferably about 0.1 to 1.5 μm. When the first electrode 3 is made of various metal materials or various carbon materials, the average thickness is preferably about 0.01 to 1 μm, and is preferably about 0.03 to 0.1 μm. More preferred.
[0023]
An electron transport layer 4 is provided on the upper surface of the first electrode 3. In the present embodiment, the electron transport layer 4 is provided on the dense layer 41 provided on the first electrode 3 side and on the upper surface of the dense layer 41 so as to be in contact with the dense layer 41. And a porous layer 42. The electron transport layer 4 has a function of capturing and transporting electrons generated in the dye layer D described later.
[0024]
The constituent material of the electron transport layer 4 is, for example, titanium dioxide (TiO 2).₂), Titanium monoxide (TiO), dititanium trioxide (Ti₂O₃), Zinc oxide (ZnO), tin oxide (SnO)₂), SrTiO₃, SiO₂, Al₂O₃, SnO₂Such as oxides, carbides such as TiC and SiC, Si₃N₄, B₄Various n-type semiconductor materials such as nitrides such as N and BN, sulfides such as CdS, and selenides such as CdSe can be used, and one or more of these can be used in combination. it can. Among them, it is preferable to use titanium oxide (particularly, titanium dioxide) as a constituent material of the electron transport layer 4. That is, the electron transport layer 4 is preferably made of titanium dioxide as a main material.
[0025]
Titanium dioxide is particularly excellent in the ability to transport electrons. In addition, titanium dioxide has high sensitivity to light, and by forming the electron transport layer 4 using titanium dioxide as a main material, the electron transport layer 4 itself can generate electrons. Thereby, the photoelectric conversion efficiency (power generation efficiency) of the photoelectric conversion element 1 can be further improved. In addition, since titanium dioxide has a stable crystal structure, the electron transport layer 4 containing titanium dioxide as a main material is stable with little aging (deterioration) even when exposed to a severe environment. This has the advantage that performance can be obtained over a long period of time.
[0026]
Further, as titanium dioxide, anatase type titanium dioxide, rutile type titanium dioxide, or a mixture thereof can be used. When a mixture of anatase-type titanium dioxide and rutile-type titanium dioxide is used as the titanium dioxide, the mixing ratio thereof is not particularly limited, but is preferably about 95: 5 to 5:95 by weight. More preferably, it is more preferably about 80:20 to 20:80.
[0027]
The porosity of the dense layer 41 is set smaller than the porosity of the porous layer 42. The dense layer 41 has a function of preventing or suppressing contact between a hole transport layer 5 described below and the first electrode 3. By providing the dense layer 41, it is possible to prevent the photoelectric conversion efficiency (energy conversion efficiency) of the photoelectric conversion element 1 from decreasing.
[0028]
On the other hand, the porosity of the porous layer 42 is set to be relatively large, and has a plurality of holes 421 as shown in FIG. The porous layer 42 is provided so as to be in contact with the dye layer D, as will be described later. By forming the porous layer 42 into a shape having a plurality of holes 421, the dye layer D 42 and the inner surface of the hole 421.
[0029]
Therefore, a sufficient contact area between the dye layer D and the porous layer 42 can be ensured. Thereby, the electrons generated in the dye layer D can be more efficiently transmitted to the electron transport layer 4. Further, the light that has entered the porous layer 42 enters the inside of the porous layer 42 and transmits through the porous layer 42 or is reflected (arbitrarily reflected, diffused, or the like) in an arbitrary direction within the hole 421, The dye in the dye layer D is absorbed with a higher probability, and electrons and holes are more efficiently generated in the dye layer D. Thus, the photoelectric conversion efficiency (energy conversion efficiency) of the photoelectric conversion element 1 can be further improved.
[0030]
From the viewpoint of allowing the dense layer 41 and the porous layer 42 to exhibit their functions, respectively, it is preferable to set the conditions of the dense layer 41 and the porous layer 42 as follows.
When the porosity of the dense layer 41 is A [%] and the porosity of the porous layer 42 is B [%], B / A is preferably 1.1 or more, and more preferably 5 or more. More preferably, it is more preferably 10 or more.
Specifically, the porosity A of the dense layer 41 is preferably less than 20%, more preferably less than 5%, and even more preferably less than 2%. On the other hand, the content of the porous layer 42 is preferably 20% or more, more preferably about 20 to 50%, and still more preferably about 20 to 40%.
[0031]
The ratio of the thickness of the dense layer 41 to the thickness of the porous layer 42 is not particularly limited, but is preferably about 1:99 to 60:40, and is preferably about 10:90 to 40:60. More preferred.
Specifically, the average thickness of the dense layer 41 is preferably about 0.01 to 10 μm, and more preferably about 0.1 to 5 μm. On the other hand, the average thickness of the porous layer 42 is preferably about 0.1 to 300 μm, more preferably about 0.5 to 100 μm, and still more preferably about 1 to 25 μm.
[0032]
The interface between the dense layer 41 and the porous layer 42 is preferably unclear, that is, the dense layer 41 and the porous layer 42 are preferably partially overlapped with each other. Thereby, electrons can be more reliably transmitted from the porous layer 42 to the dense layer 41.
Note that the dense layer 41 may be omitted depending on, for example, the type of a constituent material of the hole transport layer 5 described later. That is, the electron transporting layer 4 may be entirely porous, different from the illustrated configuration. Further, for example, the electron transport layer 4 may have a configuration in which the dense layer 41 is provided in the middle of the thickness direction.
[0033]
The dye layer D is provided so as to contact the porous layer 42. The dye layer D is mainly composed of a dye, and is formed along the outer surface of the porous layer 42 and the inner surface of the holes 421.
The dye layer D (dye) generates electrons and holes by receiving light. Of these, electrons are transmitted to the electron transport layer 4 and holes are transmitted to the hole transport layer 5 described later.
[0034]
For this dye, for example, various pigments and various dyes can be used alone or in combination, but the pigment is transferred to the electron transport layer 4 (porous layer 42) in that there is little deterioration (deterioration) with time. It is preferable to use a dye from the viewpoint of excellent adsorbability.
Examples of the pigment include phthalocyanine pigments, azo pigments, anthraquinone pigments, azomethine pigments, quinophthalone pigments, isoindoline pigments, nitroso pigments, perinone pigments, quinacridone pigments, perylene pigments, and pyrrolopyrrole pigments Pigments, various organic pigments such as dioxazine pigments, carbon pigments, chromate pigments, sulfide pigments, oxide pigments, hydroxide pigments, ferrocyanide pigments, silicate pigments, Various inorganic pigments such as phosphate pigments and others (for example, cadmium sulfide, cadmium selenide, etc.) are exemplified.
[0035]
As the dye, for example, RuL₂(SCN)₂, RuL₂Cl₂, RuL₂(CN)₂, Rutenium 535-bisTBA (manufactured by Solaronics), [RuL₂(NCS)₂]₂H₂Examples include metal complex dyes such as O, cyan dyes, xanthene dyes, azo dyes, hibiscus dyes, blackberry dyes, raspberry dyes, pomegranate juice dyes, chlorophyll dyes, and the like. Note that L in the above composition formula represents 2,2'-bipyridine or a derivative thereof.
[0036]
On the upper surface of the electron transport layer 4 on which the dye layer D is formed, a layered hole transport layer 5 is provided so as to contact the dye layer D. The hole transport layer 5 has a function of capturing and transporting holes generated in the dye layer D.
As a constituent material of the hole transport layer 5, for example, a substance having various ion conductive properties, triphenyldiamine (monomer, polymer, etc.), polyaniline, polypyrrole, polythiophene, a phthalocyanine compound (eg, copper phthalocyanine) or a derivative thereof is used. Such various p-type semiconductor materials can be mentioned, and one or more of these can be used in combination. Among these, as a constituent material of the hole transport layer 5, a substance having an ion conductive property (an ion conductive substance) is particularly preferable. That is, it is preferable that the hole transporting layer 5 is mainly composed of a substance having ion conduction properties. By configuring the hole transport layer 5 using a substance having ion conduction properties as a main material, the hole transport layer 5 can more efficiently capture and transport holes generated in the dye layer D. become able to. Thereby, the photoelectric conversion efficiency (power generation efficiency) of the photoelectric conversion element 1 can be further improved.
[0037]
Examples of the substance having ion conduction properties include iodides such as CuI and AgI, halides such as bromide such as AgBr, and thiocyanates (rhodanides) such as CuSCN. One or two or more of them can be used in combination. Among these, as the substance having ion conduction properties, halides such as iodide and bromide are preferable, and iodide is more preferable. Halides (especially iodides) are particularly excellent in hole transporting ability. Therefore, by forming the hole transport layer 5 using iodide as a main material, the photoelectric conversion efficiency of the photoelectric conversion element 1 can be further improved.
[0038]
Further, as shown in FIG. 2, the hole transport layer 5 is formed by penetrating into the holes 421 of the porous layer 42 on which the dye layer D is formed, and the contact between the dye layer D and the hole transport layer 5 is formed. The area is sufficiently secured. Therefore, holes generated in the dye layer D can be more efficiently transmitted to the hole transport layer 5.
The average thickness of the hole transport layer 5 is not particularly limited, but is preferably about 1 to 500 μm, more preferably about 10 to 300 μm, and still more preferably about 10 to 30 μm.
[0039]
On the upper surface of the hole transport layer 5, a layered second electrode 6 is provided.
As a constituent material of the second electrode 6, for example, various metal materials such as aluminum, nickel, cobalt, platinum, silver, gold, copper, molybdenum, titanium, tantalum, or alloys containing these, or graphite such as Various carbon materials and the like, and one or more of them can be used in combination. In addition, various transparent conductive oxides can be used as the constituent material of the second electrode 6.
The average thickness of the second electrode 6 is appropriately set depending on the material, use, and the like, and is not particularly limited, but is preferably about 0.01 to 5 μm, and more preferably about 0.03 to 1.5 μm. preferable.
[0040]
When light enters the photoelectric conversion element 1 configured as described above from the substrate 2 side, electrons are mainly excited in the dye layer D (dye), and electrons (e⁻) And holes (h⁺) Occurs. Of these, electrons are transmitted to the electron transport layer 4 and holes are transmitted to the hole transport layer 5, and are transported in each layer. Thereby, a potential difference (photoelectromotive force) occurs between the first electrode 3 and the second electrode 6. Then, when the first electrode 3 and the second electrode 6 of the photoelectric conversion element 1 are connected by the external circuit 8, a current (photoexcitation current) flows through the external circuit 8.
[0041]
In such a photoelectric conversion element 1, as shown in FIG. 1, each layer of the first electrode 3, the dense layer 41, the porous layer 42, the dye layer D, the hole transport layer 5, and the second electrode 6 is formed. Are formed in a shape of a capital letter "E" (a shape for displaying predetermined information). Hereinafter, the portion formed in the shape of the alphabetical capital letter “E” is referred to as “display shape portion X”.
[0042]
As described above, the photoelectric conversion element 1 is used with light incident from the substrate 2 side. That is, the photoelectric conversion element 1 is used such that the lower surface of the substrate 2 (the lower surface in FIG. 1) is the front surface. For this reason, in the use state of the photoelectric conversion element 1, the display shape part X of the alphabetical capital letter "E" is visually recognized. Therefore, the photoelectric conversion element 1 is excellent in design.
The area of the display shape portion X in plan view is appropriately set depending on the use and the like, and is not particularly limited.²About 500 to 1000 mm²More preferably, it is about Thereby, the photoelectric conversion efficiency of the photoelectric conversion element 1 can be further improved.
[0043]
In addition, as shown in FIGS. 2 and 3, such a photoelectric conversion element 1 has, on the lower surface of the substrate 2 (the surface opposite to the first electrode 3), a band shape that outlines the contour of the display shape portion X. May be provided. By providing the decorative portion 7, the contour of the display shape portion X can be made clearer. Accordingly, the display shape portion X can be more clearly recognized from the substrate 2 side, which is effective in displaying information of the photoelectric conversion element 1 or in the configuration of the design.
[0044]
It is preferable that the color of the decorative portion 7 and the color of the display shape portion X are selected so as to increase the difference in lightness. For example, a combination of complementary colors or a combination of similar colors having different shades is used. You can choose.
Examples of the constituent material of the decorative portion 7 include various metal materials, various resin materials, and various ceramic materials.
The decorative portion 7 may be provided so as to cover the entire lower surface of the substrate 2 except for a portion corresponding to the display shape portion X, as shown in FIG.
[0045]
Hereinafter, the method for manufacturing the photoelectric conversion element of the present invention will be described in detail.
In the present invention, at least one of the first electrode 3, the dense layer 41, the porous layer 42, the dye layer D, the hole transport layer 5, and the second electrode 6 is formed by using a printing method. Is formed in a shape having a portion for displaying the above information or a portion constituting a predetermined design. Accordingly, a fine shape can be formed with high accuracy without requiring large-scale equipment.
[0046]
5 and 6 are diagrams (longitudinal sectional views) for explaining the method for manufacturing the photoelectric conversion element of the present invention. In the following description, the upper side of the paper in FIGS. 5 and 6 is referred to as “upper” or “upper”, the lower side is referred to as “lower” or “lower”, and the upper side of each layer (each member) is referred to. The “upper surface” and the lower surface are referred to as “lower surface”.
In the present embodiment, each layer (the first electrode 3, the dense layer 41, the porous layer 42, the dye layer D, the hole transport layer 5, and the second electrode 6) of the photoelectric conversion element 1 is printed by a printing method. Is formed in the shape of the display shape portion X.
[0047]
In the printing method, as shown in FIGS. 5 and 6, a mask 90 having a through-hole 901 in the shape of the display shape portion X is used.
In the present embodiment, the mask 90 is fixed to the substrate 2, and a squeegee 91 is used to sweep a liquid containing a constituent material of a layer to be formed or a precursor thereof using a printing method, and supply the liquid into the through-hole 901. The above-described layers are formed.
The viscosity (normal temperature) of the liquid used is not particularly limited, but is usually preferably about 10 to 40 cps, and more preferably about 15 to 30 cps. By setting the viscosity of the liquid used in such a range, handling becomes easy.
[0048]
The mask 90 is not particularly limited as long as the mask 90 has a through hole 901 having a shape corresponding to the shape of the display shape portion X. For example, (I) etching, electroforming, laser processing, press processing, and the like A metal plate formed into a predetermined shape by (1), (II) a resin nonwoven fabric or a resin film formed into a predetermined shape by press working, cutting, or the like is suitably used. These are preferable because they have good solvent resistance (chemical resistance) and heat resistance.
[0049]
As a constituent material of the metal plate, for example, aluminum or an aluminum alloy, stainless steel, brass, nickel silver, or the like can be used.
Examples of the constituent materials of the resin nonwoven fabric and the resin film include, for example, polyester, polyolefin, polyurethane, polyethylene or copolymers, blends, and polymer alloys mainly containing these.
[0050]
Further, as shown in FIGS. 5 and 6, the mask 90 is fixed (fixed) to the upper surface of the substrate 2 by a pressure-sensitive adhesive 92. As a result, the gap between the mask 90 and the substrate 2 is sealed by the pressure-sensitive adhesive 92, so that the liquid for forming each layer can be prevented from flowing out from this gap. As a result, the display shape portion X Can be made sharper. The use of the pressure-sensitive adhesive 92 also has an advantage that the mask 90 can be easily installed and removed.
Examples of such a pressure-sensitive adhesive 92 include acrylic, silicone, polyester, polyurethane, polyether, and rubber-based adhesives, and one or more of them may be used. Can be used in combination.
Note that the pressure-sensitive adhesive 92 can be omitted as necessary.
[0051]
Hereinafter, each step of the method for manufacturing the photoelectric conversion element 1 will be sequentially described.
[1] Formation of first electrode 3
First, the substrate 2 is prepared. As the substrate 2, a substrate having a uniform thickness and no bending is preferably used.
A liquid for forming the first electrode 3 is supplied to the upper surface of the substrate 2 by using a printing method to form the first electrode 3 (see FIG. 5A).
[0052]
For example, the following liquid can be used as the liquid for forming the first electrode 3.
{Circle around (1)} When the first electrode 3 is composed of various metal oxides, various metal materials, and various carbon materials, the liquid for forming the first electrode 3 is a dispersion containing particles composed of these materials. A liquid (suspension) can be used.
In this case, the content of the particles in the liquid for forming the first electrode 3 is not particularly limited, but is preferably about 0.5 to 25 wt%, and more preferably about 2 to 15 wt%.
[0053]
The average particle size of the particles used is not particularly limited, but is preferably about 1 to 30 nm, more preferably about 2 to 10 nm.
Further, it is preferable to use particles coated with an aggregation inhibitor (dispersant) for inhibiting aggregation at room temperature. Examples of the aggregation inhibitor include a compound having a group containing a nitrogen atom such as an alkylamine, a compound having a group containing an oxygen atom such as an alkanediol, and a group containing a sulfur atom such as an alkylthiol and an alkanedithiol. And the like.
[0054]
In this case, a removing agent capable of removing the aggregation inhibitor is added to the liquid for forming the first electrode 3 by a predetermined process (for example, heating). Examples of the removing agent include linear or branched saturated carboxylic acids having 1 to 10 carbon atoms such as formic acid, acetic acid, propionic acid, butanoic acid, hexanoic acid, and octylic acid, acrylic acid, methacrylic acid, and croton. Acids, cinnamic acid, benzoic acid, unsaturated carboxylic acids such as sorbic acid, various carboxylic acids such as oxalic acid, malonic acid, sebacic acid, maleic acid, fumaric acid, and dibasic acids such as itaconic acid; Organic acids such as various phosphoric acids and various sulfonic acids in which a carboxyl group of a carboxylic acid is substituted with a phosphoric acid group or a sulfonyl group, or an organic acid ester thereof, other phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, Benzophenonetetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimeltate) Aromatic acid anhydrides such as maleic anhydride, maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, alkenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride Examples thereof include acids, cyclic aliphatic acid anhydrides such as methylcyclohexenetetracarboxylic anhydride, and aliphatic acid anhydrides such as polyadipic anhydride, polyazeleic anhydride, and polysebacic anhydride.
As the dispersion medium, for example, terpineol, mineral spirit, xylene, toluene, ethylbenzene, mesitylene, hexane, heptane, octane, decane, dodecane, cyclohexane, cyclooctane, or a mixed solution containing these can be used.
[0055]
Further, in the liquid for forming the first electrode 3, phenol resin, epoxy resin, unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, oligoester acrylate resin, xylene resin, bismaleimide triazine resin, furan resin, Precursors of various thermosetting resins such as urea resin, polyurethane resin, melamine resin, and silicone resin may be added (mixed).
The viscosity of the liquid for forming the first electrode 3 can be adjusted, for example, by appropriately setting the content of the particles, the type and composition of the dispersion medium, the presence and the type of the additive, and the like. .
[0056]
{Circle around (2)} When the first electrode 3 is composed of various metal materials, the liquid for forming the first electrode 3 may be a metal salt composed of a metal complex or the like, which is a precursor of the various metal materials, or a reduction liquid. (Suspension) containing the agent.
In this case, the content of the metal in the liquid for forming the first electrode 3 is not particularly limited, but is preferably about 0.1 to 5 wt%, more preferably about 0.5 to 2 wt%. preferable.
The average particle size of the particles to be molded is not particularly limited, but is preferably about 10 to 100 nm, and more preferably about 30 to 70 nm.
[0057]
In addition, examples of the reducing agent include glucose, fructose, hydrazine, and formalin.
As the dispersion medium, for example, methanol, ethanol, water, ethylene glycol, glycerin and the like or a mixed liquid containing these can be used.
The viscosity of the liquid for forming the first electrode 3 can be adjusted by, for example, appropriately setting the metal content, the type and composition of the dispersion medium, and the like.
[0058]
{Circle around (3)} When the first electrode 3 is composed of various metal oxides, a solution containing a precursor of various metal oxides can be used as the liquid for forming the first electrode 3.
Examples of the metal oxide precursor to be used include metal alkoxides, organic metal compounds such as acetic acid or metal salts of acetic acid derivatives, metal chlorides, metal sulfides, and inorganic metal compounds such as metal cyanides. One or more of these can be used in combination.
The concentration (content) of the metal oxide precursor in the liquid for forming the first electrode 3 is not particularly limited, but is preferably about 0.5 to 25 wt%, and is about 2 to 15 wt%. Is more preferred.
[0059]
Examples of the solvent include water, ethylene glycol, glycerin, diethylene glycol, polyhydric alcohols such as triethanolamine, methanol, ethanol, isopropanol, butanol, allyl alcohol, furfuryl alcohol, and ethylene glycol monoacetate. A monovalent alcohol or a mixed solution containing these can be used.
The viscosity of the liquid for forming the first electrode 3 can be adjusted, for example, by appropriately setting the concentration of the metal oxide precursor, the type and composition of the solvent, and the like.
[0060]
A mask 90 is fixed on the upper surface of the substrate 2 via a pressure-sensitive adhesive 92. By using this mask 90, the liquid for forming the first electrode 3 is swept by a squeegee 91 and supplied into the through-hole 901 to form a film (thin film or thick film).
Next, after removing the mask 90, the film is subjected to, for example, heat treatment or irradiation with ultraviolet rays, electron beams, radiation, or the like.
If necessary, the above operation is repeated to form the first electrode 3 having a desired thickness.
[0061]
[2] Formation of electron transport layer 4
Next, the electron transport layer 4 is formed on the upper surface of the first electrode 3. Hereinafter, a case where the electron transport layer 4 mainly composed of titanium dioxide is formed will be described as an example.
[2-1] Formation of dense layer 41
First, a liquid for forming the dense layer 41 is supplied to the upper surface of the first electrode 3 by a printing method to form the dense layer 41 (see FIG. 5B).
[0062]
As the liquid for forming the dense layer 41, for example, a solution containing a precursor of titanium dioxide can be used.
As a precursor of titanium dioxide, for example, titanium titanium alkoxide such as titanium tetraisopropoxide (TPT), titanium tetramethoxide, titanium tetraethoxide, titanium tetrabutoxide, and organic titanium such as titanium oxyacetylacetonate (TOA) Examples thereof include compounds and inorganic titanium compounds such as titanium tetrachloride (TTC), and one or more of these can be used as a mixture.
[0063]
The concentration (content) of the titanium dioxide precursor in the liquid for forming the dense layer 41 is not particularly limited, but is preferably about 0.1 to 10 mol / L, and about 0.5 to 5 mol / L. Is more preferable.
Further, as the solvent, for example, anhydrous ethanol, 2-butanol, 2-propanol, 2-n-butoxyethanol, propylene glycol, monobutyl ether, or a mixed solution containing these can be used.
[0064]
When using titanium alkoxide as a precursor of titanium dioxide, it is preferable to add various additives such as titanium tetrachloride, acetic acid, acetylacetone, and triethanolamine in the liquid for forming the dense layer 41. . Thereby, the hydrolysis reaction of the titanium alkoxide can be suppressed. The mixing ratio of this additive and titanium alkoxide is not particularly limited, but is preferably about 1: 2 to 8: 1 in molar ratio.
[0065]
The viscosity of the liquid for forming the dense layer 41 may be determined, for example, by appropriately setting the concentration of the titanium dioxide precursor, the type and composition of the solvent, the presence or absence of the additive, the type, the composition and the concentration, and the like. Can be adjusted.
A mask 90 thicker than the mask 90 used in the step [1] is fixed on the upper surface of the substrate 2 via a pressure-sensitive adhesive 92. Using this mask 90, the liquid for forming the dense layer 41 is swept by a squeegee 91 and supplied into the through-hole 901 to form a film (thin film or thick film).
[0066]
Next, after removing the mask 90, the film is subjected to a heat treatment (drying). Thereby, the solvent is volatilized and removed. The condition of this heat treatment is preferably about 50 to 250 ° C. × 1 to 60 minutes, more preferably about 100 to 200 ° C. × 5 to 30 minutes. The atmosphere for the heat treatment can be, for example, air, nitrogen gas, an inert gas, or a non-oxidizing atmosphere such as a vacuum or reduced pressure state.
[0067]
Further, the film is subjected to a heat treatment (firing) at a higher temperature than the heat treatment. As a result, the organic components (solvent, additives, and the like) remaining in the film can be removed, and amorphous or anatase-type titanium dioxide is generated. The conditions of this heat treatment are preferably about 300 to 700 ° C for about 1 to 70 minutes, and more preferably about 400 to 550 ° C for about 5 to 45 minutes. The atmosphere for the heat treatment may be the same as the above.
[0068]
When a substrate mainly composed of a resin material (flexible substrate) is used as the substrate 2, it is preferable to perform a hydrothermal synthesis process (hydrothermal treatment) on the film.
Here, the hydrothermal synthesis means that the membrane is treated with high-pressure steam (saturated steam). Specifically, the hydrothermal synthesis treatment is performed by storing the substrate on which the film is formed in a closed container together with a small amount of water and heating the closed container. In the closed container, water becomes water vapor by heating, and the pressure in the closed container increases. The high-pressure steam removes the organic components present in the film, and at the same time, a hydrolysis reaction proceeds to the titanium dioxide precursor to form amorphous titanium dioxide. According to the hydrothermal synthesis process, there is an advantage that the film can be processed at a relatively low temperature at which water evaporates (for example, about 100 to 200 ° C.).
[0069]
The above operation is repeated as necessary to form the dense layer 41 having a desired thickness.
Prior to the formation of the dense layer 41, for example, O₂The organic substances adhering to the upper surface of the first electrode 3 may be removed by performing a plasma treatment, an EB treatment, a cleaning treatment with an organic solvent (for example, ethanol, acetone, or the like), or the like.
[0070]
[2-2] Formation of porous layer 42
Next, a liquid for forming the porous layer 42 is supplied to the upper surface of the dense layer 41 using a printing method to form the porous layer 42 (see FIG. 5C).
As the liquid for forming the porous layer 42, for example, a dispersion liquid (sol liquid) containing titanium dioxide powder and a precursor of titanium dioxide can be used. Thereby, the porous layer 42 having the above-described configuration can be relatively easily obtained.
As the titanium dioxide powder (particles) to be used, any of anatase type titanium dioxide powder alone, rutile type titanium dioxide powder alone or a mixture thereof may be used.
[0071]
The average particle size of the titanium dioxide powder is not particularly limited, but is preferably about 1 nm to 1 μm, more preferably about 1 to 100 nm, and still more preferably about 5 to 50 nm. Thereby, the titanium dioxide powder can be more uniformly dispersed in the liquid for forming the porous layer 42, and the control of the pore form (for example, the porosity, the distribution of the pores, etc.) of the porous layer 42 is easy. It becomes.
[0072]
When a mixture of anatase-type titanium dioxide powder and rutile-type titanium dioxide powder is used, these two types of powders may have different or different average particle diameters. .
The content of the titanium dioxide powder in the liquid for forming the porous layer 42 is not particularly limited, but is preferably about 0.1 to 10 wt%, and more preferably about 0.5 to 5 wt%.
[0073]
The liquid for forming the porous layer 42 can be prepared as follows.
That is, first, a liquid similar to the liquid for forming the dense layer 41 described above is prepared. The concentration (content) of the titanium dioxide precursor in this liquid is not particularly limited, but is preferably about 0.1 to 3 mol / L, and is preferably about 0.5 to 2 mol / L. More preferred.
[0074]
Next, water is mixed with the liquid. The mixing ratio of the water and the titanium dioxide precursor is not particularly limited, but is preferably about 1: 4 to 4: 1 in molar ratio.
Next, a liquid for forming the porous layer 42 is obtained by mixing titanium dioxide powder with the mixed liquid. The liquid for forming the porous layer 42 may be diluted with a solvent used for the liquid for forming the dense layer 41, if necessary, for example.
The viscosity of the liquid for forming the porous layer 42 is, for example, the content of the titanium dioxide powder, the concentration of the titanium dioxide precursor, the type and composition of the solvent, the presence or absence of the additive, the type, the composition and the concentration. It can be adjusted by appropriately setting the degree of dilution (dilution ratio) and the like.
[0075]
A mask 90 thicker than the mask 90 used in the step [2-1] is fixed on the upper surface of the substrate 2 via a pressure-sensitive adhesive 92. Using this mask 90, the liquid for forming the dense layer 41 is swept by a squeegee 91 and supplied into the through-hole 901 to form a film (thin film or thick film).
At this time, it is preferable to supply the liquid for forming the porous layer 42 to the upper surface of the dense layer 41 while heating the dense layer 41. The heating temperature is not particularly limited, but is preferably about 80 to 180 ° C, more preferably about 100 to 160 ° C.
[0076]
Next, this film may be subjected to a heat treatment (for example, baking or the like) as necessary. The condition of this heat treatment is preferably, for example, a temperature of 250 to 500 ° C. × 0.5 to 3 hours.
When a substrate (flexible substrate) mainly composed of a resin material is used as the substrate 2, the above-described hydrothermal synthesis process (hydrothermal treatment) may be performed instead of this heat treatment. Good.
If necessary, the above operations are repeated to form the porous layer 42 having a desired thickness.
[0077]
[3] Formation of dye layer D
Next, a liquid for forming the dye layer D is supplied to the upper surface of the porous layer 42 (electron transport layer 4) using a printing method to form the dye layer D (see FIG. 5D).
As the liquid for forming the dye layer D, for example, a solution or a dispersion (suspension) containing a dye can be used.
The concentration (content) of the dye in the liquid for forming the dye layer D is not particularly limited, but is preferably about 0.01 to 1 wt%, more preferably about 0.05 to 0.1 wt%. preferable.
[0078]
Examples of the solvent or the dispersion medium include water, methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, ether, methylene chloride, NMP (N-methyl-2-pyrrolidone), glycerin, polyethylene glycol, monobutyl ether and the like. A mixed solution containing the same can be used.
The viscosity of the liquid for forming the dye layer D can be adjusted by, for example, appropriately setting the concentration of the dye, the type and composition of the solvent or the dispersion medium, and the like.
[0079]
A mask 90 thicker than the mask 90 used in the step [2-2] is fixed on the upper surface of the substrate 2 via a pressure-sensitive adhesive 92. Using this mask 90, the liquid for forming the dye layer D is swept with a squeegee 91 to supply the liquid into the through-hole 901 to form a film (thin film or thick film).
Next, after removing the mask 90, the solvent is removed by, for example, a method of natural drying, a method of blowing a gas such as air or nitrogen gas, or the like. Further, if necessary, drying may be performed by performing a heat treatment or the like at, for example, about 60 to 100 ° C. × about 0.5 to 2 hours. As a result, the dye is adsorbed (chemically adsorbed), bonded (covalent bond, coordinate bond) or the like on the outer surface of the porous layer 42 and the inner surface of the pore 421, for example.
If necessary, the above operation is repeated to form the dye layer D having a desired thickness.
[0080]
[4] Formation of hole transport layer 5
Next, a liquid for forming the hole transport layer 5 is supplied to the upper surface of the porous layer 42 (electron transport layer 4) on which the dye layer D is formed by using a printing method, and the hole transport layer 5 is formed. It is formed (see FIG. 6E). Hereinafter, a case in which the hole transport layer 5 mainly formed of a substance having ion conduction properties (ion conductive substance) will be described as an example.
[0081]
As the liquid for forming the hole transport layer 5, for example, a solution containing a substance having ion conduction properties can be used.
The concentration (content) of the substance having ion conduction properties in the liquid for forming the hole transport layer 5 is not particularly limited, but may be 5 × 10 5^-4About 0.1 mol / L, preferably 5 × 10^-3~ 5 × 10^-2More preferably, it is about mol / L.
Further, as the solvent, for example, water, acetonitrile, ethanol, methanol, isopropyl alcohol, glycerin, polyethylene glycol, monobutyl ether or a mixed solution containing these can be used, and among these, acetonitrile is particularly preferable.
[0082]
When a substance having ion conduction properties is used as a constituent material of the hole transport layer 5, it is preferable to add a cyanoethylated compound such as cyanoresin as a binder in the liquid for forming the hole transport layer 5. . In this case, the concentration (content) of the cyanoethylated compound in the liquid for forming the hole transport layer 5 is not particularly limited, but is 1 × 10^-6Preferably, the content is about 1 to 10 wt%.^-4~ 1 × 10^-2More preferably, it is about wt%.
In addition, it is preferable to add a hole transport efficiency improving substance having a function of improving hole transport efficiency to the liquid for forming the hole transport layer 5. Thereby, the carrier mobility (hole transport ability) of the hole transport layer 5 can be further improved.
[0083]
As the hole transport efficiency improving substance, for example, various halides such as ammonium halide can be used, and tetrapropylammonium iodide (TPAI) is particularly preferable.
The concentration (content) of the hole transport efficiency improving substance in the liquid for forming the hole transport layer 5 is not particularly limited, but is 1 × 10 5^-4~ 1 × 10^-1It is preferably about 1% by weight.^-4~ 1 × 10^-2More preferably, it is about wt%. Thereby, the effect can be further improved.
[0084]
Further, in the liquid for forming the hole transport layer 5, it is preferable to add a crystal size coarsening suppressing substance that suppresses an increase in the crystal size when the substance having ion conduction properties crystallizes. . This prevents or suppresses an increase in the crystal size of the substance having ion conduction properties during crystallization. Therefore, inconveniences such as generation of cracks in the electron transport layer 4 and a decrease in contact between the dye layer D and the hole transport layer 5 can be suitably prevented. As a result, deterioration (deterioration) of characteristics such as the photoelectric conversion efficiency of the photoelectric conversion element 1 can be prevented.
[0085]
Examples of the crystal size coarsening suppressing substance include, for example, sodium cyanide (NaSCN), potassium thiocyanate (KSCN), copper thiocyanate (CuSCN), and thiocyanate, in addition to the cyanoethylated compound and the hole transport efficiency improving substance described above. Ammonium salt (NH₄One or a combination of two or more of thiocyanates (rhodanides) such as SCN) can be used.
[0086]
The concentration (content) of the crystal size coarsening suppressing substance in the liquid for forming the hole transport layer 5 is not particularly limited, but is 1 × 10^{− 6}It is preferably about 10 to 10% by weight.^-4~ 1 × 10^-2More preferably, it is about wt%. Thereby, the effect can be further improved.
The viscosity of the liquid for forming the hole transport layer 5 may be, for example, the type, composition and concentration of the constituent material of the hole transport layer, the type and concentration of the hole transport efficiency improving substance, and the type and composition of the solvent. It can be adjusted by appropriately setting the presence / absence, type, concentration and the like of the additive.
[0087]
A mask 90 thicker than the mask 90 used in the step [3] is fixed on the upper surface of the substrate 2 via a pressure-sensitive adhesive 92. Using this mask 90, the liquid for forming the hole transport layer 5 is swept by a squeegee 91 to supply the liquid into the through-hole 901 to form a film (thin film or thick film).
At this time, the droplet 70 is landed (supplied) on the upper surface of the porous layer 42 on which the dye layer D is formed while heating the dye layer D (the porous layer 42 on which the dye layer D is formed). preferable. The heating temperature is not particularly limited, but is preferably about 50 to 150 ° C, more preferably about 80 to 100 ° C.
If necessary, the above operation is repeated to form the hole transport layer 5 having a desired thickness.
[0088]
[5] Formation of second electrode 6
Next, a liquid for forming the second electrode 6 is supplied to the upper surface of the hole transport layer 5 by a printing method to form the second electrode 6 (see FIG. 6F).
The second electrode 6 can be formed in the same manner as in the step [1].
[0089]
[6] Formation of decorative part 7
Next, the decorative portion 7 is formed on the lower surface of the substrate 2 (see FIG. 6G).
The decorative portion 7 can be formed by, for example, a method using a printing method, an inkjet method, or the like, a method of bonding a sheet-shaped member, a method of bonding a decorative metal member, or the like.
Through the steps described above, the photoelectric conversion element 1 is manufactured.
[0090]
In the present embodiment, the case where one photoelectric conversion element 1 is manufactured alone has been described. However, the method for manufacturing a photoelectric conversion element according to the present invention includes manufacturing a plurality of photoelectric conversion elements 1 at the same time, The present invention can also be applied to so-called multi-cavity manufacturing in which the photoelectric conversion element 1 is separated and manufactured.
A new mask 90 may be used for each of the steps [1] to [5], or a common mask may be used in two or more successive steps.
[0091]
Although the photoelectric conversion element 1 described above has a configuration in which one display shape portion X is provided, a plurality of display shape portions X may be provided in the present invention.
In the photoelectric conversion element 1 of the present embodiment, each of the first electrode 3, the dense layer 41, the porous layer 42, the dye layer D, the hole transport layer 5, and the second electrode 6 is substantially the same. In the present invention, the first electrode 3, the dense layer 41, the porous layer 42, the dye layer D, the hole transport layer 5, and the second electrode 6 are formed. The display shape part X may be constituted by at least one of the above. That is, in the present invention, at least one of the first electrode 3, the dense layer 41, the porous layer 42, the dye layer D, the hole transport layer 5, and the second electrode 6 has the shape of the display shape portion X. What is necessary is just to be formed. From the viewpoint of making the photoelectric conversion element 1 more excellent in design, it is preferable that the dye layer D and at least one of the other layers are formed in the shape of the display shape portion X.
[0092]
Further, as in the above-described embodiment, the shape of the display shape portion X is not limited to a character, and may be a shape for displaying predetermined information such as a symbol, a graphic, or a segment constituting a part thereof. Or, it may be a shape constituting a predetermined design.
Further, in the above embodiment, each layer is entirely formed in the shape of the display shape portion X, but may be configured to have the shape of the display shape portion X in a part.
[0093]
An electronic device of the present invention includes such a photoelectric conversion element 1.
Hereinafter, the electronic device of the present invention will be described with reference to FIGS.
FIG. 7 is a plan view showing a calculator to which the electronic device of the present invention is applied, and FIG. 8 is a perspective view showing a mobile phone (including PHS) to which the electronic device of the present invention is applied.
The calculator 100 shown in FIG. 7 includes a main body 101, a display section 102 provided on the upper surface (front surface) of the main body 101, a plurality of operation buttons 103, and a photoelectric conversion element installation section 104.
[0094]
In the configuration illustrated in FIG. 7, the photoelectric conversion element installation unit 104 includes the display shape parts X each having a capital letter “E”, “P”, “S”, “O”, and “N”. Are connected in series and arranged.
This allows the photoelectric conversion element 1 to be used as a power source and also to be used as an element for displaying information, so that the design of the calculator 100 can be improved. Further, a place for separately installing a photoelectric conversion element can be omitted, which is advantageous.
[0095]
A mobile phone 200 shown in FIG. 8 includes a main body 201, a display 202 provided on the front surface of the main body 201, a plurality of operation buttons 203, an earpiece 204, a mouthpiece 205, and a photoelectric conversion element installation part 206. Have.
In the configuration illustrated in FIG. 8, the photoelectric conversion element installation unit 206 is provided so as to surround the periphery of the display unit 202, and a plurality of photoelectric conversion elements 1 including a display shape part X that forms a square in plan view are connected in series. Are located.
[0096]
In this case, the photoelectric conversion element 1 can be arranged in an inconspicuous manner, and does not hinder the design of the mobile phone 200, thereby making the mobile phone 200 excellent in design.
In addition, by providing the photoelectric conversion element 1 with a function as a power supply and a function of displaying information, a place for separately installing the photoelectric conversion element can be omitted, which is advantageous.
Note that the electronic device of the present invention can be applied to, for example, an optical sensor, an optical switch, an electronic notebook, an electronic dictionary, a wristwatch, a clock, and the like, in addition to the calculator shown in FIG. 7 and the mobile phone shown in FIG.
[0097]
As described above, according to the present invention, it is possible to release the design restrictions of the conventional photoelectric conversion element and obtain a photoelectric conversion element excellent in design.
Further, in the photoelectric conversion element of the present invention, a function as a power supply and a function of displaying information (or a function of forming a design) can be combined, so that a place for separately installing a photoelectric conversion element is omitted. Can be. For this reason, the photoelectric conversion element of the present invention is particularly suitable for application to small devices.
In addition, setting the color of the dye layer in accordance with the location of the photoelectric conversion element, design requirements, and the like is effective in improving the design.
Further, according to the method for manufacturing a photoelectric conversion element of the present invention, a photoelectric conversion element can be manufactured inexpensively and efficiently.
[0098]
As described above, the illustrated embodiment of the method for manufacturing a photoelectric conversion element, the photoelectric conversion element, and the electronic apparatus of the present invention has been described. However, the present invention is not limited to this, and the configuration of each unit has the same function. The structure can be replaced with any structure to be exhibited, and another structure (for example, one or more layers for any purpose between layers) may be added.
[Brief description of the drawings]
FIG. 1 is a perspective view showing an embodiment of a photoelectric conversion element of the present invention.
FIG. 2 is a sectional view taken along line AA in FIG.
FIG. 3 is a view of the photoelectric conversion element shown in FIG. 1 as viewed from below.
FIG. 4 is a view of the photoelectric conversion element shown in FIG. 1 as viewed from below.
FIG. 5 is a diagram illustrating a method for manufacturing a photoelectric conversion element according to the present invention.
FIG. 6 is a diagram illustrating a method for manufacturing a photoelectric conversion element according to the present invention.
FIG. 7 is a plan view showing a calculator to which the electronic apparatus according to the invention is applied.
FIG. 8 is a perspective view showing a mobile phone to which the electronic device according to the invention is applied.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Photoelectric conversion element 2 ... Substrate 3 ... 1st electrode 4 ... Electron transport layer 41 ... Dense layer 42 ... Porous layer 421 ... Hole 5 ... Hole transport layer 6 ... Second electrode 7 Decorative part 8 External circuit D Dye layer X Display shape part 90 Mask 901 Through hole 91 Squeegee 92 Pressure sensitive adhesive 100 Calculator 101 ...... Main unit 102 ... Display unit 103 ... Operation buttons 104 ... Photoelectric conversion element installation unit 200 ... Mobile phone 201 ... Main unit 202 ... Display unit 203 ... Operation buttons 204 ... Mouthpiece 206 ... Photoelectric conversion element installation part

Claims (10)

Forming a first electrode on the substrate;
Forming at least a partly porous electron transport layer on the first electrode;
Forming a dye layer to contact the electron transport layer;
Forming a hole transport layer to contact the dye layer,
Forming a second electrode on the hole transport layer, the method comprising the steps of:
At least one of the first electrode, the electron transport layer, the dye layer, the hole transport layer, and the second electrode is formed by using a printing method to display predetermined information or a predetermined portion. A method for manufacturing a photoelectric conversion element, comprising forming a shape having a part constituting a design. The dye layer and at least one of the second electrode, the electron transport layer, the hole transport layer, and the first electrode constitute a portion for displaying the predetermined information or a predetermined design. The method for manufacturing a photoelectric conversion element according to claim 1, wherein the photoelectric conversion element is formed into a shape having a portion. Forming a first electrode on the substrate;
Forming a dense electron transport layer on the first electrode;
Forming a porous electron transporting layer to contact the dense electron transporting layer,
Forming a dye layer to be in contact with the porous electron transport layer;
Forming a hole transport layer to contact the dye layer,
Forming a second electrode on the hole transport layer, the method comprising the steps of:
At least one of the first electrode, the dense electron transport layer, the porous electron transport layer, the dye layer, the hole transport layer, and the second electrode is formed using a printing method. A method for manufacturing a photoelectric conversion element, comprising: forming a portion having a portion for displaying predetermined information or a portion constituting a predetermined design. The dye layer and at least one of the first electrode, the dense electron transport layer, the porous electron transport layer, the hole transport layer, and the second electrode are connected to the predetermined information. The method for manufacturing a photoelectric conversion element according to claim 3, wherein the photoelectric conversion element is formed into a shape having a portion that displays a symbol or a portion that forms a predetermined design. The method for manufacturing a photoelectric conversion element according to claim 1, wherein the mask used in the printing method is formed of a metal plate, a resin nonwoven fabric, or a resin film. The method according to claim 5, wherein the mask is fixed with a pressure-sensitive adhesive. The method for manufacturing a photoelectric conversion element according to claim 1, wherein the predetermined information is a character, a number, a symbol, a graphic, or a segment constituting a part thereof. After the step of forming the second electrode, a decorative portion is formed on the opposite side of the substrate from the first electrode to border a contour of a portion displaying the predetermined information or a portion constituting a predetermined design. The method for manufacturing a photoelectric conversion element according to claim 1, further comprising: A photoelectric conversion element manufactured by the method for manufacturing a photoelectric conversion element according to claim 1. An electronic device comprising the photoelectric conversion element according to claim 9.

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