JP2007194000A - Method of manufacturing composition for forming photoelectric conversion layer, composition for forming photoelectric conversion later, method of manufacturing photoelectric conversion element, photoelectric conversion element, and electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the method of manufacturing a composition for forming a photoelectric conversion layer capable of manufacturing the composition for forming the photoelectric conversion layer capable of efficiently manufacturing the photoelectric conversion layer; to provide the composition for forming the photoelectric conversion layer manufactured by this method; to provide the method of manufacturing the photoelectric conversion element capable of simplifying a manufacturing process and suppressing the amount of dye used; to provide the photoelectric conversion element manufactured by this method, and to provide electronic equipment having the photoelectric conversion element. <P>SOLUTION: A solar cell 1 has a substrate 2, a first electrode 3, a second electrode 6, a counter substrate 7, the photoelectric conversion layer 4 positioned on the first electrode 3 side between the electrodes 3, 6, and a hole transport layer 5 coming in contact with the photoelectric conversion layer 4. The photoelectric conversion layer 4 can be formed through a process obtaining aggregate particles by aggregating particles of electron transport material, a process carrying dye in the aggregate particles, and a process dispersing the aggregate particles carried with dye into a dispersion medium and obtaining the composition for forming the photoelectric conversion layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a composition for forming a photoelectric conversion layer, a composition for forming a photoelectric conversion layer, a method for producing a photoelectric conversion element, a photoelectric conversion element, and an electronic apparatus.

  2. Description of the Related Art Conventionally, photoelectric conversion elements using silicon, so-called solar cells, have attracted attention as environmentally friendly power supplies. Among solar cells using silicon, there are single crystal silicon type solar cells used for artificial satellites and the like. However, as practical ones, especially solar cells using polycrystalline silicon and amorphous silicon are used. Practical use of solar cells for industrial use and home use has begun.

However, all of these solar cells using silicon are expensive to manufacture and require a great deal of energy for manufacturing, and thus cannot always be said to be energy-saving power sources.
A dye-sensitized solar cell that has been developed as a next-generation solar cell that replaces this and has low manufacturing cost and low manufacturing energy has been proposed (see, for example, Patent Documents 1 and 2).

  However, in the production of such a dye-sensitized solar cell, generally, after the dye is adsorbed to the electron transport layer, it is necessary to remove excess dye by washing or the like, which requires a large amount of washing equipment and a lot of work. It is said. In addition, although the dyes used in the dye-sensitized solar cell are expensive, many of them are discarded by washing, resulting in an increase in manufacturing cost.

In addition, according to such a manufacturing method, for example, in a single dye-sensitized solar cell, when different color dyes are supplied to regions separated from each other, the dyes are mixed with each other at the time of cleaning. The saturation and vividness of the image are reduced. For this reason, it is difficult to use a plurality of types of dyes in a region subjected to the same cleaning process.
Furthermore, the electron transport layer is generally obtained by applying a liquid material containing semiconductor particles on the base layer and firing it. However, at this time, a high temperature treatment of 300 ° C. or higher is required. The constituent material of the substrate that supports the transport layer and the like was limited.

JP 2002-252040 A JP 2002-314107 A

  The objective of this invention is the manufacturing method of the composition for photoelectric conversion layer formation which can manufacture the composition for photoelectric conversion layer formation which can manufacture a photoelectric conversion layer efficiently, The composition for photoelectric conversion layer formation manufactured by this method To provide a method for manufacturing a photoelectric conversion element that can simplify the manufacturing process and reduce the amount of dye used, a photoelectric conversion element manufactured by such a method, and an electronic device including the photoelectric conversion element. is there.

Such an object is achieved by the present invention described below.
The method for producing a composition for forming a photoelectric conversion layer of the present invention is a method for producing a composition for forming a photoelectric conversion layer used for forming a photoelectric conversion layer provided in a photoelectric conversion element,
Collecting the electron transport material to obtain aggregate particles of the electron transport material;
A step of supporting a dye on the aggregated particles;
A step of dispersing aggregated particles carrying the dye in a dispersion medium to obtain a composition for forming a photoelectric conversion layer.
Thereby, the composition for photoelectric conversion layer formation which can manufacture a photoelectric converting layer efficiently can be obtained.

In the method for producing a composition for forming a photoelectric conversion layer of the present invention, it is preferable that the dye is supported on the aggregated particles by bringing the aggregated particles into contact with a dye solution containing the dye.
Thereby, the pigment | dye can be efficiently carry | supported collectively with respect to the particle | grains of a lot of electron transport materials.
In the manufacturing method of the composition for photoelectric conversion layer formation of this invention, it is preferable that the time of the said immersion is 1 to 30 hours.
Thereby, a sufficient amount of the dye can be carried on the aggregated particles.

In the manufacturing method of the composition for photoelectric conversion layer formation of this invention, it is preferable that the temperature of the pigment solution which immerses the said aggregated particle is 10-40 degreeC.
Thereby, the pigment | dye can be efficiently carry | supported with respect to the particle | grains of an electron transport material, preventing the discoloration accompanying the alteration of a pigment | dye, the fall of photoelectric conversion ability, etc.
In the method for producing a composition for forming a photoelectric conversion layer of the present invention, it is preferable that the aggregated particles are obtained by partially joining the electron transport materials by subjecting a plurality of the electron transport materials to a heat treatment. .
Thereby, the particles of the electron transport material can be partially efficiently joined (necked) to obtain aggregate particles.

In the method for producing a composition for forming a photoelectric conversion layer of the present invention, the aggregate particles preferably have an average particle size of 20 to 100 nm.
This makes it possible to apply the liquid material to, for example, a droplet discharge method while appropriately bonding the particles of the electron transport material. That is, a liquid material capable of forming a photoelectric conversion layer having excellent characteristics can be obtained while preventing the liquid material from staying in the discharge nozzle.
In the manufacturing method of the composition for photoelectric conversion layer formation of this invention, it is preferable that the number of the electron transport material which comprises one said aggregate particle is 2-100 pieces.
Thereby, the surface area of the aggregate particles becomes sufficiently large, and the amount of the dye supported on the aggregate particles can be increased.

The composition for forming a photoelectric conversion layer of the present invention is manufactured by the method for manufacturing a composition for forming a photoelectric conversion layer of the present invention.
Thereby, the composition for photoelectric conversion layer formation which can manufacture a photoelectric converting layer efficiently is obtained.
The method for producing a photoelectric conversion element of the present invention is a photoelectric conversion element for producing a photoelectric conversion element having a photoelectric conversion layer containing aggregated particles of an electron transport material and a dye between a first electrode and a second electrode. A manufacturing method of
A first step of forming a liquid film by supplying the photoelectric conversion layer forming composition of the present invention to one surface side of the first electrode;
And a second step of forming the photoelectric conversion layer by removing the dispersion medium from the liquid film.
Thereby, while simplifying the manufacturing process of a photoelectric conversion element, the usage-amount of a pigment | dye can be suppressed.

In the method for producing a photoelectric conversion element of the present invention, in the first step, the composition for forming a photoelectric conversion layer is preferably supplied by a droplet discharge method while controlling a supply position.
Thereby, liquid material can be supplied, controlling a supply position with high precision. In addition, a plurality of types of liquid materials can be supplied so as not to be mixed with each other. As a result, contamination (contamination), alteration, and the like of the liquid material due to mixing can be reliably prevented.

In the method for manufacturing a photoelectric conversion element of the present invention, in the first step, the liquid coating or the aggregate thereof preferably constitutes predetermined information or a predetermined design.
Thus, the photoelectric conversion layer formed from the liquid film has predetermined information (characters, numbers, symbols, figures, or segments constituting a part thereof) or a portion constituting a predetermined design.

In the method for producing a photoelectric conversion element of the present invention, in the first step, a plurality of types of the composition for forming a photoelectric conversion layer containing the dyes of different colors are selectively supplied, whereby a plurality of the plurality of compositions separated from each other are provided. The liquid coating preferably constitutes an image as a whole.
Thereby, for example, it is possible to form a photoelectric conversion element excellent in design utilizing a color of a pigment such as a photograph or a painting.

In the method for producing a photoelectric conversion element of the present invention, it is preferable that a plurality of the liquid films are formed in a matrix in the first step.
Thereby, one liquid film can be handled as one of the pixels (pixels) forming the image. A photoelectric conversion element that can display an image with more excellent designability can be manufactured.

In the manufacturing method of the photoelectric conversion element of this invention, it is preferable that the planar area of one said liquid film is 100-10000 micrometer < ² >.
A pixel having such a size can prevent a significant decrease in carrier mobility in the surface, that is, a significant decrease in photoelectric conversion efficiency, and can display a precise image with excellent design.
In the method for manufacturing a photoelectric conversion element of the present invention, it is preferable to have a step of forming a partition for defining the contour shape of the liquid film prior to the first step.
Thereby, the outline shape of a liquid film can be prescribed | regulated and the photoelectric converting layer of desired shape (contour shape and thickness) can be formed.

The manufacturing method of the photoelectric conversion element of this invention manufactures the photoelectric conversion element which manufactures the photoelectric conversion layer which has a photoelectric converting layer containing an electron transport material and a pigment | dye between the 1st electrode and the 2nd electrode. Because
A first step of preparing a composition for forming a photoelectric conversion layer in which the electron transport material carrying the dye is dispersed in a dispersion medium;
And a second step of supplying the composition for forming a photoelectric conversion layer to one surface side of the first electrode by a droplet discharge method.
Thereby, while simplifying the manufacturing process of a photoelectric conversion element, the usage-amount of a pigment | dye can be suppressed.

The photoelectric conversion element of the present invention is manufactured by the method for manufacturing a photoelectric conversion element of the present invention.
Thereby, the photoelectric conversion element excellent in the designability is obtained.
In the photoelectric conversion element of the present invention, it is preferable that the photoelectric conversion layer or the aggregate thereof constitute predetermined information or a predetermined design.
As a result, for example, a photoelectric conversion element that can be used as part of an advertising medium such as a signboard or a poster or a design of clothes, a bag, or the like is obtained.
The electronic device of the present invention includes the photoelectric conversion element of the present invention.
Thereby, an electronic device with a high design freedom is obtained.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a preferred embodiment of a method for producing a composition for forming a photoelectric conversion layer, a composition for forming a photoelectric conversion layer, a method for producing a photoelectric conversion element, a photoelectric conversion element and an electronic device according to the present invention will be described in detail. To do.
First, the case where the photoelectric conversion element of this invention is applied to a solar cell is demonstrated to an example.
FIG. 1 is a partial cross-sectional view showing an embodiment in which the photoelectric conversion element of the present invention is applied to a solar cell, FIG. 2 is a cross-sectional view (schematic diagram) of the solar cell shown in FIG. These are the figures for demonstrating the manufacturing method of the solar cell shown in FIG. 1 and FIG.

A solar cell 1 shown in FIG. 1 is provided on a first electrode 3 provided on a substrate 2, a second electrode 6 provided opposite to the first electrode 3, and a second electrode 6. The counter substrate 7, the photoelectric conversion layer 4 located on the first electrode 3 side, and the hole transport layer 5 in contact with the photoelectric conversion layer 4 are provided between the electrodes 3 and 6.
Hereinafter, the configuration of each unit will be described. In the following description, for convenience of explanation, the upper side is “upper” and the lower side is “lower” in FIGS.

The substrate 2 and the counter substrate 7 are for supporting the first electrode 3, the photoelectric conversion layer 4, the hole transport layer 5, and the second electrode 6, and are configured by flat members.
In the solar cell 1 of this embodiment, as shown in FIG. 1, for example, light such as sunlight (hereinafter simply referred to as “light”) is incident from the substrate 2 and the first electrode 3 side described later. (Irradiated) for use. For this reason, each of the substrate 2 and the first electrode 3 is preferably substantially transparent (colorless transparent, colored transparent, or translucent). Thereby, light can be efficiently made to reach the photoelectric conversion layer 4 described later.

Examples of constituent materials of the substrate 2 and the counter substrate 7 include glass materials, ceramic materials, resin materials such as polycarbonate (PC) and polyethylene terephthalate (PET), and metal materials such as aluminum.
The average thicknesses of the substrate 2 and the counter substrate 7 are appropriately set depending on the constituent materials, the use of the solar cell 1, and the like, and are not particularly limited.

When the board | substrate 2 and the opposing board | substrate 7 are comprised with a hard material, it is preferable that the average thickness is about 0.1-1.5 mm, and it is more preferable that it is about 0.8-1.2 mm. Moreover, when the board | substrate 2 is comprised with a flexible material, it is preferable that the average thickness is about 0.5-150 micrometers, and it is more preferable that it is about 10-75 micrometers.
Note that the counter substrate 7 may be omitted as necessary.

A first electrode 3 is provided on the substrate 2 (one surface side of the substrate 2). The first electrode 3 receives electrons generated by a dye, which will be described later, via an electron transport material and transmits the electrons to an external circuit 10 connected thereto.
Examples of the constituent material of the first electrode 3 include metal oxide materials such as indium tin oxide (ITO), tin oxide containing fluorine atoms (FTO), indium oxide (IO), and tin oxide (SnO ₂ ). , Aluminum, nickel, cobalt, platinum, silver, gold, copper, molybdenum, titanium, tantalum or a metal material such as an alloy containing these, carbon materials such as graphite, etc., one or two of these A combination of two or more species can be used (for example, as a multi-layer laminate).

The average thickness of the first electrode 3 is appropriately set depending on the constituent material thereof, the use of the solar cell 1, and the like, and is not particularly limited, but can be set as follows, for example.
When the first electrode 3 is made of a metal oxide material (transparent conductive metal oxide material), the average thickness is preferably about 0.05 to 5 μm, and preferably about 0.1 to 1.5 μm. More preferably. Further, when the first electrode 3 is made of a metal material or a carbon material, the average thickness is preferably about 0.01 to 1 μm, more preferably about 0.03 to 0.1 μm. .

In addition, the 1st electrode 3 is not limited to the shape shown in figure, For example, the thing etc. of the shape which has several comb teeth may be sufficient. In this case, since the light passes between the plurality of comb teeth and reaches the photoelectric conversion layer 4, the first electrode 3 may not be substantially transparent. Thereby, the range of selection of the constituent material, the formation method (manufacturing method), and the like of the first electrode 3 can be expanded.
The first electrode 3 can also be used by combining (for example, laminating) such a comb-like electrode and a layered electrode.

On the first electrode 3, a film-like barrier layer 8 and a porous photoelectric conversion layer 4 are provided in this order.
The photoelectric conversion layer 4 includes an electron transport material and a dye supported on the surface of the electron transport material, and has a function of transporting at least electrons generated by the dye.
As the electron transport material, a material containing at least one of a semiconductor material and a metal material is preferable.

Among these, as the semiconductor material, various inorganic or organic n-type semiconductor materials can be used alone or in combination of two or more. Among these, examples of the inorganic n-type semiconductor material include titanium oxide such as titanium dioxide (TiO ₂ ), titanium monoxide (TiO), and dititanium trioxide (Ti ₂ O ₃ ), zinc oxide (ZnO), and oxide. An oxide semiconductor material such as tin (SnO ₂ ) is suitable.

Among these, as a constituent material of the semiconductor particles, a material mainly composed of titanium dioxide is preferable. Titanium dioxide is particularly excellent in the ability to transport electrons and is highly sensitive to light, so that even semiconductor particles themselves can generate electrons. As a result, the power generation efficiency (photoelectric conversion efficiency) of the solar cell 1 is further improved.
In addition, since the crystal structure of titanium dioxide is stable, semiconductor particles mainly composed of titanium dioxide have little secular change (deterioration) and stable performance even when exposed to harsh environments. It has the advantage that it can be obtained continuously for a long time.
Further, as titanium dioxide, any of those whose crystal structure is mainly composed of anatase type, those composed mainly of rutile type, and a mixture of anatase type and rutile type may be used. Good.

When rutile titanium dioxide and anatase titanium dioxide are mixed, the mixing ratio is not particularly limited, but is preferably about 95: 5 to 5:95 by weight, and 80:20 More preferably, it is about ˜20: 80.
In addition, examples of the metal material include gold, silver, platinum, and the like, and one or more of these can be used in combination.

The photoelectric conversion layer 4 includes, for example, aggregated particles of particles (particles) of the electron transport material as described above.
The average particle diameter of the particles (granular material) of the electron transport material is preferably about 1 nm to 1 μm, and more preferably about 5 to 50 nm.
Further, on the outer surface of the photoelectric conversion layer 4 and the inner surface of the pores, a coat layer having a function of preventing or suppressing the transfer of electrons received from the dye to the dye again (reverse electron transfer) is formed. May be. Thereby, recombination of electrons and holes can be prevented or suppressed more reliably.

This coat layer is a substance having a lower end potential of the conduction band lower than the lower end potential of the conduction band of the electron transport material included in the photoelectric conversion layer 4, in other words, an electron transport included in the photoelectric conversion layer 4. It can be composed of a substance having a lower end potential of the conduction band on the Valence Band side of the lower end potential of the conduction band of the material.
As such a substance, when an electron transporting material mainly composed of titanium dioxide is used, a metal oxide is preferable. For example, zirconium oxide, strontium titanate, niobium oxide, magnesium oxide, zinc oxide, oxidation One or more of tin and the like can be used in combination.
The average thickness of such a coat layer is preferably about 0.1 to 10 nm.
Further, it is preferable that these are sufficiently diffused and bonded at the contact interface between the granular materials. Thereby, in the photoelectric converting layer 4, it is prevented that the movement of an electron is suppressed and the recombination of an electron and a hole can be prevented or suppressed more reliably.

The porosity of the photoelectric conversion layer 4 is not particularly limited, but is preferably about 5 to 90%, more preferably about 15 to 50%, and about 20 to 40%. Further preferred. By setting the porosity of the photoelectric conversion layer 4 in such a range, the specific surface area of the particles of the electron transport material can be sufficiently increased. Thereby, the formation area (formation region) of the dye (see below) carried on the outer surface of the electron transport material particles and the inner surface of the pores can be sufficiently increased. For this reason, the dye can generate sufficient electrons and can efficiently transfer the electrons to the particles of the electron transport material. As a result, the power generation efficiency of the solar cell 1 can be further improved.
The average thickness of the photoelectric conversion layer 4 is not particularly limited, but is preferably about 0.1 to 300 μm, more preferably about 0.5 to 100 μm, and about 1 to 25 μm. Further preferred.

The barrier layer 8 is set to have a lower porosity than the photoelectric conversion layer 4, and thereby functions to prevent or suppress contact between the hole transport layer 5 and the first electrode 3 described later. Thereby, generation | occurrence | production of leakage current can be prevented and the fall of the luminous efficiency of the solar cell 1 can be prevented.
The average thickness (film thickness) of the barrier layer 8 is preferably about 0.01 to 10 μm, more preferably about 0.1 to 5 μm, and further preferably about 0.5 to 2 μm. . Thereby, the said effect can be improved more.

The constituent material of the barrier layer 8 is not particularly limited. For example, in addition to titanium oxide which is a main constituent material of semiconductor particles, for example, SrTiO ₃ , ZnO, SiO ₂ , Al ₂ O ₃ , SnO ₂ , CdS, CdSe, TiC, Si ₃ N ₄ , SiC, B ₄ N, BN and the like can be mentioned, and one or more of these can be used in combination.
Among these, as a constituent material of the barrier layer 8, it is preferable that it has the electrical conductivity equivalent to the photoelectric converting layer 4, and the thing which has titanium dioxide as a main component is especially more preferable. By configuring the barrier layer 8 with such a material, electrons generated in the pigment can be more efficiently transferred from the particles of the electron transport material to the barrier layer 8, and as a result, the power generation efficiency of the solar cell 1 can be improved. It can be improved further.

  Further, the interface between the barrier layer 8 and the photoelectric conversion layer 4 may not be clear or may be clear, but is preferably not clear (unclear). That is, it is preferable that the barrier layer 8 and the photoelectric conversion layer 4 are integrally formed and partially overlap each other. Thereby, the transmission (delivery) of electrons between the barrier layer 8 and the photoelectric conversion layer 4 can be performed more reliably (efficiently).

The photoelectric conversion layer 4 is in contact with the dye by, for example, adsorption, bonding (covalent bond, coordinate bond), or the like.
This dye has a function of generating electrons and holes by receiving light, and is formed along the outer surfaces of the particles of the electron transport material and the inner surfaces of the holes as shown in FIG. Thereby, the electrons generated in the dye can be efficiently transferred to the particles of the electron transport material.

As this pigment, pigments and dyes can be used alone or in combination. In addition, it is preferable to use a pigment from the viewpoint that the deterioration and deterioration with time are less, and the dye from the viewpoint that the adsorptivity to the particles of the electron transport material (bondability with the particles of the electron transport material) is more excellent.
Here, examples of the pigment include phthalocyanine pigments such as phthalocyanine green and phthalocyanine blue, fast yellow, disazo yellow, condensed azo yellow, benzoimidazolone yellow, dinitroaniline orange, benzimidazolone orange, toluidine red, and permanent carmine. Azo pigments such as permanent red, naphthol red, condensed azo red, benzimidazolone carmine, benzimidazolone brown, anthraquinone pigments such as anthrapyrimidine yellow and anthraquinonyl red, azomethine pigments such as copper azomethine yellow, quinophthalone yellow Quinophthalone pigments such as isoindoline yellow, nitroso pigments such as nickel dioxime yellow, perinone Perinone pigments such as orange, quinacridone magenta, quinacridone maroon, quinacridone scarlet, quinacridone pigments such as quinacridone red, perylene pigments such as perylene red and perylene maroon, pyrrolopyrrole pigments such as diketopyrrolopyrrole red, dioxazine violet Organic pigments such as dioxazine pigments such as carbon black, lamp black, furnace black, ivory black, carbon pigments such as graphite and fullerene, chromate pigments such as chrome lead and molybdate orange, cadmium yellow, cadmium lith Pong yellow, cadmium orange, cadmium lithopone orange, silver vermilion, cadmium red, cadmium lithopon red, sulfide pigments such as sulfide, ocher, titanium yellow, titanium barium Neckel yellow, red rose, red lead, amber, brown iron oxide, zinc iron chrome brown, chromium oxide, cobalt green, cobalt chrome green, titanium cobalt green, cobalt blue, cerulean blue, cobalt aluminum chrome blue, iron black, manganese ferrite black, Oxide pigments such as cobalt ferrite black, copper chrome black, copper chrome manganese black, hydroxide pigments such as viridian, ferrocyanide pigments such as bitumen, silicate pigments such as ultramarine, cobalt violet, minerals Examples thereof include phosphate pigments such as violet, and other inorganic pigments such as cadmium sulfide and cadmium selenide, and one or more of these can be used in combination.

On the other hand, as the dye, for _{example, RuL 2 (SCN) 2,} RuL ( manufactured by Solaronics, _{Inc.) 2 Cl 2, RuL 2 CN} 2, Rutenium535-bisTBA, [RuL 2 metal complexes such as _{(NCS 2) 2 H 2} O Examples include dyes, cyan dyes, xanthene dyes, azo dyes, hibiscus dyes, blackberry dyes, raspberry dyes, pomegranate juice dyes, chlorophyll dyes, and the like. Use one or more of these in combination. Can do. In addition, L in the said composition formula shows 2,2'-bipyridine, or its derivative (s).

A hole transport layer 5 is provided in contact with the photoelectric conversion layer 4. The hole transport layer 5 has a function of capturing and transporting holes generated in the photoelectric conversion layer 4.
Although the hole transport layer 5 has a layer shape as a whole, a part of the hole transport layer 5 enters the pores of the photoelectric conversion layer 4 on the photoelectric conversion layer 4 side as shown in FIG. Thereby, the contact area between the photoelectric conversion layer 4 and the hole transport layer 5 can be increased, and holes generated in the photoelectric conversion layer 4 are more efficiently transferred to the hole transport layer 5. Can do. As a result, the power generation efficiency of the solar cell 1 can be further improved.

Such a hole transport layer 5 may be solid, liquid or gel.
Specifically, the solid hole transport layer 5 is made of, for example, polyarylamine, fluorene-arylamine copolymer, fluorene-bithiophene copolymer, poly (N-vinylcarbazole), polyvinylpyrene, polyvinylanthracene, Organic polymers such as polythiophene, polyalkylthiophene, polyhexylthiophene, poly (p-phenylene vinylene), polytinylene vinylene, pyrene formaldehyde resin, ethyl carbazole formaldehyde resin or derivatives thereof, and dendrimers having thiophene as a skeleton Organic polymer, naphthalene, anthracene, tetracene, pentacene, hexacene, phthalocyanine, perylene, hydrazone, triphenylmethane, diphenylmethane, stilbene, arylvinyl, pyrazoline, Examples include organic low molecules such as rephenylamine, triarylamine, oligothiophene, phthalocyanine or derivatives thereof, and inorganic materials such as CuI, AgI, AgBr, CuSCN, etc., and one or more of these are combined. Can be configured.
In addition, the said organic polymer can also be used as a mixture with another polymer. As an example, the polythiophene-containing mixture includes poly (3,4-ethylenedioxythiophene / styrene sulfonic acid) (PEDOT / PSS).

Further, the liquid hole transport layer 5 may be, for example, a redox such as a halogen type such as I / I ₃ type, Br / Br ₃ type, Cl / Cl ₃ type, F / F ₃ type, quinone / hydroquinone type, etc. One or a combination of two or more electrolytes (redox substances: electrolyte components) was dissolved in various solvents such as water, acetonitrile, ethylene carbonate, propylene carbonate, and polyethylene glycol (or mixed solvents thereof). It can be composed of an electrolyte solution.

Among these, an iodine solution (I / I ₃ -based solution) is particularly preferably used as the electrolyte solution. More specifically, the electrolyte solution is, for example, a solution in which iodine and potassium iodide are dissolved in ethylene glycol, dimethylhexylimidazolium, iodine and lithium iodide are dissolved in acetonitrile to which a predetermined amount of Tertiary-butylpyridine is added. A solution, Iodolyte TG50 (manufactured by Solaronics), 1,2-dimethyl-3-propylimidazolium iodide and the like can be used.
Although it does not specifically limit as a density | concentration (content) of the electrolyte component in electrolyte solution, For example, it is preferable that it is about 0.1-25 wt%, and it is more preferable that it is about 0.5-15 wt%.

Moreover, the gel-like hole transport layer 5 can be composed of, for example, a solution in which the above-described electrolyte solution is held in a gel-like base material (gel base material).
Examples of the gel base material include those mainly composed of thermoplastic resins, those mainly composed of thermosetting resins, those mainly composed of copolymers, and mainly composed of compounds having a siloxane bond. A thing etc. can be used, Furthermore, arbitrary 2 or more types of these can also be used in combination.

Examples of the thermoplastic resin include polyethylene oxide (PEO), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), and the like, and one or more of these are used in combination. be able to.
Examples of the thermosetting resin include polyimide resin (PI), epoxy resin, carboxylic acid resin, urea resin, and the like.

  The copolymer is obtained by polymerizing at least two kinds of compounds (copolymer precursors), for example, ionic polymerization (cationic polymerization, anionic polymerization), radical polymerization, or the like, or a combination thereof. For example, epoxy copolymer, vinyl ether copolymer, oxedan copolymer, urethane acrylate copolymer, epoxy acrylate copolymer, ester acrylate copolymer, acrylate copolymer, etc. Is mentioned.

Accordingly, as the compound (copolymer precursor), for example, any two or more of urethane, polyacene, polyacetylene, polyethylene, polycarbon, polypyrrole, polyaniline, active sulfur, and the like are appropriately selected and used. be able to.
Examples of the compound having a siloxane bond include polysiloxane, polydimethylsiloxane, polyalkylphenylsiloxane, and polymetallosiloxane in which a part of silicon atoms is substituted with other metal atoms (for example, aluminum, titanium, etc.). .

The average thickness of the hole transport layer 5 (excluding the part that has entered the pores) is not particularly limited, but is preferably about 1 to 500 μm, more preferably about 10 to 300 μm, More preferably, it is about 30 μm.
A second electrode 6 facing the first electrode 3 is provided on the hole transport layer 5 (on the side opposite to the first electrode 3).

Examples of the constituent material of the second electrode 6 include metal oxides such as indium tin oxide (ITO), tin oxide containing fluorine atoms (FTO), indium oxide (IO), and tin oxide (SnO ₂ ). Examples include materials, metals such as aluminum, nickel, cobalt, platinum, silver, gold, copper, molybdenum, titanium, and tantalum, alloys containing these, and various carbon materials such as graphite. Species or a combination of two or more can be used.

In addition, the second electrode 6 is preferably used by combining (for example, laminating) layered electrodes.
In this case, the combination of the second electrode 6 and the layered electrode uses, for example, indium tin oxide as a constituent material of the second electrode 6, and a layered layer composed of titanium oxide (TiO 2) on the lower side. The combination using an electrode is mentioned. Titanium oxide has a higher conductivity than indium tin oxide, so that the internal resistance of the second electrode 6 can be reduced. In addition, since titanium oxide has high reflectance and high whiteness, when the solar cell 1 is viewed from the substrate 2 side, there is an advantage that the color saturation of the pigment is improved and the aesthetic appearance is excellent.

The average thickness of the second electrode 6 is appropriately set depending on the constituent material, the use of the solar cell 1 and the like, and is not particularly limited.
In such a solar cell 1, when light is incident, electrons are excited mainly in the dye, and electrons (e ⁻ ) and holes (h ⁺ ) are generated. Among these, electrons move to particles of the electron transport material, holes move to the hole transport layer 5, and a potential difference (photoelectromotive force) is generated between the first electrode 3 and the second electrode 6. Thus, a current (photoexcitation current) flows through the external circuit 10.

Moreover, in such a solar cell 1, when a voltage of 0.5 V is applied so that the first electrode 3 is positive and the second electrode 6 is negative, the resistance value is 100 Ω / cm ² or more. It is more preferable to have a characteristic of (preferably 1 kΩ / cm ² or more). In the solar cell 1 having such characteristics, a short circuit (leakage) due to contact between the first electrode 3 and the hole transport layer 5 is preferably prevented or suppressed, The power generation efficiency (photoelectric conversion efficiency) can be further improved.

In such a solar cell 1, as shown in FIG. 1, a plurality of photoelectric conversion layers 4 are arranged in a matrix on the barrier layer 8, and the photoelectric conversion layers 4 are partitioned by partition walls 91. .
Further, the upper surface of the photoelectric conversion layer 4 and the upper end surface of the partition wall 91 are substantially flush with the upper surface of the substrate 2. A hole transport layer 5 is provided on the photoelectric conversion layer 4 and the partition wall 91.
Further, a partition wall 92 is provided so as to surround the outer periphery of the photoelectric conversion layer 4, the partition wall 91 and the hole transport layer 5.

The solar cell 1 as described above can be manufactured, for example, as follows.
[1] A laminate in which the substrate 2, the first electrode 3, and the barrier layer 8 are laminated is prepared.
[1-1] First, the substrate 2 is prepared, and the first electrode 3 is formed on the substrate 2.
The first electrode 3 can be formed by, for example, a vapor deposition method, a sputtering method, a printing method, or the like.

[1-2] Next, the barrier layer 8 is formed on the first electrode 3.
The barrier layer 8 is formed by, for example, a sol-gel method, a vapor deposition (vacuum vapor deposition) method, a sputtering method (high frequency sputtering, DC sputtering), a spray pyrolysis method, a jet mold (plasma spraying) method, a CVD method, or the like. Among these, the sol-gel method is preferable.

  This sol-gel method is very easy to operate. Further, by using the sol-gel method, the barrier layer forming material for forming the barrier layer 8 may be, for example, dipping method, dropping, doctor blade method, spin coating method, brush coating, spray coating method, roll coating. The barrier layer 8 having a desired film thickness can be formed relatively easily without requiring a large-scale apparatus.

In particular, for the formation of the barrier layer 8, it is preferable to use a metal organic deposition (or decomposition) method (hereinafter abbreviated as “MOD method”), which is a kind of sol-gel method.
According to this MOD method, the reaction of the precursor of the constituent material of the barrier layer 8 (for example, hydrolysis, polycondensation, etc.) is prevented in the barrier layer forming material. (With good reproducibility). Further, the obtained barrier layer 8 can be dense (with a porosity within the above range).
When the barrier layer 8 is composed of titanium dioxide as a main material, as a precursor thereof, for example, an organic titanium compound such as titanium tetraisopropoxide (TPT), titanium tetramethoxide, titanium tetraethoxide, titanium tetrabutoxide, or the like is used. Can be used.

[2] Next, a liquid material (composition for forming a photoelectric conversion layer of the present invention) used for forming the photoelectric conversion layer 4 is prepared.
[2-1] First, particles of an electron transport material such as semiconductor particles are prepared, and aggregate particles in which the particles of the electron transport material are aggregated are prepared.
Examples of the method for assembling the particles of the electron transport material include heat treatment, pressure pressing, ultraviolet irradiation, microwave irradiation, electrostatic electrodeposition, and the like. Among these, heat treatment is preferable. According to the heat treatment, particles of the electron transport material can be partially efficiently joined (necked) to obtain aggregate particles.

For example, when the electron transport material particles are titanium dioxide particles, the heat treatment temperature is preferably about 300 to 700 ° C, more preferably about 400 to 600 ° C.
The heat treatment time varies slightly depending on the heat treatment temperature, but is preferably about 1 to 180 minutes, more preferably about 5 to 60 minutes.
The heat treatment atmosphere is preferably an oxidizing atmosphere or an inert atmosphere, but is particularly preferably a water vapor atmosphere. When heat treatment is performed in a water vapor atmosphere, the surface of the particles of the electron transport material becomes more active due to the action of water vapor, so that partial bonding of the particles of the electron transport material can be performed more efficiently.

In addition, the aggregated particles of the electron transport material produced as described above are porous, and include a large number of continuous holes in which adjacent holes communicate with each other. As a result, the surface area of the aggregated particles of the electron transport material is increased, so that the amount of the dye supported on the particles of the electron transport material can be increased in the steps described later. As a result, the photoelectric conversion efficiency of the solar cell 1 can be increased.
Further, the dye supported on the inner surface of the continuous pores has an advantage that once it is supported, it is difficult to desorb from the particles of the electron transport material, which is particularly effective in the present invention.

The average particle size of the aggregated particles thus obtained varies depending on the average particle size of the particles of the electron transport material. In particular, the thickness is preferably about 20 to 200 nm, and more preferably about 50 to 100 nm. If the average particle diameter of the aggregate particles is within the above range, the liquid material can be applied to, for example, a droplet discharge method while appropriately bonding the particles of the electron transport material. In other words, this makes it possible to obtain a liquid material that can form a photoelectric conversion layer with better characteristics while preventing the liquid material from staying in the discharge nozzle.
In this case, the number of particles of the electron transport material constituting one aggregate particle is preferably about 2 to 100, and more preferably about 9 to 30. Thereby, the surface area of the aggregate particles becomes sufficiently large, and the amount of the dye supported on the aggregate particles can be increased.

[2-2] Next, a dye is supported on the aggregated particles.
For the support, the aggregated particles are preferably brought into contact with the surface of the aggregated particles or the inner surface of the continuous pores by bringing the aggregated particles into contact with a dye solution containing the dye (chemical adsorption) and bonded (covalent bond, coordinate bond). . Thereby, the pigment | dye can be efficiently carry | supported collectively with respect to the particle | grains of a lot of electron transport materials.

As a method for bringing the dye into contact with the aggregated particles, for example, a method of immersing the aggregated particles in the dye liquid (immersion method), a method of supplying the dye liquid to the aggregated particles in a shower form (spray method), or the like can be used. However, the immersion method is particularly preferable. Thereby, a pigment | dye can be carry | supported uniformly with respect to the particle | grains of a lot of electron transport materials.
In this case, the time for immersing the aggregated particles in the dye solution is not particularly limited, but is preferably about 1 to 30 hours, and more preferably about 5 to 24 hours. Thereby, a sufficient amount of the dye can be carried on the aggregated particles. Although the immersion time may be longer than the upper limit, further loading cannot be expected.

The temperature of the dye solution at this time is not particularly limited, but is preferably about 10 to 40 ° C, more preferably about 15 to 30 ° C. Thereby, the pigment | dye can be efficiently carry | supported with respect to the particle | grains of an electron transport material, preventing the discoloration accompanying the alteration of a pigment | dye, the fall of photoelectric conversion ability, etc.
The aggregate particles carrying the dye may be transferred to the next step together with the dye solution, or may be recovered from the dye solution and transferred to the next step.
As a recovery method, for example, a method of removing excess dispersion medium by natural drying, blowing a gas such as air or nitrogen gas, and heating (heating), etc., and collecting aggregated particles carrying a dye with a filter paper or the like And the like.

[2-3] Next, aggregated particles carrying the pigment are dispersed in a dispersion medium to prepare a liquid material (a composition for forming a photoelectric conversion layer).
Examples of the dispersion medium include various types of water (distilled water, pure water, ion exchange water, RO water, etc.), alcohols such as methanol, ethanol, isopropanol, butanol, octanol, ethylene glycol, diethylene glycol, and glycerin, methyl cellosolve, and ethyl. Cellosolves such as cellosolve and phenyl cellosolve, esters such as methyl acetate, ethyl acetate, butyl acetate and ethyl formate, ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone and cyclohexanone, pentane, hexane , Aliphatic hydrocarbons such as octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, benzene, toluene, xylene, hexylbenzene, hebutylbenzene, octylbenzene, noni Aromatic hydrocarbons such as benzene having a long chain alkyl group such as benzene, decylbenzene, undecylbenzene, dodecylbenzene, tridecylbenzene, tetradecylbenzene, methylene chloride, chloroform, carbon tetrachloride, 1, 2 -Halogenated hydrocarbons such as dichloroethane, aromatic heterocycles such as pyridine, pyrazine, furan, pyrrole, thiophene, methylpyrrolidone, nitriles such as acetonitrile, propionitrile, acrylonitrile, N, N-dimethylformamide, N , N-dimethylacetamide and other amides, carboxylates or other various oils, and the like can be used alone or as a mixture.
Further, in the dispersion medium, a binder (binder) having a function of binding the aggregate particles to each other and the aggregate particles and the first electrode 3 may be added.

Examples of the binder include various amide compounds such as N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, and one of these compounds. Species or a combination of two or more can be used.
You may knead | mix etc. with respect to the dispersion medium which added these as needed.

The kneading can be performed using various kneaders such as a kneader, batch type triaxial roll, continuous biaxial roll, wheel mixer, blade type mixer, and various mills such as a ball mill and a bead mill.
Furthermore, you may adjust a viscosity with respect to the liquid material obtained in this way as needed.

The viscosity of the liquid material can be determined, for example, by a method such as adding a viscosity modifier, adjusting the temperature of the liquid material, or removing the dispersion medium.
Examples of the viscosity modifier include polyethylene glycol, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, water-soluble acrylic resin, polyvinyl pyrrolidone, gum arabic starch and the like, one or two of these. A combination of more than one species can be used.

Further, the viscosity of the liquid material to be adjusted is appropriately set according to the supply method in the liquid material supply step described later. For example, when the liquid material is supplied by a droplet discharge method, the viscosity of the liquid material at room temperature is , Preferably about 5 to 50 cp, and more preferably about 10 to 30 cp. Thus, when the liquid material is discharged as droplets, the spread of the landed droplets can be controlled within an appropriate range while preventing the liquid material from staying in the discharge nozzle.
In addition, a drying inhibitor, a pH adjuster, a preservative, a fungicide, and the like may be added to the liquid material.
As described above, a liquid material (a composition for forming a photoelectric conversion layer of the present invention) can be produced. Such a liquid material can efficiently produce the photoelectric conversion layer 4 in the steps described later.

[3] Next, as shown in FIG. 3A, partition walls 91 and 92 are formed on the barrier layer 8.
The partition walls 91 and 92 can be formed by forming an insulating film so as to cover the barrier layer 8 and then patterning using a photolithography method or the like.
The constituent materials of the partition walls 91 and 92 are selected in consideration of liquid repellency, ink solvent resistance, adhesion to the barrier layer 8, and the like.
Specifically, examples of the constituent material of the partition walls 91 and 92 include an organic material such as an acrylic resin, a polyimide resin, and a fluorine resin, and an inorganic material such as SiO ₂ .
Moreover, it is preferable that the partition walls 91 and 92 have a matrix shape (lattice shape). Thereby, in the process described later, if a liquid material is supplied to the plurality of spaces 93 defined by the partition walls 91 and 92, a plurality of liquid coatings arranged in a matrix can be efficiently formed.

The partition walls 91 and 92 as described above can define the contour shape of the liquid film formed in the process described later, and the photoelectric conversion layer 4 having a desired shape (contour shape and thickness) can be formed. .
In addition, the shape of the opening of the partition walls 91 and 92 may be any shape such as a polygon such as a circle, an ellipse, a rectangle, and a hexagon.
In addition, an opening (not shown) for injecting the hole transport layer 5 (electrolyte solution) is provided in a part of the partition wall 92 in a process described later.

[4] Next, in the plurality of spaces 93 on the barrier layer 8 (one surface side of the first electrode 3) shown in FIG. A photoelectric conversion layer forming composition) is supplied (first step). Thereby, the liquid film 41 as shown in FIG.3 (b) can be formed. And in the process mentioned later, the photoelectric converting layer 4 which makes the shape of this liquid film 41 can be formed.
Here, conventionally, in the formation of the photoelectric conversion layer, a liquid material containing particles of an electron transport material is applied on the base layer (in this embodiment, the barrier layer 8) to form a liquid film, and this liquid film is baked. Thus, after particles of the electron transport material were joined to form a layer (electron transport layer), a dye was adsorbed on the electron transport layer to form a photoelectric conversion layer.

However, when adsorbing the dye, as described above, the aggregate particles are immersed in the dye solution containing the dye together with the base layer. In this method, an excessive amount of the dye is added to the aggregate particles. It will adhere.
In general, in a dye-sensitized solar cell such as the solar cell 1, the state in which the dye is not overlapped with the particles of the electron transport material, that is, carried in a single layer (monolayer) has the least series resistance component, It is said that the conversion efficiency is high.

Therefore, conventionally, this excess dye was removed by washing or the like. However, since cleaning requires a large cleaning device and a lot of labor, the cost of the manufacturing process has been increased.
In addition, although the dyes are very expensive, many of them are discarded by washing, causing further cost increase.

  Further, in such a method, for example, when a plurality of types of dyes are adsorbed on the particles of the electron transport material in a region separated from each other for one solar cell, these dyes are mixed together at the time of cleaning. Saturation, vividness, and further photoelectric conversion ability are reduced. For this reason, there also existed a problem that a multiple types of pigment | dye could not be supplied separately with respect to the solar cell provided to the same washing | cleaning.

Conventionally, the liquid film on the base film is subjected to a high-temperature treatment of 300 ° C. or higher to bond the particles of the electron transport material to each other. Therefore, the base layer and the substrate supporting it have heat resistance. These constituent materials were limited as required.
On the other hand, in the present invention, before disposing the electron transport material particles on the underlayer, the electron transport material particles are partially joined in advance to form aggregate particles. The liquid material containing the particles of the electron transport material carrying the dye was supplied onto the underlayer. This eliminates the need for a cleaning operation and simplifies the manufacturing process. In addition, since a necessary and sufficient amount of the dye can be supported on the particles of the electron transport material, the amount of the dye used can be minimized and the photoelectric conversion efficiency can be increased.
Furthermore, since the particles of the electron transport material are partially bonded in advance, high temperature treatment is not required after the aggregated particles of the electron transport material are disposed on the base layer. For this reason, the selection range of the constituent material of the base layer and the substrate can be widened.

Supply of liquid material is spin coating method (pyrosol method), casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method , A liquid phase process using a flexographic printing method, an offset printing method, a droplet discharge method, or the like.
In particular, the liquid material is preferably supplied by a droplet discharge method (inkjet method). Thereby, liquid material can be supplied, controlling a supply position with high precision.

In addition, a plurality of types of liquid materials can be supplied so as not to be mixed with each other. As a result, contamination (contamination), alteration, and the like of the liquid material due to mixing can be reliably prevented.
In addition, it is preferable that the liquid film 41 formed using the droplet discharge method or the aggregate thereof constitute predetermined information or a predetermined design. Thereby, in the process described later, the photoelectric conversion layer 4 formed from such a liquid film 41 has predetermined information (characters, numbers, symbols, figures or segments constituting a part thereof) or a predetermined design. It will have the part which comprises. As a result, the solar cell 1 can be used as part of a design such as advertising media such as signs and posters, clothes, bags, and the like.

In particular, by selectively supplying a plurality of types of liquid materials (photoelectric conversion layer forming composition of the present invention) containing pigments of different colors, a plurality of liquid coatings 41 that are separated from each other form an image as a whole. Is preferred. Thereby, the solar cell 1 excellent in the designability which utilized the color of pigment | dyes like a photograph, a picture, etc. can be formed, for example.
Moreover, it is preferable to form the plurality of liquid coatings 41 in a matrix. Thereby, one liquid film 41 can be handled as one of the pixels (pixels) forming the image. As a result, the solar cell 1 that can display an image with more excellent designability can be manufactured.

Note that one pixel, i.e. the plane area of one liquid coating that corresponds to one pixel, the average value thereof is preferably from about ² 100～10000Myuemu, and more preferably about ² 100～3000Myuemu. A pixel having such a size can prevent a significant decrease in carrier mobility in the surface, that is, a significant decrease in photoelectric conversion efficiency, and can display a precise image with excellent design.

  In this embodiment, the liquid material is supplied to the plurality of spaces 93 defined by the partition walls 91 and 92 to form the liquid film 41. However, the liquid material is supplied in a state where the partition walls 91 and 92 are omitted. Alternatively, the liquid coating 41 may be formed. In this case, since the process of forming the partition walls 91 and 92 can be omitted, the manufacturing process of the solar cell 1 can be simplified. Furthermore, in this case, a frame-like spacer or the like that substitutes for the partition wall 92 may be used to prevent the liquid coating 41 from being dissipated outside the solar cell 1.

[5] Next, the dispersion medium is removed from the liquid coating 41. Thereby, the photoelectric conversion layer 4 as shown in FIG. 3C is formed (second step).
The dispersion medium can be removed by, for example, a method of natural drying, a method of blowing a gas such as air or nitrogen gas, a method of freeze drying, a method of heat treatment at a relatively low temperature, or the like.

[6] Next, a laminate in which the second electrode 6 is laminated on the counter substrate 7 is prepared.
This laminate can be manufactured by preparing the counter substrate 7 and forming the second electrode 6 on the counter substrate 7.
The second electrode 6 can be formed by, for example, a vapor deposition method, a sputtering method, a printing method, or the like.
[7] Next, as shown in FIG. 3D, the obtained laminate is laminated on the partition wall 92 so that the second electrode 6 faces the first electrode 3, and an adhesive is used. Fix with etc.

[8] Next, in the space 94 defined by the upper surface of the photoelectric conversion layer 4, the lower surface of the first electrode 3, and the partition wall 92 shown in FIG. The transport layer 5 is formed.
Below, the case where the positive hole transport layer 5 is a liquid is demonstrated as a representative.
The electrolyte solution is injected and filled into the space 94 through an opening provided in the partition wall 92.

Thereafter, after the electrolyte solution is filled, the opening is sealed.
In addition, what is necessary is just to form the positive hole transport layer 5 on the photoelectric converting layer 4 prior to the said process [7], when making the positive hole transport layer 5 into a solid state.
Further, when the hole transport layer 5 is made into a gel, a liquid material containing a gelling agent may be injected into the space 94 and then the liquid material may be gelled.

[9] Next, end portions of the external circuit 10 are connected to the first electrode 3 and the second electrode 6, respectively.
The solar cell (photoelectric conversion element of the present invention) 1 is manufactured through the above steps.
The electronic device of the present invention includes such a solar cell 1. Such an electronic device has a high degree of design freedom.

Hereinafter, the electronic apparatus of the present invention will be described with reference to FIGS.
FIG. 4 is a plan view showing a calculator to which the electronic device of the present invention is applied, and FIG. 5 is a perspective view showing a mobile phone (including PHS) to which the electronic device of the present invention is applied.
A calculator 100 illustrated in FIG. 4 includes a main body 101, a display unit 102 provided on the upper surface (front surface) of the main body 101, a plurality of operation buttons 103, and a solar cell installation unit 104.
In the configuration shown in FIG. 4, five solar cells 1 are connected in series to the solar cell installation unit 104.

A mobile phone 200 shown in FIG. 5 includes a main body 201, a display unit 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 solar cell installation unit 206. ing.
In the configuration shown in FIG. 5, a plurality of solar cells 1 are arranged in series so that the solar cell installation unit 206 surrounds the periphery of the display unit 202.

As mentioned above, although the manufacturing method of the composition for photoelectric conversion layer formation of this invention, the composition for photoelectric conversion layer formation, the manufacturing method of a photoelectric conversion element, the photoelectric conversion element, and the electronic device were demonstrated based on each embodiment of illustration, The present invention is not limited to these.
For example, each part which comprises a photoelectric conversion element and an electronic device can be substituted with the thing of the arbitrary structures which can exhibit the same function.

The photoelectric conversion element of the present invention can be applied not only to solar cells but also to various elements (light receiving elements) that receive light and convert it into electrical energy, such as optical sensors and optical switches. It is.
Moreover, in the photoelectric conversion element of this invention, the incident direction of light may be from the reverse direction unlike the thing of illustration. That is, the incident direction of light is arbitrary.
Moreover, the manufacturing method of the composition for photoelectric conversion layer formation of this invention and the manufacturing method of a photoelectric conversion element may respectively add the process of the arbitrary objective 1 or 2 or more.

Next, specific examples of the present invention will be described.
1. Manufacture of solar cells (photoelectric conversion elements) (Examples)
The solar cell shown in FIG. 1 was manufactured as follows.
<1> First, a soda glass substrate having dimensions: length 30 mm × width 35 mm × thickness 1.0 mm was prepared.
Then, this soda glass substrate was cleaned by immersing it in a cleaning solution (mixed solution of sulfuric acid and hydrogen peroxide solution) at 85 ° C. to clean the surface.
<2> Next, an ITO electrode (first electrode) having dimensions: 30 mm long × 35 mm wide × 1 μm thick was formed on the soda glass substrate by vapor deposition.
<3> Next, on the ITO electrode, a barrier layer composed of titanium dioxide as a main material was formed by a MOD method in an area of 30 mm length × 30 mm width.

<4> Next, the liquid material used in order to form a photoelectric converting layer was produced. This was done as follows.
First, titanium dioxide powder was prepared. The average particle size of the titanium dioxide powder was 40 nm.
Next, the titanium dioxide powder was heated at 500 ° C. to obtain a powder of aggregated particles formed by partially joining a part of the titanium dioxide powder.

Next, the powder of the aggregated particles was divided into A and B.
Then, the powder of A is in a saturated ethanol solution (dye solution) of ruthenium trisbipidyl (N3) (orange), and the powder of B is in a saturated ethanol solution of a tetrasulfonic acid phthalocyanine metal complex (blue). Each was immersed and left for 12 hours. As a result, the dye was supported on the aggregated particles.

Next, a mixture of the powder of A, N-vinylacetamide (binder) and distilled water (dispersion medium) was kneaded for 12 hours with a ball mill to obtain paste A.
Similarly, paste B was obtained.
Next, polyethylene glycol (viscosity modifier) was added to these pastes A and B, respectively, to obtain liquid materials (photoelectric conversion layer forming compositions) A and B. In addition, the viscosity of these liquid materials was 20 cp, respectively.

<5> Next, a matrix-like (lattice-like) partition wall was formed on the barrier layer formed in the step <3>. This was done as follows.
First, an insulating film was formed so as to cover the barrier layer.
Next, the partition wall was formed by patterning the insulating film using a photolithography method and an etching method. In the formation of the partition walls, the inner lattice portion was formed to be lower in height than the outer peripheral frame portion. As a result, holes defined by the partition walls and having an opening size of 20 μm in length × 20 μm in width were formed in a matrix.
In addition, an opening was provided in a part of the outer frame-like portion.

<6> Next, the liquid material produced in the step <4> was supplied into the space (pixel space) defined by the partition walls to form a liquid film. This was done as follows.
First, the liquid material A was ejected in a zigzag manner to the pixel spaces arranged in a matrix by an ink jet method (droplet ejection method) to form a liquid film A having an average thickness of 4 μm.
Next, in the same manner, the liquid material B was discharged into the pixel space where the liquid film A was not formed to form the liquid film B having an average thickness of 4 μm.

<7> Next, the glass substrate on which the liquid coatings A and B were formed was placed on a hot plate and heated at 120 ° C. Thereby, the dispersion medium of the liquid films A and B was volatilized, and the photoelectric conversion layers A and B were obtained.
<8> Next, a soda glass substrate having dimensions: length 30 mm × width 35 mm × thickness 1.0 mm was prepared.
Then, this soda glass substrate was cleaned by immersing it in a cleaning solution (mixed solution of sulfuric acid and hydrogen peroxide solution) at 85 ° C. to clean the surface.
<9> Next, an FTO film having dimensions: 30 mm long × 35 mm wide × 1 μm thick was formed on the soda glass substrate by vapor deposition. Subsequently, a titanium dioxide film having a thickness of 0.1 μm was formed on the FTO film by sputtering to form a second electrode.

<10> Next, the glass substrate provided with the second electrode was laminated on the partition wall so that the second electrode opposed the first electrode.
<11> Next, an iodine solution (TG50, manufactured by SOLARONIX SA) was injected as an electrolyte solution into the inside of the partition wall from the opening of the partition wall and filled. And the opening part was sealed.
<12> Next, the edge part of the external circuit was connected to the 1st electrode and the 2nd electrode, respectively, and the solar cell was completed.

2. Evaluation The solar cells obtained in the examples were each irradiated with simulated sunlight (100 mW / cm ² ) under the condition: AM1.5.
As a result, an electromotive force was obtained between both electrodes, and a current flowed in the external circuit.
Moreover, when the pixel which has the photoelectric converting layer A formed using the liquid film A and the pixel which has the photoelectric converting layer B formed using the liquid film B were each examined with the optical microscope, the photoelectric converting layer A Was orange and the photoelectric conversion layer B was blue. Thereby, it became clear that mixing of a pigment | dye etc. was not recognized.

It is a fragmentary sectional view showing an embodiment at the time of applying a photoelectric conversion element of the present invention to a solar cell. It is AA sectional view taken on the line of the solar cell shown in FIG. It is a figure for demonstrating the manufacturing method of the solar cell shown in FIG. 1 and FIG. It is a top view which shows the calculator to which the electronic device of this invention is applied. It is a perspective view which shows the mobile telephone (PHS is also included) to which the electronic device of this invention is applied.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Solar cell 2 ... Substrate 3 ... 1st electrode 4 ... Photoelectric conversion layer 41 ... Liquid coating 5 ... Hole transport layer 6 ... 2nd electrode 7 ... Opposite substrate 8 ... Barrier Layers 91, 92 ...... Bulkhead 10 ...... External circuit 93, 94 …… Space 100 …… Calculator 101 ...... Body part 102 ...... Display part 103 ...... Operation button 104 …… Solar cell installation part 200 …… Cell phone 201 …… Main body 202 …… Display unit 203 …… Operation buttons 204 …… Earpiece 205 …… Transmission port 206 …… Solar cell installation unit

Claims (19)

A method for producing a composition for forming a photoelectric conversion layer used for forming a photoelectric conversion layer provided in a photoelectric conversion element,
Collecting the electron transport material to obtain aggregate particles of the electron transport material;
A step of supporting a dye on the aggregated particles;
A method for producing a composition for forming a photoelectric conversion layer, comprising the step of dispersing aggregated particles carrying the dye in a dispersion medium to obtain a composition for forming a photoelectric conversion layer.   The method for producing a composition for forming a photoelectric conversion layer according to claim 1, wherein the dye is supported on the aggregated particles by bringing the aggregated particles into contact with a dye solution containing the dye.   The method for producing a composition for forming a photoelectric conversion layer according to claim 2, wherein the immersion time is 1 to 30 hours.   The method for producing a composition for forming a photoelectric conversion layer according to claim 2 or 3, wherein the temperature of the dye solution in which the aggregate particles are immersed is 10 to 40 ° C.   The composition for forming a photoelectric conversion layer according to any one of claims 1 to 4, wherein the aggregated particles are obtained by partially joining the electron transport materials by performing a heat treatment on the plurality of electron transport materials. Manufacturing method.   The method for producing a composition for forming a photoelectric conversion layer according to claim 1, wherein the aggregate particle has an average particle diameter of 20 to 100 nm.   The method for producing a composition for forming a photoelectric conversion layer according to any one of claims 1 to 6, wherein the number of electron transport materials constituting one aggregated particle is 2 to 100.   A composition for forming a photoelectric conversion layer, which is produced by the method for producing a composition for forming a photoelectric conversion layer according to claim 1. A method for manufacturing a photoelectric conversion element, which manufactures a photoelectric conversion element having a photoelectric conversion layer containing aggregated particles of an electron transport material and a dye between a first electrode and a second electrode,
A first step of forming a liquid film by supplying the composition for forming a photoelectric conversion layer according to claim 8 on one surface side of the first electrode;
And a second step of forming the photoelectric conversion layer by removing the dispersion medium from the liquid film.   The method for producing a photoelectric conversion element according to claim 9, wherein in the first step, the composition for forming a photoelectric conversion layer is supplied by a droplet discharge method while controlling a supply position.   The method for manufacturing a photoelectric conversion element according to claim 10, wherein in the first step, the liquid film or the aggregate thereof constitutes predetermined information or a predetermined design.   In the first step, by selectively supplying a plurality of types of the composition for forming a photoelectric conversion layer containing the dyes of different colors, a plurality of liquid coatings separated from each other constitute an image as a whole. Item 12. A method for producing a photoelectric conversion element according to Item 10 or 11.   The method for manufacturing a photoelectric conversion element according to claim 10, wherein in the first step, a plurality of the liquid films are formed in a matrix. The method for manufacturing a photoelectric conversion element according to claim 13, wherein a plane area of one liquid coating film is 100 to 10,000 μm ² .   The method for producing a photoelectric conversion element according to claim 9, further comprising a step of forming a partition that defines a contour shape of the liquid film prior to the first step. A method for manufacturing a photoelectric conversion element for manufacturing a photoelectric conversion element having a photoelectric conversion layer containing an electron transport material and a dye between a first electrode and a second electrode,
A first step of preparing a composition for forming a photoelectric conversion layer in which the electron transport material carrying the dye is dispersed in a dispersion medium;
And a second step of supplying the composition for forming a photoelectric conversion layer to one surface side of the first electrode by a droplet discharge method.   A photoelectric conversion element manufactured by the method for manufacturing a photoelectric conversion element according to claim 9.   The photoelectric conversion element according to claim 17, wherein the photoelectric conversion layer or the aggregate thereof constitutes predetermined information or a predetermined design.   An electronic device comprising the photoelectric conversion element according to claim 17.

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