JP2001357897A - Photoelectric conversion module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectric conversion module capable of providing a high voltage and manufacturable at a low cost. SOLUTION: This photoelectric conversion module has an insulating transparent backing 1 and an opposed insulating backing 5 with a plurality of photoelectric conversion element 10 and 10' parallel disposed between them, and it is characterized in that the conversion element 10 and 10' comprise transparent conductive members 2 and 2' provided on a surface of the backing 1, photo- semiconductor electrodes 3 and 3' provided on surfaces of the members 2 and 2', counter electrode members 6 and 6' provided on a surface of the insulating backing 5, and oxidizing and reducing media 9 and 9' sealed between the electrode members 6 and 6' and the electrodes 3 and 3', that the peripheries of the conversion element 10 and 10' are sealed and insulated by sealing means 8, and that a conduction means 11a capable of causing the conductive member 2 of the conversion element 10 to conduct to the electrode member 6' of the neighboring conversion element 10' is disposed between the conversion element 10 and 10'.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoelectric conversion module having a plurality of photoelectric conversion elements, and more particularly to a low-cost photoelectric conversion module having a high output voltage.

[0002]

2. Description of the Related Art Global warming due to the burning of fossil fuels and an increase in energy demand due to an increase in population have become a major problem relating to the survival of humankind. Under such circumstances, utilization of sunlight as an infinite and clean energy source that does not generate harmful substances is being studied. The sun has nurtured the earth's environment since ancient times and has been a source of energy for all living beings, including humans. Above all, so-called solar cells that convert light energy into electrical energy
It is drawing attention as a powerful technical tool.

As photovoltaic materials for solar cells, single crystal, polycrystal, amorphous silicon, CuInSe, G
Compound semiconductors such as aAs and CdS are used. Solar cells using these inorganic semiconductors exhibit relatively high energy conversion efficiencies of 10 to 20%, and are therefore widely used as power supplies for remote locations and as auxiliary power supplies for small portable electronic devices.

[0004] However, in light of the purpose of suppressing the consumption of fossil fuels and preventing the deterioration of the global environment as described above, at present, a solar cell using an inorganic semiconductor is not sufficiently effective. Hard to say. This is because a solar cell using an inorganic semiconductor is manufactured by a plasma CVD method or a high-temperature crystal growth process, and requires a lot of energy to manufacture an element. Also, Cd, A
It contains components that may have a harmful effect on the environment, such as s and Se, and there is a concern about the possibility of environmental destruction due to element disposal.

[0005] On the other hand, many solar cells using organic materials have been proposed for the purpose of increasing the area and reducing the cost (for example, JP-A-53-131782, JP-A-54-17882). 27387, JP-A-56-35577, JP-A-1-215070, JP-A-4-105
76, JP-A-6-85294. But,
All of them have not been put into practical use due to the problems of low conversion efficiency and poor durability.

Under these circumstances, Nature (No. 3)
53, 737-740, 1991), U.S. Patent Nos. 4,927,721, 4,684,537 and 50.
No. 84365, No. 5350644, No. 54630
Nos. 57 and 5525440, JP-A 1-2
JP-A-20380 and JP-B-8-15097 disclose a photoelectric conversion element using semiconductor fine particles sensitized by a dye (hereinafter, may be referred to as a "dye-sensitized photoelectric conversion element") and a method of manufacturing the same. Materials and manufacturing techniques have been disclosed.

The disclosed dye-sensitized photoelectric conversion element is characterized in that a titanium dioxide porous thin film spectrally sensitized with a ruthenium complex is used as a working electrode. Since this element can be used without purification of an inexpensive oxide semiconductor to high purity, it is expected that a photoelectric conversion element can be provided at low cost. Further, the absorption wavelength region of the dye used is wide, and a high energy conversion efficiency of about 10% (AM1.5) is achieved. As described above, the dye-sensitized photoelectric conversion element has a possibility of realizing high energy conversion efficiency at low cost, and active research has been conducted for the purpose of elucidating its principle and realizing higher conversion efficiency. I have.

Since the output voltage (open-circuit voltage) of the dye-sensitized photoelectric conversion element is usually less than 1 V, it is necessary to connect a plurality of elements in series in order to obtain a voltage exceeding 1 V which is generally required. . However, for example, in order to obtain an output of 12 V by connecting elements having an open-circuit voltage of 0.6 V in series, it is necessary to connect as many as 20 elements in series, which results in an overall increase. Although it is possible to reduce the size of one element, the manufacturing efficiency is reduced and the cost is increased.
Therefore, there is a need for an element configuration and a module manufacturing method that can obtain a high voltage by a simple method.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photoelectric conversion module which can obtain a high voltage and can be manufactured at low cost.

[0010]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have found that at least the transparent conductive member of one photoelectric conversion element and the counter electrode member of the adjacent photoelectric conversion element The present inventors have found that providing a conducting means capable of conducting both allows a photoelectric conversion module having a high output voltage to be manufactured at low cost, and reached the present invention. That is, the present invention

<1> A photoelectric conversion module in which an insulating transparent support and an insulating support are opposed to each other and a plurality of photoelectric conversion elements are provided in parallel therebetween, wherein the photoelectric conversion element is
A transparent conductive member provided on the surface of the insulating transparent support, an optical semiconductor electrode provided on the surface of the transparent conductive member, a counter electrode member provided on the surface of the insulating support, A counter-electrode member and an oxidation-reduction medium sealed between the optical semiconductor electrodes, and the periphery of the photoelectric conversion element including between the adjacent photoelectric conversion elements is sealed and insulated by sealing means, and The transparent conductive member of the photoelectric conversion element except for the one located at one end of the photoelectric conversion element, and a conduction unit capable of conducting between the opposing electrode member of the adjacent photoelectric conversion element is provided between adjacent photoelectric conversion elements. It is a photoelectric conversion module characterized by being arranged.

<2> The transparent conductive member and the counter electrode member which are conducted by the conducting means have portions facing each other between adjacent photoelectric conversion elements. <1>
>

<3> The sealing means is a sealing member, a conductive connecting member as the conducting means is covered with the sealing member, and one of the conductive connecting members is connected to the transparent conductive member. The other is a photoelectric conversion module described in <1> or <2>, wherein the other is connected to a counter electrode member of an adjacent photoelectric conversion element.

<4> The conductive means is formed of an insulating transparent support and an anisotropic conductive member having conductivity only in a direction substantially perpendicular to the insulating support, and sealing between the adjacent photoelectric conversion elements. The photoelectric conversion module according to any one of <1> to <3>, which also serves as at least a part of the means.

<5> The photoelectric conversion module according to <4>, wherein the anisotropic conductive member is obtained by dispersing conductive particles in an insulating member.

<6> The photoelectric conversion module according to <5>, wherein the insulating member is made of the same material as that of the sealing member except between the adjacent photoelectric conversion elements.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The photoelectric conversion module of the present invention
The insulating transparent support and the insulating support are opposed to each other, and a plurality of photoelectric conversion elements are provided in parallel therebetween, and the photoelectric conversion element is provided on the surface of the insulating transparent support. A member, an optical semiconductor electrode provided on the surface of the transparent conductive member, a counter electrode member provided on the surface of the insulating support, and a redox sealed between the counter electrode member and the optical semiconductor electrode. Medium, and the periphery of the photoelectric conversion element including between the adjacent photoelectric conversion elements is sealed and insulated by sealing means, and the photoelectric conversion element excluding the one located at one end of the photoelectric conversion elements Conducting means for conducting between the transparent conductive member of the conversion element and the counter electrode member of the adjacent photoelectric conversion element is disposed between the adjacent photoelectric conversion elements.

The photoelectric conversion elements are connected in series by the above configuration. It should be noted that "excluding the one located at one end of the photoelectric conversion elements" means that when connected in series from one side, the transparent conductive member of the photoelectric conversion element at the end thereof is further converted to another photoelectric conversion element. This is because the terminal is not connected to the opposing electrode member of the element but is a terminal terminal. That is, in the photoelectric conversion module of the present invention, the photoelectric conversion elements located at both ends thereof are not provided for series connection,
The transparent conductive member and the counter electrode member serve as terminal terminals.
Hereinafter, the photoelectric conversion module of the present invention will be described in detail.

{1. Configuration of photoelectric conversion module≫As described above, the photoelectric conversion module of the present invention includes an insulating transparent support, a transparent conductive member, an optical semiconductor electrode, an insulating support, a counter electrode member, an oxidation-reduction medium, a sealing unit,
Conducting means. Hereinafter, these will be described.

<Insulating Transparent Support> Conventionally known insulating transparent supports can be used, and various types of glass and organic polymer films can be used. In particular,
Glasses such as soda glass, fused silica glass, and crystal quartz glass; resin plates such as acrylic resin, methacrylic resin, polycarbonate resin, polyester resin, polyvinyl acetal resin, polystyrene resin, styrene-acrylic resin, phenol-formaldehyde resin, and silicone resin Or a resin film; The insulative transparent support is not necessarily required to have transparency to all light, as long as at least an optical semiconductor electrode described later substantially transmits light having a wavelength having an effective sensitivity. Good.

<Transparent Conductive Member> The transparent conductive layer provided on the surface of the insulating transparent support is made of ITO (indium-tin composite oxide), tin oxide doped with fluorine,
Transparent conductive metal oxides such as aluminum-doped zinc oxide and niobium-doped titanium oxide are used. The transparent conductive member is not necessarily required to have transparency to all light, and it is sufficient that at least an optical semiconductor electrode described later substantially transmits light having a wavelength having an effective sensitivity. .

<Optical Semiconductor Electrode> As the optical semiconductor electrode provided on the surface of the transparent conductive layer, a conventionally known one is used. Specifically, a single crystal, polycrystal, amorphous silicon, inorganic or organic semiconductor layer is used. An optical semiconductor made of, for example, is used.

In addition, it is preferable that the optical semiconductor layer has a large surface area with respect to the projected area of the electrode and has a porous shape. As such an optical semiconductor, metal chalcogenides such as metal oxides, metal sulfides, and metal selenides; perovskites; and the like can be used.
Metal chalcogenides include titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum,
Oxides such as ruthenium, vanadium, niobium, and tantalum; cadmium sulfide, cadmium selenide, and the like are preferable.

On the other hand, as the perovskites, metal oxides containing at least one selected from strontium titanate, calcium titanate, barium titanate, titanium oxide, zinc oxide, tin oxide and ruthenium oxide are preferred. . Among these, metal oxides containing at least one selected from titanium oxide, zinc oxide, tin oxide, and ruthenium oxide are more preferable in terms of transparency, photoelectric conversion characteristics, and the like.

In order to efficiently absorb light, a conventionally known sensitizing dye may be supported on the photosemiconductor electrode. Any sensitizing dye can be used as long as it has a sensitizing effect. Specifically, xanthene dyes such as rhodamine B, rose bengal, eosin, and erythrosine; cyanine dyes such as quinocyanine and cryptocyanine; basic dyes such as phenosafranine, thiosine, and methylene blue; chlorophyll, zinc porphyrin, and magnesium porphyrin Porphyrin compounds; azo dyes, phthalocyanine compounds, Ru trisbipyridyl, complex compounds such as Ru complexes of the following structural formulas; and anthraquinone dyes, polycyclic quinone dyes, and thionin dyes.

[0026]

Embedded image

The sensitizing dye can be carried by a known method. Specific examples include a dry process such as a vacuum evaporation method, a coating method such as spin coating, an electric field deposition method, an electric field polymerization method, and a method such as a natural adsorption method of dipping in a solution of a compound to be supported. Above all, the natural adsorption method is
The sensitizing dye molecules can be uniformly supported in the pores of the porous photosemiconductor electrode, and no special device is required. This is a preferred method because it has many advantages such as being hardly carried on a substrate.

After adding (introducing) a compound having a reactive group capable of chemically reacting with the sensitizing dye (self-assembled molecule such as a silane compound or a thiol compound) to the semiconductor surface, the sensitizing dye and the compound (Self-assembled molecule) to chemically bond the sensitizing dye to the surface of the photosemiconductor electrode.

<Insulating Support> As the insulating support, any material may be used as long as it is electrically insulative and can form a counter electrode member on its surface, such as soda glass, fused silica glass, and crystal quartz glass. Glasses; resins such as acrylic resin, methacrylic resin, polycarbonate resin, polyester resin, polyvinyl acetal resin, polystyrene resin, styrene-acrylic resin, phenol-formaldehyde resin, silicone resin; iron, aluminum,
Metals such as nickel, chromium, stainless steel and the like or alloys thereof or metal oxides coated on the surface of the above-mentioned resin, and those obtained by laminating a sheet of the above-mentioned resin can be used. Note that, unlike the insulating transparent support described above, the insulating support does not need to be transparent.

<Counter electrode member> The counter electrode member formed on the surface of the insulating support has high conductivity, and the oxidation-reduction reaction with the electrolytic solution is rapidly performed at the interface, and
Anything can be used as long as it is not redox itself. Specifically, platinum, palladium, rhodium, ruthenium, carbon, or the like that has a small overvoltage for the oxidation-reduction reaction can be used.

It is preferable that the counter electrode member has a sufficiently low resistance value. Specifically, when the counter electrode member is in the form of a layer, the surface resistance is preferably 1000 Ω / □ or less, more preferably 10 Ω / □ or less, and 1 Ω / □ or less.
/ □ or less is more preferable. Further, it is preferable that the counter electrode member has a property of reflecting light.
If the counter electrode member having such a property is used, it is possible to improve the utilization efficiency of the irradiation light by reflecting the irradiation light passing through the optical semiconductor electrode and irradiating the light to the optical semiconductor electrode again.

<Oxidation-Reduction Medium> The oxidation-reduction medium is obtained by dissolving an electrolyte in a solvent and functions as an electrolyte. The oxidation-reduction medium is required to be a material that allows the oxidation-reduction reaction in the optical semiconductor electrode and the counter electrode member to rapidly progress, and that quickly transports the charges in the oxidation-reduction medium.

The electrolyte used for such a redox medium includes iodide ion / iodine, bromide ion /
Bromine, quinone / hydroquinone, iron (II) ion / iron (III) ion, copper (I) ion / copper (II) ion, and the like. As a solvent used for the electrolytic solution, water or a polar solvent such as acetonitrile, pyridine, dimethylacetamide, propylene carbonate, ethylene carbonate, or a mixture thereof can be used. For the purpose of increasing the electrical conductivity of the redox medium, a supporting electrolyte may be added. As the supporting electrolyte, calcium chloride, sodium sulfate, ammonium chloride and the like can be used.

<Sealing Means> The sealing means in the present invention is mainly a sealing member, which is provided outside each photoelectric conversion element and plays a role of maintaining the sealing property as the photoelectric conversion element.

As a sealant for forming a seal member, a sealant which is insoluble in an electrolytic solution and has good adhesion to an adhesive surface is used. Specific examples include a silicone resin, an epoxy resin, an acrylic resin, and a glass powder paste. Of these, the resin may be either a thermosetting type or an ultraviolet setting type, but is preferably an ultraviolet setting type from the viewpoint of workability. A well-known sealing agent used for manufacturing a liquid crystal display panel or a plasma display panel may be used. In addition, a configuration may be adopted in which a conduction unit described later also serves as a sealing unit, but details thereof will be described later.

<Conducting Means> The conducting means is capable of conducting between the transparent conductive member of one photoelectric conversion element and the opposing electrode member of the adjacent photoelectric conversion element, and connects adjacent photoelectric conversion elements in series. It has the function of connecting to

As an example of the conducting means, there is a conductive connecting member in which one is connected to a transparent conductive member and the other is connected to a counter electrode member of an adjacent photoelectric conversion element. In this case, the conductive connection member needs to be covered with a sealing member as sealing means in order to ensure insulation between adjacent photoelectric conversion elements. As the material of the conductive connecting member,
Metals such as gold, silver, copper, iron, aluminum, nickel, and chromium; conductive metal oxides such as tin oxide and indium oxide; or conductive fine particles and / or conductive fine powder such as carbon were formed into a paste. And the like can be preferably used. Specifically, for example, a gold paste in which gold is dispersed, a silver paste in which silver is dispersed, a carbon paste in which carbon is dispersed, and the like can be preferably used. In addition, a material such as gold, indium, graphite, or the like, which has conductivity and can be deformed and pressed by mechanical pressing to be electrically connected can be used.

Further, an anisotropic conductive member having conductivity only in one direction and insulating property in the other direction may be used as the conduction means. If an anisotropic conductive member is used, it has not only the function of the conducting means but also the function of the sealing means described above. Therefore, it is not necessary to newly provide the seal member for a portion disposed between the adjacent photoelectric conversion elements on the anisotropic conductive member.

As such an anisotropic conductive member, an ultra-thin conductive resin, a conductive resin fiber, a metal sheet, or a metal fiber and an insulating resin sheet are alternately bonded to each other and pressed. Anisotropic conductive sheet manufactured by slicing thinly in the cross-sectional direction, or a thin linear conductive fiber such as metal fiber is coated with insulating resin and bundled into multiple pieces and crimped. A conventionally known sheet such as an anisotropic conductive sheet manufactured by slicing thinly can be used.

Further, as the anisotropic conductive member, a member in which conductive particles are dispersed in an insulating member can be used.
In this case, as the insulating member, the same material as the sealing member (seal member) other than between the adjacent photoelectric conversion elements can be used. It may be made of a material. For example,
An acrylic thermosetting resin may be used for a sealing member other than between adjacent photoelectric conversion elements, and an epoxy thermosetting resin may be used as an insulating resin for the anisotropic conductive member. A silicon-based ultraviolet curable resin may be used. Preferred examples of the conductive particles include metal particles, metal oxide particles, resin particles, glass particles, and conductive rubber particles that have been subjected to a conductive treatment on the surface or the whole.

When the spacer particles are added to the outer peripheral sealing member as spacers for maintaining the distance between the optical semiconductor electrode and the counter electrode member, the conductive particles have the same size as the spacer particles. It is desirable that If the spacer particles are too large compared to the conductive particles, care must be taken because conduction between the transparent conductive member and the opposing electrode member of the adjacent photoelectric conversion element may be insufficient.

The conductive particles can also have the function of the spacer particles. In this case,
It is desired that the spacer has a size suitable for functioning as the spacer. In each case, specifically, 0.1
Is preferably selected from the range of
More preferably, it is selected from the range of 0.1 to 50 μm.

{2. Specific Example of Photoelectric Conversion Module 1 <First Example of Photoelectric Conversion Module> FIG. 1 is a schematic sectional view showing a first example of a photoelectric conversion module of the present invention.
This is because the two photoelectric conversion elements 10, 10 'provided between the same substrate (insulating support and insulating transparent support) are provided.
Are formed so as to be internally connected in series.

As a first example of the photoelectric conversion module,
The insulating transparent support 1 and the insulating support 5 face each other, and the transparent conductive members 2 and 2 ′ provided on the surface of the insulating transparent support 1 and the transparent conductive members 2 and 2 ′ therebetween. Between the opto-electrode members 6, 6 'and the opto-electrode members 6, 6' and the opto-semiconductor electrodes 3, 3 'provided on the surface of the insulating support 5. Photoelectric conversion elements 10, 1 comprising oxidation-reduction media 9, 9 'sealed in
0 ′ are provided in parallel, and two photoelectric conversion elements 1
The periphery of the photoelectric conversion elements 10 and 10 ′ including between 0 and 10 ′ is sealed by a seal member 8 as sealing means.

Further, the transparent conductive member 2 of the photoelectric conversion element 10 and the counter electrode member 6 'of the adjacent photoelectric conversion element 10'.
Conductive connecting member 11a as a conduction means capable of conducting
Is provided between the two photoelectric conversion elements 10 and 10 ′ with the periphery thereof covered with a seal member 8. In order for the transparent conductive member 2 and the counter electrode member 6 ′ to be connected by the conductive connection member 11 a, a portion of the transparent conductive member 2 in the photoelectric conversion element 10 and a portion in the photoelectric conversion element 10 ′ As shown in FIG. 1, it is preferable that a part of a certain counter electrode member 6 ′ has a facing portion (hereinafter, sometimes referred to as “overlapping portion”). With such a configuration having the overlapping portion, the transparent conductive member 2 and the counter electrode member 6 ′ can be easily connected to each other simply by overlapping the upper and lower substrates in a method of manufacturing a photoelectric conversion module described later. And high accuracy is not required for the alignment between the two.

Although one end of the conductive connecting member 11a is connected to only the transparent conductive member 2, it may be connected to both the transparent conductive member 2 and the optical semiconductor electrode 3. Although there is no problem in principle if it is connected only to the optical semiconductor electrode 3, it is preferable that it is connected to at least the transparent electrode member 2 in order to keep the internal resistance low.

FIG. 2A is a schematic cross-sectional view of the photoelectric conversion module of FIG. 1 as viewed from the AA direction. FIG.
FIG. 2B shows a state in which the conductive connecting member 11a and the sealing member (sealing member) 8 are removed from FIG. That is, FIG. 2B shows a structure in which transparent conductive members 2 and 2 ′ and optical semiconductor electrodes 3 and 3 ′ are sequentially formed on the surface of the insulating transparent support 1, and FIG. And a conductive connecting member 11a and a sealing member (sealing member) 8 are further provided.

FIG. 2B shows the case where the optical semiconductor electrode 3 is formed on a part of the surface of the transparent conductive member 2. May be formed so as to partially protrude from the periphery thereof, or may be formed so as not to contact at least the adjacent optical semiconductor electrode 3 ′. In addition, since the optical semiconductor electrodes 3 and 3 ′ are often porous as described above, the optical semiconductor electrodes 3 and 3 ′ penetrate the area where the sealing member 8 shown in FIG.
It is preferable to be configured so as not to contact with.

The conductive connecting member 11a provided between the photoelectric conversion elements 10 and 10 'is provided at least in a part of the overlapping portion 4, and is connected to the opposing electrode member 6, the transparent conductive member 2' and the optical semiconductor electrode 3 '. If the insulation between the conductive connection member 11 a and the conductive member 11 a is ensured by the seal member 8, it may be provided so as to protrude from the overlapping portion 4. Further, the conductive connecting member 11a does not need to be provided in the entire overlapping portion, but may be provided in at least one place, and may be provided separately in several places.

FIG. 3A is a schematic cross-sectional view of the photoelectric conversion module of FIG. 1 as viewed from the BB direction. FIG.
FIG. 3B shows a state in which the conductive connecting member 11a and the sealing member (sealing member) 8 are removed from FIG. That is, FIG. 3B shows that the counter electrode members 6 and 6 ′ are provided on the surface of the insulating support 5.
FIG. 3A shows a case where a conductive connecting member 11a and a seal member 8 are further provided thereon. Similar to the case where the optical semiconductor electrodes 3 and 3 ′ are provided, the counter electrode members 6 and 6 ′ may be formed so as not to be in contact with each other at least. .

FIGS. 2 and 3 show a state in which the injection ports 13, 13 'for introducing the oxidation-reduction medium 9 are provided in the photoelectric conversion elements 10, 10', which will be described later. It is drawn for convenience in the description of the manufacturing method. In these sectional views, the injection ports 13, 1
3 'are all closed by the sealing member 8.

According to the first example of the photoelectric conversion module of the present invention as described above, the transparent conductive member 2 and the counter electrode member 6 'are electrically connected by the conductive connecting member 11a, and Since the elements 10 and 10 ′ are joined in series, the voltage taken out from the protruding terminals of the counter electrode member 6 and the transparent conductive member 2 ′ (portions protruding left and right in each drawing) is one photoelectric. This is twice the voltage obtained from only the conversion element, and a high output voltage can be easily obtained.

The first embodiment of the photoelectric conversion module according to the present invention is described below.
Modifications of the example shown in FIGS. 4 and 5 are shown in FIGS. FIGS. 4A and 4B show the modified example in FIGS. 2A and 2B in the first example, and FIGS. 5A and 5B show FIGS. 3A and 3B in the first example. FIGS. 4A and 4B correspond to FIGS. 2A and 2B, respectively.
Members having the same functions as those in FIG. 3 are denoted by the same reference numerals as those in the drawings, and detailed description thereof will be omitted.

As shown in FIGS. 4 and 5, the overlapping portion 4 between the transparent conductive member 2 and the counter electrode member 6 'may be reduced. By doing so, the optical semiconductor electrodes 3 and
The area of 3 ′ can be made larger, and the amount of irradiation light can be more effectively utilized. 4 and 5
In the example shown in FIG. 2, the overlapping portion 4 is formed at one center, but may be at two places at both ends or three places at both ends and the center.
More may be formed according to the size of the substrate (insulating transparent support 1 and insulating support 5).

<Second Example of Photoelectric Conversion Module> FIG.
FIG. 4 is a schematic sectional view showing a second example of the photoelectric conversion module of the present invention. The second example is similar to the first example except that the anisotropic conductive member 11b is used as the conductive connection member.
Is the same as the example. Therefore, members having the same functions as in FIG. 1 of the first example are denoted by the same reference numerals as in FIG. 1, and detailed description thereof is omitted (the same applies to FIGS. 6 and 7 described later).

When the anisotropic conductive member 11b is used, the seal member 8 provided between the photoelectric conversion elements for insulation and sealing becomes unnecessary. The anisotropic conductive member 11b is provided so as to be perpendicular to the insulating transparent support 1 and the insulating support 5 and to cover at least the end face of the overlapping portion. Otherwise, there is a possibility that the transparent conductive member 2 or the counter electrode member 6 ′ may be in electrical contact with the adjacent redox media 9, 9 ′.

The anisotropic conductive connection member 11b has conductivity in a direction perpendicular to the insulating transparent support 1 and the insulating support 5, and electrically connects the transparent conductive member 2 and the counter electrode member 6 '. Although they are connected, they have insulating properties in a direction horizontal to the insulating transparent support 1 and the insulating support 5. Therefore, the adjacent oxidation-reduction media 9, 9 'are electrically insulated from each other. Therefore, in the first example, the conductive connection member 11
The seal member 8 arranged so as to surround “a” becomes unnecessary.

As such an anisotropic conductive connection member 11b, a known one can be used as long as it has conductivity only in a direction perpendicular to the bonding surface. In particular,
An anisotropic conductive adhesive film, an anisotropic conductive adhesive, and the like used for bonding various circuit boards and the like can be used.

FIG. 7A is a schematic cross-sectional view of the photoelectric conversion module of FIG. 6 as viewed from the AA direction. FIG.
FIG. 7B shows a state in which the anisotropic conductive member 11b and the sealing member (sealing member) 8 are removed from FIG. That is, FIG. 7B shows a structure in which transparent conductive members 2 and 2 ′ and optical semiconductor electrodes 3 and 3 ′ are sequentially formed on the surface of the insulating transparent support 1, and FIG. It shows a member provided with an anisotropic conductive member 11b and a sealing member (sealing member) 8.

On the other hand, BB of the photoelectric conversion module of FIG.
FIG. 8A is a schematic sectional view viewed from the direction. FIG. 8B shows a state in which the anisotropic conductive member 11b and the sealing member (sealing member) 8 are removed from FIG. 8A. That is, FIG. 8B shows a structure in which opposing electrode members 6 and 6 ′ are formed on the surface of the insulating support member 5, and FIG. Represents what is provided. The opposing electrode members 6, 6 '
Similarly to the case where 3 ′ is provided, the seal member 8 may be formed so as not to contact at least the adjacent photoelectric conversion element.
There is no problem even if the size is such that it comes into contact with.

As the anisotropic conductive member 11b, a material obtained by separating and dispersing conductive particles in a curable medium (insulating member) can be used. For example, a material obtained by separating and dispersing conductive particles in an epoxy adhesive (epoxy resin) can be printed by the same method as a sealant such as screen printing, so that the method of use is simple. As the curable medium, the same material as the sealant can be used as it is, so that the substrate (the above-mentioned various electrodes are formed in a desired pattern on the insulating transparent support 1 or the insulating support 5 as necessary) After printing the sealant on the surface, the conductive particles can be printed only on the portion where the anisotropic conductivity is desired to be imparted.
In order to print the conductive particles later, the conductive particles may be directly sprayed, or a sealant in which the conductive particles are dispersed may be printed.

FIG. 9 is a schematic cross-sectional view showing an example in which conductive particles separated and dispersed in a curable medium (insulating member) are also used as anisotropic conductive members. In FIG. 9 as well, the basic configuration is the same as that of the first example except that an anisotropic conductive member composed of a curable medium 15 and conductive particles 14 is used as the conductive connection member. Therefore, the first
Members having the same functions as in FIG. 1 of the example of FIG. 1 are denoted by the same reference numerals as in FIG. 1, and detailed description thereof will be omitted. In FIG. 9, the periphery of the overlapping portion (the portion of the conductive connection member including the curable medium 15 and the conductive particles 14) is exaggerated in the horizontal direction in the drawing.

As the material of the curable medium 15, it is preferable to use the same member as the seal member 8 from the viewpoint of manufacturing easiness (in this example, the same material will be described). In the figure, conductive particles 14 are separated and dispersed in a curable medium 15 to electrically connect the transparent conductive member 2 and the counter electrode member 6 ', and to adjacent redox media 9, 9'.
Keeps the insulation.

The conductive connecting member composed of the curable medium 15 and the conductive particles 14 includes a transparent conductive member 2, 2 'and an optical semiconductor electrode 3, 3' on the surface of the insulating transparent support 1 together with the sealing member 8. After coating (including the case where the conductive particles 14 are printed later) on the formed substrate or the substrate on which the opposing electrode members 6 and 6 ′ are formed on the surface of the insulating support 5, these substrates are bonded together. By simply pressing, the transparent conductive member 2 and the counter electrode member 6 ′ are in an electrically conductive state, and the curable medium 15 made of the same material as the seal member 8 exists in the horizontal direction in the drawing. Sex is maintained.

According to the above-described second embodiment of the photoelectric conversion module of the present invention, the transparent conductive member 2 and the counter electrode member 6 ′ are electrically connected by the anisotropic conductive member 11 b (or the conductive particles 14). Electrically conductive, the photoelectric conversion element 1
Since 0 and 10 'are joined in series, the voltage taken out from the protruding terminal (the portion protruding left and right in each drawing) of the counter electrode member 6 and the transparent conductive member 2' is one photoelectric conversion. This is twice the voltage obtained from only the conversion element, and a high output voltage can be easily obtained. Further, the anisotropic conductive member 11b (or the curable medium 15) also serves as a sealing means, so that there is no need to newly provide a sealing member, the manufacture is easy, and the area of the photoelectric conversion element per unit area is increased. Can be increased.

Although the photoelectric conversion module of the present invention has been described with reference to two examples, the present invention is not limited to the configurations of these examples. For example, in the above three examples, two photoelectric conversion elements are all arranged in parallel, and an example in which these are connected in series has been described. However, in the present invention,
Three or more photoelectric conversion elements may be arranged in parallel, and these may be connected in series. In this case, the connection between the first and second photoelectric conversion elements is the same as in the above three examples, and the connection between the second and third and subsequent photoelectric conversion elements is in accordance with this. Is repeated. Therefore, according to the present invention, any number of photoelectric conversion elements can be easily connected in series, and a photoelectric conversion module having a high output voltage can be manufactured at low cost.

{3. Method of Manufacturing Photoelectric Conversion Module Next, a method of manufacturing the photoelectric conversion module of the present invention will be described with reference to FIGS. 1 to 3 by taking the photoelectric conversion module of the second example of the present invention as an example. . Conventionally, the transparent conductive connecting members 2 and 2 ′ and the optical semiconductor electrodes 3 and 3 ′ formed on the surface of the insulating transparent support 1 and the counter electrode members 6 and 6 ′ formed on the surface of the insulating support 5 are conventional. By a known method, it is formed in a pattern shown in FIGS. 2B and 3B. For example,
A film formed on the entire surface of these supports, a method of forming an arbitrary shape by various lithography methods, or a desired pattern on the surface of the support by vapor deposition, sputtering, printing, or the like through a mask provided in advance. A method for forming a layer can be given.

A sealing member 8 is provided on the surface of one of the insulating transparent substrate 1 on which the optical semiconductor electrodes 3 and 3 'are formed and the substrate on which the opposing electrode member 6 is formed. Is applied. The sealant is applied by a conventionally known method such as screen printing or a manipulator. Further, similarly, a conductive connecting member precursor such as paste-like silver which can be used as the conductive connecting member 11a is applied. Thus, the substrate in the state of FIG. 2A or FIG. 3A is manufactured. Here, FIG.
The description proceeds assuming that the substrate in the state of FIG.

Next, the substrate shown in FIG. 2B and the substrate shown in FIG.
The substrate in the state of FIG. In this state, the sealing member 8 and the conductive connecting member precursor are cured to form a hollow space surrounded by the sealing member 8 between the optical semiconductor electrodes 3, 3 ′ and the counter electrode members 6, 6 ′. Is formed.

When an ultraviolet-curable sealant is used,
After curing by ultraviolet irradiation, before injecting the oxidation-reduction medium 9 described below, a further heat treatment may be performed.
It is preferable from the viewpoint of promoting the curing reaction more completely and improving the performance and the life as a photoelectric conversion module. The temperature of the heat treatment is desirably set slightly higher than the use temperature of the photoelectric conversion module. For example, if the temperature is to be used for a solar cell that is mounted on a roof, the temperature should be set to 80 to 120 ° C. Is desirable.

At this time, at least one sealing member 8 is not provided for one photoelectric conversion element, or one of the insulating transparent support 1 and the insulating support 5 is attached to the substrate on one of the electrodes. By providing at least one through hole per one photoelectric conversion element, the gap is connected to an external space. As means for providing the through holes, conventionally known means such as drilling, ultrasonic processing, laser processing and the like can be used. In FIG. 3A, two sealing members 8 are not provided for one photoelectric conversion element, and injection ports 13 and 13 'are provided.

In order to maintain a constant distance between the photoelectric conversion electrode 3 and the counter electrode member 6, spacer particles are sprayed on one of the substrates and / or the sealing member 8
May be added with spacer particles. As the spacer particles, conventionally known ones used in the production of liquid crystal display panels and the like are preferably used as they are, and resin particles, resin fibers, glass particles, and various kinds of glass fiber-like spacer particles are used. The distance (size of spacer particles) between the photoelectric conversion electrode 3 and the counter electrode member 6 is generally 500 μm or less, and is preferably as small as possible as long as the function as a spacer is not impaired. Specifically, it is preferably selected from the range of 0.1 to 500 μm, and more preferably selected from the range of 0.1 to 50 μm.

Through the above steps, a group of element precursors having voids whose periphery is sealed except for the injection ports 13 and 13 'are formed. Subsequently, the oxidation-reduction medium 9 is injected from the injection ports 13, 13 '. As a method of injecting, the redox medium 9 may be injected by utilizing the pressure difference between the inside and the outside after once depressurizing the void from the inlets 13 and 13 '.

The oxidation-reduction medium 9 is injected into every corner of the void.
For this purpose, the pressure is once reduced, and then the oxidation-reduction medium 9 is injected.
Is preferred. One example is the above process.
Insert each void provided in the device precursor group
Air is exhausted from the inlets 13 and 13 'by a vacuum device. That
Thereafter, with the pressure in the gap portion reduced, the injection ports 13 and 13 ′ are formed.
Is brought into contact with the redox medium 9, the redox medium 9 becomes empty.
Injected into the gap due to the pressure difference between the inside of the gap and the outside atmospheric pressure
Is done. The degree of vacuum in the depressurized state of the gap is 1 × 10^Four
Pa or less and 1 × 10^ThreeLess than Pa
Preferably 1 × 10 ^TwoMore preferably, it is Pa or less.
New After contacting with the oxidation-reduction medium 9 by reducing the pressure,
When injecting the redox medium 9 with a force difference, apply a total pressure difference
Immediate injection may cause uneven injection
Inject so that it is gradually injected using a variable valve, etc.
The speed may be adjusted.

After the voids are filled with the redox medium 9,
The inlets 13, 13 'are sealed. Sealing is performed for the injection port 13,
13 'and its surroundings may be applied and cured by applying the same sealing agent as described above. Also in this case, it is desirable to use an ultraviolet-curable sealant that does not require heating or the like and can be cured in a short time with a simple device. When the injection ports 13, 13 'are sealed by curing the sealant by irradiating ultraviolet rays, it is preferable to further perform a heat treatment as described above.

According to the above-described method, if the transparent conductive member 2 and the counter electrode member 6 'are patterned in advance so as to have an overlap, the sealant is provided at an appropriate position, and the conductive material is provided at the overlapped portion. The two photoelectric conversion elements 10 and 1 can be formed simply by applying and bonding the precursor of the conductive connection member.
One photoelectric conversion module in which 0's are internally connected in series can be manufactured easily and with good reproducibility.

If the anisotropic conductive member 11b as shown in FIGS. 6 to 8 is used as the conducting means, the insulation between the oxidation-reduction media 9, 9 'of the adjacent photoelectric conversion elements 10, 10' is separated. And the anisotropic conductive member 11b
It is not necessary to newly provide a sealing member for covering.

Transparent conductive member 2 and counter electrode member 6 '
Can be easily formed by known etching or masking. The formation of the seal member 8 and the conductive connecting member precursor (or the anisotropic conductive member) can be easily performed by a known screen printing or manipulator coating method, so that there is almost no increase in cost due to modularization.

[0079]

EXAMPLES Hereinafter, the photoelectric conversion module of the present invention will be specifically described, but the present invention is not limited thereto.

Example 1 20 × 40 × 1.1 (mm)
Was used as an insulating transparent support, an ITO etching pattern as shown in FIG. 2B was formed on the surface thereof, and transparent conductive members 2 and 2 ′ of 18 × 13 (mm) were provided. The sheet resistance of ITO is 10Ω / □
Met.

Titanium tetraisopropoxide 6.4
1 g was diluted with 20 ml of ethanol, and 0.514 g of nitric acid having a specific gravity of 1.38 and 0.2 ml of water were added with stirring. The above mixing operation was performed in a dry nitrogen atmosphere. This mixture was heated to 80 ° C. and reduced under a stream of dry nitrogen for 2 hours to obtain a colorless and transparent sol. After the sol was cooled to room temperature, 0.1 g of polyacrylic acid was dissolved in 2 g of the sol while stirring. Water 2 is added to the obtained sol solution.
The resulting solution was added to obtain a colorless, transparent and uniform sol solution. The sol was sealed in a glass container and heated to 80 ° C. The sol liquid gelled in about 5 minutes and became a nearly transparent and uniform gel.
When the gel was kept at 80 ° C. for further 15 hours, the gel was dissolved again to form a whitish translucent sol solution.

This sol solution was applied to the surface of the insulating transparent support 1 on which the transparent conductive members 2 and 2 ′ were formed. The sol solution was applied on the transparent conductive members 2 and 2 ′ in a pattern as shown in FIG. 2B by a screen printing method, heated to 450 ° C., held for 20 minutes, and fired. This coating and baking process was repeated 20 times to obtain a film thickness of 3.5 μm.
The optical semiconductor electrodes 3 and 3 ′ made of a porous TiO ₂ film having a thickness of m were formed.

A substrate in the state shown in FIG. 2B was placed in an ethanol solution of Ru complex having the following structural formula (concentration: 10 ⁻³ mol)
/ L) to adsorb a Ru complex as a sensitizing dye on the surfaces of the photosemiconductor electrodes 3 and 3 '. Thus, FIG.
A photoelectric conversion substrate in the state shown in (b) was obtained.

[0084]

Embedded image

On the photoelectric conversion substrate, a sealant as the seal member 8 and a conductive connection member 11a were formed by screen printing according to the pattern shown in FIG.
Note that the application width of the sealant was 2 mm, and the area of ITO (effective area per photoelectric conversion element of the finally manufactured photoelectric conversion module) was 18 (mm) × 13 (m).
m) = 234 (mm ² ). Thermosetting epoxy resin, conductive connection member 11 as a sealant
Silver paste was used as a. In addition, a total of four injection ports 13, 13 'are provided, two for one photoelectric conversion element.

A 20 × 40 × 1.1 (mm) soda glass was used as an insulating support, and Pt as shown in FIG.
A counter electrode member made of a thin film was formed by a sputtering method to obtain a counter substrate. The sheet resistance values of the counter electrode members 6 and 6 ′ were about 2Ω / □. A resin spacer having a diameter of 10 μm as spacer particles dispersed in acetonitrile was spin-cast on the surface of the opposing substrate to provide a spacer for maintaining a distance.

The photoelectric conversion substrate and the opposite substrate are connected to each other as shown in FIG.
Then, the overlapping portions 4 shown in FIG. 3B were adhered so as to be properly overlapped, and heated at 100 ° C. for 2 hours to cure the sealant.

In a mixed solution of ethylene carbonate and acetonitrile (volume mixing ratio = 4/1), tetrapropylammonium iodide (0.46 mol / l) and iodine (0.06 mol / l) were dissolved. Was prepared. This oxidation-reduction medium was injected into the gap from one of the injection ports provided in each photoelectric conversion element by utilizing the capillary phenomenon. All the injection ports 13, 13 'were sealed with an ultraviolet curing acrylic sealant. As described above, the photoelectric conversion module of the present invention was manufactured.

The thus obtained photoelectric conversion module was applied to a solar simulator with AM 1.5, 100 m
Irradiation with W / cm ² light resulted in an open-circuit voltage of 1.2 V. This is the same voltage as a commonly used nickel-metal hydride dry battery (rechargeable battery).

Comparative Example 1 The optical semiconductor electrode and the counter electrode member were not divided into a plurality of patterns, the internal connection was not performed by the conductive connection member, and only one photoelectric conversion element was provided (ie, the conductive connection in FIG. 1). No member 11a and no sealing member disposed on both sides thereof, and there is no distinction between the photoelectric conversion element 10 and the photoelectric conversion element 10 '. One form as a whole is formed. It was produced in the same manner as in Example 1.

When this photoelectric conversion module was irradiated with light of AM 1.5 and 100 mW / cm ² by a solar simulator, the open-circuit voltage was 0.6 V.

(Example 2) The anisotropic conductive member 11b was used as the conducting means, and the photoelectric conversion substrate formed in the pattern shown in FIG. 7B and the opposing photoelectric conversion substrate formed in the pattern shown in FIG. Substrates were manufactured in the same manner as in Example 1, and a photoelectric conversion module was manufactured. The anisotropic conductive member 11b was formed by attaching the anisotropic conductive double-sided tape to the overlapping portion 4 and then using the same thermosetting sealant as in Example 1 using a manipulator.

The thus produced photoelectric conversion module of the present invention was added to a solar simulator with AM1.5,
Irradiation with light of 100 mW / cm ² resulted in an open-circuit voltage of 1.2 V.

(Example 3) The sealant used in Example 1 was printed by screen printing around the photoelectric conversion element including the overlapping portion 4 shown in FIG. Example 2 except that resin particles having a diameter of about 10 μm were sprayed on the overlapping portion 4 to impart anisotropic conductivity.
In the same manner as in the above, a photoelectric conversion module was produced.

The thus prepared photoelectric conversion module of the present invention was added to a solar simulator with AM1.5,
Irradiation with light of 100 mW / cm ² resulted in an open-circuit voltage of 1.2 V.

[0096]

As described in detail above, since the photoelectric conversion module of the present invention has a plurality of photoelectric conversion elements internally connected in series, a high output voltage (for example, 1 V or more) can be easily obtained. Further, since it can be manufactured from a known material, the cost can be reduced.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a first example of a photoelectric conversion module according to the present invention.

FIG. 2 (a) is a diagram illustrating the photoelectric conversion module of FIG.
FIG. 2B is a schematic cross-sectional view as viewed from the direction A, and FIG.
It is a schematic diagram which shows the state which removed 8.

FIG. 3 (a) is a diagram illustrating the photoelectric conversion module of FIG.
FIG. 3B is a schematic cross-sectional view as viewed from the direction B, and FIG.
It is a schematic diagram which shows the state which removed 8.

4A and 4B show a modification of the first example of the photoelectric conversion module of the present invention, and FIG. 4A corresponds to a schematic cross-sectional view of the photoelectric conversion module of FIG.
(B) corresponds to a schematic diagram illustrating a state in which the conductive connection member 11a and the sealing member (sealing member) 8 are removed from (a).

5A and 5B show a modification of the first example of the photoelectric conversion module of the present invention. FIG. 5A corresponds to a schematic cross-sectional view of the photoelectric conversion module of FIG.
(B) corresponds to a schematic diagram illustrating a state in which the conductive connection member 11a and the sealing member (sealing member) 8 are removed from (a).

FIG. 6 is a schematic sectional view showing a second example of the photoelectric conversion module of the present invention.

FIG. 7A is a diagram illustrating A- of the photoelectric conversion module of FIG. 6;
FIG. 2B is a schematic cross-sectional view as viewed from the direction A, and FIG.
It is a schematic diagram which shows the state which removed 8.

FIG. 8A is a diagram illustrating the photoelectric conversion module of FIG.
FIG. 2B is a schematic cross-sectional view as viewed from the direction B, and FIG. 2B shows the conductive connecting member 11b and the sealing member (sealing member) from FIG.
It is a schematic diagram which shows the state which removed 8.

FIG. 9 is a schematic sectional view showing another embodiment of the second example of the photoelectric conversion module of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Insulating transparent support 2, 2 '... Transparent conductive support 3, 3' ... Optosemiconductor electrode 5 ... Insulating support 6,6 '... Counter electrode member 8 ... Seal member 9 ... Redox medium 10,10 '... Photoelectric conversion element 11a ... Conductive connection member 11b ... Anisotropic conductive member 13,13' ... Injection port 14. ..Conductive particles 15 ... Curable medium

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yoshiyuki Ono 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture F-Xerox Co., Ltd. F-term (reference) 5F051 BA11 DA20 EA02 FA02 FA06 FA10 FA11 FA16 FA30 GA03 5H032 AA06 AS16 EE16

Claims (6)

[Claims] 1. A photoelectric conversion module in which an insulative transparent support and an insulative support are opposed to each other and a plurality of photoelectric conversion elements are provided in parallel between the insulative transparent support and the insulative transparent support. A transparent conductive member provided on the surface of the body, an optical semiconductor electrode provided on the surface of the transparent conductive member, a counter electrode member provided on the surface of the insulating support, the counter electrode member and the An oxidation-reduction medium sealed between the optical semiconductor electrodes,
The periphery of the photoelectric conversion element including between the adjacent photoelectric conversion elements is sealed and insulated by sealing means, and the transparent conductivity of the photoelectric conversion element excluding the one located at one end of the photoelectric conversion elements A photoelectric conversion module, characterized in that conducting means capable of conducting between a member and a counter electrode member of an adjacent photoelectric conversion element is disposed between adjacent photoelectric conversion elements. 2. The photoelectric conversion module according to claim 1, wherein the transparent conductive member and the counter electrode member which are conducted by the conducting means have portions facing each other between adjacent photoelectric conversion elements. . 3. The sealing means is a sealing member, a conductive connecting member as the conducting means is covered with the sealing member, one of the conductive connecting members is connected to a transparent conductive member, and the other is. 3. The photoelectric conversion module according to claim 1, wherein the photoelectric conversion module is connected to a counter electrode member of an adjacent photoelectric conversion element. 4. The conductive means comprises an insulating transparent support and an anisotropic conductive member having conductivity only in a direction substantially perpendicular to the insulating support, and sealing means between the adjacent photoelectric conversion elements. The photoelectric conversion module according to any one of claims 1 to 3, wherein the photoelectric conversion module also serves as at least a part of: 5. The photoelectric conversion module according to claim 4, wherein the anisotropic conductive member is formed by dispersing conductive particles in an insulating member. 6. The photoelectric conversion module according to claim 5, wherein the insulating member is made of the same material as a member of the sealing unit except between the adjacent photoelectric conversion elements.