WO2014168119A1 - 光電変換素子、色素増感太陽電池およびこれに用いる金属錯体色素 - Google Patents
光電変換素子、色素増感太陽電池およびこれに用いる金属錯体色素 Download PDFInfo
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- WO2014168119A1 WO2014168119A1 PCT/JP2014/060108 JP2014060108W WO2014168119A1 WO 2014168119 A1 WO2014168119 A1 WO 2014168119A1 JP 2014060108 W JP2014060108 W JP 2014060108W WO 2014168119 A1 WO2014168119 A1 WO 2014168119A1
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- photoelectric conversion
- alkyl group
- dye
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 107
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B19/00—Oxazine dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B21/00—Thiazine dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/008—Dyes containing a substituent, which contains a silicium atom
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a photoelectric conversion element, a dye-sensitized solar cell, and a metal complex dye used therefor.
- Photoelectric conversion elements are used in various optical sensors, copiers, solar cells and the like.
- Various types of photoelectric conversion elements have been put to practical use, such as those using metals, semiconductors, organic pigments and dyes, or combinations thereof.
- a solar cell using non-depleting solar energy does not require fuel, and its full-scale practical use is expected as an inexhaustible clean energy.
- silicon solar cells have been researched and developed for a long time. It is spreading due to the policy considerations of each country.
- silicon is an inorganic material and naturally has limitations in throughput and molecular modification.
- Patent Document 1 describes a dye-sensitized photoelectric conversion element using semiconductor fine particles sensitized with a ruthenium complex dye by applying this technique. Furthermore, the development of ruthenium complex-based sensitizing dyes continues to improve the photoelectric conversion efficiency (see Patent Document 2).
- Patent Document 2 is an improvement of this. These metal complex dyes are not sufficiently durable, and further improvement in photoelectric conversion efficiency has been demanded. However, it has been difficult to achieve both durability and photoelectric conversion efficiency.
- an object of the present invention is to provide a photoelectric conversion element, a dye-sensitized solar cell, and a metal complex dye used therefor, which are excellent in both durability and photoelectric conversion efficiency.
- M 1 represents a metal atom
- Z 1 represents a monodentate ligand
- LA represents a tridentate ligand represented by the following formula (AL-1).
- LD represents a bidentate ligand represented by the following formula (DL-1).
- CI represents a counter ion necessary for neutralizing the electric charge.
- Za, Zb and Zc represent a nonmetallic atom group necessary for forming a 5-membered ring or a 6-membered ring. However, at least one of the rings formed by Za, Zb and Zc has an acidic group.
- m1 represents an integer of 0 to 3
- m2 represents an integer of 1 to 4
- n1 represents an integer of 1 to 4.
- L 1 represents an arylene group, an alkynylene group or an alkynylene arylene group
- R 1 represents an amino group, an alkylamino group, an arylamino group, a heteroarylamino group, a halogen atom, an alkyl group, an alkynyl group, an alkoxy group, an aryloxy group.
- l1 represents an integer of 0 to 3
- R 2a represents a substituent different from-[(L 1 ) m1- (R 1 ) m2].
- E represents a group represented by the following formulas (E-1) to (E-6), (E-21) or (E-22).
- R represents a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group.
- m represents an integer of 0 or more.
- * indicates a bonding position for bonding to the 2-position of the pyridine ring.
- R represents a hydrogen atom, an alkyl group, a phenyl group, or an aryloxy group.
- E, L 1 , m1, m2, n1, R 2a and l1 have the same meanings as E, L 1 , m1, m2, n1, R2a and l1 in formula (DL-1).
- R 21 and R 22 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. R 21 and R 22 may be bonded to each other to form a ring.
- L 1 is an arylene group.
- ⁇ 4> The photoelectric conversion element according to ⁇ 1> or ⁇ 2>, wherein the bidentate ligand represented by the formula (DL-1) is represented by the following formula (DL-3).
- E, R 21, R 22, n1, R 2a and l1 are the same E, and R 21, R 22, n1, R 2a and l1 in formula (DL-2).
- ⁇ 5> The photoelectric conversion device according to any one of ⁇ 1> to ⁇ 4>, wherein M 1 is Ru.
- ⁇ 6> The photoelectric conversion device according to any one of ⁇ 1> to ⁇ 5>, wherein LA is represented by the following formula (AL-3).
- R A1 , R A2 and R A3 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or an acidic group. However, at least one of R A1 , R A2 and R A3 is an acidic group.
- E is a formula (E-2) or a formula (E-5).
- ⁇ 8> The photoelectric conversion element according to any one of ⁇ 1> to ⁇ 7>, wherein the metal complex dye is represented by the following formula (II).
- R A1 ⁇ R A3 have the same meanings as R A1 ⁇ R A3 in the formula (AL-3).
- R 21, R 22, L 1 , m1 and m2 have the same meanings as R 21, R 22, L 1 , m1 and m2 in formula (DL-2).
- W represents a nitrogen atom or CH.
- R 10 represents a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group or a heteroaryl group.
- Z 2 represents an isothiocyanate group, an isoselenocyanate group, an isocyanate group, a halogen atom or a cyano group.
- R A1 ⁇ R A3 have the same meanings as R A1 ⁇ R A3 in the formula (AL-3).
- ⁇ 10> The photoelectric conversion device according to any one of ⁇ 2> to ⁇ 9>, wherein R 21 and R 22 are selected from an alkyl group and an aryl group.
- ⁇ 11> The photoelectric conversion device according to any one of ⁇ 2> to ⁇ 10>, wherein R 21 is an alkyl group or an aryl group, and R 22 is an aryl group.
- LD is represented by any of the following formulas (DL-2) to (DL-4).
- E, R 1 and m2 are E in the formula (DL-1), R 1 and m2 synonymous.
- X 1 represents —C (Ra) (Rb) —, an ethynylene group, —S— or —O—.
- Ra and Rb each independently represents a hydrogen atom or an alkyl group.
- R 2 represents a halogen atom.
- R 3 represents a hydrogen atom or an alkyl group when X 1 is —C (Ra) (Rb) —, and represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group when X 1 is an ethynylene group, When X 1 is —S— or —O—, it represents an alkyl group or an aryl group.
- m2 is 2 or more, the plurality of R 1 may be the same as or different from each other.
- LD is represented by any of the following formulas (DL-23a) to (DL-23d) or (DL-24a) to (DL-24c): element.
- E has the same meaning as E in formula (DL-1).
- X 1 and R 3 have the same meaning as X 1 and R 3 in the formula (DL-3).
- X 2 represents —C (Ra) (Rb) —, an ethynylene group, —S— or —O—.
- Ra and Rb each independently represents a hydrogen atom or an alkyl group.
- R 4 represents a hydrogen atom or an alkyl group when X 2 is —C (Ra) (Rb) —, and represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group when X 2 is an ethynylene group, When X 2 is —S— or —O—, it represents an alkyl group or an aryl group.
- X 1 or X 2 is —C (Ra) (Rb) —, an ethynylene group, or —O—.
- ⁇ 16> The photoelectric conversion device according to ⁇ 14>, wherein X 1 or X 2 is —C (Ra) (Rb) —, an ethynylene group, or —O—.
- X 1 or X 2 is —C (Ra) (Rb) —, an ethynylene group, or —O—.
- R 3 is an alkyl group having 5 or more carbon atoms.
- R 3 or R 4 is an alkyl group having 5 or more carbon atoms.
- ⁇ 19> The photoelectric conversion device according to any one of ⁇ 13> to ⁇ 18>, wherein R 3 is a linear alkyl group having 5 or more carbon atoms.
- R A1 ⁇ R A3 have the same meanings as R A1 ⁇ R A3 in the formula (AL-3).
- R 1, L 1, m1 and m2 have the same meanings as R 1, L 1, m1 and m2 in formula (DL-1).
- W represents CH.
- Z 2 represents an isothiocyanate group, an isoselenocyanate group, an isocyanate group, a halogen atom or a cyano group.
- R A1 ⁇ R A3 have the same meanings as R A1 ⁇ R A3 in the formula (AL-3).
- R 1 and m2 have the same meanings as R 1 and m2 in formula (DL-1).
- Z 2 has the same meaning as Z 2 in Formula (XXII).
- R C1 represents a substituent having an acidic group.
- R C2 represents a substituent.
- lc represents an integer of 0 or more.
- M 1 represents a metal atom
- Z 1 represents a monodentate ligand
- LA represents a tridentate ligand represented by the following formula (AL-1).
- LD represents a bidentate ligand represented by the following formula (DL-1).
- CI represents a counter ion necessary for neutralizing the electric charge.
- Za, Zb and Zc represent a nonmetallic atom group necessary for forming a 5-membered ring or a 6-membered ring. However, at least one of the rings formed by Za, Zb and Zc has an acidic group.
- m1 represents an integer of 0 to 3
- m2 represents an integer of 1 to 4
- n1 represents an integer of 1 to 4.
- L 1 represents an arylene group, an alkynylene group or an alkynylene arylene group
- R 1 represents an amino group, an alkylamino group, an arylamino group, a heteroarylamino group, a halogen atom, an alkyl group, an alkynyl group, an alkoxy group, an aryloxy group.
- l1 represents an integer of 0 to 3
- R 2a represents a substituent different from-[(L 1 ) m1- (R 1 ) m2].
- E represents a group represented by the following formulas (E-1) to (E-6), (E-21) or (E-22).
- R represents a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group.
- m represents an integer of 0 or more.
- * indicates a bonding position for bonding to the 2-position of the pyridine ring.
- R represents a hydrogen atom, an alkyl group, a phenyl group or an aryloxy group.
- R represents a hydrogen atom, an alkyl group, a phenyl group or an aryloxy group.
- R A1 ⁇ R A3 have the same meanings as R A1 ⁇ R A3 in the formula (AL-3).
- R 21, R 22, L 1 , m1 and m2 have the same meanings as R 21, R 22, L 1 , m1 and m2 in formula (DL-2).
- W represents a nitrogen atom or CH.
- R 10 represents a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group or a heteroaryl group.
- Z 2 represents an isothiocyanate group, an isoselenocyanate group, an isocyanate group, a halogen atom or a cyano group.
- R A1 ⁇ R A3 have the same meanings as R A1 ⁇ R A3 in the formula (AL-3). W, R 21, R 22, R 10 and Z 2, W in Formula (II), and R 21, R 22, R 10 and Z 2 synonymous.
- R represents a hydrogen atom, an alkyl group, a phenyl group or an aryloxy group.
- the carbon-carbon double bond may be any of E type and Z type in the molecule, or a mixture thereof.
- substituents, etc. linking groups, ligands, etc.
- substituents etc.
- a special notice is given.
- each substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like.
- substituents and the like when a plurality of substituents and the like are close to each other (especially when they are adjacent to each other), they may be connected to each other to form a ring unless otherwise specified.
- a ring such as an alicyclic ring, an aromatic ring, or a hetero ring may be further condensed to form a condensed ring.
- each substituent may be further substituted with a substituent unless otherwise specified.
- the present invention it has become possible to provide a photoelectric conversion element, a dye-sensitized solar cell, and a metal complex dye used therefor, both having excellent durability and photoelectric conversion efficiency.
- a photoelectric conversion element 10 includes a conductive support 1, a photoreceptor layer 2 including semiconductor fine particles 22 sensitized by a dye (metal complex dye) 21, It has a charge transfer layer 3 that is a hole transport layer and a counter electrode 4.
- the conductive support 1 provided with the photoreceptor layer 2 functions as a working electrode in the photoelectric conversion element 10.
- this photoelectric conversion element 10 is included in a system 100 using a dye-sensitized solar cell.
- the system 100 using a dye-sensitized solar cell enables the photoelectric conversion element 10 to be used as a battery for causing an external motor 6 to work an electric motor (electric fan) M as an operation means.
- the light-receiving electrode 5 includes a conductive support 1 and a photoreceptor layer 2 including semiconductor fine particles 22 adsorbed with a dye (metal complex dye) 21.
- the photoreceptor layer 2 is designed according to the purpose, and may be a single layer structure or a multilayer structure.
- the dye (metal complex dye) 21 in one layer of the photoreceptor layer may be one kind or a mixture of many kinds, and at least one of them is the metal complex dye of the present invention described later.
- the light incident on the photoreceptor layer 2 excites the dye (metal complex dye) 21.
- the excited dye has high energy electrons, and the electrons are transferred from the dye (metal complex dye) 21 to the conduction band of the semiconductor fine particles 22 and reach the conductive support 1 by diffusion. At this time, the dye (metal complex dye) 21 is an oxidant. Electrons on the electrodes work in the external circuit 6 and return to the photoreceptor layer 2 where the oxidant and electrolyte of the dye (metal complex dye) 21 are present via the counter electrode 4 to work as a solar cell.
- a manufacturing method usually used in this type of material may be employed.
- a manufacturing method usually used in this type of material may be employed.
- an outline of the main members will be described.
- the photoreceptor layer is a layer containing semiconductor fine particles containing an electrolyte described later and carrying a sensitizing dye containing the metal complex dye of the present invention described below.
- the metal complex dye of the first embodiment is represented by the following formula (I).
- M 1 represents a metal atom
- Z 1 represents a monodentate ligand
- LA represents a tridentate ligand represented by the following formula (AL-1).
- LD represents a bidentate ligand represented by the following formula (DL-1).
- CI represents a counter ion necessary for neutralizing the electric charge.
- Za, Zb and Zc represent a nonmetallic atom group necessary for forming a 5-membered ring or a 6-membered ring. However, at least one of the rings formed by Za, Zb and Zc has an acidic group.
- m1 represents an integer of 0 to 3
- m2 represents an integer of 1 to 4
- n1 represents an integer of 1 to 4.
- L 1 represents an arylene group, an alkynylene group or an alkynylene arylene group
- R 1 represents an amino group, an alkylamino group, an arylamino group or a heteroarylamino group.
- E represents a group represented by any of the following formulas (E-1) to (E-6).
- R represents a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group.
- m represents an integer of 0 or more.
- * indicates a bonding position for bonding to the 2-position of the pyridine ring.
- M 1 represents a metal atom.
- M 1 is preferably a metal capable of tetracoordination or hexacoordination, and examples thereof include elements of groups 6 to 12 on the long periodic table.
- M 1 is more preferably Ru, Os, Zn, Cu, Rh, Re, Mn or Zn.
- M 1 is particularly preferably Ru, Os, Zn or Cu, and most preferably Ru.
- the ligand LA is represented by the formula (AL-1).
- Za, Zb and Zc represent a nonmetallic atom group necessary for forming a 5-membered ring or a 6-membered ring.
- the 5-membered or 6-membered ring formed by Za, Zb and Zc may be substituted or unsubstituted, and may be monocyclic or condensed.
- Za, Zb and Zc are preferably atoms whose ring-constituting atoms are selected from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom.
- the ring atom may be substituted with a substituent including a hydrogen atom or a halogen atom.
- the ring formed by Za, Zb and Zc is more preferably an aromatic ring, that is, a nitrogen-containing aromatic ring.
- an imidazole ring, an oxazole ring, a thiazole ring or a triazole ring is preferably formed.
- a 6-membered ring a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferably formed.
- an imidazole ring or a pyridine ring is more preferable.
- At least one of the rings formed by Za, Zb and Zc has an acidic group.
- the acidic group is a substituent having a dissociable proton, and examples thereof include a carboxy group, a phosphonyl group, a phosphoryl group, a sulfo group, and a boric acid group, and a carboxy group is preferable.
- the acidic group may be in a dissociated state by releasing a proton or may be a salt. Although it does not specifically limit as a counter ion in the case of becoming a salt, For example, the example of the positive ion in the following counter ion CI is mentioned.
- the acidic group mentioned here and its preferable range may be called acidic group Ac.
- Examples of the counter ion CI include alkali metal ions and onium ions.
- Alkali metal ions include K ions, Na ions, Li ions, and cesium ions. Preferably they are K ion, Na ion, cesium ion, More preferably, it is K ion.
- Examples of onium ions include ammonium ions and pyridinium ions. Examples of ammonium ions include tetraalkylammonium ions, benzyltrialkylammonium ions, and quaternary ammonium ions in which aryl groups and alkyl groups are mixed. Ammonium ions are preferred.
- the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 2 to 6 carbon atoms. Of these, tetrabutylammonium ions are preferred.
- the ligand LA is preferably a ligand represented by the following formula (AL-2).
- Ac 1 , Ac 2 and Ac 3 each independently represents an acidic group.
- the acidic group those exemplified as the acidic group Ac are preferable.
- R L1 , R L2 and R L3 each independently represent a substituent. As for this substituent, the below-mentioned substituent T is mentioned, for example.
- R L1 , R L2 and R L3 are preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an amino group, an alkylamino group or an arylamino group, and an alkyl group, an aryl group or a heteroaryl group Are more preferable, and a heteroaryl group is particularly preferable.
- a1, a3, b1 and b3 each independently represents an integer of 0 to 4
- a2 and b2 each independently represent an integer of 0 to 3.
- a1 to a3 are not all 0.
- the ligand LA is preferably a ligand represented by the following formula (AL-3).
- R A1 , R A2 and R A3 each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acidic group or a group containing an acidic group. However, at least one of R A1 , R A2 and R A3 is an acidic group or a group containing an acidic group.
- the acidic group is preferably an acidic group Ac.
- R A1 , R A2 and R A3 are preferably acidic groups, and more preferably all three are acidic groups. Especially, it is preferable that all are a carboxy group or its salt.
- the ligand LD is represented by the formula (DL-1).
- L 1 represents an arylene group, an alkynylene group or an alkynylene arylene group, and among them, an arylene group is preferable.
- Examples of the arylene group in L 1 include phenylene and naphthylene, and phenylene is preferable.
- Examples of phenylene include 1,4-phenylene, 1,3-phenylene, and 1,2-phenylene, and 1,4-phenylene is preferable.
- the arylene group may have a substituent. Examples of the substituent include the substituent T described later, and a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkylthio group, an amino group, an alkylamino group, an arylamino group, and a heteroarylamino group.
- an amino group, an alkylamino group, an arylamino group, and a heteroarylamino group are more preferable.
- the substituent and R 1 may be bonded to each other to form a ring, and when having a plurality of substituents, these may be bonded to each other to form a ring.
- the alkynylene group and alkynylene arylene group in L 1 are preferably groups represented by the following formula (LT).
- L x represents a single bond or an arylene group. * Represents a position bonded to the pyridine ring.
- Examples of the arylene group in L x include the arylene group in L 1 , and the preferred range is also the same.
- the arylene group in L x may have a substituent, and examples of the substituent include the substituent T described below.
- the substituent with respect to the arylene group is preferably the substituent described when L 1 is an arylene group.
- R 1 represents an amino group, an alkylamino group, an arylamino group, or a heteroarylamino group.
- the amino group is —NH 2 .
- the alkylamino group includes an N-alkylamino group and an N, N-dialkylamino group.
- the arylamino group includes an N-arylamino group, an N-alkyl-N-arylamino group, and an N, N-diarylamino group.
- the heteroarylamino group includes an N-heteroarylamino group, an N-alkyl-N-heteroarylamino group, and an N-aryl-N-heteroarylamino group.
- the number of carbon atoms of the alkyl group substituted on the nitrogen atom in each amino group is preferably 1-18, and more preferably 4-12.
- the alkyl group may be linear or branched. Examples of the alkyl group include methyl, ethyl, isopropyl, n-butyl, t-butyl, isobutyl, n-hexyl, n-octyl, 2-ethylhexyl, n-dodecyl and n-hexadecyl.
- the number of carbon atoms of the aryl group substituted on the nitrogen atom in each amino group is preferably 6 to 24, more preferably 6 to 18.
- Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
- the aryl ring may be condensed with an aromatic carbocyclic ring, an aliphatic carbocyclic ring, a heterocyclic ring, or the like.
- the number of carbon atoms of the heteroaryl group substituted on the nitrogen atom in each amino group is preferably from 0 to 24, and more preferably from 1 to 18.
- the heteroaryl group in the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
- the hetero atom constituting the hetero ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
- the heteroaryl ring may be condensed with an aromatic carbocyclic ring, an aliphatic carbocyclic ring, a heterocyclic ring, or the like.
- the alkyl group, aryl group, and heteroaryl group substituted on the nitrogen atom in each amino group may have a substituent, and examples of the substituent include the substituent T described below.
- substituent T examples of the substituent include the substituent T described below.
- a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkylthio group, an amino group, an alkylamino group, an arylamino group, and a heteroarylamino group are preferable, and an alkyl group, an aryl group, an alkoxy group, and an alkylthio group are preferable.
- Groups are more preferred.
- each amino group is an N, N-disubstituted amino group
- the two substituents may be bonded to each other to form a ring.
- amino group, alkylamino group, arylamino group, and heteroarylamino group examples include amino (—NH 2 ), methylamino, ethylamino, n-hexylamino, 2-ethylhexylamino, n-octadecylamino, N, N-dimethylamino, N, N-diethylamino, N, N-bis (n-hexyl) amino, N-methyl-Nn-hexylamino, N, N-bis (2-ethylhexyl) amino, phenylamino, N , N-diphenylamino, N-naphthylamino, N-methyl-N-phenylamino, N-imidazolylamino, pyrrolylamino, thienylamino.
- —NR 21 R 22 is preferably a group represented by the following formula (AM).
- R AM1 and R AM2 each independently represents an alkyl group or an aryl group.
- R AM1 and R AM2 may be bonded to each other to form a ring.
- One of R AM1 and R AM2 is preferably an aryl group, and both R AM1 and R AM2 are more preferably aryl groups.
- the group formed by combining R AM1 and R AM2 is preferably the following group.
- R AM3 and R AM4 each independently represents an alkyl group or an aryl group.
- the said ring may have a substituent and the substituent T is mentioned as this substituent.
- n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1.
- a plurality of — [(L 1 ) m1- (R 1 ) m2] may be bonded to each other to form a ring.
- R 2a represents a substituent different from — [(L 1 ) m1- (R 1 ) m2], and examples of such a substituent include the substituent T described later.
- a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, and an alkylthio group are preferable, and an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, and an alkylthio group are more preferable.
- R 2a may combine with — [(L 1 ) m1- (R 1 ) m2] to form a ring.
- l1 represents an integer of 0 to 3, preferably 0 or 1, more preferably 0.
- R 2a is, if there are a plurality, the plurality of R 2a may be bonded to each other to form a ring.
- the bidentate ligand represented by the formula (DL-1) is preferably a bidentate ligand represented by the following formula (DL-2), and represented by the following formula (DL-3) Ligands are more preferred.
- E, L 1 , m1, m2, n1, R 2a and l1 have the same meanings as E, L 1 , m1, m2, n1, R2a and l1 in formula (DL-1), The preferred range is also the same.
- R 21 and R 22 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group. R 21 and R 22 may be bonded to each other to form a ring.
- E, R 21, R 22, n1, R 2a and l1 are synonymous E, and R 21, R 22, n1, R 2a and l1 in formula (DL-2), preferred The range is the same.
- E represents a group represented by any one of formulas (E-1) to (E-6).
- R in the formulas (E-1) to (E-5) represents a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group.
- Examples of the halogen atom in R in the formulas (E-1) to (E-5) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom, a chlorine atom and a bromine atom, and more preferably a fluorine atom. .
- the alkyl group in R of the formulas (E-1) to (E-5) is a linear or branched alkyl group, preferably having 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms such as methyl, ethyl, Examples include isopropyl, n-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-dodecyl, and n-hexadecyl.
- the alkyl group is preferably an alkyl group substituted with a halogen atom, more preferably an alkyl group substituted with a fluorine atom, and more preferably a perfluoroalkyl group, particularly perfluoromethyl.
- the alkoxy group in R of the formulas (E-1) to (E-5) is a linear or branched alkoxy group, preferably having 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms such as methoxy, ethoxy, Examples include isopropyloxy, n-butyloxy, s-butyloxy, n-hexyloxy, n-octyloxy, 2-ethylhexyloxy, n-dodecyloxy, and n-hexadecyloxy.
- the aryl group in R in the formulas (E-1) to (E-5) is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl.
- the aryl group is preferably a phenyl group which may have a substituent.
- the heteroaryl group in R of formulas (E-1) to (E-5) is preferably a 5-membered or 6-membered heteroaryl group
- the heteroaryl ring in the heteroaryl group is an aryl ring or alicyclic ring , It may be condensed with a heterocycle and may have a substituent.
- the substituent include the substituent T described later.
- As a ring-constituting hetero atom of the heteroaryl ring an oxygen atom, a sulfur atom, a nitrogen atom, and a selenium atom are preferable.
- the heteroaryl ring in the heteroaryl group include a furan ring, a thiophene ring, and a pyrrole ring, and a thiophene ring is preferable.
- m represents an integer of 0 or more, preferably 1 or 2, and more preferably 1.
- E is preferably the formulas (E-1), (E-2), (E-4), (E-5) and (E-6) among the formulas (E-1) to (E-6).
- Formula (E-2), (E-4) and (E-5) are more preferable, Formula (E-2) and (E-5) are more preferable, and Formula (E-2) is particularly preferable.
- Z 1 represents a monodentate ligand.
- Z 1 is, for example, an acyloxy group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, a dithiocarbamate group, a thiocarbonate group, a dithiocarbonate group, a trithiocarbonate group, an acyl group A thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a selenate group, an isoselenate group, an isoselenocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group, and an aryloxy group.
- Z 1 is preferably an isothiocyanate group, an isoselenocyanate group, an isocyanate group, a halogen atom or a cyano group.
- ligand Z 1 is the alkyl moiety, alkenyl part, alkynyl site, if it contains alkylene moiety such as, they may be linear or branched, may be either unsubstituted substituted. Further, when an aryl moiety, a heterocyclic moiety, a cycloalkyl moiety and the like are included, they may be substituted or unsubstituted, and may be monocyclic or condensed.
- -Charge neutralization counter ion CI- CI represents a counter ion when a counter ion is required to neutralize the charge.
- a dye is a cation or an anion or has a net ionic charge depends on the metal, ligand and substituent in the metal complex dye.
- the metal complex dye may be dissociated and have a negative charge because the substituent has a dissociable group. In this case, the entire charge of the metal complex dye is electrically neutralized by CI.
- the counter ion CI is a positive counter ion
- the counter ion CI is an inorganic or organic ammonium ion (for example, tetraalkylammonium ion, pyridinium ion, etc.), phosphonium ion (for example, tetraalkylphosphonium ion, alkyltriphenylphosphonium ion). Etc.), alkali metal ions, metal complex ions or protons.
- the positive counter ion is preferably an inorganic or organic ammonium ion (such as triethylammonium ion or tetrabutylammonium ion) or a proton.
- the counter ion CI may be an inorganic anion or an organic anion.
- the counter ion CI may be an inorganic anion or an organic anion.
- hydroxide ion, halogen anion eg fluoride ion, chloride ion, bromide ion, iodide ion etc.
- substituted or unsubstituted alkylcarboxylate ion acetate ion, trifluoroacetate ion etc.
- Substituted or unsubstituted arylcarboxylate ions (benzoate ions, etc.)
- substituted or unsubstituted alkylsulfonate ions methanesulfonate ions, trifluoromethanesulfonate ions, etc.
- substituted or unsubstituted arylsulfonate ions eg p-toluenesulfonate ion, p
- an ionic polymer or another dye having a charge opposite to that of the dye may be used as the charge balance counter ion, and a metal complex ion (for example, bis (benzene-1,2-dithiolato) nickel (III)) can also be used. It is.
- Negative counter ions include halogen anions, substituted or unsubstituted alkyl carboxylate ions, substituted or unsubstituted alkyl sulfonate ions, substituted or unsubstituted aryl sulfonate ions, aryl disulfonate ions, perchlorate ions , Hexafluorophosphate ions are preferred, and halogen anions and hexafluorophosphate ions are more preferred.
- the metal complex dye represented by the formula (I) is preferably a metal complex dye represented by the following formula (II), more preferably a metal complex dye represented by the following formula (III). .
- R A1 ⁇ R A3 have the same meanings as R A1 ⁇ R A3 in the formula (AL-3).
- R 21, R 22, L 1 , m1 and m2 have the same meanings as R 21, R 22, L 1 , m1 and m2 in formula (DL-2), and the preferred range is also the same.
- W represents a nitrogen atom or CH.
- R 10 represents a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group or a heteroaryl group.
- Z 2 represents an isothiocyanate group, an isoselenocyanate group, an isocyanate group, a halogen atom or a cyano group.
- R A1 ⁇ R A3 have the same meanings as R A1 ⁇ R A3 in the formula (AL-3).
- W, R 21, R 22, R 10 and Z 2 are as defined W, R 21, R 22, and R 10 and Z 2 in formula (II), and preferred ranges are also the same.
- the metal complex dye represented by the formula (I) of the first aspect is shown below, but the present invention is not limited thereto.
- the ligand is coordinated to a metal atom, that is, an atom coordinated by an anion is represented by an anion, but it is not necessarily coordinated by an anion.
- the metal complex dye omits a counter ion, but does not need a counter ion but can hold an arbitrary counter ion.
- the above-mentioned CI is mentioned as a counter ion.
- the metal complex dye of the second embodiment is represented by the following formula (I).
- M 1 represents a metal atom
- Z 1 represents a monodentate ligand
- LA represents a tridentate ligand represented by the following formula (AL-21).
- LD represents a bidentate ligand represented by the following formula (DL-21).
- CI represents a counter ion necessary for neutralizing the electric charge.
- Za, Zb and Zc represent a nonmetallic atom group necessary for forming a 5-membered ring or a 6-membered ring. However, at least one of the rings formed by Za, Zb and Zc has an acidic group.
- m1 represents an integer of 0 to 3
- m2 represents an integer of 1 to 4
- n1 represents an integer of 1 to 4.
- L 1 represents an arylene group
- R 1 represents a halogen atom, an alkyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.
- E represents a group represented by the following formula (E-21) or formula (E-22).
- R represents a hydrogen atom, an alkyl group, a phenyl group or an aryloxy group.
- M 1 represents a metal atom.
- M 1 is preferably a metal capable of tetracoordination or hexacoordination, and examples thereof include elements of groups 6 to 12 on the long periodic table, and more preferably Ru, Fe, Os, Cu, W, Cr, Mo , Ni, Pd, Pt, Co, Ir, Rh, Re, Mn or Zn. Particularly preferred is Ru, Os, Zn or Cu, and most preferred is Ru.
- the ligand LA is represented by the formula (AL-21).
- Za, Zb and Zc represent a nonmetallic atom group necessary for forming a 5-membered ring or a 6-membered ring.
- the 5-membered or 6-membered ring formed by Za, Zb and Zc may be substituted or unsubstituted, and may be monocyclic or condensed. When condensed, it is preferable that the benzene ring is condensed.
- Za, Zb and Zc are preferably atoms whose ring members are selected from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom, and are atoms selected from a carbon atom and a nitrogen atom. More preferred.
- the ring atom may be substituted with a substituent including a hydrogen atom or a halogen atom.
- the ring formed by Za, Zb and Zc is more preferably an aromatic ring, that is, a nitrogen-containing aromatic ring.
- an imidazole ring, a benzimidazole ring, an oxazole ring, a thiazole ring or a triazole ring is preferably formed.
- a 6-membered ring a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is formed.
- an imidazole ring, a benzimidazole ring, or a pyridine ring is more preferable.
- At least one of the rings formed by Za, Zb and Zc has an acidic group.
- the acidic group the acidic group Ac described in the first embodiment is preferable.
- the ligand LA is preferably a ligand represented by the following formula (AL-2).
- Ac 1 , Ac 2 and Ac 3 each independently represents an acidic group.
- the acidic group those exemplified as the acidic group Ac are preferable.
- R L1 , R L2 and R L3 each independently represent a substituent. As for this substituent, the below-mentioned substituent T is mentioned, for example.
- R L1 , R L2 and R L3 are preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an amino group, an alkylamino group or an arylamino group, and an alkyl group, an aryl group or a heteroaryl group Are more preferable, and a heteroaryl group is particularly preferable.
- a1, a3, b1 and b3 each independently represents an integer of 0 to 4
- a2 and b2 each independently represent an integer of 0 to 3.
- a1 to a3 are not all 0.
- the ligand LA is preferably a ligand represented by the following formula (AL-3).
- R A1 , R A2 and R A3 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or an acidic group. However, at least one of R A1 , R A2 and R A3 is an acidic group.
- the acidic group is preferably an acidic group Ac.
- R A1 , R A2 and R A3 are preferably acidic groups, and more preferably all three are acidic groups. Especially, it is preferable that all are a carboxy group or its salt.
- ligand LA of the second aspect Specific examples of the ligand LA of the second aspect are shown below, but the present invention is not limited thereto.
- the ligand LD is represented by the formula (DL-21).
- L 1 represents an arylene group, and examples thereof include phenylene and naphthylene, and phenylene is preferable.
- phenylene include 1,4-phenylene, 1,3-phenylene, and 1,2-phenylene, and 1,4-phenylene is preferable.
- the arylene group may have a substituent. Examples of the substituent include the substituent T described later, and a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, and an alkylthio group are preferable.
- the substituent and R 1 may be bonded to each other to form a ring, and when having a plurality of substituents, these may be bonded to each other to form a ring.
- R 1 represents a halogen atom, an alkyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group, preferably a halogen atom, an alkyl group, an alkynyl group, an alkoxy group or an alkylthio group.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- a fluorine atom, a chlorine atom, and a bromine atom are preferable, and a fluorine atom is more preferable.
- the alkyl group is a linear or branched alkyl group, preferably having 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, t-butyl, n-hexyl, n -Octyl, 2-ethylhexyl, n-dodecyl, n-hexadecyl.
- the alkenyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms.
- vinyl, allyl, and oleyl are mentioned.
- the alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples include ethynyl, heptan-1-yl, 2-phenylethynyl.
- the alkynyl group is preferably a group represented by the following formula (SA).
- R X represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
- the alkyl group in R X is preferably an alkyl group in R 1 of the formula (DL-21).
- the aryl group in R X is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl.
- the aryl group is preferably a phenyl group which may have a substituent.
- the heteroaryl group in R X is preferably a 5-membered or 6-membered heteroaryl group, and the heteroaryl ring in the heteroaryl group may be condensed with an aryl ring, an alicyclic ring, or a heterocyclic ring, You may have a substituent.
- the substituent include the substituent T described later.
- As a ring-constituting hetero atom of the heteroaryl ring an oxygen atom, a sulfur atom, a nitrogen atom, and a selenium atom are preferable.
- the heteroaryl ring in the heteroaryl group include a furan ring, a thiophene ring, and a pyrrole ring.
- a thiophene ring is preferable, and a ring obtained by condensing a benzene ring or a thiophene ring to the thiophene ring is preferable.
- the alkoxy group is a linear or branched alkoxy group, preferably having 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms.
- Examples of the alkoxy group include methoxy, ethoxy, isopropyloxy, n-butyloxy, s-butyloxy, n-hexyloxy, n-octyloxy, 2-ethylhexyloxy, n-dodecyloxy and n-hexadecyloxy.
- the alkylthio group is a linear or branched alkylthio group, preferably having 1 to 20 carbon atoms, more preferably 1 to 18, for example, methylthio, ethylthio, isopropylthio, n-butylthio, t-butylthio, n-hexylthio, Examples include n-octylthio, 2-ethylhexylthio, n-dodecylthio, and n-hexadecylthio.
- the aryloxy group preferably has 6 to 20 carbon atoms, more preferably 6 to 18 carbon atoms, and examples thereof include phenoxy, p-methylphenoxy, p-methoxyphenoxy, m-chlorophenoxy and naphthoxy.
- the arylthio group preferably has 6 to 20 carbon atoms, more preferably 6 to 18 carbon atoms, and examples thereof include phenylthio, p-methylphenylthio, p-methoxyphenylthio, m-chlorophenylthio, and naphthylthio.
- Each of these groups may be substituted with a substituent.
- substituents include a substituent T described later, and among them, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, and an alkylthio group are preferable.
- m1 represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
- m2 represents an integer of 1 to 4, and when m2 is 2 or more, a plurality of R 1 may be the same or different. Moreover, it may combine with each other to form a ring.
- m2 is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.
- n1 represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.
- E represents a group represented by the formula (E-21) or (E-22).
- R represents a hydrogen atom, an alkyl group, a phenyl group or an aryloxy group, and these may have a substituent.
- the substituent include the substituent T described later.
- an electron donating group is preferable, and an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group are more preferable.
- the alkyl group in R is a linear or branched alkyl group, preferably having 1 to 20 carbon atoms, more preferably 1 to 16 and even more preferably 1 to 12.
- Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, octyl, 2-ethylhexyl, and dodecyl.
- the aryloxy group in R preferably has 6 to 20 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 12 carbon atoms. Examples of the aryloxy group include phenoxy, p-methylphenoxy, p-methoxyphenoxy, and p-fluorophenoxy.
- E is preferably a group represented by the formula (E-21) among the formulas (E-21) and (E-22).
- the ligand LD is preferably a ligand represented by any of the following formulas (DL-22) to (DL-24), and among these, the ligand is represented by the formula (DL-23) or (DL-24).
- the ligand is preferred.
- E, R 1 and m2 has the same meaning as E, R 1 and m2 in formula (DL-21), and the preferred range is also the same.
- X 1 represents —C (Ra) (Rb) —, an ethynylene group, —S— or —O—.
- Ra and Rb each independently represent a hydrogen atom or an alkyl group.
- R 2 represents a halogen atom.
- R 3 represents a hydrogen atom or an alkyl group when X 1 is —C (Ra) (Rb) —, and represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group when X 1 is an ethynylene group, When X 1 is —S— or —O—, it represents an alkyl group or an aryl group.
- m2 is 2 or more, the plurality of R 1 may be the same as or different from each other.
- the alkyl group in Ra and Rb is a linear or branched alkyl group, preferably having 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, and still more preferably 1 to 12 carbon atoms.
- Ra and Rb are also preferably those in which at least one is a hydrogen atom, both are hydrogen atoms, or both are alkyl groups.
- X 1 is preferably —C (Ra) (Rb) —, an ethynylene group or —O—.
- the halogen atom in R 2 is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a fluorine atom or a chlorine atom, and even more preferably a fluorine atom.
- the alkyl group for R 3 is preferably an alkyl group having 5 or more carbon atoms, and more preferably an alkyl group having 5 to 20 carbon atoms.
- R 3 is preferably an unsubstituted alkyl group, more preferably a linear alkyl group.
- the aryl group and heteroaryl group in R 3 are synonymous with the aryl group and heteroaryl group in R X , and the preferred range is also the same.
- any of the following formulas (DL-23a) to (DL-23d) or (DL-24a) to (DL-24c) Is more preferable.
- E has the same meaning as E in formula (DL-21), and the preferred range is also the same.
- X 1 and R 3 have the same meaning as X 1 and R 3 in the formula (DL-23).
- X 2 represents —C (Ra) (Rb) —, an ethynylene group, —S— or —O—.
- Ra and Rb each independently represent a hydrogen atom or an alkyl group.
- R 4 represents a hydrogen atom or an alkyl group when X 2 is —C (Ra) (Rb) —, and represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group when X 2 is an ethynylene group, When X 2 is —S— or —O—, it represents an alkyl group or an aryl group.
- —C (Ra) (Rb) —, ethynylene group, —S—, and —O— in X 2 have the same meaning as —C (Ra) (Rb) —, ethynylene group, —S—, and —O— in X 1 .
- the preferred range is also the same.
- X 2 is preferably —C (Ra) (Rb) —, an ethynylene group, or —O—.
- R 4 has the same meaning as R 3 , and the preferred range is also the same.
- the “ligand Z 1 ” and “charge neutralization counter ion CI” in the formula (I) of the second embodiment have the same meaning as described above in the metal complex dye of the first embodiment.
- the metal complex dye represented by the formula (I) is preferably a metal complex dye represented by the following formula (XXII), more preferably a metal complex dye represented by the following formula (XXIII). .
- R A1 ⁇ R A3 have the same meanings as R A1 ⁇ R A3 in the formula (AL-3).
- R 1, L 1, m1 and m2 have the same meanings as R 1, L 1, m1 and m2 in formula (DL-21).
- W represents CH.
- Z 2 represents an isothiocyanate group, an isoselenocyanate group, an isocyanate group, a halogen atom or a cyano group.
- R A1 ⁇ R A3 have the same meanings as R A1 ⁇ R A3 in the formula (AL-3).
- R 1 and m2 have the same meanings as R 1 and m2 in formula (DL-21).
- Z 2 has the same meaning as Z 2 in Formula (XXII).
- the metal complex dye represented by the formula (I) of the second aspect is shown below, but the present invention is not limited thereto.
- the ligand is coordinated to a metal atom, that is, an atom coordinated by an anion is represented by an anion, but it is not necessarily coordinated by an anion.
- the metal complex dye omits a counter ion, but does not need a counter ion but can hold an arbitrary counter ion.
- the above-mentioned CI is mentioned as a counter ion.
- the metal complex dyes described in Patent Documents 1 and 2 have a large voltage concentration dependency on the electrolyte.
- the metal complex dye of the second embodiment improves durability and photoelectric conversion efficiency, and further reduces the dependency of voltage on the electrolyte concentration.
- the metal complex dyes represented by the formula (I) of the first and second aspects are disclosed in US Patent Application Publication No. 2010 / 0258175A1, Japanese Patent No. 4298799, Angew. Chem. Int. Ed. , 2011, 50, 2054-2058, the method described in the reference cited in the document, or a method analogous thereto.
- the maximum absorption wavelength in the solution is preferably in the range of 300 to 1000 nm, more preferably in the range of 350 to 950 nm, and particularly preferably in the range of 370 to 900 nm.
- the metal complex dye of the present invention may be used in combination with another dye.
- the dye used in combination include Ru complex dyes described in JP-A-7-500630 (particularly the dyes synthesized in Examples 1 to 19 on page 5, lower left column, line 5 to page 7, upper right column, line 7). ), Ru complex dyes described in JP-T-2002-512729 (especially dyes synthesized in Examples 1 to 16 from the third line to the 29th page and the 23rd line from the bottom of page 20), JP-A-2001- Ru complex dyes described in Japanese Patent No. 59062 (particularly dyes described in paragraphs 0087 to 0104), Ru complex dyes described in Japanese Patent Application Laid-Open No.
- Ru complex dyes described in JP2012-012570A in particular, dyes described in paragraphs 0095 to 0103
- Ru complex dyes described in WO2013 / 47615 in particular, [ 0078] to [0082]
- squarylium cyanine dye described in JP-A-11-214730 particularly, dye described in paragraphs 0036 to 0047
- squarylium described in JP2012-144688 Cyanine dyes (particularly described in paragraphs 0039 to 0046 and paragraphs 0054 to 0060) Dyes), squarylium cyanine dyes described in JP 2012-84503 A (particularly dyes described in paragraph Nos.
- organic dyes described in JP 2004-063274 A are organic dyes described in JP 2004-063274 A (particularly paragraph No. 0017).
- organic dyes described in JP-A-2005-123033 are particularly dyes described in paragraph Nos. 0021 to 0028
- organic dyes described in JP-A-2007-287694 are organic dyes described in JP-A-2008-71648 (particularly, dyes described in paragraphs 0030 to 0034), organic dyes described in International Publication No. 2007/119525 pamphlet (In particular, the dye described in [0024]), Angew. Chem. Int. Ed. , 49, 1-5 (2010), etc., Angew. Chem. Int. Ed. , 46, 8358 (2007), and the like.
- the dye used in combination is preferably a Ru complex dye, a squarylium cyanine dye, or an organic dye.
- the ratio of the mass of the metal complex dye of the present invention to the mass of the other dye is preferably 95/5 to 10/90, and 95/5 to 50/50. Is more preferable, 95/5 to 60/40 is further preferable, 95/5 to 65/35 is particularly preferable, and 95/5 to 70/30 is most preferable.
- the conductive support is preferably a support made of glass or plastic having a conductive film layer on the surface, such as a metal, which is conductive in itself.
- the plastic support include a transparent polymer film described in paragraph No. 0153 of JP-A No. 2001-291534.
- the support in addition to glass and plastic, ceramic (Japanese Patent Laid-Open No. 2005-135902) or conductive resin (Japanese Patent Laid-Open No. 2001-160425) may be used.
- the surface may be provided with a light management function. For example, an antireflection film in which high refractive films and low refractive index oxide films described in JP-A-2003-123859 are alternately laminated Or a light guide function described in JP-A-2002-260746.
- the thickness of the conductive film layer is preferably 0.01 to 30 ⁇ m, more preferably 0.03 to 25 ⁇ m, and particularly preferably 0.05 to 20 ⁇ m.
- the conductive support is substantially transparent.
- substantially transparent means that the light transmittance is 10% or more.
- the light transmittance of the conductive support is preferably 50% or more, and particularly preferably 80% or more.
- a glass or plastic coated with a conductive metal oxide is preferable.
- the metal oxide tin oxide is preferable, and indium-tin oxide and fluorine-doped oxide are particularly preferable.
- the coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of the glass or plastic support. When a transparent conductive support is used, light is preferably incident from the support side.
- the semiconductor fine particles are preferably metal chalcogenide (for example, oxide, sulfide, selenide, etc.) or perovskite fine particles.
- metal chalcogenide for example, oxide, sulfide, selenide, etc.
- perovskite fine particles Preferred examples of the metal chalcogenide include titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum, oxides thereof, cadmium sulfide, cadmium selenide, and the like.
- Preferred perovskites include strontium titanate and calcium titanate. Of these, titanium oxide (titania), zinc oxide, tin oxide, and tungsten oxide are particularly preferable.
- titania examples include anatase type, brookite type, and rutile type, and anatase type and brookite type are preferable. Titania nanotubes, titania nanowires, or nanorods may be mixed with titania microparticles or used as semiconductor electrodes.
- the particle size of the semiconductor fine particles is 0.001 to 1 ⁇ m as the primary particle and 0.01 to 100 ⁇ m as the average particle size of the dispersion in the average particle size using the diameter when the projected area is converted into a circle. Is preferred.
- Examples of the method for coating the semiconductor fine particles on the conductive support include a wet method, a dry method, and other methods.
- the semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed.
- the surface area is preferably 10 times or more, more preferably 100 times or more the projected area.
- the preferred thickness of the photoreceptor layer which is a semiconductor layer, varies depending on the use of the device, but is typically 0.1 to 100 ⁇ m. When used as a dye-sensitized solar cell, the thickness of the photoreceptor layer is preferably 1 to 50 ⁇ m, and more preferably 3 to 30 ⁇ m.
- the semiconductor fine particles may be fired at a temperature of 100 to 800 ° C. for 10 minutes to 10 hours in order to adhere the particles to each other after being applied to the support. When glass is used as the support, the film forming temperature is preferably 60 to 400 ° C.
- the coating amount of semiconductor fine particles per 1 m 2 of support is preferably 0.5 to 500 g, more preferably 5 to 100 g.
- the total amount of the dye used is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, and particularly preferably 0.1 to 10 mmol per 1 m 2 of the support.
- the amount of the metal complex dye of the present invention is preferably 5 mol% or more.
- the adsorption amount of the dye to the semiconductor fine particles is preferably 0.001 to 1 mmol, more preferably 0.1 to 0.5 mmol, with respect to 1 g of the semiconductor fine particles. By using such a dye amount, the sensitizing effect in the semiconductor fine particles can be sufficiently obtained.
- the counter ion of the specific metal complex dye is not particularly limited, and examples thereof include alkali metal ions and quaternary ammonium ions.
- the surface of the semiconductor fine particles may be treated with amines.
- amines include pyridines (for example, 4-tert-butylpyridine, polyvinylpyridine) and the like. These may be used as they are in the case of a liquid, or may be used by dissolving in an organic solvent.
- the photoelectric conversion element for example, the photoelectric conversion element 10
- the dye-sensitized solar cell for example, the dye-sensitized solar cell 20
- at least the metal complex dye of the present invention is used.
- the charge transfer layer used in the photoelectric conversion element of the present invention is a layer having a function of replenishing electrons to the dye oxidant, and is provided between the light receiving electrode and the counter electrode (counter electrode).
- the charge transfer layer includes an electrolyte.
- electrolytes include a liquid electrolyte in which a redox couple is dissolved in an organic solvent, an electrolyte in which a polymer matrix is impregnated with a liquid in which the redox couple is dissolved in an organic solvent (so-called gel electrolyte), a molten salt containing the redox couple, and the like. Is mentioned.
- a liquid electrolyte is preferable.
- a nitrile compound As the solvent for the liquid electrolyte, a nitrile compound, an ether compound, an ester compound or the like is used. As a solvent for the liquid electrolyte, a nitrile compound is preferable, and acetonitrile and methoxypropionitrile are particularly preferable.
- iodine and iodide iodide salt, ionic liquid is preferred, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, methylpropylimidazolium iodide are more preferred
- alkyl viologen for example, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate
- polyhydroxybenzenes for example, hydroquinone, naphthohydroquinone, etc.
- 2 Combinations of valent and trivalent iron complexes for example, combinations of red blood salt and yellow blood salt
- divalent and trivalent cobalt complexes and the like.
- the cobalt complex is preferably a complex represented by the following formula (CC).
- LL represents a bidentate or tridentate ligand.
- X represents a monodentate ligand.
- ma represents an integer of 0 to 3.
- mb represents an integer of 0-6.
- CI represents a counter ion when a counter ion is required to neutralize the charge.
- CI in formula (CC) includes CI in formula (I).
- LL is preferably a ligand represented by the following formula (LC).
- X LC1 and X LC3 each independently represent a carbon atom or a nitrogen atom.
- XLC1 N
- XLC3 N
- X LC3 N
- X LC1 N
- X LC3 N
- X LC1 N
- X LC3 N
- X LC1 N
- X LC1 N
- X LC3 N
- X LC1 N
- the bond between X LC1 and the N atom represents a single bond
- Z LC1 , Z LC2 and Z LC3 each independently represent a nonmetallic atom group necessary for forming a 5-membered ring or a 6-membered ring.
- Z LC1 , Z LC2 and Z LC3 may have a substituent and may be closed with an adjacent ring via the substituent.
- q represents 0 or 1; Examples of the substituent include the substituent T described later.
- the carbon atom at the position where X LC3 is bonded to the 5-membered ring or 6-membered ring formed by Z LC2 is a hydrogen atom or a substituent other than the heterocyclic group formed by Z LC3 Join.
- X is Z 1 in formula (I), and a halogen ion is preferable.
- the ligand represented by the above formula (LC) is more preferably a ligand represented by the following formulas (LC-1) to (LC-4).
- R LC1 to R LC11 each independently represents a substituent.
- q1, q2, q6 and q7 each independently represents an integer of 0 to 4.
- q3, q5, q10 and q11 each independently represents an integer of 0 to 3.
- q4 represents an integer of 0-2.
- examples of the substituent represented by R LC1 to R LC11 include an aliphatic group, an aromatic group, and a heterocyclic group.
- Specific examples of the substituent represented by R LC1 to R LC11 include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, and a heterocyclic group.
- Preferred examples include alkyl groups (eg methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, benzyl etc.), aryl groups (eg phenyl, tolyl, naphthyl).
- alkyl groups eg methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, benzyl etc.
- aryl groups eg phenyl, tolyl, naphthyl
- alkoxy groups eg methoxy, ethoxy, isopropoxy, butoxy etc.
- alkylthio groups eg methylthio, n-butylthio, n-hexylthio, 2-ethylhexylthio etc.
- aryloxy groups eg phenoxy, naphthoxy etc.
- arylthio groups eg, phenylthio, naphthylthio, etc.
- heterocyclic groups eg, 2-thienyl, 2-furyl, etc.
- cobalt complex having a ligand represented by the formula (LC) include the following complexes.
- iodine and iodide When a combination of iodine and iodide is used as the electrolyte, it is preferable to further use an iodine salt of a 5-membered or 6-membered nitrogen-containing aromatic cation.
- the organic solvent that dissolves the redox couple is preferably an aprotic polar solvent (eg, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, sulfolane, 1,3-dimethylimidazolinone, 3-methyloxazolidinone, etc.).
- aprotic polar solvent eg, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, sulfolane, 1,3-dimethylimidazolinone, 3-methyloxazolidinone, etc.
- the polymer used for the matrix of the gel electrolyte include polyacrylonitrile and polyvinylidene fluoride.
- the molten salt include those imparted with fluidity at room temperature by mixing polyethylene oxide with lithium iodide and at least one other lithium salt (such as lithium acetate and lithium perchlorate). It is done. In this
- aminopyridine compounds As an additive to the electrolyte, in addition to the aforementioned 4-tert-butylpyridine, aminopyridine compounds, benzimidazole compounds, aminotriazole compounds and aminothiazole compounds, imidazole compounds, aminotriazine compounds, urea derivatives, Amide compounds, pyrimidine compounds and nitrogen-free heterocycles can be added.
- a method of controlling the moisture of the electrolytic solution may be taken.
- Preferred methods for controlling moisture include a method for controlling the concentration and a method in which a dehydrating agent is allowed to coexist.
- an inclusion compound of iodine and cyclodextrin may be used, or a method of constantly supplying water may be used.
- Cyclic amidine may be used, and an antioxidant, hydrolysis inhibitor, decomposition inhibitor, and zinc iodide may be added.
- a molten salt may be used as the electrolyte, and preferred molten salts include ionic liquids containing imidazolium or triazolium type cations, oxazolium-based, pyridinium-based, guanidinium-based, and combinations thereof. These cationic systems may be combined with specific anions. Additives may be added to these molten salts. You may have a liquid crystalline substituent. Further, a quaternary ammonium salt-based molten salt may be used.
- molten salt other than these for example, flowability at room temperature was imparted by mixing polyethylene oxide with lithium iodide and at least one other lithium salt (for example, lithium acetate, lithium perchlorate, etc.). And the like.
- the electrolyte may be quasi-solidified by adding a gelling agent to an electrolyte solution composed of an electrolyte and a solvent for gelation.
- a gelling agent include organic compounds having a molecular weight of 1000 or less, Si-containing compounds having a molecular weight in the range of 500 to 5000, organic salts composed of a specific acidic compound and a basic compound, sorbitol derivatives, and polyvinylpyridine.
- the matrix polymer is preferably a polymer having a nitrogen-containing heterocycle in the repeating unit of the main chain or side chain, a crosslinked product obtained by reacting these nitrogen-containing heterocycle with an electrophilic compound, or a polymer having a triazine structure , Polymer having ureido structure, liquid crystal compound-containing polymer, ether-bonded polymer, polyvinylidene fluoride, methacrylate / acrylate, thermosetting resin, crosslinked polysiloxane, polyvinyl alcohol (PVA), polyalkylene glycol And inclusion compounds such as dextrin, systems containing oxygen-containing or sulfur-containing polymers, natural polymers, and the like.
- the matrix polymer a system containing a cross-linked polymer obtained by reacting a bifunctional or higher isocyanate with one functional group such as a hydroxy group, an amino group, or a carboxy group may be used.
- a crosslinking method in which a crosslinked polymer composed of a hydrosilyl group and a double bond compound, polysulfonic acid, polycarboxylic acid, or the like is reacted with a divalent or higher-valent metal ion compound may be used.
- Examples of the solvent that can be preferably used in combination with the quasi-solid electrolyte include a specific phosphate ester, a mixed solvent containing ethylene carbonate, and a solvent having a specific dielectric constant.
- the liquid electrolyte solution may be held in a solid electrolyte membrane or pores, and preferred examples of the method include conductive polymer membranes, fibrous solids, and cloth-like solids such as filters.
- a solid charge transport layer such as a p-type semiconductor or a hole transport material, for example, CuI, CuNCS, or the like can be used. Also, Nature, vol. 486, p. The electrolyte described in 487 (2012) or the like may be used.
- An organic hole transport material may be used as the solid charge transport layer.
- the hole transport layer is preferably a conductive polymer such as polythiophene, polyaniline, polypyrrole, or polysilane, a spiro compound in which two rings share a tetrahedral structure such as C or Si, and an aromatic such as triarylamine. Group amine derivatives, triphenylene derivatives, nitrogen-containing heterocyclic derivatives, and liquid crystalline cyano derivatives.
- a preferable concentration is 0.01 mol / L or more in total, more preferably 0.1 mol / L or more, and particularly preferably 0.3 mol / L or more.
- the upper limit in this case is not particularly limited, but is usually about 5 mol / L.
- a coadsorbent In the photoelectric conversion element of this invention, it is preferable to use a coadsorbent with the metal complex dye of this invention or the pigment
- a co-adsorbent a co-adsorbent having at least one acidic group (preferably a carboxy group or a salt group thereof) is preferable, and examples thereof include compounds having a fatty acid or a steroid skeleton.
- the fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and examples thereof include butanoic acid, hexanoic acid, octanoic acid, decanoic acid, hexadecanoic acid, dodecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid.
- Examples of the compound having a steroid skeleton include cholic acid, glycocholic acid, chenodeoxycholic acid, hyocholic acid, deoxycholic acid, lithocholic acid, ursodeoxycholic acid and the like. Preferred are cholic acid, deoxycholic acid and chenodeoxycholic acid, and more preferred are chenodeoxycholic acid.
- a preferred co-adsorbent is a compound represented by the following formula (CA).
- R C1 represents a substituent having an acidic group.
- R C2 represents a substituent.
- lc represents an integer of 0 or more.
- An acidic group is synonymous with what was shown previously, and its preferable range is also the same.
- R C1 is preferably a carboxy group, an alkyl group substituted with a sulfo group or a salt thereof, —CH (CH 3 ) CH 2 CH 2 CO 2 H, —CH (CH 3 ) CH 2 CH 2 CONHCH More preferred is 2 CH 2 SO 3 H.
- R C2 examples include the substituent T described later, and among them, an alkyl group, a hydroxy group, an acyloxy group, an alkylaminocarbonyloxy group, and an arylaminocarbonyloxy group are preferable, and an alkyl group, a hydroxy group, and an acyloxy group are more preferable.
- nA is preferably 2 to 4.
- These specific compounds include the compounds exemplified as the compounds having the steroid skeleton described above.
- the co-adsorbent has an effect of suppressing inefficient association of dyes by adsorbing to semiconductor fine particles and an effect of preventing reverse electron transfer from the surface of semiconductor fine particles to the redox system in the electrolyte.
- the amount of coadsorbent used is not particularly limited, but it is preferably 1 to 200 mol, more preferably 10 to 150 mol, and particularly preferably 20 to 50 mol with respect to 1 mol of the dye. It is preferable from the viewpoint of effective expression.
- ⁇ Substituent T> In this specification, about the display of a compound (a complex and a pigment
- a substituent that does not specify substitution / non-substitution means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution.
- Preferred substituents include the following substituent T. Further, in the present specification, when only described as a substituent, it refers to this substituent T, and each group, for example, an alkyl group, is only described. The preferred range and specific examples of the corresponding group of the substituent T are applied.
- substituent T examples include the following.
- An alkyl group preferably having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, trifluoromethyl, etc.
- Alkenyl groups preferably having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.
- alkynyl groups preferably having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.
- cycloalkyl groups preferably Has 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl and the like, cycloalkenyl group (preferably having 5 to 20 carbon
- alkoxycarbonyl group preferably having 2 to 20 carbon atoms such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.
- a cycloalkoxycarbonyl group preferably having 4 to 20 carbon atoms such as cyclopropyloxycarbonyl, cyclopentyloxycarbonyl, etc.
- Cyclohexyloxycarbonyl, etc. aryloxycarbonyl groups (preferably having 6 to 20 carbon atoms, such as phenyloxycarbonyl, naphthyloxycarbonyl, etc.)
- amino groups preferably having 0 to 20 carbon atoms, alkylamino groups, alkenyls
- An acyl group preferably having 1 to 20 carbon atoms such as acetyl, cyclohexylcarbonyl, benzoyl, etc.
- an acyloxy group preferably having 1 to 20 carbon atoms such as acetyloxy, cyclohexylcarbonyloxy).
- Benzoyloxy, etc. carbamoyl group (preferably an carbamoyl group having 1 to 20 carbon atoms, alkyl, cycloalkyl or aryl, such as N, N-dimethylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, etc.)
- N, N-dimethylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, etc.
- An acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, cyclohexylcarbonylamino, benzoylamino, etc.), a sulfonamide group (preferably an alkyl, cycloalkyl or aryl sulfonamide having 0 to 20 carbon atoms) Groups such as methanesulfonamide, benzenesulfonamide, N-methylmethanesulfonamide, N-cyclohexylsulfonamide, N-ethylbenzenesulfonamide, etc., alkylthio groups (preferably having 1 to 20 carbon atoms, eg, methylthio , Ethylthio, isopropylthio, benzylthio, etc.), cycloalkylthio groups (preferably having 3 to 20 carbon atoms, such as cyclopropylthio, cyclopent
- a silyl group (preferably a silyl group having 1 to 20 carbon atoms and substituted by alkyl, aryl, alkoxy and aryloxy, such as triethylsilyl, triphenylsilyl, diethylbenzylsilyl, dimethylphenylsilyl, etc.), silyloxy group ( Preferably, it is a silyloxy group having 1 to 20 carbon atoms and substituted with alkyl, aryl, alkoxy and aryloxy, such as triethylsilyloxy, triphenylsilyloxy, diethylbenzylsilyloxy, dimethylphenylsilyloxy, etc.), hydroxy group , Cyano group, nitro group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), carboxy group, sulfo group, phosphonyl group, phosphoryl group, boric acid group, more
- a compound or a substituent when a compound or a substituent includes an alkyl group, an alkenyl group, etc., these may be linear or branched, and may be substituted or unsubstituted. When an aryl group, a heterocyclic group or the like is included, they may be monocyclic or condensed, and may be substituted or unsubstituted.
- the counter electrode preferably works as a positive electrode of a dye-sensitized solar cell (photoelectrochemical cell).
- the counter electrode is usually synonymous with the conductive support described above. In a configuration where the strength is sufficiently maintained, the support is not always necessary.
- As the structure of the counter electrode a structure having a high current collecting effect is preferable.
- At least one of the conductive support and the counter electrode described above must be substantially transparent.
- the conductive support is preferably transparent, and sunlight is preferably incident from the support side. In this case, it is more preferable that the counter electrode has a property of reflecting light.
- a counter electrode of the dye-sensitized solar cell glass or plastic on which metal or conductive oxide is vapor-deposited is preferable, and glass on which platinum is vapor-deposited is particularly preferable.
- the dye-sensitized solar cell it is preferable to seal the side surface of the battery with a polymer, an adhesive or the like in order to prevent the constituents from evaporating.
- the present invention is disclosed in Japanese Patent No. 4260494, Japanese Patent Application Laid-Open No. 2004-146425, Japanese Patent Application Laid-Open No. 2000-340269, Japanese Patent Application Laid-Open No. 2002-289274, Japanese Patent Application Laid-Open No. 2004-152613, and Japanese Patent Application Laid-Open No. 9-27352. It can apply to the described photoelectric conversion element and a dye-sensitized solar cell.
- a dye adsorption electrode using a dye solution containing the metal complex dye of the present invention.
- the dye solution is obtained by dissolving the metal complex dye of the present invention in a solvent, and may contain a co-adsorbent and other components as necessary.
- the solvent to be used include, but are not particularly limited to, the solvents described in JP-A No. 2001-291534.
- an organic solvent is preferable, and alcohols, amides, nitriles, hydrocarbons, and a mixed solvent of two or more of these are preferable.
- a mixed solvent of an alcohol and a solvent selected from amides, nitriles or hydrocarbons is preferable. Further preferred are alcohols and amides, mixed solvents of alcohols and hydrocarbons, and particularly preferred are mixed solvents of alcohols and amides. Specifically, methanol, ethanol, propanol, butanol, dimethylformamide, and dimethylacetamide are preferable.
- the dye solution preferably contains a co-adsorbent.
- the co-adsorbent the above-described co-adsorbent is preferable, and a compound represented by the formula (CA) is particularly preferable.
- the dye solution is preferably one in which the concentration of the metal complex dye or coadsorbent is adjusted so that the solution can be used as it is when a photoelectric conversion element or a dye-sensitized solar cell is produced. It is preferable to contain 0.001 to 0.1% by mass of the metal complex dye of the present invention.
- the water content of the dye solution It is particularly preferable to adjust the water content of the dye solution, and therefore it is preferable to adjust the water content (content) to 0 to 0.1% by mass.
- adjustment of the water content of the electrolytic solution in the photoelectric conversion element or the dye-sensitized solar cell is also preferable in order to achieve the effect effectively. It is preferable to adjust the water content (content ratio) of this electrolytic solution to 0 to 0.1% by mass.
- the electrolytic solution is particularly preferably adjusted with a dye solution.
- a dye-adsorbing electrode that is a semiconductor electrode for a dye-sensitized solar cell in which a metal complex dye is supported on the surface of semiconductor fine particles provided in the semiconductor electrode using the dye solution is preferable. That is, a dye-adsorbing electrode for a dye-sensitized solar cell is obtained by applying a composition obtained from the dye solution onto a conductive support provided with semiconductor fine particles, and curing the composition after application. What was made into the photoreceptor layer is preferable. It is preferable to produce a dye-sensitized solar cell by using the dye-adsorbing electrode for the dye-sensitized solar cell, preparing an electrolyte and a counter electrode, and assembling them using these.
- FIGS. 1 The visible absorption spectrum of the metal complex dye DN-1 is shown in FIGS.
- the metal complex dye DN-1 was measured at a concentration of 17 ⁇ mol / L using UV-3600 manufactured by Shimadzu Corporation.
- FIG. 3 is a spectrum diagram of a measurement solvent in a methanol solution of 340 mmol / L tetrabutylammonium hydroxide (TBAOH).
- FIG. 4 shows a visible absorption spectrum of a model semiconductor film (a titanium oxide film on which a metal complex dye DN-1 is adsorbed) according to sample number 101 in Example 1 described later.
- each metal complex dye was confirmed by mass spectrum (MS) measurement.
- Table 1 below collectively shows the MS measurement results of the metal complex dyes.
- a titania slurry was prepared by putting spherical TiO 2 particles (anatase, average particle diameter; 25 nm, hereinafter referred to as “spherical TiO 2 particles A”) into a nitric acid solution and stirring. Next, a cellulosic binder was added to the titania slurry as a thickener and kneaded to prepare paste A.
- rod-like TiO 2 particles C anatase, diameter: 100 nm, aspect ratio: 5, hereinafter referred to as “rod-like TiO 2 particles C”
- a photoelectrode having the same configuration as the photoelectrode 12 shown in FIG. 5 described in JP-A No. 2002-289274 was produced by the following procedure. Then, using this photoelectrode, a 10 mm ⁇ 10 mm scale dye-sensitized solar cell 1 having the same configuration as that of the dye-sensitized solar cell 20 except for the photoelectrode shown in FIG. Produced. A specific configuration is shown in FIG. 2 attached to the present application.
- the dye-sensitized solar cell 20 includes a transparent electrode 41, a semiconductor electrode 42, a transparent conductive film 43, a substrate 44, a semiconductor layer 45, a light scattering layer 46, a photoelectrode 40, a counter electrode CE, an electrolyte E, and a spacer S.
- a transparent electrode in which a fluorine-doped SnO 2 conductive film (film thickness: 500 nm) was formed on a glass substrate was prepared. Then, the SnO 2 conductive film, a paste 1 of the above screen printing and then dried. Then, it baked on the conditions of 450 degreeC in the air. Furthermore, by repeating this screen printing and baking using the paste 2, the semiconductor electrode A having the same configuration as the semiconductor electrode 42 shown in FIG.
- Photoelectrode A containing no sensitizing dye was prepared.
- the dye was adsorbed on the photoelectrode A (precursor of dye adsorption electrode) produced as described above as follows.
- the metal complex dyes listed in Table 2 below were adjusted to 3 ⁇ 10 ⁇ 4 mol / L. Dissolved in.
- an equimolar mixture of chenodeoxycholic acid and cholic acid was added in an amount of 20 moles per mole of the metal complex dye to prepare each dye solution.
- this dye solution When the water content of this dye solution was measured by Karl Fischer titration, the water content was less than 0.01% by mass.
- the semiconductor electrode is immersed in this solution at 40 ° C. for 10 hours, and then pulled up and dried at 50 ° C., thereby completing the photoelectrode 40 in which the dye is adsorbed to the semiconductor electrode by about 2 ⁇ 10 ⁇ 7 mol / cm 2. It was.
- a platinum electrode (Pt thin film thickness: 100 nm) having the same shape and size as the photoelectrode 40 was prepared as a counter electrode.
- a DuPont spacer S (trade name: “Surlin”) having a shape corresponding to the size of the semiconductor electrode is prepared, as shown in FIG. 3 described in Japanese Patent Application Laid-Open No. 2002-289274.
- the photoelectrode 40, the counter electrode CE, and the spacer S were opposed to each other, and the inside was filled with an electrolyte E.
- the dye-sensitized solar cell (cell A) which consists of a photoelectric conversion element using the photoelectrode A was completed.
- ⁇ Photoelectric conversion efficiency ( ⁇ /%)> A battery characteristic test was conducted, and the photoelectric conversion efficiency ( ⁇ /%) was measured for each dye-sensitized solar cell.
- the battery characteristic test was performed by irradiating 1000 W / m 2 of pseudo-sunlight from a xenon lamp through an AM1.5 filter using a solar simulator (manufactured by WACOM, WXS-85H). The current-voltage characteristics were measured using an IV tester to determine the photoelectric conversion efficiency ( ⁇ /%).
- the photoelectric conversion efficiency of each dye-sensitized solar cell was evaluated according to the following rank, based on the photoelectric conversion efficiency of the following comparative compound S-3. Rank B or higher is an acceptable level (passed level).
- Evaluation rank AA 1.15 times or more A: 1.1 times or more and less than 1.15 times B: 1.03 times or more and less than 1.1 times C: less than 1.03 times
- Evaluation rank A Less than 0.9 times B: 0.9 times or more and less than 1 time C: 1 time or more
- Evaluation rank A Less than 0.9 times B: 0.9 times or more and less than 1 time C: 1 time or more
- the metal complex dye of the present invention has high photoelectric conversion efficiency and excellent durability such as thermal deterioration and heat cycle property.
- the obtained solution was cooled and then neutralized with aqueous sodium hydrogen carbonate, and ethyl acetate was added for liquid separation and extraction, and the organic layer was concentrated.
- the resulting concentrate was purified by silica gel column chromatography to obtain 10.5 g of compound d-1-3.
- exemplary metal complex dyes can also be synthesized by combining the above synthesis method with various coupling reactions.
- the following exemplary metal complex dyes were synthesized in the same manner as the above exemplary metal complex dye D-1-5a.
- each metal complex dye was confirmed by MS measurement and 1 H-NMR.
- the MS measurement results of the metal complex dyes are summarized in Table 3 below.
- a titania slurry was prepared by putting spherical TiO 2 particles (anatase, average particle diameter; 25 nm, hereinafter referred to as “spherical TiO 2 particles A”) into a nitric acid solution and stirring. Next, a cellulosic binder was added to the titania slurry as a thickener and kneaded to prepare paste A.
- rod-like TiO 2 particles C anatase, diameter: 100 nm, aspect ratio: 5, hereinafter referred to as “rod-like TiO 2 particles C”
- a photoelectrode having the same configuration as the photoelectrode 12 shown in FIG. 5 described in JP-A No. 2002-289274 was produced by the following procedure. Then, using this photoelectrode, a 10 mm ⁇ 10 mm scale dye-sensitized solar cell having the same configuration as that of the dye-sensitized solar cell 20 except for the photoelectrode shown in FIG. did. A specific configuration of the dye-sensitized solar cell 20 is shown in FIG. 2 attached to the present application.
- a transparent electrode in which a fluorine-doped SnO 2 conductive film (film thickness: 500 nm) was formed on a glass substrate was prepared. Then, the SnO 2 conductive film, a paste 1 of the above screen printing and then dried. Then, it baked on the conditions of 450 degreeC in the air. Furthermore, by repeating this screen printing and baking using the paste 2, the semiconductor electrode A having the same configuration as the semiconductor electrode 42 shown in FIG.
- Photoelectrode A containing no sensitizing dye was prepared.
- the dye was adsorbed to the photoelectrode A (precursor of the dye adsorption electrode) produced as described above as follows.
- the metal complex dyes listed in Table 4 below were dissolved to 3 ⁇ 10 ⁇ 4 mol / L. did.
- an equimolar mixture of chenodeoxycholic acid and cholic acid was added in an amount of 20 moles per mole of the metal complex dye to prepare each dye solution.
- this dye solution When the water content of this dye solution was measured by Karl Fischer titration, the water content was less than 0.01% by mass.
- the semiconductor electrode is immersed in this solution at 40 ° C. for 10 hours, and then pulled up and dried at 50 ° C., thereby completing the photoelectrode 40 in which the dye is adsorbed to the semiconductor electrode by about 2 ⁇ 10 ⁇ 7 mol / cm 2. It was.
- a platinum electrode (Pt thin film thickness: 100 nm) having the same shape and size as the photoelectrode 40 was prepared as a counter electrode.
- a DuPont spacer S (trade name: “Surlin”) having a shape corresponding to the size of the semiconductor electrode is prepared, as shown in FIG. 3 described in Japanese Patent Application Laid-Open No. 2002-289274.
- the photoelectrode 40, the counter electrode CE, and the spacer S were opposed to each other, and the inside was filled with an electrolyte E.
- the dye-sensitized solar cell (cell A) which consists of a photoelectric conversion element using the photoelectrode A was completed.
- Photoelectric conversion efficiency ( ⁇ /%) A battery characteristic test was conducted, and the photoelectric conversion efficiency ( ⁇ /%) was measured for each dye-sensitized solar cell.
- the battery characteristic test was performed by irradiating 1000 W / m 2 of pseudo-sunlight from a xenon lamp through an AM1.5 filter using a solar simulator (manufactured by WACOM, WXS-85H). The current-voltage characteristics were measured using an IV tester to determine the photoelectric conversion efficiency ( ⁇ /%). In Table 4 below, the initial conversion efficiency is shown. Rank B or higher is an acceptable level (passed level).
- Adsorption amount A dye was adsorbed on a titanium oxide film having the same area as the photoelectrode 40 by the same method as the dye adsorption described above. Thereafter, using a base (10% tetrabutylammonium hydroxide / methanol solution), the dye was desorbed from the titanium oxide film at a temperature of 25 ° C. for 20 hours, and it was confirmed that the dye was completely desorbed.
- the solvent containing the desorbed dye was diluted with methanol, and the solution absorption was measured using UV-3600 (manufactured by Shimadzu Corporation). The amount of dye adsorbed was quantified based on a previously prepared calibration curve for solution absorption. The dye adsorption amount obtained for each metal complex dye was divided by the dye adsorption amount of Comparative Compound S-1, and the relative adsorption amount was determined.
- Electrolytes with different iodine concentrations were prepared, and their dependency on iodine concentration was evaluated. Specifically, instead of the electrolyte E, an electrolyte in which each iodine source (iodine, lithium iodide, 1-propyl-3-methylimidazolium iodide) is 1.5 times the amount of the electrolyte E is used. The voltage was measured. This measured voltage was compared with the voltage when electrolyte E was used. And the fall rate with respect to the voltage at the time of electrolyte E use was evaluated. Rank B or higher is an acceptable level (passed level).
- each iodine source iodine, lithium iodide, 1-propyl-3-methylimidazolium iodide
- Evaluation criteria (decrease rate) A: Less than 2% B: 2% or more and less than 4% C: 4% or more and less than 6% D: 6% or more
- the metal complex dyes S-1 to S-5 used in sample numbers C11 to C15 are the same as the metal complex dyes used in Example 1.
- the metal complex dye of the present invention is excellent in photoelectric conversion efficiency and durability, and has a small dependence of voltage on iodine concentration. Moreover, it can be seen that the amount of adsorption to the surface of the semiconductor fine particles is large, and desorption by a base hardly occurs.
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Abstract
Description
しかしながら、耐久性と光電変換効率を両立させることは、厳しい状況であった。
このような現状に鑑み、本発明は耐久性および光電変換効率がともに優れた光電変換素子、色素増感太陽電池およびこれに用いる金属錯体色素を提供することを課題とする。
<1>導電性支持体、電解質を含む感光体層、電解質を含む電荷移動体層および対極を有する光電変換素子であって、感光体層が、下記式(I)で表される金属錯体色素が担持された半導体微粒子を有する光電変換素子。
式(DL-1)において、m1は0~3の整数を表し、m2は1~4の整数を表し、n1は1~4の整数を表す。L1はアリーレン基、アルキニレン基またはアルキニレンアリーレン基を表し、R1はアミノ基、アルキルアミノ基、アリールアミノ基、ヘテロアリールアミノ基、ハロゲン原子、アルキル基、アルキニル基、アルコキシ基、アリールオキシ基、アルキルチオ基またはアリールチオ基を表す。l1は0~3の整数を表し、R2aは、-[(L1)m1-(R1)m2]とは異なる置換基を表す。Eは下記式(E-1)~(E-6)、(E-21)または(E-22)で表される基を表す。
<3>L1が、アリーレン基である<1>または<2>に記載の光電変換素子。
<4>式(DL-1)で表される2座の配位子が、下記式(DL-3)で表される<1>または<2>に記載の光電変換素子。
<5>M1が、Ruである<1>~<4>のいずれかに記載の光電変換素子。
<6>LAが、下記式(AL-3)で表される<1>~<5>のいずれかに記載の光電変換素子。
<7>Eが、式(E-2)または式(E-5)である<1>~<6>のいずれかに記載の光電変換素子。
<8>金属錯体色素が、下記式(II)で表される<1>~<7>のいずれかに記載の光電変換素子。
<9>金属錯体色素が、下記式(III)で表される<1>~<8>のいずれかに記載の光電変換素子。
<10>R21およびR22が、アルキル基およびアリール基から選択される<2>~<9>のいずれかに記載の光電変換素子。
<11>R21がアルキル基またはアリール基であり、R22がアリール基である<2>~<10>のいずれかに記載の光電変換素子。
<15>X1またはX2が、-C(Ra)(Rb)-、エチニレン基または-O-である<13>に記載の光電変換素子。
<16>X1またはX2が、-C(Ra)(Rb)-、エチニレン基または-O-である<14>に記載の光電変換素子。
<17>R3が、炭素数5以上のアルキル基である<13>~<16>のいずれかに記載の光電変換素子。
<18>R3またはR4が、炭素数5以上のアルキル基である<14>~<16>のいずれかに記載の光電変換素子。
<19>R3が、炭素数5以上の直鎖のアルキル基である<13>~<18>のいずれかに記載の光電変換素子。
<20>R3またはR4が、炭素数5以上の直鎖のアルキル基である<14>~<18>のいずれかに記載の光電変換素子。
<21>金属錯体色素が、下記式(XXII)で表される<12>~<20>のいずれかに記載の光電変換素子。
<22>金属錯体色素が、下記式(XXIII)で表される<12>~<21>のいずれかに記載の光電変換素子。
<24>共吸着剤が、下記式(CA)で表される<23>に記載の光電変換素子。
<25>前記<1>~<24>のいずれかに記載の光電変換素子を具備する色素増感太陽電池。
<26>下記式(I)で表される金属錯体色素。
式(DL-1)において、m1は0~3の整数を表し、m2は1~4の整数を表し、n1は1~4の整数を表す。L1はアリーレン基、アルキニレン基またはアルキニレンアリーレン基を表し、R1はアミノ基、アルキルアミノ基、アリールアミノ基、ヘテロアリールアミノ基、ハロゲン原子、アルキル基、アルキニル基、アルコキシ基、アリールオキシ基、アルキルチオ基またはアリールチオ基を表す。l1は0~3の整数を表し、R2aは、-[(L1)m1-(R1)m2]とは異なる置換基を表す。Eは下記式(E-1)~(E-6)、(E-21)または(E-22)で表される基を表す。
<27>金属錯体色素が、下記式(II)で表される<26>に記載の金属錯体色素。
<28>金属錯体色素が、下記式(III)で表される<26>または<27>に記載の金属錯体色素。
本発明においては、各置換基は、特に断らない限り、さらに置換基で置換されていてもよい。
図1に示すように、本発明の一実施形態の光電変換素子10は、導電性支持体1と、色素(金属錯体色素)21により増感された半導体微粒子22を含む感光体層2と、正孔輸送層である電荷移動体層3と、対極4とを有する。感光体層2を設置した導電性支持体1は、光電変換素子10において作用電極として機能する。本実施形態においては、この光電変換素子10は、色素増感太陽電池を利用したシステム100に含まれる。色素増感太陽電池を利用したシステム100は、外部回路6で動作手段としての電動モーター(扇風機)Mに仕事をさせる電池用途として光電変換素子10を使用できるようにしている。
以下、主たる部材について概略を説明する。
感光体層は後述する電解質を含み、下記本発明の金属錯体色素を含む増感色素が担持された半導体微粒子を含む層である。
[第一の態様の金属錯体色素]
第一の態様の金属錯体色素は、下記式(I)で表される。
式(DL-1)において、m1は0~3の整数を表し、m2は1~4の整数を表し、n1は1~4の整数を表す。L1はアリーレン基、アルキニレン基またはアルキニレンアリーレン基を表し、R1はアミノ基、アルキルアミノ基、アリールアミノ基またはヘテロアリールアミノ基を表す。l1は0~3の整数を表し、R2aは、-[(L1)m1-(R1)m2]とは異なる置換基を表す。Eは下記式(E-1)~(E-6)のいずれかで表される基を表す。
M1は金属原子を表す。M1は好ましくは4配位または6配位が可能な金属であり、長周期律表上6~12族の元素が挙げられる。M1は、より好ましくはRu、Os、Zn、Cu、Rh、Re、MnまたはZnである。M1は、特に好ましくは、Ru、Os、ZnまたはCuであり、最も好ましくはRuである。
第一の態様において、配位子LAは、式(AL-1)で表される。
Za、ZbおよびZcは5員環または6員環を形成するのに必要な非金属原子群を表す。
Za、ZbおよびZcにより形成される5員環または6員環は、置換されていても無置換でもよく、単環でも縮環していてもよい。Za、ZbおよびZcは環構成原子が、炭素原子、窒素原子、酸素原子、硫黄原子およびリン原子から選択される原子であることが好ましい。環構成原子は、水素原子や、ハロゲン原子を含めた置換基で置換されていてもよい。
Za、ZbおよびZcにより形成される環は、芳香族環、すなわち、含窒素芳香族環がより好ましい。
5員環の場合はイミダゾール環、オキサゾール環、チアゾール環またはトリアゾール環を形成するのが好ましく、6員環の場合はピリジン環、ピリミジン環、ピリダジン環またはピラジン環を形成するのが好ましい。なかでもイミダゾール環またはピリジン環がより好ましい。
本発明において酸性基とは、解離性のプロトンを有する置換基であり、例えば、カルボキシ基、ホスホニル基、ホスホリル基、スルホ基、ホウ酸基等が挙げられ、好ましくはカルボキシ基である。また酸性基はプロトンを放出して解離した状態であってもよく、塩であってもよい。塩となる場合の対イオンとしては特に限定されないが、例えば、下記対イオンCIにおける正のイオンの例が挙げられる。なお、ここで挙げた酸性基及びその好ましい範囲を酸性基Acということがある。
オニウムイオンとしてはアンモニウムイオン、ピリジニウムイオンが挙げられ、アンモニウムイオンとしては、テトラアルキルアンモニウムイオン、ベンジルトリアルキルアンモニウムイオン、アリール基とアルキル基が混在した第四級アンモニウムイオンが挙げられ、このうちテトラアルキルアンモニウムイオンが好ましい。テトラアルキルアンモニウムイオンでは、アルキル基の炭素数は1~12が好ましく、1~8がより好ましく、2~6がさらに好ましい。なかでもテトラブチルアンモニウムイオンが好ましい。
該酸性基としては、上記酸性基Acとして挙げたものが好ましい。
RL1、RL2およびRL3は各々独立に、置換基を表す。該置換基は、例えば後述の置換基Tが挙げられる。RL1、RL2およびRL3はアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、アルコキシ基、アミノ基、アルキルアミノ基、アリールアミノ基が好ましく、アルキル基、アリール基、ヘテロアリール基がより好ましく、ヘテロアリール基が特に好ましい。
a1、a3、b1およびb3は各々独立に、0~4の整数を表し、a2およびb2は各々独立に、0~3の整数を表す。ただし、a1~a3が全て0であることはない。
第一の態様において、配位子LDは、式(DL-1)で表される。
L1はアリーレン基、アルキニレン基またはアルキニレンアリーレン基を表し、なかでもアリーレン基が好ましい。
アリーレン基は、置換基を有していてもよい。該置換基としては、後述の置換基Tが挙げられ、ハロゲン原子、アルキル基、アリール基、ヘテロ環基、アルコキシ基、アルキルチオ基、アミノ基、アルキルアミノ基、アリールアミノ基、ヘテロアリールアミノ基が好ましく、なかでもアミノ基、アルキルアミノ基、アリールアミノ基、ヘテロアリールアミノ基がより好ましい。
また、該置換基とR1が互いに結合して環を形成してもよく、さらに複数の置換基を有する場合、これらが互いに結合して環を形成してもよい。
Lxにおけるアリーレン基は置換基を有していてもよく、該置換基としては後述の置換基Tが挙げられる。ここで、アリーレン基に対する置換基はL1がアリーレン基である場合に挙げた置換基が好ましい。
ここで、アミノ基は-NH2である。アルキルアミノ基は、N-アルキルアミノ基、N,N-ジアルキルアミノ基を含む。アリールアミノ基は、N-アリールアミノ基、N-アルキル-N-アリールアミノ基、N,N-ジアリールアミノ基を含む。ヘテロアリールアミノ基は、N-ヘテロアリールアミノ基、N-アルキル-N-ヘテロアリールアミノ基、N-アリール-N-ヘテロアリールアミノ基を含む。
上記各アミノ基における窒素原子に置換するヘテロアリール基の炭素数は0~24が好ましく、1~18がより好ましい。該ヘテロアリール基におけるヘテロ環としては、5員環または6員環が好まし。ヘテロ環を構成するヘテロ原子は、窒素原子、酸素原子、硫黄原子が好ましく、例えば、チオフェン環、フラン環、ピロール環、ピラゾール環、イミダゾール環、トリアゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環等が挙げられる。また、該ヘテロアリール環は、芳香族炭素環、脂肪族炭素環、ヘテロ環等で縮環していても構わない。
このうち、ハロゲン原子、アルキル基、アリール基、ヘテロ環基、アルコキシ基、アルキルチオ基、アミノ基、アルキルアミノ基、アリールアミノ基、ヘテロアリールアミノ基が好ましく、アルキル基、アリール基、アルコキシ基、アルキルチオ基がより好ましい。
なお、上記環は、置換基を有してもよく、該置換基としては置換基Tが挙げられる。
m2は、1~4の整数を表し、1または2が好ましく、1がより好ましい。
n1は1~4の整数を表すが、1または2が好ましく、1がより好ましい。
n1が2以上の場合、複数の-[(L1)m1-(R1)m2]が互いに結合して環を形成してもよい。
R2aが、複数存在する場合、複数のR2aは互いに結合して環を形成してもよい。
式(DL-3)において、式(E-1)~(E-5)のRはハロゲン原子、アルキル基、アルコキシ基、アリール基またはヘテロアリール基を表す。
式(E-1)~(E-5)のRにおけるハロゲン原子は、フッ素原子、塩素原子、臭素原子、沃素原子が挙げられ、フッ素原子、塩素原子、臭素原子が好ましく、フッ素原子がより好ましい。
ヘテロアリール環の環構成ヘテロ原子としては、酸素原子、硫黄原子、窒素原子、セレン原子が好ましい。
該ヘテロアリール基におけるヘテロアリール環としては、例えば、フラン環、チオフェン環、ピロール環が挙げられ、チオフェン環が好ましい。
Z1は、単座の配位子を表す。Z1は、例えば、アシルオキシ基、アシルチオ基、チオアシルオキシ基、チオアシルチオ基、アシルアミノオキシ基、チオカルバメート基、ジチオカルバメート基、チオカルボネート基、ジチオカルボネート基、トリチオカルボネート基、アシル基、チオシアネート基、イソチオシアネート基、シアネート基、イソシアネート基、セレネート基、イソセレネート基、イソセレノシアネート基、シアノ基、アルキルチオ基、アリールチオ基、アルコキシ基およびアリールオキシ基からなる群より選ばれた基で配位する単座の配位子、またはハロゲン原子、ホスフィン配位子、カルボニル、ジアルキルケトン、カルボンアミド、チオカルボンアミドおよびチオ尿素からなる群より選ばれる単座の配位子を挙げることができる。Z1は、好ましくは、イソチオシアネート基、イソセレノシアネート基、イソシアネート基、ハロゲン原子またはシアノ基である。なお配位子Z1がアルキル部位、アルケニル部位、アルキニル部位、アルキレン部位等を含む場合、それらは直鎖状でも分岐状でもよく、置換されていても無置換でもよい。またアリール部位、ヘテロ環部位、シクロアルキル部位等を含む場合、それらは置換されていても無置換でもよく、単環でも縮環していてもよい。
CIは電荷を中和させるのに対イオンが必要な場合の対イオンを表す。一般に、色素が陽イオンまたは陰イオンであるか、あるいは正味のイオン電荷を有するかどうかは、金属錯体色素中の金属、配位子および置換基に依存する。
置換基が解離性基を有すること等により、金属錯体色素は解離して負電荷を持ってもよい。この場合、金属錯体色素全体の電荷はCIにより電気的に中性とされる。
なお、配位子は、金属原子に配位している状態、すなわちアニオンで配位している原子はアニオンで表示したが、必ずしもアニオンで配位する必要はない。
また、金属錯体色素は、対イオンを省略しているが、対イオンが不要であるのではなく、任意の対イオンを保持し得るものである。対イオンとしては前述のCIが挙げられる。
第二の態様の金属錯体色素は、下記式(I)で表される。
式(DL-21)において、m1は0~3の整数を表し、m2は1~4の整数を表し、n1は1~4の整数を表す。L1はアリーレン基を表し、R1はハロゲン原子、アルキル基、アルキニル基、アルコキシ基、アリールオキシ基、アルキルチオ基またはアリールチオ基を表す。Eは下記式(E-21)または式(E-22)で表される基を表す。
M1は金属原子を表す。M1は好ましくは4配位または6配位が可能な金属であり、長周期律表上6~12族の元素が挙げられ、より好ましくはRu、Fe、Os、Cu、W、Cr、Mo、Ni、Pd、Pt、Co、Ir、Rh、Re、MnまたはZnである。特に好ましくは、Ru、Os、ZnまたはCuであり、最も好ましくはRuである。
第二の態様において、配位子LAは、式(AL-21)で表される。
Za、ZbおよびZcは5員環または6員環を形成するのに必要な非金属原子群を表す。
Za、ZbおよびZcにより形成される5員環または6員環は置換されていても無置換でもよく、単環でも縮環していてもよい。縮環している場合、ベンゼン環が縮環していることが好ましい。Za、ZbおよびZcは環構成原子が、炭素原子、窒素原子、酸素原子、硫黄原子およびリン原子から選択される原子であることが好ましく、炭素原子および窒素原子から選択される原子であることがより好ましい。環構成原子は、水素原子や、ハロゲン原子を含めた置換基で置換されていてもよい。
Za、ZbおよびZcにより形成される環は、芳香族環、すなわち、含窒素芳香族環がより好ましい。
5員環の場合はイミダゾール環、ベンゾイミダゾール環、オキサゾール環、チアゾール環またはトリアゾール環を形成するのが好ましく、6員環の場合はピリジン環、ピリミジン環、ピリダジン環またはピラジン環を形成するのが好ましい。なかでもイミダゾール環、ベンゾイミダゾール環またはピリジン環がより好ましい。
該酸性基としては、上記酸性基Acとして挙げたものが好ましい。
RL1、RL2およびRL3は各々独立に、置換基を表す。該置換基は、例えば後述の置換基Tが挙げられる。RL1、RL2およびRL3はアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、アルコキシ基、アミノ基、アルキルアミノ基、アリールアミノ基が好ましく、アルキル基、アリール基、ヘテロアリール基がより好ましく、ヘテロアリール基が特に好ましい。
a1、a3、b1およびb3は各々独立に、0~4の整数を表し、a2およびb2は各々独立に、0~3の整数を表す。ただし、a1~a3が全て0であることはない。
第二の態様において、配位子LDは、式(DL-21)で表される。
L1はアリーレン基を表し、例えば、フェニレン、ナフチレンが挙げられ、フェニレンが好ましい。フェニレンとしては、1,4-フェニレン、1,3-フェニレン、1,2-フェニレンが挙げられ、1,4-フェニレンが好ましい。
アリーレン基は、置換基を有していてもよい。該置換基としては、後述の置換基Tが挙げられ、ハロゲン原子、アルキル基、アリール基、ヘテロ環基、アルコキシ基、アルキルチオ基が好ましい。
また、該置換基とR1が互いに結合して環を形成してもよく、さらに複数の置換基を有する場合、これらが互いに結合して環を形成してもよい。
アルキニル基は、下記式(SA)で表される基が好ましい。
RXにおけるアルキル基は、式(DL-21)のR1におけるアルキル基が好ましい。
RXにおけるアリール基は、炭素数6~20のアリール基が好ましく、例えば、フェニル、ナフチルが挙げられる。アリール基は、置換基を有してもよいフェニル基が好ましい。
RXにおけるヘテロアリール基としては、5員環または6員環のヘテロアリール基が好ましく、該ヘテロアリール基におけるヘテロアリール環は、アリール環、脂環、ヘテロ環で縮環していてもよく、置換基を有してもよい。該置換基としては、後述の置換基Tが挙げられる。
ヘテロアリール環の環構成ヘテロ原子としては、酸素原子、硫黄原子、窒素原子、セレン原子が好ましい。
該ヘテロアリール基におけるヘテロアリール環としては、例えば、フラン環、チオフェン環、ピロール環が挙げられ、チオフェン環が好ましく、また該チオフェン環にベンゼン環やチオフェン環が縮環した環が好ましい。
アルキルチオ基は、直鎖もしくは分岐のアルキルチオ基で、炭素数は1~20が好ましく、1~18がより好ましく、例えば、メチルチオ、エチルチオ、イソプロピルチオ、n-ブチルチオ、t-ブチルチオ、n-ヘキシルチオ、n-オクチルチオ、2-エチルヘキシルチオ、n-ドデシルチオ、n-ヘキサデシルチオが挙げられる。
アリールオキシ基は、炭素数は6~20が好ましく、6~18がより好ましく、例えば、フェノキシ、p-メチルフェノキシ、p-メトキシフェノキシ、m-クロロフェノキシ、ナフトキシが挙げられる。
アリールチオ基は、炭素数は6~20が好ましく、6~18がより好ましく、例えば、フェニルチオ、p-メチルフェニルチオ、p-メトキシフェニルチオ、m-クロロフェニルチオ、ナフチルチオが挙げられる。
m2は、1~4の整数を表し、m2が2以上の場合、複数のR1は同一でも異なっていてもよい。また、互いに結合して環を形成していてもよい。
m2は1~3の整数が好ましく、1または2がより好ましく、1が特に好ましい。
n1は1~4の整数を表し、1~3の整数が好ましく、1または2がより好ましく、1が特に好ましい。
式(E-22)において、Rは水素原子、アルキル基、フェニル基またはアリールオキシ基を表し、これらは置換基を有していてもよい。該置換基としては、後述の置換基Tが挙げられる。該置換基としては、なかでも電子供与性の基が好ましく、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基がより好ましい。
Rにおけるアリールオキシ基は、炭素数は6~20が好ましく、6~18がより好ましく、6~12がさらに好ましい。アリールオキシ基としては、例えば、フェノキシ、p-メチルフェノキシ、p-メトキシフェノキシ、p-フルオロフェノキシが挙げられる。
Ra、Rbは少なくとも一方が水素原子、両方が水素原子または両方がアルキル基のものも好ましい。
R2におけるハロゲン原子はフッ素原子、塩素原子、臭素原子が好ましく、フッ素原子、塩素原子がより好ましく、フッ素原子がさらに好ましい。
R3におけるアルキル基は、炭素数5以上のアルキル基が好ましく、炭素数5~20のアルキル基がより好ましい。またR3は無置換のアルキル基が好ましく、直鎖のアルキル基がさらに好ましい。
R3におけるアリール基、ヘテロアリール基は、RXにおけるアリール基、ヘテロアリール基と同義であり、好ましい範囲も同じである。
また、R4は、R3と同義であり、好ましい範囲も同じである。
なお、配位子は、金属原子に配位している状態、すなわちアニオンで配位している原子はアニオンで表示したが、必ずしもアニオンで配位する必要はない。
また、金属錯体色素は、対イオンを省略しているが、対イオンが不要であるのではなく、任意の対イオンを保持し得るものである。対イオンとしては前述のCIが挙げられる。
併用する色素としては、特表平7-500630号公報に記載のRu錯体色素(特に第5頁左下欄5行目~第7頁右上欄7行目に例1~例19で合成された色素)、特表2002-512729号公報に記載のRu錯体色素(特に第20頁の下から3行目~第29頁23行目に例1~例16で合成された色素)、特開2001-59062号公報に記載のRu錯体色素(特に、段落番号0087~0104に記載の色素)、特開2001-6760号公報に記載のRu錯体色素(特に、段落番号0093~0102に記載の色素)、特開2001-253894号公報に記載のRu錯体色素(特に、段落番号0009~0010に記載の色素)、特開2003-212851号公報に記載のRu錯体色素(特に、段落番号0005に記載の色素)、国際公開第2007/91525号パンフレットに記載のRu錯体色素(特に、[0067]に記載の色素)、特開2001-291534号公報に記載のRu錯体色素(特に、段落番号0120~0144に記載の色素)、特開2012-012570号公報に記載のRu錯体色素(特に、段落番号0095~0103に記載の色素)、国際公開第2013/47615号パンフレットに記載のRu錯体色素(特に、[0078]~[0082]に記載の色素)、特開平11-214730号公報に記載のスクアリリウムシアニン色素(特に、段落番号0036~0047に記載の色素)、特開2012-144688号公報に記載のスクアリリウムシアニン色素(特に、段落番号0039~0046および段落番号0054~0060に記載の色素)、特開2012-84503号公報に記載のスクアリリウムシアニン色素(特に、段落番号0066~0076等に記載の色素)、特開2004-063274号公報に記載の有機色素(特に、段落番号0017~0021に記載の色素)、特開2005-123033号公報に記載の有機色素(特に、段落番号0021~0028に記載の色素)、特開2007-287694号公報に記載の有機色素(特に、段落番号0091~0096に記載の色素)、特開2008-71648号公報に記載の有機色素(特に、段落番号0030~0034に記載の色素)、国際公開第2007/119525号パンフレットに記載の有機色素(特に、[0024]に記載の色素)、Angew.Chem.Int.Ed.,49,1~5(2010)等に記載のポルフィリン色素、Angew.Chem.Int.Ed.,46,8358(2007)等に記載のフタロシアニン色素が挙げられる。
併用する色素として好ましくは、Ru錯体色素、スクアリリウムシアニン色素、または有機色素が挙げられる。
導電性支持体は、金属のように支持体そのものに導電性があるものか、または表面に導電膜層を有するガラスもしくはプラスチックの支持体であるのが好ましい。プラスチックの支持体としては、例えば、特開2001-291534号公報の段落番号0153に記載の透明ポリマーフィルムが挙げられる。支持体としては、ガラスおよびプラスチックの他、セラミック(特開2005-135902号公報)、導電性樹脂(特開2001-160425号公報)を用いてもよい。導電性支持体上には、表面に光マネージメント機能を施してもよく、例えば、特開2003-123859号公報に記載の高屈折膜および低屈折率の酸化物膜を交互に積層した反射防止膜を有してもよく、特開2002-260746号公報に記載のライトガイド機能を有してもよい。
半導体微粒子は、好ましくは金属のカルコゲニド(例えば酸化物、硫化物、セレン化物等)またはペロブスカイトの微粒子である。金属のカルコゲニドとしては、好ましくはチタン、スズ、亜鉛、タングステン、ジルコニウム、ハフニウム、ストロンチウム、インジウム、セリウム、イットリウム、ランタン、バナジウム、ニオブまたはタンタルこれらの酸化物、硫化カドミウム、セレン化カドミウム等が挙げられる。ペロブスカイトとしては、好ましくはチタン酸ストロンチウム、チタン酸カルシウム等が挙げられる。これらのうち酸化チタン(チタニア)、酸化亜鉛、酸化スズ、酸化タングステンが特に好ましい。
色素が塩である場合、特定の金属錯体色素の対イオンは特に限定されず、例えばアルカリ金属イオンまたは4級アンモニウムイオン等が挙げられる。
本発明の光電変換素子に用いられる電荷移動体層は、色素の酸化体に電子を補充する機能を有する層であり、受光電極と対極(対向電極)との間に設けられる。電荷移動体層は電解質を含む。電解質の例としては、酸化還元対を有機溶媒に溶解した液体電解質、酸化還元対を有機溶媒に溶解した液体をポリマーマトリクスに含浸した電解質(いわゆるゲル電解質)、酸化還元対を含有する溶融塩等が挙げられる。光電変換効率を高めるためには液体電解質が好ましい。液体電解質の溶媒はニトリル化合物、エーテル化合物、エステル化合物等が用いられる。液体電解質の溶媒としては、ニトリル化合物が好ましく、アセトニトリル、メトキシプロピオニトリルが特に好ましい。
ZLC1、ZLC2およびZLC3は各々独立に、5員環または6員環を形成するのに必要な非金属原子群を表す。ZLC1、ZLC2およびZLC3は置換基を有していてもよく、置換基を介して隣接する環と閉環していてもよい。qは0または1を表す。該置換基としては、後述の置換基Tが挙げられる。なお、qが0の場合、XLC3がZLC2で形成される5員環または6員環に結合する位置の炭素原子は、水素原子、またはZLC3で形成されるヘテロ環基以外の置換基が結合する。
マトリックス高分子として好ましくは、含窒素複素環を主鎖あるいは側鎖の繰り返し単位中に持つ高分子およびこれらの含窒素複素環を求電子性化合物と反応させた架橋体、トリアジン構造を持つ高分子、ウレイド構造をもつ高分子、液晶性化合物を含むもの、エーテル結合を有する高分子、ポリフッ化ビニリデン系、メタクリレート・アクリレート系、熱硬化性樹脂、架橋ポリシロキサン、ポリビニルアルコール(PVA)、ポリアルキレングリコールとデキストリン等の包摂化合物、含酸素または含硫黄高分子を添加した系、天然高分子等が挙げられる。これらにアルカリ膨潤型高分子、一つの高分子内にカチオン部位とヨウ素との電荷移動錯体を形成できる化合物を持った高分子等を添加してもよい。
本発明の光電変換素子においては、本発明の金属錯体色素または必要により併用する色素とともに共吸着剤を使用することが好ましい。このような共吸着剤としては酸性基(好ましくは、カルボキシ基もしくはその塩の基)を1つ以上有する共吸着剤が好ましく、例えば、脂肪酸やステロイド骨格を有する化合物が挙げられる。脂肪酸は、飽和脂肪酸でも不飽和脂肪酸でもよく、例えばブタン酸、ヘキサン酸、オクタン酸、デカン酸、ヘキサデカン酸、ドデカン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸等が挙げられる。
ステロイド骨格を有する化合物として、コール酸、グリココール酸、ケノデオキシコール酸、ヒオコール酸、デオキシコール酸、リトコール酸、ウルソデオキシコール酸等が挙げられる。好ましくはコール酸、デオキシコール酸、ケノデオキシコール酸であり、さらに好ましくはケノデオキシコール酸である。
酸性基は、先に示したものと同義であり、好ましい範囲も同じである。
RC1は、これらの中でも、カルボキシ基またはスルホ基もしくはそれらの塩が置換したアルキル基が好ましく、-CH(CH3)CH2CH2CO2H、-CH(CH3)CH2CH2CONHCH2CH2SO3Hがさらに好ましい。
nAは2~4が好ましい。
本明細書において化合物(錯体、色素を含む)の表示については、当該化合物そのもののほか、その塩、そのイオンを含む意味に用いる。また、本明細書において置換・無置換を明記していない置換基(連結基および配位子についても同様)については、その基に任意の置換基を有していてもよい意味である。これは置換・無置換を明記していない化合物についても同義である。好ましい置換基としては、下記置換基Tが挙げられる。
また、本明細書において、単に置換基としてしか記載されていない場合は、この置換基Tを参照するものであり、また、各々の基、例えば、アルキル基、が記載されているのみの時は、この置換基Tの対応する基における好ましい範囲、具体例が適用される。
アルキル基(好ましくは炭素数1~20で、例えばメチル、エチル、イソプロピル、t-ブチル、ペンチル、ヘプチル、1-エチルペンチル、ベンジル、2-エトキシエチル、1-カルボキシメチル、トリフルオロメチル等)、アルケニル基(好ましくは炭素数2~20で、例えば、ビニル、アリル、オレイル等)、アルキニル基(好ましくは炭素数2~20で、例えば、エチニル、ブタジイニル、フェニルエチニル等)、シクロアルキル基(好ましくは炭素数3~20で、例えば、シクロプロピル、シクロペンチル、シクロヘキシル、4-メチルシクロヘキシル等)、シクロアルケニル基(好ましくは炭素数5~20で、例えばシクロペンテニル、シクロヘキセニル等)、アリール基(好ましくは炭素数6~26で、例えば、フェニル、1-ナフチル、4-メトキシフェニル、2-クロロフェニル、3-メチルフェニル等)、ヘテロ環基(好ましくは炭素数2~20で、少なくとも1つの酸素原子、硫黄原子、窒素原子を有する5員環または6員環のヘテロ環基がより好ましく、例えば、2-ピリジル、4-ピリジル、2-イミダゾリル、2-ベンゾイミダゾリル、2-チアゾリル、2-オキサゾリル等)、アルコキシ基(好ましくは炭素数1~20で、例えば、メトキシ、エトキシ、イソプロピルオキシ、ベンジルオキシ等)、アルケニルオキシ基(好ましくは炭素数2~20で、例えば、ビニルオキシ、アリルオキシ等)、アルキニルオキシ基(好ましくは炭素数2~20で、例えば、2-プロピニルオキシ、4-ブチニルオキシ等)、シクロアルキルオキシ基(好ましくは炭素数3~20で、例えば、シクロプロピルオキシ、シクロペンチルオキシ、シクロヘキシルオキシ、4-メチルシクロヘキシルオキシ等)、アリールオキシ基(好ましくは炭素数6~26で、例えば、フェノキシ、1-ナフチルオキシ、3-メチルフェノキシ、4-メトキシフェノキシ等)、ヘテロ環オキシ基(例えば、イミダゾリルオキシ、ベンゾイミダゾリルオキシ、チアゾリルオキシ、ベンゾチアゾリルオキシ、トリアジニルオキシ、プリニルオキシ)、
対極は、色素増感太陽電池(光電気化学電池)の正極として働くことが好ましい。対極は、通常前述の導電性支持体と同義である。強度が十分に保たれるような構成においては、支持体は必ずしも必要でない。対極の構造としては、集電効果が高い構造が好ましい。感光体層に光が到達するためには、前述の導電性支持体と対極との少なくとも一方は実質的に透明でなければならない。色素増感太陽電池においては、導電性支持体が透明であって太陽光を支持体側から入射させるのが好ましい。この場合、対極は光を反射する性質を有することがさらに好ましい。色素増感太陽電池の対極としては、金属もしくは導電性の酸化物を蒸着したガラス、またはプラスチックが好ましく、白金を蒸着したガラスが特に好ましい。色素増感太陽電池では、構成物の蒸散を防止するために、電池の側面をポリマーや接着剤等で密封することが好ましい。
本発明においては、本発明の金属錯体色素を含有する色素溶液を使用して色素吸着電極を製造することが好ましい。
色素溶液は、本発明の金属錯体色素が溶媒に溶解されてなり、必要により共吸着剤や他の成分を含んでもよい。
使用する溶媒としては、特開2001-291534号公報に記載の溶媒が挙げられるが特に限定されない。本実施形態においては有機溶媒が好ましく、さらにアルコール類、アミド類、ニトリル類、炭化水素類、および、これらの2種以上の混合溶媒が好ましい。混合溶媒としては、アルコール類と、アミド類、ニトリル類または炭化水素類から選択される溶媒との混合溶媒が好ましい。さらに好ましくはアルコール類とアミド類、アルコール類と炭化水素類の混合溶媒、特に好ましくはアルコール類とアミド類の混合溶媒である。具体的にはメタノール、エタノール、プロパノール、ブタノール、ジメチルホルムアミド、ジメチルアセトアミドが好ましい。
ここで、色素溶液は、光電変換素子や色素増感太陽電池を製造する際に、この溶液をこのまま使用できるように、金属錯体色素や共吸着剤が濃度調整されているものが好ましい。本発明の金属錯体色素を、0.001~0.1質量%含有することが好ましい。
同様に、光電変換素子や色素増感太陽電池における電解液の水分含有量の調整も、効果を効果的に奏するために好ましい。この電解液の水分含有量(含有率)を0~0.1質量%に調整することが好ましい。この電解液の調整は、色素溶液で行なうのが特に好ましい。
すなわち、色素増感太陽電池用の色素吸着電極は、上記色素溶液から得られてなる組成物を、半導体微粒子を付与した導電性支持体上に塗布し、塗布後の該組成物を硬化させて感光体層としたものが好ましい。
この色素増感太陽電池用の色素吸着電極を使用し、電解質、および対極を準備し、これらを用いて組み立てることで、色素増感太陽電池を製造することが好ましい。
<金属錯体色素の合成>
以下に、実施例により第一の態様の色素の合成法を詳しく説明するが、出発物質、色素中間体および合成ルートについてはこれらにより限定されるものではない。
まず、下記の例示金属錯体色素を合成した。
下記のスキームの方法に従って化合物(45)を合成し、例示金属錯体色素DN-1を合成した。
ナトリウム-tert-ブトキシド2.47g、キシレン25ml、4-アミノ-2-クロロピリジン1.5g、4-ヨードペンチルベンゼン9.60gを三つ口フラスコに入れ、窒素置換した。撹拌しながらトリス(ジベンジリデンアセトン)ジパラジウム(0)0.534g、トリ-tert-ブチルホスフィン0.472gを加え、2時間加熱還流させた。室温に戻し、氷水、酢酸エチルを加え、有機層を減圧濃縮した。ヘキサン/酢酸エチルを溶離液としたシリカゲルカラムクロマトグラフィーにより精製し、化合物(42)を3.7g得た。
J.Org.Chem.,2008,73,p.4309-4312に記載の方法に従って合成した化合物(43)2.66g、化合物(42)2.70g、三リン酸カリウム5.45g、1,2-ジメトキシエタン54mlを三つ口フラスコに入れ、窒素置換した。撹拌しながら0.54gのXphos G3を加え、3時間加熱還流させた。室温に戻し、セライトろ過を施し、溶媒を減圧留去した後、ヘキサン/酢酸エチルを溶離液としたシリカゲルカラムクロマトグラフィーにより精製し、化合物(44)を1.82g得た。
化合物(44)1.70g、塩酸/酢酸エチル溶液28mlを三つ口フラスコに入れ、1時間撹拌させた。その後、重曹水を加えて、分液操作を施し、有機層を濃縮した。140℃で減圧させることで、化合物(45)を3.7g得た。
2.94gの[Ru(p-cymene)Cl2]2、5.00gの化合物(45)をエタノール192mlに加え3時間加熱還流させた。その後、溶媒を減圧留去し、酢酸エチル、重曹水で分液操作を施し、有機層を濃縮した。アセトニトリルに加熱完溶させ、約20mlまで濃縮した後、放冷させ沈殿させた。ろ過、アセトニトリル洗浄、乾燥を施し、金属錯体DN-1Aを4.93gを得た。
100mlの三つ口フラスコに、0.8gの金属錯体DN-1A、0.455gの化合物d-1-8、10mlのN,N-ジメチルホルムアミド(DMF)を入れ、加熱還流させた。反応終了後、溶媒を減圧留去し、塩化メチレン/酢酸エチルを溶離液としたシリカゲルカラムクロマトグラフィーにより精製を施すことで、金属錯体DN-1Bを0.5g得た。
100mlの三つ口フラスコに、0.26gの金属錯体DN-1B、179mgのNH4SCN、4mlのDMFを加え、130℃で5時間加熱攪拌させた。反応終了後、溶媒を減圧留去し、塩化メチレン/酢酸エチルを溶離液としたシリカゲルカラムクロマトグラフィーにより精製を施すことで、金属錯体DN-1Cを90mg得た。
100mlの三つ口フラスコに、90mgの金属錯体DN-1C、30mlのDMFを加え、室温で攪拌しながら1N水酸化ナトリウム水溶液を滴下し。1時間攪拌させた後、トリフルオロメタンスルホン酸メタノール溶液と水を加え、得られた沈殿物をろ過、水洗、乾燥させることで、金属錯体色素DN-1を77mg得た。得られた化合物の同定はMS測定により行った。
金属錯体色素DN-1を17μモル/Lの濃度にして、島津製作所社製のUV-3600で測定した。
図3は測定溶媒が340mmol/Lテトラブチルアンモニウムヒドロキサイド(TBAOH)のメタノール溶液でのスペクトル図である。
また、後述の実施例1における試料番号101に準じてモデル的な半導体膜(金属錯体色素DN-1を吸着させた酸化チタン膜)での可視吸収スペクトルを図4に示す。
例示金属錯体色素DN-1と同様にして、例示金属錯体色素DN-2、DN-13、DN-21、DN―22、DA-1、DA-2を合成した。得られた化合物の同定はMS測定により行った。
下記表1に、金属錯体色素のMS測定結果をまとめて示した。
光電極を構成する半導体電極の半導体層または光散乱層を形成するため、下記のペーストを調製し、このペーストを用いて、色素増感太陽電池を作製した。
(ペーストA)
球形のTiO2粒子(アナターゼ、平均粒径;25nm、以下「球形TiO2粒子A」という。)を硝酸溶液に入れて撹拌することによりチタニアスラリーを調製した。次に、チタニアスラリーに増粘剤としてセルロース系バインダーを加え、混練してペーストAを調製した。
(ペースト1)
球形TiO2粒子Aと、球形のTiO2粒子(アナターゼ、平均粒径;200nm、以下「球形TiO2粒子B」という。)を硝酸溶液に入れて撹拌することによりチタニアスラリーを調製した。次に、チタニアスラリーに増粘剤としてセルロース系バインダーを加え、混練してペースト1(TiO2粒子Aの質量:TiO2粒子Bの質量=30:70)を調製した。
(ペースト2)
ペーストAに、棒状TiO2粒子(アナターゼ、直径;100nm、アスペクト比;5、以下「棒状TiO2粒子C」という。)を混合し、棒状TiO2粒子Cの質量:ペーストAの質量=30:70のペースト2を調製した。
以下に示す手順により、特開2002-289274号公報に記載の図5に示されている光電極12と同様の構成を有する光電極を作製した。そして、この光電極を用いて、同公報に記載の図3に示されている光電極以外は色素増感太陽電池20と同様の構成を有する10mm×10mmのスケールの色素増感太陽電池1を作製した。具体的な構成は本願に添付の図2に示した。色素増感太陽電池20は、透明電極41、半導体電極42、透明導電膜43、基板44、半導体層45、光散乱層46、光電極40、対極CE、電解質E、スペーサーSを有する。
次に、上記のようにして作製した光電極A(色素吸着電極の前駆体)に、色素を以下のようにして吸着させた。先ず、マグネシウムエトキシドで脱水した無水tert-ブタノールとジメチルホルムアミドの1:1(体積比)の混合物を溶媒として、下記表2に記載の金属錯体色素を3×10-4モル/Lとなるように溶解した。さらに共吸着剤として、ケノデオキシコール酸とコール酸の等モル混合物を金属錯体色素1モルに対して20モル加え、各色素溶液を調製した。この色素溶液をカール・フィッシャー滴定により水分量を測定したところ、水は0.01質量%未満であった。次に、この溶液に半導体電極を40℃10時間浸漬し、引き上げ後50℃で乾燥させることにより、半導体電極に色素が約2×10-7mol/cm2吸着した光電極40をそれぞれ完成させた。
次に、対極として光電極40と同様の形状と大きさを有する白金電極(Pt薄膜の厚さ;100nm)を準備した。電解質Eとして、0.1Mヨウ素、0.1Mヨウ化リチウム、0.6M 1-プロピル-3-メチルイミダゾリウムヨージドおよび4-tert-ブチルピリジン、を含むヨウ素系レドックス溶液を調製した。更に、半導体電極の大きさに合わせた形状を有するデュポン社製のスペーサーS(商品名:「サーリン」)を準備し、特開2002-289274号公報に記載の図3に示されているように、光電極40と対極CEとスペーサーSを介して対向させ、内部に電解質Eを充填した。このようにして、光電極Aを使用した光電変換素子からなる色素増感太陽電池(セルA)を完成させた。
電池特性試験を行い、それぞれの色素増感太陽電池について、光電変換効率(η/%)を測定した。電池特性試験は、ソーラーシミュレーター(WACOM製、WXS-85H)を用い、AM1.5フィルタを通したキセノンランプから1000W/m2の疑似太陽光を照射することにより行った。I-Vテスターを用いて電流-電圧特性を測定し、光電変換効率(η/%)を求めた。それぞれの色素増感太陽電池の光電変換効率について、下記の比較化合物S-3の光電変換効率を基準として、以下のランクで評価した。
ランクB以上が許容される水準(合格レベル)である。
AA:1.15倍以上
A:1.1倍以上1.15倍未満
B:1.03倍以上1.1倍未満
C:1.03倍未満
作製したそれぞれの色素増感太陽電池を、40℃の恒温槽に入れて耐熱試験を行った。耐熱試験前の色素増感太陽電池および耐熱試験12時間後の色素増感太陽電池について電流を評価した。「耐熱試験後の電流値の減少分」を「耐熱試験前の電流値」で割った値に100を掛けた値を熱劣化率として算出した。それぞれの色素増感太陽電池の熱劣化率について、下記の比較化合物S-3で得られた熱劣化率を基準として、以下のランクで評価した。下記表2には、「熱劣化」として表示した。
A:0.9倍未満
B:0.9倍以上1倍未満
C:1倍以上
作製したそれぞれの色素増感太陽電池を、-10℃の冷凍庫と40℃の恒温槽へ2時間毎に交互に入れて冷却と加温を繰り返し、ヒートサイクル試験を行った。ヒートサイクル試験前の色素増感太陽電池およびヒートサイクル試験24時間後の色素増感太陽電池について、電流を評価した。「耐熱試験後の電流値の減少分」を「耐熱試験前の電流値」で割った値に100を掛けた値を劣化率として算出した。それぞれの色素増感太陽電池の劣化率について、下記の比較化合物S-3で得られた劣化率を基準として、以下のランクで評価した。下記表2には、「ヒートサイクル」として表示した。
A:0.9倍未満
B:0.9倍以上1倍未満
C:1倍以上
<金属錯体色素の合成>
以下に、実施例により第二の態様の色素の合成法を詳しく説明するが、出発物質、色素中間体および合成ルートについてはこれらにより限定されるものではない。
まず、下記の例示金属錯体色素を合成した。
(例示金属錯体色素D-1-5aの合成)
下記のスキームの方法に従って例示金属錯体色素D-1-5aを合成した。
21gの化合物d-1-1をEtOH(エタノール)300mlに溶解し、硫酸15mlを加え、70℃で3時間攪拌した。その後、得られた溶液を冷却し、重曹水で中和処理を行った後に酢酸エチルを加え分液・抽出し、有機層の濃縮を行った。得られた濃縮物をシリカゲルカラムクロマトグラフィーで精製し、化合物d-1-2を15g得た。
19gの化合物d-1-2と酢酸エチル8.5gをトルエン100mlに入れ、窒素雰囲気下で混合した。得られた溶液を氷浴で冷却後、18gのt-BuOKを数回に分けて添加し、3時間攪拌した。1N塩酸水で中和処理を行った後に、酢酸エチルを加え分液・抽出し、有機層の濃縮を行った。得られた濃縮物を2N塩酸水200mlに入れ、外温100℃で12時間加熱した。得られた溶液を冷却後、重曹水で中和処理を行い、酢酸エチルを加え分液・抽出し、有機層の濃縮を行った。得られた濃縮物をシリカゲルカラムクロマトグラフィーで精製し、化合物d-1-3を10.5g得た。
2.2gの化合物d-1-3に対し、DMF(ジメチルホルムアミド)溶媒30ml中でCuIを0.05当量、Pd(PPh3)2Cl2を0.05当量、1-ヘプチンを1.4g、トリエチルアミンを4当量加え、室温で窒素雰囲気下、3時間攪拌した。得られた溶液に1N塩酸と酢酸エチルを加え分液・抽出し、有機層の濃縮を行った。得られた濃縮物をシリカゲルカラムクロマトグラフィーで精製し、化合物d-1-4を1.8g得た。
1.5gの化合物d-1-4をTHF(テトラヒドロフラン)20mlに溶解し、窒素雰囲気下、0℃で攪拌しながら、ナトリウムエトキシド2.2当量を添加し15分攪拌した。その後、得られた溶液にトリフルオロ酢酸エチル1.1当量を滴下し、外温70℃で20時間攪拌した。得られた溶液を室温に戻した後、塩化アンモニウム水溶液を滴下、分液し、有機層を濃縮し、粗精製物d-1-5を1.3g得た。
1.3gの化合物d-1-5をエタノール20mlに溶解し窒素雰囲気下、室温で攪拌しながら、ヒドラジン1水和物を1.0当量添加し、外温90℃で12時間加熱した。その後、得られた溶液に濃塩酸0.5mlを添加し、1時間攪拌した。得られた溶液を濃縮後、重曹水と酢酸エチルで抽出・分液後、有機層を濃縮した。得られた濃縮物をシリカゲルカラムクロマトグラフィーで精製し、化合物d-1-6を1.3g得た。
1.3gの化合物d-1-6と1当量の化合物d-1-7をNMP(N-メチルピロリドン)150mlに加え窒素雰囲気下70℃で3時間攪拌した。その後化合物d-1-8を1当量加え、160℃で8時間加熱攪拌した後、チオシアン酸アンモニウムを10当量加え160℃で8時間攪拌した。得られた溶液を濃縮後、水を加え、ろ過した。ろ物をシリカゲルカラムクロマトグラフィーで精製し、化合物d-1-9を得た後、アセトン30mlと1N水酸化ナトリウム水溶液40mlの混合溶媒に加え、外温65℃で24時間攪拌した。室温に戻し、塩酸でpHを3に調整し、析出物をろ過し、粗精製物D-1-5aを2.5g得た。
これをTBAOH(水酸化テトラブチルアンモニウム)と共にメタノール溶液に溶解し、SephadexLH-20カラムで精製した。主層の分画を回収し濃縮後トリフルオロメタンスルホン酸0.1M溶液を加え、pH3に調整し、析出物をろ過し、例示金属錯体色素D-1-5aを2.0g得た。
得られた例示金属錯体色素D-1-5aの構造はMS(マススペクトル)測定により確認した。ESI-MS m/z=832.1(M+H)+
金属錯体色素のMS測定結果を下記表3にまとめて示す。
光電極を構成する半導体電極の半導体層または光散乱層を形成するため、下記のペーストを調製し、このペーストを用いて、色素増感太陽電池を作製した。
(ペーストA)
球形のTiO2粒子(アナターゼ、平均粒径;25nm、以下「球形TiO2粒子A」という。)を硝酸溶液に入れて撹拌することによりチタニアスラリーを調製した。次に、チタニアスラリーに増粘剤としてセルロース系バインダーを加え、混練してペーストAを調製した。
(ペースト1)
球形TiO2粒子Aと、球形のTiO2粒子(アナターゼ、平均粒径;200nm、以下「球形TiO2粒子B」という。)を硝酸溶液に入れて撹拌することによりチタニアスラリーを調製した。次に、チタニアスラリーに増粘剤としてセルロース系バインダーを加え、混練してペースト1(TiO2粒子Aの質量:TiO2粒子Bの質量=30:70)を調製した。
(ペースト2)
ペーストAに、棒状TiO2粒子(アナターゼ、直径;100nm、アスペクト比;5、以下「棒状TiO2粒子C」という。)を混合し、棒状TiO2粒子Cの質量:ペーストAの質量=30:70のペースト2を調製した。
以下に示す手順により、特開2002-289274号公報に記載の図5に示されている光電極12と同様の構成を有する光電極を作製した。そして、この光電極を用いて、同公報に記載の図3に示されている光電極以外は色素増感太陽電池20と同様の構成を有する10mm×10mmのスケールの色素増感太陽電池を作製した。色素増感型太陽電池20の具体的な構成は本願に添付の図2に示した。
次に、上記のようにして作製した光電極A(色素吸着電極の前駆体)に色素を以下のようにして吸着させた。先ず、マグネシウムエトキシドで脱水した無水ブタノールとジメチルホルムアミドの1:1(体積比)の混合物を溶媒として、下記表4に記載の金属錯体色素を3×10-4モル/Lとなるように溶解した。さらに共吸着剤として、ケノデオキシコール酸とコール酸の等モル混合物を金属錯体色素1モルに対して20モル加え、各色素溶液を調製した。この色素溶液をカール・フィッシャー滴定により水分量を測定したところ、水は0.01質量%未満であった。次に、この溶液に半導体電極を40℃10時間浸漬し、引き上げ後50℃で乾燥させることにより、半導体電極に色素が約2×10-7mol/cm2吸着した光電極40をそれぞれ完成させた。
次に、対極として光電極40と同様の形状と大きさを有する白金電極(Pt薄膜の厚さ;100nm)を準備した。電解質Eとして、0.05Mヨウ素、0.01Mヨウ化リチウム、0.6M 1-プロピル-3-メチルイミダゾリウムヨージドおよび4-tert-ブチルピリジン、を含むヨウ素系レドックス溶液を調製した。更に、半導体電極の大きさに合わせた形状を有するデュポン社製のスペーサーS(商品名:「サーリン」)を準備し、特開2002-289274号公報に記載の図3に示されているように、光電極40と対極CEとスペーサーSを介して対向させ、内部に電解質Eを充填した。このようにして、光電極Aを使用した光電変換素子からなる色素増感太陽電池(セルA)を完成させた。
電池特性試験を行い、それぞれの色素増感太陽電池について、光電変換効率(η/%)を測定した。電池特性試験は、ソーラーシミュレーター(WACOM製、WXS-85H)を用い、AM1.5フィルタを通したキセノンランプから1000W/m2の疑似太陽光を照射することにより行った。I-Vテスターを用いて電流-電圧特性を測定し、光電変換効率(η/%)を求めた。下記表4では、初期変換効率として表記した。
ランクB以上が許容される水準(合格レベル)である。
AA:7.5%以上
A:7.3%以上7.5%未満
B:7.0%以上7.3%未満
C:6.7%以上7.0%未満
D:6.4%以上6.7%未満
E:6.4%未満
作製した色素増感太陽電池の光電変換効率を測定した後、80℃、30時間暗所で経時後に光電変換効率を測定し、耐久性として光電変換効率の低下率(%)を求めた。
光電変換効率の低下率(%)は、以下の式により求めた。
〔(初期の効率-暗所経時後の効率)/初期の効率〕×100
ランクC以上が許容される水準(合格レベル)である。
A:5.5%未満
B:5.5%以上7.0%未満
C:7.0%以上10.0%未満
D:10.0%以上
光電極40と同面積の酸化チタン膜に、前述の色素吸着と同様の方法で色素を吸着させた。その後、塩基(10%テトラブチルアンモニウムヒドロキサイド/メタノール溶液)を用いて、酸化チタン膜から温度25℃、20時間かけて色素を脱着させ、完全に色素が脱着したのを確認した。そして、脱着した色素を含む溶媒をメタノールで希釈し、この溶液吸収をUV-3600(島津製作所製)を用いて測定した。予め作成した溶液吸収の検量線を基に、色素吸着量を定量した。
それぞれの金属錯体色素について得られた色素吸着量を、比較化合物S-1の色素吸着量で割り、相対吸着量を求めた。
水を強制添加した溶液による吸着安定性試験を下記のようにして行った。
脱着試験を実施した後に、酸化チタン膜に残る色素量(残色素量)を測定した。具体的には、アセトニトリル中に水を1体積%添加した溶液10mlに、色素を吸着させた酸化チタン膜を40℃で50時間浸した。その後、上記3)吸着量の手順と同様にして、塩基(10%テトラブチルアンモニウムヒドロキサイド/メタノール溶液)を用いて、酸化チタンから色素を脱着させた。そして、溶液吸収を測定して定量した。脱着試験前の吸着量は、同条件で作製した酸化チタン膜を、脱着試験を実施せずに脱着及び定量したものを用いた。ばらつきを考慮し、n=3で実施してその平均値を求めた。この平均値を下記の基準で評価した。
ランクB以上が許容される水準(合格レベル)である。
A:80%以上
B:70%以上80%未満
C:60%以上70%未満
D:60%未満
ヨウ素濃度を変更した電解質を調製して、ヨウ素濃度に対する依存性を評価した。
具体的には、電解質Eに代えて、電解質Eに対して各ヨウ素源(ヨウ素、ヨウ化リチウム、1-プロピル-3-メチルイミダゾリウムヨージド)を1.5倍量にした電解質を用いて電圧を測定した。この測定した電圧を、電解質Eを用いた場合の電圧と比較した。そして、電解質E使用時の電圧に対する低下率を評価した。
ランクB以上が許容される水準(合格レベル)である。
A:2%未満
B:2%以上4%未満
C:4%以上6%未満
D:6%以上
また、半導体微粒子表面への吸着量も多く、塩基による脱着も起きにくいことがわかる。
2 感光体層
21 色素
22 半導体微粒子
3 電荷移動体層
4 対極
5 受光電極
6 回路
10 光電変換素子
100 色素増感太陽電池を利用したシステム
M 電動モーター(扇風機)
40 光電極
41 透明電極
42 半導体電極
43 透明導電膜
44 基板
45 半導体層
46 光散乱層
CE 対極
E 電解質
S スペーサー
Claims (29)
- 導電性支持体、電解質を含む感光体層、電解質を含む電荷移動体層および対極を有する光電変換素子であって、該感光体層が、下記式(I)で表される金属錯体色素が担持された半導体微粒子を有する光電変換素子。
M1(LA)(LD)(Z1)・(CI) 式(I)
式(I)において、M1は金属原子を表し、Z1は単座の配位子を表す。LAは下記式(AL-1)で表される3座の配位子を表す。LDは下記式(DL-1)で表される2座の配位子を表す。CIは電荷を中和するのに必要な対イオンを表す。
式(DL-1)において、m1は0~3の整数を表し、m2は1~4の整数を表し、n1は1~4の整数を表す。L1はアリーレン基、アルキニレン基またはアルキニレンアリーレン基を表し、R1はアミノ基、アルキルアミノ基、アリールアミノ基、ヘテロアリールアミノ基、ハロゲン原子、アルキル基、アルキニル基、アルコキシ基、アリールオキシ基、アルキルチオ基またはアリールチオ基を表す。l1は0~3の整数を表し、R2aは、-[(L1)m1-(R1)m2]とは異なる置換基を表す。Eは下記式(E-1)~(E-6)、(E-21)または(E-22)で表される基を表す。
- 前記L1が、アリーレン基である請求項1または2に記載の光電変換素子。
- 前記M1が、Ruである請求項1~4のいずれか1項に記載の光電変換素子。
- 前記Eが、前記式(E-2)または前記式(E-5)である請求項1~6のいずれか1項に記載の光電変換素子。
- 前記金属錯体色素が、下記式(II)で表される請求項1~7のいずれか1項に記載の光電変換素子。
R21およびR22は各々独立に水素原子、アルキル基、アリール基またはヘテロアリール基を表す。R21とR22が互いに結合して環を形成してもよい。L1、m1およびm2は、前記式(DL-1)におけるL1、m1およびm2と同義である。Wは窒素原子またはCHを表す。R10は水素原子、アルキル基、パーフルオロアルキル基、アリール基またはヘテロアリール基を表す。Z2はイソチオシアネート基、イソセレノシアネート基、イソシアネート基、ハロゲン原子またはシアノ基を表す。
- 前記R21およびR22が、アルキル基およびアリール基から選択される請求項2~9のいずれか1項に記載の光電変換素子。
- 前記R21がアルキル基またはアリール基であり、前記R22がアリール基である請求項2~10のいずれか1項に記載の光電変換素子。
- 前記式(DL-1)が、下記の条件を満たす請求項1に記載の光電変換素子。
式(DL-1)において、l1は0である。L1はアリーレン基を表し、R1はハロゲン原子、アルキル基、アルキニル基、アルコキシ基、アリールオキシ基、アルキルチオ基またはアリールチオ基を表す。Eは前記式(E-21)または(E-22)で表される基を表す。
- 前記LDが、下記式(DL-22)~(DL-24)のいずれかで表される請求項12に記載の光電変換素子。
- 前記LDが、下記式(DL-23a)~(DL-23d)または(DL-24a)~(DL-24c)のいずれかで表される請求項12または13に記載の光電変換素子。
- 前記X1が、-C(Ra)(Rb)-、エチニレン基または-O-である請求項13に記載の光電変換素子。
- 前記X1またはX2が、-C(Ra)(Rb)-、エチニレン基または-O-である請求項14に記載の光電変換素子。
- 前記R3が、炭素数5以上のアルキル基である請求項13~16のいずれか1項に記載の光電変換素子。
- 前記R3またはR4が、炭素数5以上のアルキル基である請求項14~16のいずれか1項に記載の光電変換素子。
- 前記R3が、炭素数5以上の直鎖のアルキル基である請求項13~18のいずれか1項に記載の光電変換素子。
- 前記R3またはR4が、炭素数5以上の直鎖のアルキル基である請求項14~18のいずれか1項に記載の光電変換素子。
- 前記半導体微粒子に、酸性基を1つ以上有する共吸着剤がさらに担持されている請求項1~22のいずれか1項に記載の光電変換素子。
- 請求項1~24のいずれか1項に記載の光電変換素子を具備する色素増感太陽電池。
- 下記式(I)で表される金属錯体色素。
M1(LA)(LD)(Z1)・(CI) 式(I)
式(I)において、M1は金属原子を表し、Z1は単座の配位子を表す。LAは下記式(AL-1)で表される3座の配位子を表す。LDは下記式(DL-1)で表される2座の配位子を表す。CIは電荷を中和するのに必要な対イオンを表す。
式(DL-1)において、m1は0~3の整数を表し、m2は1~4の整数を表し、n1は1~4の整数を表す。L1はアリーレン基、アルキニレン基またはアルキニレンアリーレン基を表し、R1はアミノ基、アルキルアミノ基、アリールアミノ基、ヘテロアリールアミノ基、ハロゲン原子、アルキル基、アルキニル基、アルコキシ基、アリールオキシ基、アルキルチオ基またはアリールチオ基を表す。l1は0~3の整数を表し、R2aは、-[(L1)m1-(R1)m2]とは異なる置換基を表す。Eは下記式(E-1)~(E-6)、(E-21)または(E-22)で表される基を表す。
- 前記金属錯体色素が、下記式(II)で表される請求項26に記載の金属錯体色素。
- 前記金属錯体色素が、下記式(III)で表される請求項26または27に記載の金属錯体色素。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106233484A (zh) * | 2014-04-18 | 2016-12-14 | 富士胶片株式会社 | 光电转换元件、使用该光电转换元件的太阳能电池以及光电转换元件的制造方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000311723A (ja) * | 1999-04-26 | 2000-11-07 | Fuji Photo Film Co Ltd | 錯体色素、光電変換素子および光電気化学電池 |
JP2001236999A (ja) * | 2000-02-22 | 2001-08-31 | Fuji Photo Film Co Ltd | 光電変換素子および光電池 |
JP2002280587A (ja) * | 2001-03-21 | 2002-09-27 | Fuji Photo Film Co Ltd | 光電変換素子の製造方法および光電変換素子、光電池 |
JP2003100357A (ja) * | 2001-09-20 | 2003-04-04 | Fuji Photo Film Co Ltd | 光電変換素子の作製方法、光電変換素子及び光電池 |
JP2012119195A (ja) * | 2010-12-01 | 2012-06-21 | National Institute For Materials Science | 金属錯体、色素増感酸化物半導体電極及び色素増感太陽能電池 |
WO2013047615A1 (ja) * | 2011-09-29 | 2013-04-04 | 富士フイルム株式会社 | 光電変換素子、光電気化学電池およびこれに用いる金属錯体色素 |
WO2013047238A1 (ja) * | 2011-09-29 | 2013-04-04 | 富士フイルム株式会社 | 光電変換素子及び光電気化学電池、これらに用いられる色素 |
-
2014
- 2014-04-07 WO PCT/JP2014/060108 patent/WO2014168119A1/ja active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000311723A (ja) * | 1999-04-26 | 2000-11-07 | Fuji Photo Film Co Ltd | 錯体色素、光電変換素子および光電気化学電池 |
JP2001236999A (ja) * | 2000-02-22 | 2001-08-31 | Fuji Photo Film Co Ltd | 光電変換素子および光電池 |
JP2002280587A (ja) * | 2001-03-21 | 2002-09-27 | Fuji Photo Film Co Ltd | 光電変換素子の製造方法および光電変換素子、光電池 |
JP2003100357A (ja) * | 2001-09-20 | 2003-04-04 | Fuji Photo Film Co Ltd | 光電変換素子の作製方法、光電変換素子及び光電池 |
JP2012119195A (ja) * | 2010-12-01 | 2012-06-21 | National Institute For Materials Science | 金属錯体、色素増感酸化物半導体電極及び色素増感太陽能電池 |
WO2013047615A1 (ja) * | 2011-09-29 | 2013-04-04 | 富士フイルム株式会社 | 光電変換素子、光電気化学電池およびこれに用いる金属錯体色素 |
WO2013047238A1 (ja) * | 2011-09-29 | 2013-04-04 | 富士フイルム株式会社 | 光電変換素子及び光電気化学電池、これらに用いられる色素 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106233484A (zh) * | 2014-04-18 | 2016-12-14 | 富士胶片株式会社 | 光电转换元件、使用该光电转换元件的太阳能电池以及光电转换元件的制造方法 |
CN106233484B (zh) * | 2014-04-18 | 2018-09-07 | 富士胶片株式会社 | 光电转换元件、使用该光电转换元件的太阳能电池以及光电转换元件的制造方法 |
US10403829B2 (en) | 2014-04-18 | 2019-09-03 | Fujifilm Corporation | Photoelectric conversion element, solar cell using the same, and method for manufacturing photoelectric conversion element |
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