Dye for photoelectric conversion device and photoelectric conversion device
View Patent ↗A photoelectric conversion device capable of improving conversion efficiency is provided. The photoelectric conversion device includes a work electrode, an opposed electrode, and an electrolyte-containing layer. In the work electrode, a metal oxide semiconductor layer supporting a dye is provided. The dye contains a cyanine compound that has a methine chain, an indolenine skeleton bonded with both ends of the methine chain, and anchor groups introduced to a nitrogen atom included in the indolenine skeleton. Electron injection efficiency to the metal oxide semiconductor layer is improved, and the dye is hardly exfoliated from the metal oxide semiconductor layer.
1. A dye for a photoelectric conversion device, comprising a cyanine compound represented by Chemical formula (3):
wherein:
ring A is a benzene ring, a naphthalene ring, a benzene ring having one or more substituent groups, or a naphthalene ring having one or more substituent groups;
R5 to R10 and R12 to R14 are independently a hyrdrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkyl group having one or more substituent groups, an alkoxy group having one or more substituent groups, or a group represented by Chemical formula (2);
at least one of R5 and R6 and at least one of R7 and R8 may be respectively detached to form an unsaturated bond, or may be respectively linked with each other to form a ring structure;
Y1 and Y2 are each an anchor group represented by —R19-Z1, where R19 is an alkylene group, and Z1 is a carboxylic acid group or a carboxylic acid ion group;
Q is a linkage group that has a methine chain having from 1 to 7 carbon atoms as a skeleton and that has one or more cyano groups, and if the methine chain has an odd number of carbon atoms, one of the one or more cyano groups is bonded to the center carbon atom of the methine chain;
X2 is a group represented by —C(R12)(R13)- or —N(R14)-, a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom;
An q− is an anion with q valency;
q is 1 or 2, and
p is a coefficient to maintain neutral electric charge; and
Chemical formula (2) is:
where:
a bond between L1 and T1 is a double bond or triple bond;
L1 represents a carbon atom;
T1 represents a carbon atom, an oxygen atom, or a nitrogen atom;
x, y, and z are independently 0 or 1; x and y being 0 where T1 is an oxygen atom, and (y+z) is 0 or 1 where T1 is a nitrogen atom;
R15 to R17 are independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group having from 1 to 4 carbon atoms, or an alkyl group having from 1 to 4 carbon atoms substituted by one or more halogen atoms;
R18 is a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, an alkyl group having from 1 to 4 carbon atoms substituted by one or more halogen atoms, or an alkoxy group having from 1 to 4 carbon atoms substituted by one or more halogen atoms;
R15 and R18/R16 and R17 may be respectively linked with each other to form a ring structure; and
n is an integer from 0 to 4;
wherein at least one of R9 and R10 of Chemical formula (3) is an alkyl group having from 6 to 25 carbon atoms.
2. The dye for a photoelectric conversion device according to claim 1 , wherein the structure represented by Chemical formula (3) is a structure represented by Chemical formula (4):
wherein:
R12 and R13 are independently a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkyl group having one or more substituent groups, an alkoxy group having one or more substituent groups, or a group represented by the Chemical formula (2); and
ring B is a benzene ring, a naphthalene ring, a benzene ring having one or more substituent groups, or a naphthalene ring having one or more substituent groups.
3. The dye for a photoelectric conversion device according to claim 2 , wherein ring A and ring B are each a benzene ring having a methoxy group.
4. The dye for a photoelectric conversion device according to claim 2 , wherein at least one of R12, and R13 is an alkyl group having from 6 to 25 carbon atoms.
5. The dye for a photoelectric conversion device according to claim 2 , wherein each of R9, R10, R12, and R13 is an alkyl group having from 6 to 25 carbon atoms.
6. The dye for a photoelectric conversion device according to claim 1 , wherein the methine chain of Q has 5 carbon atoms, and R19 has from 1 to 4 carbon atoms.
7. The dye for a photoelectric conversion device according to claim 1 , wherein the anchor group is a group represented by —CH 2 —CH 2 —C(═O)—OH or a group represented by —CH 2 —CH 2 —C(═O)—O − .
8. The dye for a photoelectric conversion device according to claim 1 , wherein Q is selected from the group consisting of linkage groups represented by Chemical formulae (6-1) to (6-10):
where R30 to R35 are independently:
a hydrogen atom,
a hydroxyl group,
a halogen atom,
a cyano group,
an aryl group having from 6 to 30 carbon atoms,
a diphenyl amino group,
an alkyl group having from 1 to 8 carbon atoms, or
an alkoxyl group having from 1 to 8 carbon atoms.