Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye solution, dye-adsorbed electrode and method of producing dye-sensitized solar cell

Patent metadata

Field	Value
Publication number	US-9614165-B2
Application number	US-201514740827-A
Country	US
Kind code	B2
Filing date	Jun 16, 2015
Priority date	Dec 17, 2012
Publication date	Apr 4, 2017
Grant date	Apr 4, 2017

Abstract

A photoelectric conversion element including a photoconductor layer, wherein the photoconductor layer contains semiconductor fine particles carrying a metal complex dye of Formula (I); a metal complex dye, a dye solution, a dye-adsorbed electrode, a dye-sensitized solar cell, and a method for producing the solar cell:

M(LD)(LA)·(CI)   Formula (I)
wherein M represents a metal ion; LD represents a tridentate ligand of formulas (DL-1) to (DL-4); LA represents a specific tridentate ligand; and CI represents a counter ion:

Y 1 and Y 2 represent an oxygen, sulfur, nitrogen, or phosphorus atom; AD and BD represent a hydrocarbon or hetero ring; L represents a linking group of formulas (L-1) to (L-4); and Ra and Rb represent a substituent,

X represents a nitrogen or carbon atom; CD represents hetero ring; T represents —O—, —S—, —NR L2 — or —PR L3 ; R L1 to R L3 represent a hydrogen atom or a substituent; and Alk represents an alkylene group.

First claim

The invention claimed is:

1. A photoelectric conversion element, having an electrically conductive support, a photoconductor layer containing an electrolyte, a charge transfer layer containing an electrolyte, and a counter electrode, wherein the photoconductor layer contains semiconductor fine particles carrying a metal complex dye represented by the following Formula (I):
M(LD)(LA)·(CI)   Formula (I)

wherein, in the formula, M represents a metal ion;
LD represents a tridentate ligand represented by any one of the following formulas (DL-1) to (DL-4);
LA represents a tridentate ligand represented by the following formula (AL); and
CI represents a counter ion necessary to neutralize an electric charge:

wherein, in the formulas, Y 1 and Y 2 each independently represent an oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom, or a substituted or unsubstituted phosphorus atom, each of which coordinates with the metal ion M; the ring AD and the ring BD each independently represents a hydrocarbon ring or a hetero ring; L represents a linking group represented by any one of the following formulas (L-1) to (L-4); and Ra and Rb each independently represent a substituent,

wherein, in the formulas, R L1 represents a hydrogen atom or a substituent; X represents a nitrogen atom or a carbon atom; the ring CD represents a nitrogen-containing hetero ring containing X; the bond between X and the carbon atom bonded with X and N may be a single bond or a double bond; the ring CD may have a substituent; T represents —O—, —S—, —NR L2 — or —PR L3 —; R L2 and R L3 each independently represent a hydrogen atom or a substituent; and Alk represents an alkylene group, which may have a substituent,

wherein, in the formulas, the ring A, the ring B, and the ring C each independently represent a nitrogen-containing aromatic hetero ring; wherein, the bond between Z 1 and N and the bond between Z 2 and N may be a single bond or a double bond; Z 1 and Z 2 each independently represent a carbon atom or a nitrogen atom;
Anc1 to Anc3 each independently represent —CO 2 H, —SO 3 H, —PO 3 H 2 , —OH, —SH or a salt thereof; X 1 , X 2 and X 3 each independently represent a single bond or a linking group; 11 to 13 each independently represent an integer of 1 to 5; m1 and m3 each independently represent an integer of 0 to 4; m2 represent an integer of 0 to 3; a total of m1 to m3 is 1 or more;
R 1 to R 3 each independently represent a substituent other than Anc1 to Anc3; n1 and n3 each independently represent an integer of 0 to 2; and n2 represents 0 or 1.

2. The photoelectric conversion element according to claim 1 , wherein M represents Fe 2+ , Ru 2+ or Os 2+ .

3. The photoelectric conversion element according to claim 1 , wherein LD represents a tridentate ligand represented by formula (DL-1) or formula (DL-2); and L in formula (DL-1) or formula (DL-2) is a linking group represented by formula (L-1) or formula (L-3).

4. The photoelectric conversion element according to claim 1 , wherein the ring CD in formula (L-3) is a pyridine ring, a pyrimidine ring, or a triazine ring.

5. The photoelectric conversion element according to claim 1 , wherein the ring AD and the ring BD in formulas (DL-1) to (DL-4) is a benzene ring, a pyrazole ring, or a triazole ring.

6. The photoelectric conversion element according to claim 1 , wherein L represents a linking group represented by formula (L-1) or a linking group represented by formula (L-3); and
when L is a linking group represented by formula (L-1),
in formula (DL-1), the ring AD and the ring BD each independently represent a benzene ring, a pyrazole ring, or an imidazole ring; Y 1 and Y 2 each independently represent —O − , —S − , or —NR − , herein R represents a hydrogen atom or a substituent;
in formula (DL-2), the ring AD represents a benzene ring, and the ring BD represents a benzene ring, a pyrazole ring, an imidazole ring, or a triazole ring; Y 1 represents —O − , —S − , or —NR − , herein R represents a hydrogen atom or a substituent;
in formula (DL-3), the ring AD represents a benzene ring; and Y 1 and Y 2 each independently represent —O − , —S − , or —NR − , herein R represents a hydrogen atom or a substituent; and

when L is a linking group represented by formula (L-3),
in formula (DL-1), the ring AD and the ring BD each represent a benzene ring; Y 1 and Y 2 each independently represent —O − , —S − , or —NR − , herein R represents a hydrogen atom or a substituent;
in formula (DL-2), the ring AD represents a benzene ring, the ring BD represents a benzene ring, a pyrazole ring, an imidazole ring, or a triazole ring; and Y 1 represents —O − , —S − , or —NR − , herein R represents a hydrogen atom or a substituent.

7. The photoelectric conversion element according to claim 1 , wherein the ring A, the ring B, and the ring C in the formula (AL) each represent a pyridine ring, a pyrimidine ring, or a thiazole ring.

8. The photoelectric conversion element according to claim 1 , wherein the formula (AL) is the following formula (AL-1) or formula (AL-2):

wherein, in the formulas, Anc 1 to Anc 3 each independently represent —CO 2 H, —SO 3 H, —PO 3 H 2 or a salt thereof; R AL represents a substituent other than Anc 1 to Anc 3 ; and b1 represents an integer of 0 to 4.

9. The photoelectric conversion element according to claim 8 , wherein the formula (AL) is the formula (AL-1).

10. The photoelectric conversion element according to claim 8 , wherein the formula (AL) is the formula (AL-2).

11. The photoelectric conversion element according to claim 1 , wherein the formula (AL) is the following formula (AL-3) or formula (AL-4):

wherein, in the formulas, Anc 1 to Anc 3 each independently represent —CO 2 H, —SO 3 H, —PO 3 H 2 or a salt thereof; X 2a represents —O—, —S—, —NR′—, a divalent saturated aliphatic group, a divalent aromatic hydrocarbon ring group, a divalent non-aromatic hydrocarbon ring group, a divalent aromatic hetero ring group, a divalent non-aromatic hetero ring group, or a linking group formed by any combination of these; wherein R′ represents a hydrogen atom or a substituent; X 1a represents a linking group; X 3 represents a single bond or a linking group; and m4 represents 0 or 1.

12. The photoelectric conversion element according to claim 1 , wherein a co-adsorbent having one or more acidic groups is carried on the semiconductor fine-particles.

13. The photoelectric conversion element according to claim 12 , wherein the co-adsorbent is represented by the following formula (CA):

wherein, in the formula, R A1 represents a substituent having an acidic group; R A2 represents a substituent; and nA represents an integer of 0 or more.

14. A dye-sensitized solar cell, containing the photoelectric conversion element according to claim 1 .

15. A metal complex dye, which is represented by the following formula (I):
M(LD)(LA)·(CI)   Formula (I)

wherein, in the formula, M repres

Assignees

• Fujifilm Corp

Inventors

• Watanabe Kousuke
• Sasaki Kouitsu
• Kobayashi Katsumi

Classifications

• C09B57/10

  Metal complexes of organic compounds not being dyes in uncomplexed form · CPC title

• C09B45/14

  Monoazo compounds · CPC title

• C09B23/04

  one >CH- group, e.g. cyanines, isocyanines, pseudocyanines · CPC title

• C07D401/04

  directly linked by a ring-member-to-ring-member bond · CPC title

• C07D401/14 Primary

  containing three or more hetero rings · CPC title