PHOTOELECTRIC CONVERSION ELEMENT, DYE-SENSITIZED SOLAR CELL, METAL COMPLEX DYE, DYE SOLUTION, DYE-ADSORBED ELECTRODE, AND METHOD FOR PRODUCING DYE-SENSITIZED SOLAR CELL

• US 20150248969A1
• Filed: 05/15/2015
• Published: 09/03/2015
• Est. Priority Date: 11/16/2012
• Status: Active Grant

• Current Assignee: Fujifilm Corporation (Fujifilm Holdings Corporation)
• Original Assignee: Fujifilm Corporation (Fujifilm Holdings Corporation)
• Inventors: TANI, Yukio, KOBAYASHI, Katsumi, WATANABE, Kousuke, SASAKI, Kouitsu, SATOU, Hirotaka, TSUNA, Kazuhiro
• Granted Patent: US 10,460,879 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C07D 213/55 Acids; Esters
• CPC Class Codes: C07D 213/57 Nitriles
• CPC Class Codes: C07D 401/14 containing three or more hetero rings
• CPC Class Codes: C07D 409/14 containing three or more hetero rings
• CPC Class Codes: C07D 495/04 Ortho-condensed systems
• CPC Class Codes: C07F 15/0046 Ruthenium compounds
• CPC Class Codes: C07F 15/0053 without a metal-carbon linkage
• CPC Class Codes: C09B 19/00 Oxazine dyes
• CPC Class Codes: C09B 21/00 Thiazine dyes
• CPC Class Codes: C09B 23/005 the substituent being a COOH and/or a functional derivative thereof
• CPC Class Codes: C09B 23/0058 the substituent being CN
• CPC Class Codes: C09B 23/105 two >CH- groups
• CPC Class Codes: C09B 57/00 Other synthetic dyes of known constitution
• CPC Class Codes: C09B 57/008 Triarylamine dyes containing no other chromophores
• CPC Class Codes: C09B 57/10 Metal complexes of organic compounds not being dyes in uncomplexed form
• CPC Class Codes: C09B 69/008 Dyes containing a substituent, which contains a silicium atom
• CPC Class Codes: H01G 9/2031 comprising titanium oxide, e.g. TiO2 H01G9/2036 takes precedence
• CPC Class Codes: H01G 9/2059 comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
• CPC Class Codes: H10K 85/344 comprising ruthenium
• CPC Class Codes: Y02E 10/542 Dye sensitized solar cells
• CPC Class Codes: Y02E 10/549 : Organic PV cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

A photoelectric conversion element, having a photoconductor layercontaining 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(LA)(LD)(LX)_mX·(CI)_mY  Formula (I)

M represents a metal ion, LA represents a ligand of Formula (AL), LD represents a bidentate or tridentate ligand, at least one of coordinating atoms being an anion; LX represents a monodentate ligand; CI represents a counter ion; mX is 0 or 1; mY is 0 to 3;

Rings A to C represent a heterocycle; Z¹ and Z² represent a carbon or nitrogen atom; Anc1 to Anc3 represent an acidic group; X¹ to X³ represent a single bond or linking group; R¹ to R³ represent a substituent; l1, l3, l2, m1, m3, m2, n1, n2, and n3 each are an integer.

Claims

1. A photoelectric conversion element, comprising 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(LA)(LD)(LX)_mX·

(CI)_mY 

 

formula (I)

wherein, in the formula, M represents a metal ion,

LA represents a tridentate ligand represented by the following Formula (AL),

LD represents a bidentate ligand or a tridentate ligand different from LA, in which, at least one of coordinating atoms which bond to the metal ion M in the bidentate ligand or the tridentate ligand is an anion,

LX represents a monodentate ligand;

mX is 1 when LD is the bidentate ligand and mX is 0 when LD is the tridentate ligand;

CI represents a counter ion necessary for neutralizing an electric charge;

mY represents an integer of 0 to 3;

2. The photoelectric conversion element according to claim 1, wherein M is Os²⁺ or Ru²⁺.

3. The photoelectric conversion element according to claim 1, wherein X² each independently represents a single bond or any one of the following Formulas (X-1) to (X-6) or a group of any combination of these:

4. The photoelectric conversion element according to claim 1, wherein at least one of X¹ and X³ is each independently any one of the following Formulas (X-1) to (X-6) or a group of any combination of these:

5. The photoelectric conversion element according to claim 3, wherein R^X1 and R^X2 in Formula (X-1) are both a hydrogen atom.

6. The photoelectric conversion element according to claim 3, wherein X² is a group represented by Formula (X-1), and R^x1 or R^x2 is an alkyl group or an aryl group.

7. The photoelectric conversion element according to claim 1, wherein X² has a structure represented by ═

C(Rz)- in a partial structure of the π

-conjugation, herein the “

═

”

bonding arm is located on the side of the ring B, the “

—

”

bonding arm is located on the side of Anc2, and Rz represents a substituent having a σ

p value in the Hammett equation of 0.05 or more.

8. The photoelectric conversion element according to claim 1, wherein X² is represented by the following Formula (X-1A) or (X-2A):

9. The photoelectric conversion element according to claim 1, wherein X¹ and X³ each independently are a linking group represented by X².

10. The photoelectric conversion element according to claim 1, wherein the ring B is a pyridine ring.

11. The photoelectric conversion element according to claim 1, wherein the ring A and the ring C each independently are a ring selected from a pyridine ring, a quinoline ring, a pyrimidine ring, a triazine ring, an imidazole ring, a benzimidazole ring, an oxazole ring, a thiazole ring, a benzothiazole ring, an oxadiazole ring, a thiadiazole ring, an isoxazole ring, an isothiazole ring, a triazole ring, and a pyrazole ring.

12. The photoelectric conversion element according to claim 1, wherein the ring A to the ring C are a pyridine ring.

13. The photoelectric conversion element according to claim 1, wherein at least one of m1 and m3 is 1 and m2 is 1.

14. The photoelectric conversion element according to claim 1, wherein m1 to m3 are all 1.

15. The photoelectric conversion element according to claim 1, wherein m1 to m3 are all 1 and X² is a single bond.

16. The photoelectric conversion element according to claim 1, wherein LD is a bidentate ligand represented by any one of the following Formulas (2L-1) to (2L-5):

17. The photoelectric conversion element according to claim 1, wherein LD is a tridentate ligand represented by any one of the following Formulas (3L-1) to (3L-4):

18. The photoelectric conversion element according to claim 1, wherein the bidentate or tridentate ligand in LD has a nitrogen anion or a carbon anion as an atom coordinating to the metal ion M and the following Formula (SA) as a partial structure:

19. The photoelectric conversion element according to claim 1, wherein Formula (I) is represented by the following Formula (I-1) or (I-2):

20. The photoelectric conversion element according to claim 19, wherein the ring D and the ring E in Formula (I-1) or (I-2) each independently are a pyrazole ring, a triazole ring or a benzene ring.

21. The photoelectric conversion element according to claim 1, wherein the semiconductor fine particles further carry a co-adsorbent having one or more acidic groups.

22. The photoelectric conversion element according to claim 21, wherein the co-adsorbent is represented by the following Formula (CA):

23. A dye-sensitized solar cell including the photoelectric conversion element according to claim 1.

24. A metal complex dye represented by the following Formula (I):

M(LA)(LD)(LX)_mX·

(CI)_mY 

 

Formula (I)

wherein, in the formula, M represents a metal ion,

LA represents a tridentate ligand represented by the following Formula (AL),

LD represents a bidentate ligand or a tridentate ligand different from LA, herein, at least one of coordinating atoms which bond to the metal ion M in the bidentate ligand or the tridentate ligand is an anion,

LX represents a monodentate ligand;

mX is 1 when LD is the bidentate ligand and mX is 0 when LD is the tridentate ligand;

CI represents a counter ion necessary for neutralizing an electric charge;

mY represents an integer of 0 to 3;

25. The metal complex dye according to claim 24, wherein X² each independently represents a single bond or any one of the following Formulas (X-1) to (X-6) or a group of any combination of these:

26. The metal complex dye according to claim 24, wherein LD is a bidentate ligand represented by any one of the following Formulas (2L-1) to (2L-5):

27. The metal complex dye according to claim 24, wherein LD is a tridentate ligand represented by any one of the following Formulas (3L-1) to (3L-4):

28. The metal complex dye according to claim 24, wherein the bidentate or tridentate ligand in LD has a nitrogen anion or a carbon anion as an atom coordinating to the metal ion M and the following Formula (SA) as a partial structure:

29. The metal complex dye according to claim 24, wherein X² is represented by the following Formula (X-1A) or (X-2A):

30. A dye solution formed by dissolving the metal complex dye according to claim 24.

31. The dye solution according to claim 30, containing, in an organic solvent, the metal complex dye in an amount of 0.001 to 0.1% by mass and water in an amount controlled to 0.1% by mass or less.

32. A dye-adsorbed electrode for dye-sensitized solar cell, wherein an electrically conductive support provided with semiconductor fine particles is coated with the dye solution according to claim 30 and cured by reaction to form a photoconductor layer.

33. A method for producing dye-sensitized solar cell, including assembling a dye-sensitized solar cell using the dye-adsorbed electrode for dye-sensitized solar cell according to claim 32, and respective materials to be an electrolyte and a counter electrode.

34. A compound represented by the following Formula (AL):

35. The compound according to claim 34, wherein X² is a single bond, m1 or m3 is an integer of 1 to 4, and X¹ or X³ is a linking group.