Photosensitizing transition metal complex and its use for photovoltaic cell

• US 20050081911A1
• Filed: 10/15/2004
• Published: 04/21/2005
• Est. Priority Date: 10/17/2003
• Status: Active Grant

• Current Assignee: Sharp Kabushiki Kaisha (Hon Hai Precision Industry Co., Ltd.)
• Original Assignee: Sharp Kabushiki Kaisha (Hon Hai Precision Industry Co., Ltd.)
• Inventors: Han, Liyuan, Islam, Ashraful, Fukui, Atsushi
• Granted Patent: US 7,812,251 B2
• Time in Patent Office: Days
• US Class Current: 136/263
• CPC Class Codes: C07F 15/0053 without a metal-carbon linkage
• 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 85/331 Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
• CPC Class Codes: H10K 85/344 comprising ruthenium
• CPC Class Codes: H10K 85/348 comprising osmium
• CPC Class Codes: Y02E 10/542 Dye sensitized solar cells
• CPC Class Codes: Y02E 10/549 Organic PV cells

Abstract

A photosensitizing transition metal complex of the formula (Ia) MLY¹, (Ib) MLX₃ (Ic) MLY²X, (Id) MLY³X or (Ie) MLY⁴X in which M is a transition metal selected from ruthenium, osmium, iron, rhenium and technetium, preferably ruthenium or osmium. X is a co-ligand independently selected from NCS—, Cl—, Br—, I—, CN—, H₂O; pyridine unsubstituted or substituted by at least one group selected from vinyl, primary, secondary or tertiary amine, OH and C_1-30 alkyl, preferably NSC and CN—; L is a tridentate polypyridine ligand, carrying at least one carboxylic, phosphoric acid or a chelating group and one substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted alkylamide group having 2 to 30 carbon atoms or substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms. A dye-sensitized electrode includes a substrate having an electrically conductive surface, an oxide semiconductor film formed on the conductive surface, and the above sensitizer of formula (Ia), (Ib), (Ic), (Id) or (Ie) as specified above, supported on the film. A solar cell includes the above electrode, a counter electrode, and an electrolyte deposited there between.

Claims

1. A photosensitizing transition metal complex having the general formula (Ia):

MLY¹ 

 

(Ia)

in which M is a transition metal selected from Ru(II), Os(II), Fe(II), Re(I) and Tc(I);

L is a polypyridine ligand having the general formula (II);

wherein at least one of A₁, A₂ and A₃ is an anchoring group selected from —

COOH, —

COON(C₄H₉)₄, —

PO(OH)₂, —

PO(OR₁)₂ (where R₁ is an alkyl group having Ito 30 carbon atoms), —

CO(NHOH), and when there is the remaining A₁, A₂ and A₃ being not said anchoring group, it may be a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, an alkylamide group having 2 to 50 carbon atoms or an aralkyl group having 7 to 50 carbon atoms, and Y¹ is a group selected from the formulae (IIa) to (IId);

where R3 is an alkyl group having 1 to 50 carbon atoms, an 25 alkoxyalkyl group having 2 to 30 carbon atoms, an aminoalkyl group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylamide group having 2 to 30 carbon atoms, a cyano group or a hydrogen atom.

2. A photosensitizing transition metal complex of claim 1, which is a complex of the general formula (Ia) in which

M is Ru(II) or Os(II);

L is a polypyrigine ligand having the subformula (IIa);

where B₁, B₂ and B₃ are H, —

COOH, —

COON(C₄H₉)₄ or —

PO(OH)₂ provided that at least one of B₁, B₂ and B₃ is different from hydrogen atom; and

R₃ is an alkyl group having 6 to 30 carbon atoms or a hydrogen atom.

3. A photosensitizing transition metal complex of claim 1, which is a complex of the general formula (Ia) in which

M is Ru(II) or Os(II);

L is a polypiridine ligand having the subformula (IIb);

where B1 and B2 are, the same or different, a hydrogen atom,

—

COOH, —

COON(C₄H₉)₄, —

PO(OH)₂, provided that any one of B₁ and B₂ is different from a hydrogen atom, and C is an alkyl group having 6 to 30 carbon atoms; and

R₃ is an alkyl group having 6 to 30 carbon atoms or a hydrogen atom.

14. A photovoltaic cell comprising a support, a conductive layer formed on the support, and a porous semiconductor layer formed on the conductive layer, a counter electrode, and an electrolyte deposited there between wherein the porous semiconductor layer carries a photosensitizing transition metal complex as claimed in claim 1.

4. A photosensitizing transition metal complex of the general formula (Ib):

MLX₃ 

 

(Ib)

in which M is the same meaning as defined in the formula (Ia);

L is a polypyridine ligand having the general formula (II), wherein A₁, A₂ and A₃ contain at least one anchoring group selected from —

COOH, —

COON(C₄H₉)₄, —

PO(OH)₂, —

PO(OR₁)₂ (where R₁ is an alkyl group having 1 to 30 carbon atoms), —

CO(NHOH), and at least one group selected from an alkyl group having 1 to 50 carbon atoms, an alkylamide group having 2 to 50 carbon atoms or an aralkyl group having 7 to 50 carbon atoms; and

X is a ligand selected from NCS—

, Cl—

, Br—

, I—

, CN—

, NCO—

, H₂O or pyridine group which may be substituted by vinyl, primary, secondary or tertiary amino, alkylthio, arylthio, hydroxyl or C_1-30 alkyl.

5. A photosensitizing transition metal complex of claim 4, which is a complex the formula (Ib) in which

M is Ru(II) or Os(II);

L is a polypyrigine ligand of subformula (IIb); and

X is NCS—

or CN—

.

6. A photosensitizing transition metal complex having the general formula (Ic):

MLY²X 

 

(Ic)

in which M, L and X are the same meaning as defined in the formula (Ib); and

Y² is a group having the general formula (IVa-1);

where R₄, R₅ and R₆ are independently an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylamide group having 2 to 30 carbon atoms, a perfluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, cyano group, hydroxyl group, nitro group, amino group, trifluoro group, halogen atom or hydrogen atom.

7. A photosensitizing transition metal complex of claim 6 which is a complex of the formula (Ic) in which

M is Ru(II) or Os(II);

L is a polypyridine ligand of the subformula (IIb);

X is NCS—

or CN—

; and

R₄, R₅ and R₆ of the formula (IVa-1) are as follows;

R₄R₅R₆CH₃HCH₃CH₃CH3CH₃t-BuHt-BuPhHCH₃PhHPhCH₃HC_1-30 alkylCF₃HCH₃CF₃HCH₂CNCF₃HCF₃CF₃HC_1-30 alkylCF₃HCF₃—

CF₂CF₃HPh

8. A photosensitizing transition metal complex having the general formula (Id):

MLY³X 

 

(Id)

in which M and L are the same meanings as defined in the formula (Ia);

X is the same meanings as defined in the formula (Ib); and

Y₃ is a group having the formula (IVa-2);

where R₇ is a trifluoro or perfluoroalkyl group having 1 to 12 carbon atoms, R₈ and R₉ are independently the same meanings as R₅ and R₆ of the formula (IVa-1).

9. A photosensitizing transition metal complex of claim 8, which is a complex of the formula (Id) in which

M is Ru(II) or Os(II);

L is polypyridine ligand of the formula (IIa) as defined above;

X is NCS—

or CN—

; and

R₇, R₈ and R₉ of the formula (IVa-2) are as follows;

R₇R₈R₉CF₃H4-FCF₃H4-ClCF₃H4-CNCF₃H4-CF₃CF₃H4-CH₃CF₃H4-NO₂CF₃—

CF₂H4-FCF₃—

CF₂H4-ClCF₃—

CF₂H4-CNCF₃F4-FCF₃F4-ClCF₃F4-CNCF₃F4-CF₃CF₃F4-CH₃CF₃HHCF₃—

CF₂H4-CF₃CF₃—

CF₂H4-CH₃CF₃—

CF₂HH

10. A photosensitizing transition metal complex of the claim 8, which is a complex of the formula (Id) in which

M is Ru(II) or Os(II);

L is a polypyridine ligand of the subformula (IIb) as defined above;

X is NCS—

or CN—

; and

R₇, R₈ and R₉ of the formula (IVa-2) are as defined above.

11. A photosensitizing transition metal complex having the general formula (Ie):

MLY⁴X 

 

(Ie)

in which M, L and X are the same meanings as defined in the formula (Ib);

Y⁴ is a group selected from the formulae (IVb-1 to

     3), (IVc-1 to

     4), (IVd-1 to

     8) and (IVe-1 to

     2);

where R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆ and R₁₇ are the same or different an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an perfluoroalkyl group having 2 to 12 carbon atoms, an alkylamide group having 2 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, trifluoro group, halogen atom or hydrogen atom.

12. A photosensitizing transition metal complex of claim 11, which is a complex of the formula (Ie) where M is Ru(II) or Os(II), X is NCS—

or CN—

, and Y⁴ is a group of the formula (IVb-1), (IVb-2) or (IVb-3).

13. A photosensitizing transition metal complex of claim 11, which is a complex of the formula (Ie) where M is Ru(II) or Os(II), L is a polypyrigine ligand of the formula (IIb) as defined above, Y⁴ is a group of the formula (IVe-1) or (IVe-2), and X is NCS—

or CN—

.