Method of producing photoelectric conversion element, photoelectric conversion element and photoelectrochemical cell

Patent metadata

Field	Value
Publication number	US-9419318-B2
Application number	US-201113578905-A
Country	US
Kind code	B2
Filing date	Mar 22, 2011
Priority date	Mar 24, 2010
Publication date	Aug 16, 2016
Grant date	Aug 16, 2016

Abstract

A method of producing a photoelectric conversion element, which contains an electrically conductive support, a photosensitive layer having porous semiconductor fine particles that have adsorbed a dye formed on the support, a charge transfer layer; and a counter electrode; containing the steps of: applying a dispersion liquid, in which the content of solids excluding semiconductor fine particles is 1% by mass or less based on the total amount of the dispersion liquid, on the support, to form a coating; heating the coating, to obtain porous semiconductor fine particles; and sensitizing the porous semiconductor fine particles by a dye having a structure represented by Formula (1):

M ( LL 1 ) m 1 ( LL 2 ) m 2 ( X ) m 3 ·CI  Formula (1)

wherein M represents a metal atom, LL 1 , LL 2 , and X each are a ligand, CI represents a counter ion, m 1 represents an integer of 1 to 3, m 2 and m 3 each represent an integer of 0 to 2.

First claim

The invention claimed is:

1. A method of producing a photoelectric conversion element, which comprises a laminated structure including:
an electrically conductive support;
a photosensitive layer having semiconductor fine particles that have adsorbed a dye, formed on the electrically conductive support;
a charge transfer layer; and
a counter electrode;

comprising the steps of:
applying a semiconductor fine particle dispersion liquid, in which the content of solids excluding semiconductor fine particles is 1% by mass or less based on the total amount of the semiconductor fine particle dispersion liquid, on the electrically conductive support, to form a coating;
heating the coating, to obtain porous semiconductor fine particles; and
sensitizing the porous semiconductor fine particles by a dye having a structure represented by Formula (1):
M ( LL 1 ) m 1 ( LL 2 ) m 2 ( X ) m 3 ·CI   Formula (1)

wherein
M represents a metal atom; LL 2 is a bidentate or terdentate ligand represented by Formula (3);
X represents a monodentate or bidentate ligand which coordinates through a group selected from the group consisting of 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 cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a monodentate or bidentate ligand composed of a halogen atom, a carbonyl, a dialkylketone, a 1,3-diketone, a carbonamide, a thiocarbonamide or a thiourea;
m 1 represents an integer of 1 to 3; when m 1 is an integer of 2 or more, LL 1 's may be the same or different from each other; m 2 represents an integer of 0 to 2; when m 2 is an integer of 2, LL 2 's may be the same or different from each other; m 3 represents an integer of 0 to 2; when m 3 is an integer of 2, X's may be the same or different from each other, or X's may be bonded to each other;
CI represents a counter ion in the case where the counter ion is necessary to neutralize a charge in Formula (1); and

wherein
Za, Zb and Zc each independently represent a group of non-metallic atoms for forming a 5- or 6-membered ring; and c represents 0 or 1; and
wherein, in Formula (1), LL 1 is represented by Formula (4):

wherein, in Formula (4), R 1 to R 4 , a 1 , a 2 , b 1 , b 2 and n have the same meaning as those in Formula (2); R 11 to R 14 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group; when R 11 to R 14 are an alkyl group, additionally the alkyl group may have a substituent; R 11 and R 12 , and R 13 and R 14 may be each bonded with each other to form a ring; R 15 and R 16 each independently represent a substituent; d1 and d 2 each independently represent an integer of 0 to 4; when d 1 is 1 or more, R 15 may be bonded with R 11 and/or R 12 to form a ring; when d 1 is 2 or more, R 15 'S may be the same or different from each other, or may be bonded with each other to form a ring; when d 2 is 1 or more, R 16 may be bonded with R 13 and/or R 14 to form a ring; and when d 2 is 2 or more, R 16 'S may be the same or different from each other, or may be bonded with each other to form a ring.

2. The method of producing a photoelectric conversion element according to claim 1 , wherein the electrically conductive support is formed of a polymeric material.

3. The method of producing a photoelectric conversion element according to claim 1 , wherein the electrically conductive support applied with the semiconductor fine particle dispersion liquid is heated at a temperature ranging from 100° C. to 250° C. in the step for obtaining the porous semiconductor fine particles.

4. The method of producing a photoelectric conversion element according to claim 1 , wherein M is Ru, Fe, Os or Cu.

5. The method of producing a photoelectric conversion element according to claim 1 , wherein M is Ru.

6. The method of producing a photoelectric conversion element according to claim 1 , wherein the content of solids excluding semiconductor fine particles is 0.3% by mass or less based on the total amount of the semiconductor fine particle dispersion liquid.

7. The method of producing a photoelectric conversion element according to claim 1 , wherein the electrically conductive support applied with the semiconductor fine particle dispersion liquid is heated at a temperature ranging from 120° C. to 150° C. in the step for obtaining the porous semiconductor fine particles.

8. The method of producing a photoelectric conversion element according to claim 1 , wherein, in formula (4), n is 1.

9. The method of producing a photoelectric conversion element according to claim 1 , wherein, in formula (4), a 1 is 0, a 2 is 0, b 1 is 0, and b 2 is 0.

10. The method of producing a photoelectric conversion element according to claim 1 , wherein the ligand represented by formula (3) is a ligand L-5 described below

11. The method of producing a photoelectric conversion element according to claim 1 , wherein the ligand represented by X in formula (1) is an isothiocyanate group.

12. The method of producing a photoelectric conversion element according to claim 1 , wherein the counter ion represented by CI in formula (1) is a tetraalkyl ammonium ion or a proton.

13. The method of producing a photoelectric conversion element according to claim 1 , wherein, in formula (1), m 1 is 1, m 2 is 1, and m 3 is 1 or 2.

14. A photoelectric conversion element, which is produced by the method according to claim 1 .

15. A photoelectrochemical cell, comprising the photoelectric conversion element according to claim 14 .

16. The method of producing a photoelectric conversion element according to claim 1 , wherein the content of solids excluding semiconductor fine particles is 0.3 to 1% by mass based on the total amount of the semiconductor fine particle dispersion liquid.

17. The method of producing a photoelectric conversion element according to claim 1 , wherein the step of heating the coating, to obtain porous semiconductor fine particles, further comprises a UV treatment.

Assignees

• Kobayashi Katsumi
• Kimura Keizo
• Fujifilm Corp

Inventors

• Kobayashi Katsumi
• Kimura Keizo

Classifications

• H01M14/005 Primary

  Photoelectrochemical storage cells (light sensitive devices H01G9/20, semiconductors sensitive to light H10F) · CPC title

• C09B57/10

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