Photoelectric material using organic photosensitising dyes and manufacturing method thereof

A photoelectric material, comprising:

• a semiconductor selected from the group consisting of titanium oxide, zinc oxide, tungsten oxide, barium titanate, strontium titanate, and cadmium sulfide;
• and
• an organic photosensitising dye attached to said semiconductor;
• wherein
• said dye has at least one interlocking group directly bonded to one of the carbon atoms forming a benzene ring, and at least one hydrophobic group selected from the group consisting of monovalent substituted and unsubstituted aliphatic hydrocarbon groups and monovalent substituted and unsubstituted alicyclic hydrocarbon groups,
• said interlocking group is at least one selected from the group consisting of carboxyl group, hydroxyalkyl group, hydroxyl group, sulfonic acid group, carboxyalkyl group, mercapto group and phosphono group,
• if said dye has a metal, said hydrophobic group does not constitute a group directly bonded to said metal, and
• said dye is not any of transition metal complexes comprising a ligand with a pyridyl group, transition metal complexes comprising a ligand with N,N,N',N'-tetra C.sub.1-4 alkyl ethylene diamine and transition metal complexes comprising a ligand with di-C.sub.1-4 alkyl glyoxime.

A method of manufacturing a photoelectric material, comprising the step of attaching a photosensitising dye represented by at least one selected from the group consisting of ##STR37## wherein A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are independently selected from the group consisting of hydrogen, carboxyl group, hydroxyalkyl group, hydroxyl group, sulfonic acid group, carboxyakyl group, mercapto group and phosphono group, and at least one of A.sub.1, A.sub.2, A.sub.3 and A.sub.4 is not hydrogen;

• B.sub.1, B.sub.2, B.sub.3 and B.sub.4 are selected from the group consisting of --R, --OR, --CH.sub.2 OR, --SR, --OCOR, --COR, --CONRR' and --NRR' (where R and R' are the same or different hydrophobic groups selected from the group consisting of substituted and unsubstituted aliphatic hydrocarbon groups with 3 to 12 carbon atoms and substituted and unsubstituted alicyclic hydxocarbon groups);
• n and m independently represent an integer of 0, 1, 2, 3 or 4, where n+m is at most 4;
• and M represents two hydrogen atoms, or an atom or a compound which may be covalently bonded or coordinately bonded to phthalocyanine,
• the formula:
• ##STR38## wherein the definitions of A.sub.1, A.sub.2, A.sub.3, A.sub.4, B.sub.1, B.sub.2, B.sub.3, B.sub.4, n and m are the same as defined above,
• the formula:
• ##STR39## wherein A.sub.5 is selected from the group consisting of --R and --COR (where R is a hydrophobic group selected from the group consisting of substituted and unsubstituted aliphatic hydrocarbon groups with 3 to 12 carbon atoms and substituted and unsubstituted alicyclic hydrocarbon groups), and A.sub.6 is selected from the group consisting of carboxyl group, hydroxyalkyl group, hydroxyl group, sulfonic acid group, carboxyalkyl group, mercapto group and phosphono group,
• the formula:
• ##STR40## wherein the definitions of A.sub.5 and A.sub.6 are the same as defined above,
• the formula:
• ##STR41## wherein the definitions of A.sub.5 and A.sub.6 are the same as defined above,
• the formula:
• ##STR42## wherein the definitions of A.sub.5 and A.sub.6 are the same as defined above,
• the formula:
• ##STR43## wherein the definitions of A.sub.5 and A.sub.6 are the same as defined above,
• the formula:
• ##STR44## wherein A.sub.11, A.sub.12, A.sub.13, A.sub.14, A.sub.15, A.sub.16, A.sub.17 and A.sub.18 are selected from the group consisting of hydrogen, Cl, Br, F, --R, --OR, --NRR', --NCOR (where R and R' are the same or different hydrophobic groups selected from the group consisting of substituted and unsubstituted aliphatic hydrocarbon groups with 3 to 12 carbon atoms and substituted and unsubstituted alicyclic hydrocarbon groups), and interlocking groups selected from the group consisting of carboxyl group, hydroxyalkyl group, hydroxyl group, sulfonic acid group, carboxyalkyl group, mercapto group and phosphono group, at least one of A.sub.11 to A.sub.18 is the interlocking group, and at least one of A.sub.11 to A.sub.18 is selected from the group consisting of --R, --OR, --NRR' and --NCOR,
• the formula:
• ##STR45## wherein R.sub.1 is a hydrophobic group selected from the group consisting of substituted and unsubstituted aliphatic hydrocarbon groups with 3-12 carbon atoms and substituted and unsubstituted alicyclic hydrocarbon groups, A.sub.21, A.sub.22, A.sub.23, A.sub.24 and A.sub.25 are selected from the group consisting of hydrogen, Cl, Br, F, carboxyl group, sulfonic acid group, carboxyalkyl group and phosphono group, and at least one of A.sub.21 to A.sub.25 is selected from the group consisting of carboxyl group, sulfonic acid group, carboxyalkyl group and phosphono group, and
• the formula:
• ##STR46## wherein M is selected from the group consisting of Ni, Pt and Cu, X and Y are selected from the group consisting of NH.sub.2, NH, S and Se, and A.sub.31, A.sub.32, A.sub.33, A.sub.34, A.sub.35, A.sub.36, A.sub.37 and A.sub.38 are selected from the group consisting of hydrogen, Cl, Br, F, --R, --OR, --NRR', --NCOR (where R and R' are the same or different hydrophobic groups selected from the group consisting of substituted and unsubstituted aliphatic hydrocabon groups with 3 to 12 carbon atoms and substituted and unsubstituted alicyclic hydrocarbon.