Polythiophenes and devices thereof
An electronic device containing a polythiophene prepared by a metal halide-mediated coupling polymerization in an appropriate solvent, and which polythiophene is comprised of at least one monomer unit selected from the group consisting of 2,5-thienylene (or 2,5-thiophenediyl) (I), 2,5-thienylene (or 2,5-thiophenediyl) (II), and a divalent linkage D wherein, for example, A is alkyl, alkoxy or derivatives thereof; B is a hydrogen atom, a small substituent like alkyl or alkoxy.
1. A device containing a polythiophene prepared by a metal halide polymerization in an aromatic solvent, and which polythiophene is comprised of at least one monomer unit selected from the group consisting of a 2,5-thienylene segment (I), and a 2,5-thienylene segment (II)
wherein A is alkyl, a halide, or alkoxy; B is a hydrogen atom, a halide, an alkyl or an alkoxy; and D is a divalent linkage for said (I) and (II).
2. A device in accordance with claim 1 wherein said metal halide is ferric chloride.
3. A device in accordance with claim 1 wherein said aromatic solvent is a halogenated solvent selected from the group consisting of bromobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, and chloronaphthalene.
4. A device in accordance with claim 1 wherein the solvent is tetrahydronaphthalene.
5. A device in accordance with claim 1 wherein A alkyl contains from about 5 to about 25 carbon atoms; B alkyl contains from 1 to about 3 carbon atoms; and D is arylene.
6. A device in accordance with claim 1 wherein said A is selected from the group consisting of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, pentyloxy, hexyloxyl, heptyloxy, octyloxy, methoxybutyl, methoxybutoxy, methoxyhexyl, methoxyheptyl, and perfluoroalkyl; B is selected from the group consisting of methyl, ethyl, methoxy, ethoxy, and propyl; and D is selected from the group consisting of phenylene, biphenylene, enanthrenylene, dihydrophenanthrenylene, fluorenylene, oligoarylene polymethylene, dialkylmethylene, dioxyalkylene, dioxyarylene, and oligoethylene oxide.
7. An electronic device containing a polythiophene prepared by a metal halide-mediated coupling polymerization in a halogenated aromatic solvent or a hydronaphthalene, and which polythiophene is derived from a monomer segment of Formula (III)
wherein R is alkyl or alkoxy; R′ is hydrogen, alkoxy, halogen, or alkyl; a and b represent the number of R and R′ substituents; Z is a divalent conjugated linkage, and x and y represent the number of segments.
8. A device in accordance with claim 7 wherein said metal halide is ferric chloride, and said a and b are 1 or 2.
9. A device in accordance with claim 7 wherein said halogenated aromatic solvent is selected from the group consisting of bromobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, and chloronaphthalene.
10. A device in accordance with claim 7 wherein alkyl contains from about 1 to about 25 carbon atoms; x is from zero to about 3, and y is from zero to about 3.
11. A device in accordance with claim 7 wherein the divalent linkage, Z, contains one or more segments selected from the group consisting of 2,5-thienylene, arylene, furandiyl, pyrrolediyl, pyridinediyl, benzofurandiyl, dibenzofurandiyl, benzothiophenediyl, dibenzothiophenedlyl, dialkylaminoarylene, and carbazolediyl.
12. A device in accordance with claim 7 wherein the divalent linkage, Z, contains at least one substituted and/or non-substituted 2,5-thienylene segment.
13. A device in accordance with claim 7 wherein R is selected from the group consisting of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, pentyloxy, hexyloxy, heptyloxy, octyloxy methoxybutyl, methoxybutoxy, methoxyhexyl, and methoxyheptyl; R′ is selected from the group consisting of methyl, ethyl, methoxy, ethoxy, bromo, and propyl.
14. A device in accordance with claim 7 wherein a=b=1, and x and y are each independently from zero to about 3.
15. A device in accordance with claim 7 wherein chlorobenzene or dichlorobenzene is selected as the solvent.
16. A device in accordance with claim 7 wherein tetrahydronaphthalene is selected as the solvent or the reaction medium for polymerization.
17. A-device in accordance with claim 7 wherein the polymerization is conducted by heating at from about 40° C. to about 100° C. for an optional period of from about 30 minutes to about 72 hours.
18. A device in accordance with claim 7 wherein the number average molecular weight (M n ) of the polythiophene is from about 2,000 to about 100,000, and the weight average molecular weight (M w ) is from about 4,000 to about 500,000, both as measured by gel permeation chromatography using polystyrene standards.
19. A device in accordance with claim 7 wherein the number average molecular weight (M n ) of the polythiophene is from about 7,000 to about 30,000, and the weight average molecular weight (M w ) is from about 10,000 to about 100,000, both as measured by gel permeation chromatography using polystyrene standards.