Highly crystalline electrically conducting organic materials, methods of manufacture thereof and articles comprising the same

Patent metadata

Field	Value
Publication number	US-10600964-B2
Application number	US-201314109032-A
Country	US
Kind code	B2
Filing date	Dec 17, 2013
Priority date	Dec 17, 2013
Publication date	Mar 24, 2020
Grant date	Mar 24, 2020

Abstract

Disclosed herein is a composition comprising a regioregular oligothiophene, a regioregular poly[2,5-bis(3-alkylthiophen-2-yl)thieno(3,2-b)thiophene] and/or a benzothiophene; where the regioregular oligothiophene, the regioregular poly[2,5-bis(3-alkylthiophen-2-yl)thieno(3,2-b)thiophene] and the benzothiophene each have a number average molecular weight of less than or equal to 475 grams per mole; where the composition is melted and then annealed at a temperature between a melting point and a glass transition temperature of the composition; the composition having a charge mobility that is greater than a comparative composition that is either not annealed or annealed at the same temperature between the melting point and the glass transition temperature but without being subjected to prior melting.

First claim

What is claimed is:

1. A melted and annealed composition comprising:
a composition comprising a regioregular oligothiophene, a benzothiophene oligomer, and/or a compound of formula (X):

where R 3 and R 4 can be the same or different and are independently a hydrogen, an alkyl group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, a polyalkylene oxide group, an alkoxy group having 1 to 13 carbon atoms, an alkenyl group having 2 to 13 carbon atoms, an alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkoxy having 3 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms, an alkylaryl group having 7 to 13 carbon atoms, or an alkylaryloxy group having 7 to 13 carbon atoms;
where the regioregular oligothiophene, the benzothiophene oligomer, and the compound of formula (X) each have a number average molecular weight of less than or equal to 475 grams per mole; and
where the composition is melted and then annealed for 5 to 1,000 seconds at a temperature between a melting point and a glass transition temperature of the composition to form the melted and annealed composition; wherein the melted and annealed composition has a charge mobility that is greater than the composition that is either not annealed or annealed at the same temperature between the melting point and the glass transition temperature but without being subjected to prior melting.

2. The melted and annealed composition of claim 1 , where the regioregular oligothiophene has the structure of formula (V):

where R is an alkyl group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, a polyalkylene oxide group of the formula —(R 3 O) p —, where R 3 is a (C 2 -C 6 )alkyl group and p is 2 to 10, an alkoxy group having 1 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and where n is 2 to 5.

3. The melted and annealed composition of claim 2 , where the regioregular oligothiophene is poly(3-hexylthiophene).

4. The melted and annealed composition of claim 1 , where the regioregular oligothiophene has the structure of formula (VI):

or the structure of formula (VII):

where R 1 and R 2 are independently a hydrogen, an alkyl group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, a polyalkylene oxide group of the formula —(R 3 O) p —, where R 3 is a (C 2 -C 6 )alkyl group and p is 2 to 10, an alkoxy group having 1 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and where n is 2 to 5 and m is 2 to 5 and where the ratio of n to m can vary from 2:5 to 5:2.

5. The melted and annealed composition of claim 4 , where R 1 and R 2 are hexyl groups or where R 1 is a hexyl group and R 2 is hydrogen.

6. The melted and annealed composition of claim 1 , where the benzothiophene oligomer has the structure of formula (IX)

where R 1 is a hydrogen, an alkyl group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or a polyalkylene oxide group of the formula —(R 3 O) p —, where R 3 is a (C 2 -C 6 )alkyl group and p is 2 to 10, and where n is 2 to 5.

7. The melted and annealed composition of claim 1 , where the compound of formula (X) is 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene.

8. The melted and annealed composition of claim 1 , where the melted and annealed composition has a higher crystallinity than the composition that is either not annealed or annealed at the same temperature between the melting point and the glass transition temperature but without being subjected to prior melting.

9. A method of manufacturing a thin film comprising:
dissolving a benzothiophene oligomer, a compound of formula (X), and/or a regioregular oligothiophene in a solvent to form a solution; where the benzothiophene oligomer, the compound of formula (X), and/or the regioregular oligothiophene each have a number average molecular weight of less than or equal to 475 grams per mole;
disposing the solution on a substrate;
melting the benzothiophene oligomer, the compound of formula (X), and/or the regioregular oligothiophene; and
quenching the melted benzothiophene oligomer, the compound of formula (X), and/or the regioregular oligothiophene to a temperature between a glass transition temperature and a melting temperature of the benzothiophene oligomer, the compound of formula (X), and/or the regioregular oligothiophene,

where R 3 and R 4 can be the same or different and are independently a hydrogen, an alkyl group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, a polyalkylene oxide group, an alkoxy group having 1 to 13 carbon atoms, an alkenyl group having 2 to 13 carbon atoms, an alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkoxy having 3 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms, an alkylaryl group having 7 to 13 carbon atoms, or an alkylaryloxy group having 7 to 13 carbon atoms.

10. The method of claim 9 , where the quenching is conducted at a temperature of 50° C. to 175° C. below the melting temperature.

11. The method of claim 10 , further comprising annealing the benzothiophene oligomer, the compound of formula (X), and/or the regioregular oligothiophene at the temperature between the glass transition temperature and the melting temperature for 5 to 1,000 seconds.

12. The method of claim 9 , further comprising evaporating the solvent from the solution disposed on the substrate.

13. The method of claim 9 , where the regioregular oligothiophene has the structure of formula (V):

where R is an alkyl group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, a polyalkylene oxide group of the formula —(R 3 O) p —, where R 3 is a (C 2 -C 6 )alkyl group and p is 2 to 10, an alkoxy group having 1 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and where n is 2 to 5.

14. The method of claim 13 , where the regioregular oligothiophene is poly(3-hexylthiophene).

15. The method of claim 9 , where the regioregular oligothiophene has the structure of formula (VI):

the structure of formula (VII):

where R 1 and R 2 are independently a hydrogen, an alkyl group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, a polyalkylene oxide group of the formula

Assignees

• Iagodkine Elissei
• Athens George L
• Gomez Enrique Daniel
• Vakhshouri Kiarash
• Rohm & Haas Elect Mat
• Dow Global Technologies Llc
• Penn State Res Found

Inventors

• Iagodkine Elissei
• Athens George L
• Gomez Enrique Daniel
• Vakhshouri Kiarash

Classifications

• H01B1/121

  Charge-transfer complexes · CPC title

• H01B1/127 Primary

  comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes · CPC title

• H01L51/0036 Primary

  Electricity · mapped topic

• H01L51/0558

  Electricity · mapped topic

• H10K85/113 Primary

  Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene · CPC title