Semiconducting co-polymers of methylenedihydropyrazines with fused thiophenes

Patent metadata

Field	Value
Publication number	US-10985321-B2
Application number	US-201916555548-A
Country	US
Kind code	B2
Filing date	Aug 29, 2019
Priority date	Aug 29, 2018
Publication date	Apr 20, 2021
Grant date	Apr 20, 2021

Abstract

Compositions are included comprising heterocyclic organic compounds based on fused thiophene compounds, polymers based on fused thiophene compounds, and methods for making the monomers and polymer along with uses in thin film-based and other devices.

First claim

What is claimed is:

1. A composition, comprising a dialkoxydimethylenedihydropyrazine (AMDHP) fused-thiophene (FT) organic semiconductor polymer having a repeat unit of Formula 2 or Formula 3, or a salt or isomer thereof:

wherein m is an integer greater than or equal to zero;
wherein n is an integer greater than or equal to one;
X and Y are, independently, a covalent bond or aryl;
A and B are, independently, a nitrogen group or a C—H group;
R 1 and R 2 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted;
R 3 and R 4 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted; and
p and q are, independently, integers greater than or equal to zero.

2. The composition of claim 1 , wherein A and B are nitrogen.

3. The composition of claim 1 , wherein at least one of R 1 and R 2 comprises a substituted or unsubstituted alkyl.

4. The composition of claim 3 , wherein at least one of R 1 and R 2 comprises an unsubstituted alkyl.

5. The composition of claim 1 , wherein at least one of R 3 and R 4 comprises a substituted or unsubstituted alkyl.

6. The composition of claim 5 , wherein at least one of R 3 and R 4 comprises a substituted or unsubstituted alkyl group comprising at least six carbon atoms.

7. The composition of claim 1 , wherein X and Y are, independently, at least one unfused thiophene groups.

8. The composition of claim 1 , wherein p and q are different values.

9. A polymer comprising the composition of claim 1 , wherein the polymer has a molecular weight in a range of 4000 Da to 180,000 Da.

10. An organic thin film transistor (OTFT) comprising:
a substrate;
a gate electrode;
a gate dielectric layer;
a patterned source and drain layer; and
an organic semiconductor layer, wherein the organic semiconductor layer comprises a polymer having the composition of claim 1 .

11. A device comprising the composition of claim 1 configured in an electronic, optoelectronic, or nonlinear optical device.

12. The device of claim 11 , wherein the device comprises a transistor (FET), a thin-film transistor (TFT), an organic light-emitting diode (OLED), an electro-optic (EO) device, a conductive material, a two photon mixing material, an organic semiconductor, a RFID tag, an electroluminescent device, or a photovoltaic and sensor device.

13. A composition having a repeat unit of Formula 4, or a salt or isomer thereof:

wherein n is an integer greater than one.

14. A method of fabricating a dialkoxydimethylenedihydropyrazine (AMDHP) fused-thiophene (FT) organic semiconductor polymer, comprising:
reacting tin-substituted dialkylated tetrathienoacene or thienyl-dialkylated tetrathienoacene with halogen-substituted thienyl-AMDHP; or
reacting halogen-substituted dialkylated tetrathienoacene or thienyl-dialkylated tetrathienoacene with tin-substituted thienyl-AMDHP.

15. The method of claim 14 , wherein the halogen-substituted dialkylated tetrathienoacene comprises:

or a salt or isomer thereof,
wherein H 1 and H 2 are, independently, chlorine (Cl), bromine (Br), and iodine (I), and
wherein R 1 and R 2 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted.

16. The method of claim 15 , wherein at least one of H 1 and H 2 are Br.

17. The method of claim 14 , wherein the tin-substituted dialkylated tetrathienoacene comprises:

or a salt or isomer thereof,
wherein R 1 , R 2 , R 5 , and R 6 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted.

18. The method of claim 17 , wherein at least one of R 5 and R 6 are substituted or unsubstituted alkyl groups.

19. The method of claim 14 , wherein the thienyl-dialkylated tetrathienoacene comprises:

or a salt or isomer thereof,
wherein R 1 and R 2 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted.

20. The method of claim 14 , wherein the halogen-substituted thienyl-AMDHP comprises:

or a salt or isomer thereof,
wherein H 3 and H 4 are, independently, chlorine (Cl), bromine (Br), and iodine (I), and
wherein R 3 and R 4 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted.

21. The method of claim 20 , wherein at least one of H 3 and H 4 are Br.

22. The method of claim 14 , wherein the tin-substituted thienyl-AMDHP comprises:

or a salt or isomer thereof,
wherein R 3 , R 4 , R 7 , and R 8 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted.

23. The method of claim 22 , wherein at least one of R 7 and R 8 are substituted or unsubstituted alkyl groups.

Assignees

• Corning Inc

Inventors

• He Mingqian
• Matthews James Robert
• Niu Weijun
• Tandia Adama
• Wallace Arthur Lawrence

Classifications

• H10K30/50

  Photovoltaic [PV] devices · CPC title

• H10K85/113

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

• C07D495/22 Primary

  in which the condensed system contains four or more hetero rings · CPC title

• C08G2261/94

  Applications in sensors, e.g. biosensors · CPC title

• C09D165/00

  Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09D107/00 - C09D157/00, C09D161/00 take precedence); Coating compositions based on derivatives of such polymers · CPC title