Doping of other polymers into organic semi-conducting polymers

Patent metadata

Field	Value
Publication number	US-11283023-B2
Application number	US-201816620050-A
Country	US
Kind code	B2
Filing date	Jun 1, 2018
Priority date	Jun 8, 2017
Publication date	Mar 22, 2022
Grant date	Mar 22, 2022

Abstract

Disclosed is a polymer blend comprising an organic semiconductor (OSC) polymer blended with an isolating polymer and method for making the same. The OSC polymer includes a diketopyrrolopyrrole fused thiophene polymeric material, and the fused thiophene is beta-substituted. The isolating polymer includes a non-conjugated backbone, and the isolating polymer may be one of polyacrylonitrile, alkyl substituted polyacrylonitrile, polystyrene, polysulfonate, polycarbonate, an elastomer block copolymer, derivatives thereof, copolymers thereof and mixtures thereof. The method includes blending the OSC polymer with an isolating polymer in an organic solvent to create a polymer blend and depositing a thin film of the polymer blend over a substrate. Also disclosed is an organic semiconductor device that includes a thin semiconducting film comprising OSC polymer.

First claim

What is claimed is:

1. A polymer blend, comprising:
an organic semiconductor polymer blended with an isolating polymer;
wherein the organic semiconductor polymer is a diketopyrrolopyrrole fused thiophene polymeric material, wherein the fused thiophene is beta-substituted,
wherein the isolating polymer has a non-conjugated backbone, and
wherein the isolating polymer is selected from the group consisting of:

polyacrylonitrile, alkyl substituted polyacrylonitrile, polystyrene, polysulfonate, polycarbonate, an elastomer block copolymer, derivatives thereof, copolymers thereof and mixtures thereof,
wherein the organic semiconductor polymer comprises the repeat unit of formula 1′ or 2′

wherein, in the structure 1′ and 2′, m is an integer greater than or equal to one; n is 0, 1, or 2; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , may be, independently, hydrogen, substituted or unsubstituted C 4 or greater alkyl, substituted or unsubstituted C 4 or greater alkenyl, substituted or unsubstituted C 4 or greater alkynyl, or C 5 or greater cycloalkyl; a, b, c, and d are independently, integers greater than or equal to 3; e and f are integers greater than or equal to zero; X and Y are, independently a covalent bond, an optionally substituted aryl group, an optionally substituted heteroaryl, an optionally substituted fused aryl or fused heteroaryl group, an alkyne or an alkene; and A and B may be, independently, either S or O, with the
provisos that:
i. at least one of R 1 or R 2 ; one of R 3 or R 4 ; one of R 5 or R 6 ; and one of R 7 or R 8 is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, or cycloalkyl;
ii. if any of R 1 , R 2 , R 3 , or R 4 is hydrogen, then none of R 5 , R 6 , R 7 , or R 8 are hydrogen;
iii. if any of R 5 , R 6 , R 7 , or R 8 is hydrogen, then none of R 1 , R 2 , R 3 , or R 4 are hydrogen;
iv. e and f cannot both be 0;
v. if either e or f is 0, then c and d, independently, are integers greater than or equal to 5; and
vi. the polymer having a molecular weight, wherein the molecular weight of the polymer is greater than 10,000.

2. The polymer blend of claim 1 , wherein the isolating polymer is polystyrene and derivatives thereof.

3. The polymer blend of claim 2 , wherein the polystyrene has a number average molecular weight of greater than 5,000.

4. The polymer blend of claim 2 , wherein the polystyrene has a number average molecular weight of greater than 10,000.

5. The polymer blend of claim 1 , wherein the isolating polymer forms an encapsulating layer between the organic semiconductor and an air interface.

6. The polymer blend of claim 1 , wherein the isolating polymer oxidizes preferentially to the organic semiconductor polymer.

7. The polymer blend of claim 6 , wherein the isolating polymer that oxidizes preferentially to the organic semiconductor polymer is polyacrylonitrile, alkyl substituted polyacrylonitrile, or copolymers thereof.

8. The polymer blend of claim 1 , wherein the weight ratio of organic semiconductor polymer to isolating polymer in the blend is between 95:5 and 5:95.

9. The polymer blend of claim 8 , wherein the weight ratio of organic semiconductor polymer to isolating polymer in the blend is between 80:20 and 40:60.

10. The polymer blend of claim 8 , wherein the weight ratio of organic semiconductor polymer to isolating polymer in the blend is between 55:45 and 65:35.

11. A method of fabricating an organic semiconductor device, comprising:
blending an organic semiconductor polymer with an isolating polymer in an organic solvent to create a polymer blend; and
depositing a thin film of the polymer blend over a substrate;
wherein:
the organic semiconductor polymer is a diketopyrrolopyrrole fused thiophene polymeric material, wherein the fused thiophene is beta-substituted,
isolating polymer has a non-conjugated backbone, and
the non-conjugated polymer is selected from the group consisting of: polyacrylonitrile, alkyl substituted polyacrylonitrile, polystyrene, polysulfonate, polycarbonate, an elastomer block copolymer, derivatives thereof, copolymers thereof and mixtures thereof,
wherein the organic semiconductor polymer comprises the repeat unit of formula 1′ or 2′

wherein, in the structure 1′ and 2′, m is an integer greater than or equal to one; n is 0, 1, or 2; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , may be, independently, hydrogen, substituted or unsubstituted C 4 or greater alkyl, substituted or unsubstituted C 4 or greater alkenyl, substituted or unsubstituted C 4 or greater alkynyl, or C 5 or greater cycloalkyl; a, b, c, and d are independently, integers greater than or equal to 3; e and f are integers greater than or equal to zero; X and Y are, independently a covalent bond, an optionally substituted aryl group, an optionally substituted heteroaryl, an optionally substituted fused aryl or fused heteroaryl group, an alkyne or an alkene; and A and B may be, independently, either S or O, with the
provisos that:
i. at least one of R 1 or R 2 ; one of R 3 or R 4 ; one of R 5 or R 6 ; and one of R 7 or R 8 is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, or cycloalkyl;
ii. if any of R 1 , R 2 , R 3 , or R 4 is hydrogen, then none of R 5 , R 6 , R 7 , or R 8 are hydrogen;
iii. if any of R 5 , R 6 , R 7 , or R 8 is hydrogen, then none of R 1 , R 2 , R 3 , or R 4 are hydrogen;
iv. e and f cannot both be 0;
v. if either e or f is 0, then c and d, independently, are integers greater than or equal to 5; and
vi. the polymer having a molecular weight, wherein the molecular weight of the polymer is greater than 10,000.

12. The method of claim 11 , further comprising thermally annealing the thin film after the thin film is deposited over the substrate.

13. The method of claim 12 , wherein the annealing step is performed at a temperature of 100° C. to 180° C.

14. The method of claim 11 , wherein the thin film is annealed in air.

15. The method of claim 11 , wherein the isolating polymer is polystyrene and derivatives thereof.

16. The method of claim 15 , wherein the polystyrene has a number average molecular weight of greater than 5,000.

17. The method of claim 15 , wherein the polystyrene has a number average molecular weight of greater than 10,000.

18. The method of claim 11 , wherein the organic solvent is a non-halogenated solvent.

19. The method of claim 18 , wherein the non-halogenated solvent is selected from the group consisting of: m-xylene, o-xylene, p-xylene, toluene, tetralin, cis-decalin, trans-decalin, mesitylene, cyclooctane, and bicyclohexyl, and mixtures thereof.

20. The method of claim 11 , wherein blending an organic semiconductor polymer with an isolating polymer in an organic solvent to create a polymer blend is performed at a temperature greater than 70° C.

21. The method of claim 11 , wherein the organic semiconductor polymer and the isolating polymer each have a solubility of 1 mg/mL or more in the non-halogenated solvent at room temperature.

22. An organic semiconductor device, comprising:
a thin semiconducting film, the thin semiconducting film comprising:
a polymer blend, the p

Assignees

• Corning Inc

Inventors

• He Mingqian
• Li Yang
• Matthews James Robert
• Mehrotra Karan
• Niu Weijun
• Wallace Arthur Lawrence

Classifications

• Y02E10/549

  Organic PV cells · CPC title

• C08G2261/344

  containing heteroatoms · CPC title

• C08G2261/3223

  containing one or more sulfur atoms as the only heteroatom, e.g. thiophene · CPC title

• C08G2261/124

  alternating · CPC title

• C08G61/126 Primary

  with a five-membered ring containing one sulfur atom in the ring · CPC title