Polymer compositions for vertical channel organic electrochemical transistors and complementary logic circuits

Patent metadata

Field	Value
Publication number	US-12364155-B2
Application number	US-202217857596-A
Country	US
Kind code	B2
Filing date	Jul 5, 2022
Priority date	Jul 6, 2021
Publication date	Jul 15, 2025
Grant date	Jul 15, 2025

Abstract

Photocurable compositions that combine redox-active semiconducting organic polymers with photocurable organic molecules are provided. Upon exposure to radiation, the photocurable compositions form ion-permeable, electrically conductive crosslinked organic films that can be used as conducting channels in n-channel or p-channel organic electrochemical transistors, including vertical organic electrochemical transistors (vOECTs). The vOECTs can be incorporated in complementary electronic circuits.

First claim

What is claimed is:

1. A polymer composition comprising an organic film comprising:
a redox-active, semiconducting organic polymer blended with;
a photocurable crosslinked carbohydrate polymer, wherein the redox-active, semiconducting organic polymer and the photocurable crosslinked carbohydrate polymer are at least partially phase-separated.

2. The composition of claim 1 , wherein the photocurable crosslinked carbohydrate polymer is functionalized with a radiation-absorbing functional group.

3. The composition of claim 1 , wherein the photocurable crosslinked carbohydrate polymer is functionalized with a cinnamate group, a dienecinnamate group, a cumarine group, a vinyl group, an allyl group, an acrylate group, an azide group, and/or an oxetane group.

4. The composition of claim 1 , wherein the redox-active, semiconducting organic polymer is a diketopyrrolopyrrole homopolymer or a diketopyrrolopyrrole copolymer.

5. The composition of claim 1 , wherein the redox-active, semiconducting organic polymer is an isoindigo (IID)-based homopolymer or copolymer, a dithienothiophene (DTT)-based homopolymer or copolymer, a benzodithiophene (BDT)-based homopolymer or copolymer, a naphthalene diimide (NDI)-based homopolymer or copolymer, a perylene diimide (PDI)-based homopolymer or copolymer, a thieno[3,4-c]pyrrole-4,6-dione (TPD)-based homopolymer or copolymer, a bithiophene imide (BTI)-based homopolymer or copolymer, a benzothiadiazole (BT)-based homopolymer or copolymer, a indocenodithiophene (IDTT)-based homopolymer or copolymer, a (2,2-((2Z,2Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2,″3:4,5]thieno[2,3:4,5]pyrrolo[3,2-g]thieno[2,3:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) (Y6)-based homopolymer, a quinoxaline (Qx) based homopolymer or copolymer, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), or poly(benzimidazobenzophenanthroline) (BBL).

6. The composition of claim 1 , having a concentration of the redox-active, semiconducting organic polymer of greater than 10 weight percent, based on the combined weight of the redox-active, semiconducting organic polymer and the photocurable crosslinked carbohydrate polymer.

7. The composition of claim 1 , wherein the redox-active, semiconducting organic polymer and the photocurable crosslinked carbohydrate polymer are dissolved in a solvent or a solvent mixture.

8. A method of forming an ion-permeable, electrically conductive crosslinked organic film, the method comprising:
forming a coating of a composition on a substrate, the composition comprising a redox-active semiconducting organic polymer and photocurable carbohydrate molecules dissolved in a solvent or a solvent mixture on a substrate; and
exposing at least a portion of the coating to radiation that induces crosslinking between the photocurable carbohydrate molecules to form a photocurable crosslinked carbohydrate polymer blended with the redox-active semiconducting organic polymer, wherein the redox-active, semiconducting organic polymer and the photocurable crosslinked carbohydrate polymer are at least partially phase-separated.

9. The method of claim 8 , wherein exposing at least a portion of the coating to radiation comprises:
exposing a first portion of the coating to the radiation; and
shielding a second portion of the coating from the radiation.

10. The method of claim 9 , further comprising selectively dissolving the composition in the second portion of the coating to form a patterned crosslinked organic film.

11. A vertical organic electrochemical transistor comprising:
a source;
a drain;
an ion-permeable semiconducting channel comprising an organic film in electrical communication with the source and the drain, the organic film comprising: a redox-active, semiconducting organic polymer blended with a photocurable crosslinked carbohydrate polymer that is functionalized with a radiation-absorbing functional group, wherein the redox-active, semiconducting organic polymer and the photocurable crosslinked carbohydrate polymer are at least partially phase-separated;
an electrolyte in contact with the ion-permeable semiconducting channel; and
a gate in contact with the organic electrolyte.

12. The transistor of claim 11 , wherein the electrolyte comprises an aqueous salt solution and ionic liquids, a polymer electrolyte comprising salt cations and anions coordinated with a polymer chain, an ion gel, a polyelectrolyte, or a lithium metal oxide.

13. A complementary circuit comprising: a first vertical organic electrochemical transistor electrically connected to a complementary channel vertical organic electrochemical transistor, wherein the first vertical organic electrochemical transistor comprises:
a source;
a drain;
an ion-permeable semiconducting channel comprising an organic film in electrical communication with the source and the drain, the organic film comprising: a redox-active, semiconducting organic polymer blended with a photocurable crosslinked carbohydrate polymer that is functionalized with a radiation-absorbing functional group, wherein the redox-active, semiconducting organic polymer and the photocurable crosslinked carbohydrate polymer are at least partially phase-separated;
an electrolyte in contact with the ion-permeable semiconducting channel; and
a gate in contact with the organic electrolyte.

14. A method of making a vertical organic electrochemical transistor, the method comprising:
forming a first electrode;
applying a composition on a surface of the first electrode, the composition comprising a blend of a redox-active, semiconducting organic polymer and a photocurable carbohydrate molecules;
exposing at least a portion of the composition to radiation that induces crosslinking the photocurable carbohydrate molecules to form a crosslinked organic film comprising a photocurable crosslinked carbohydrate polymer blended with the redox-active, semiconducting organic polymer, wherein the redox-active, semiconducting organic polymer and the photocurable crosslinked carbohydrate polymer are at least partially phase-separated;
forming a second electrode on a surface of the crosslinked organic film;
placing an electrolyte in contact with the crosslinked organic film; and
placing a gate in contact with the electrolyte.

15. The method of claim 14 , wherein the composition comprises the redox-active, semiconducting organic polymer and the photocurable carbohydrate molecules dissolved in a solvent or a solvent mixture.

16. The method of claim 14 , wherein exposing at least a portion of the composition to radiation comprises:
exposing a first portion of the composition to the radiation; and
shielding a second portion of the composition from the radiation, and the method further comprises selectively dissolving the composition in the second portion of the coating.

Assignees

• Univ Northwestern
• Flexterra Inc

Inventors

• Facchetti Antonio F
• Marks Tobin J
• Huang Wei
• Chen Jianhua
• Xia Yu

Classifications

• H10K10/488

  the channel region comprising a layer of composite material having interpenetrating or embedded materials, e.g. a mixture of donor and acceptor moieties, that form a bulk heterojunction · CPC title

• H10K85/151

  Copolymers · CPC title

• H10K19/10

  comprising field-effect transistors · 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

• H01G9/26

  Structural combinations of electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices with each other · CPC title