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