Organic semiconductor thin film and method of manufacturing the same and thin film transistor and electronic device

1. An organic semiconductor thin film, comprising

a matrix including an elastomer and nanoconfined polymer structures embedded in the matrix,

the nanoconfined polymer structures forming a polymer network,

the nanoconfined polymer structures including a conjugation semiconductor polymer,

the conjugation semiconductor polymer including a repeating unit having at least one conjugation system in its main chain,

the nanoconfined polymer structures being present in an upper surface layer and a lower surface layer of the organic semiconductor thin film respectively,

the nanoconfined polymer structures are distributed in a different amount in a thickness direction of the organic semiconductor thin film,

the nanoconfined polymer structures are mainly distributed in an upper surface layer and a lower surface layer of the organic semiconductor thin film, and

the conjugation system includes at least one moiety represented by one of Chemical Formulae 1-1 to 1-10:

wherein, in Chemical Formula 1-1 or 1-2, A is O, S, Se, or NH, R 1 is a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon group, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, or a halogen, a is an integer ranging from 0 to 2, and * is a linking point with an adjacent moiety,

wherein, in Chemical Formula 1-3, R 2 and R 3 are independently hydrogen, a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, and * is a linking point with an adjacent moiety,

wherein, in Chemical Formula 1-4, R 1 and R 2 are independently hydrogen, a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, and * is a linking point with an adjacent moiety,

wherein, in Chemical Formula 1-5, R is independently hydrogen, a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, and * is a linking point with an adjacent moiety,

wherein, in Chemical Formula 1-6 or 1-7, * is a linking point with an adjacent moiety,

wherein, in Chemical Formula 1-8, R is hydrogen, a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, and * is a linking point with an adjacent moiety,

wherein, in Chemical Formula 1-9, X 1 and X 2 are independently halogen and * is a linking point with an adjacent moiety, and

wherein, in Chemical Formula 1-10, R's are independently hydrogen, a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, and * is a linking point with an adjacent moiety.

2. The organic semiconductor thin film of claim 1 , wherein the nanoconfined polymer structure is a nanofibril having a continuous pathway.

3. The organic semiconductor thin film of claim 2 , wherein the nanofibril has a diameter of less than or equal to about 50 nm.

4. The organic semiconductor thin film of claim 1 , wherein the nanoconfined polymer structures includes aggregations of the conjugation semiconductor polymer.

5. The organic semiconductor thin film of claim 1 , wherein the polymer network includes a web-like nanofibril semiconducting polymer.

6. The organic semiconductor thin film of claim 1 , wherein the elastomer and the conjugation semiconductor polymer are phase separated.

7. The organic semiconductor thin film of claim 1 , wherein the conjugation semiconductor polymer and the elastomer are included in a weight ratio of about 70:30 to about 5:95.

8. The organic semiconductor thin film of claim 1 , wherein the conjugation semiconductor polymer and the elastomer are included in a weight ratio of about 50:50 to about 10:90.

9. The organic semiconductor thin film of claim 1 , wherein the elastomer includes an elastic rubber.

10. The organic semiconductor thin film of claim 1 , wherein the elastomer includes one of polybutadiene (PB), a styrene-butadiene copolymer (SB), a styrene-butadiene-styrene copolymer (SBS), a styrene-ethylene-butylene-styrene copolymer (SEBS), an ethylene propylene diene rubber (EPDR), an acrylic rubber, a polychloroprene rubber, polyurethane, a fluoro-rubber, a butyl rubber, a silicone rubber, and a combination thereof.

11. The organic semiconductor thin film of claim 1 , wherein the conjugation semiconductor polymer is a donor-acceptor type polymer having an electron donating moiety and an electron accepting moiety.

12. The organic semiconductor thin film of claim 1 , wherein the conjugation system further includes one of a substituted or unsubstituted phenylene group, a substituted or unsubstituted thiazoline group, a substituted or unsubstituted pyridine group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted anthracene group, a substituted or unsubstituted naphtacene group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted thienothiophene group, a substituted or unsubstituted thieno benzothiophene group, and a combination thereof.

13. The organic semiconductor thin film of claim 1 , wherein the organic semiconductor thin film is a stretchable thin film.

14. A thin film transistor comprising

a gate electrode,

a semiconductor layer including the organic semiconductor thin film of claim 1 ,

a gate insulating layer between the gate electrode and the semiconductor layer, and

a source electrode and a drain electrode electrically connected to the semiconductor layer.

15. An electronic device comprising: the thin film transistor of claim 14 .

16. An electronic device comprising: the organic semiconductor thin film of claim 1 .

17. An organic semiconductor thin film, comprising

an elastomer including a first region, a second region, and a third region, the second region being between the first region and the third region; and

a plurality of nanoconfined polymer structures,

the nanoconfined polymer structures including a conjugation semiconductor polymer,

the conjugation semiconductor polymer including a repeating unit having at least one conjugation system in its main chain, and

the nanoconfined polymer structures forming a first polymer network in the first region of the elastomer and a second polymer network in the third region of the elastomer, wherein

the nanoconfined polymer structures are distributed in a different amount in a thickness direction of the organic semiconductor thin film,

the nanoconfined polymer structures are mainly distributed in an upper surface layer and a lower surface layer of the organic semiconductor thin film, and

the conjugation system includes at least one moiety represented by one of Chemical Formulae 1-1 to 1-10:

wherein, in Chemical Formula 1-1 or 1-2, A is O, S, Se, or NH, R 1 is a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon group, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, or a halogen, a is an integer ranging from 0 to 2, and * is a linking point with an adjacent moiety,

wherein, in Chemical Formula 1-3, R 2 and R 3 are independently hydrogen, a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, and * is a linking point with an adjacent moiety,

wherein, in Chemical Formula 1-4, R 1 and R 2 are independently hydrogen, a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, and * is a linking point with an adjacent moiety,

wherein, in Chemical Formula 1-5, R is independently hydrogen, a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, and * is a linking point with an adjacent moiety,

wherein, in Chemical Formula 1-6 or 1-7, * is a linking point with an adjacent moiety,

wherein, in Chemical Formula 1-8, R is hydrogen, a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, and * is a linking point with an adjacent moiety,

wherein, in Chemical Formula 1-9, X 1 and X 2 are independently halogen and * is a linking point with an adjacent moiety, and

wherein, in Chemical Formula 1-10, R's are independently hydrogen, a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon group or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, and * is a linking point with an adjacent moiety.

18. The organic semiconductor thin film of claim 17 , wherein

the conjugation semiconductor polymer and the elastomer are included in a weight ratio of about 70:30 to about 5:95, and

the elastomer includes one of polybutadiene (PB), a styrene-butadiene copolymer (SB), a styrene-butadiene-styrene copolymer (SBS), a styrene-ethylene-butylene-styrene copolymer (SEBS), an ethylene propylene diene rubber (EPDR), an acrylic rubber, a polychloroprene rubber, polyurethane, a fluoro-rubber, a butyl rubber, a silicone rubber, and a combination thereof.

19. The organic semiconductor thin film of claim 17 , wherein

the nanoconfined polymer structures include a nanofibril, and

the nanofibril has a diameter of less than or equal to about 50 nm.

20. A thin film transistor comprising

a gate electrode,

a semiconductor layer including the organic semiconductor thin film of claim 17 ,

a gate insulating layer between the gate electrode and the semiconductor layer, and

a source electrode and a drain electrode electrically connected to the semiconductor layer.