Vapor-deposited nanoscale ionic liquid gels as gate insulators for low-voltage high-speed thin film transistors
Described are materials and methods for fabricating low-voltage MHz ion-gel-gated thin film transistor devices using patternable defect-free ionic liquid gels. Ionic liquid gels made by the initiated chemical vapor deposition methods described herein exhibit a capacitance of about 1 μF cm −2 at about 1 MHz, and can be as thin as about 20 nm to about 400 nm.
1. A film comprising a crosslinked polymer and an ionic liquid, wherein the ionic liquid is dispersed in the crosslinked polymer; the crosslinked polymer comprises a plurality of residues of a monomer and a plurality of residues of a crosslinker; the film has a thickness of about 20 nm to about 1000 nm; and the film has a capacitance of about 1 μF/cm 2 to about 5 μF/cm 2 at a frequency of about 1 MHz.
2. The film of claim 1 , wherein the ionic liquid is selected from the group consisting of: 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide, 1,2-dimethyl-3-propylimidazolium tris(trifluoromethylsulfonyl)methide, 1-dodecyl-3-methylimidazolium iodide, 1-ethyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 3-methyl-1-propylpyridinium bis(trifluoromethylsulfonyl)imide, 1-methyl-3-octylimidazolium tetrafluoroborate, methyl-trioctylammonium bis(trifluoromethylsulfonyl)imide, tetrabutylammonium bis(trifluoromethylsulfonyl)imide, tetrabutylammonium bromide, tetrabutylphosphonium tetrafluoroborate, tetraethylammonium trifluoromethanesulfonate, and triethylsulfonium bis(trifluoromethylsulfonyl)imide.
3. The film of claim 1 , wherein the ionic liquid is 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-ethyl-3-methylimidazolium dicyanamide.
4. The film of claim 1 , wherein each monomer is independently selected from the group consisting of: acrylamide, acrylic acid (AA), N-acryloyltris(hydroxymethyl)methylamine, 2-aminoethyl methacrylate, N-(3-aminopropyl)methacrylamide, butyl acrylate and methacrylate, diallylamine, diallylammonium chloride, N,N-diethylacrylamide, N,N-dimethylacrylamide, 2-(N,N-dimethylamino)ethyl acrylate and methacrylate, 2-(dimethylamino)ethyl acrylate and methacrylate, N-[3-(N,N-dimethylamino)propyl]methacrylamide, ethoxyethyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate and methacrylate, 2,3-dihydroxypropyl acrylate and methacrylate, glyceryl monomethacrylate, glycidyl acrylate and methacrylate, 2-hydroxyethyl acrylate and methacrylate, N-(2-hydroxypropyl)methacrylamide, hydroxypropyl acrylate and methacrylate, methacrylamide, methacrylic acid (MAA), methacrylic anhydride, 2-(2-methoxy)ethyl acrylate and methacrylate, 2-methoxyethyl methacrylate, N-iso-propylacrylamide, poly(ethylene glycol) methyl ether methacrylate, 4-styrenesulfonic acid, 4-vinylpyridine, vinylsulfonic acid, and N-vinyl-2-pyrrodinone.
5. The film of claim 1 , wherein each monomer is N,N-dimethylacrylamide.
6. The film of claim 1 , wherein each crosslinker is independently selected from the group consisting of: 2,2-bis[4-(2-acryloxyethoxy)phenyl]propane, 2,2-bis(4-methacryloxyphenyl)propane, butanediol diacrylate and dimethacrylate, 1,4-butanediol divinyl ether, 1,4-cyclohexanediol diacrylate and dimethacrylate, 1,4-diacryloylpiperazine, diallylphthalate, diethylene glycol diacrylate and dimethacrylate, 2,2-dimethylpropanediol diacrylate and dimethacrylate, dipentaerythritol pentaacrylate, dipropylene glycol diacrylate and dimethacrylate, divinylbenzene, glycerol trimethacrylate, N,N′-hexamethylenebisacrylamide, N,N′-octamethylenebisacrylamide, 1,5-pentanediol diacrylate and dimethacrylate, 1,3-phenylenediacrylate, poly(ethylene glycol)diacrylate and dimethacrylate, poly(propylene)diacrylate and dimethacrylate, triethylene glycol diacrylate and dimethacrylate, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tripropylene glycol diacrylate or dimethacrylate, diallyl diglycol carbonate, poly(ethylene glycol) divinyl ether, N,N′-dimethacryloylpiperazine, divinyl glycol, ethylene glycol diacrylate, ethylene glycol dimethacrylate, N,N′-methylenebisacrylamide, tetra(ethylene glycol)diacrylate, 1,1,1-trimethylolethane trimethacrylate, 1,1,1-trimethylolpropane triacrylate, 1,1,1-trimethylolpropane trimethacrylate, 1,6-hexanediol diacrylate and dimethacrylate, 1,3-butylene glycol diacrylate and dimethacrylate, alkoxylated cyclohexane dimethanol dicarylate, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate and dimethacrylate, ethoxylated bisphenol diacrylate and dimethacrylate, neopentyl glycol diacrylate and dimethacrylate, ethoxylated trimethylolpropane triarylate, propoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, pentaerythritol triacrylate, tris (2-hydroxy ethyl)isocyanurate triacrylate, di-trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, ethoxylated pentaerythritol tetraacrylate, pentaacrylate ester, and pentaerythritol tetraacrylate.
7. The film of claim 1 , wherein each crosslinker is diethylene glycol divinyl ether.
8. The film of claim 1 , wherein the crosslinked polymer is poly(N,N -dimethylacrylamide-co-diethylene glycol divinyl ether) (pDAx).
9. The film of claim 1 , wherein the monomer has a solubility parameter (δ) within 10% of the solubility parameter (δ) of the ionic liquid.
10. The film of claim 1 , wherein the crosslinked polymer has a solubility parameter (δ) of about 15 to about 25 MPa 1/2 .
11. The film of claim 1 , wherein the ionic liquid has a solubility parameter (δ) of about 15 to about 25 MPa 1/2 .
12. The film of claim 1 , wherein the film is disposed on a substrate.
13. The film of claim 12 , wherein the film is disposed on the substrate in a pattern of a plurality of features; and each feature has a length or a width less than about 10 μm.
14. The film of claim 1 , wherein the film has an elastic modulus of about 1 MPa to about 100 MPa.
15. The film of claim 1 , wherein the monomer or the crosslinker comprises a nitrogen atom in its structure; and the presence of the nitrogen atom is detectable by N 1s ARXPS of the film at a 30°, 55°, or 70° emission angle (with reference to surface normal).
16. The film of claim 1 , wherein the film has a RMS roughness of about 0.1 nm to about 1.0 nm.
17. The film of claim 1 , wherein the ratio of the capacitance of the film at 1 MHz to the capacitance of the film at 10 Hz is greater than about ⅓.
18. A method of making a film, comprising the steps of:
by iCVD, synthesizing and depositing on a substrate a crosslinked polymer, wherein the crosslinked polymer comprises a plurality of residues of a monomer and a plurality of residues of a crosslinker;
synthesizing a matrix comprising a bulk polymer and an ionic liquid; and
contacting the crosslinked polymer with the matrix for a period of time sufficient to allow the ionic liquid to diffuse into the crosslinked polymer, thereby forming the film,
wherein the film has a thickness of about 20 nm to about 1000 nm.
19. The method of claim 18 , further comprising the step of: before synthesizing and depositing the crosslinked polymer on the substrate, covering a portion of the surface of the substrate with a mask, thereby forming a covered portion and an exposed surface of the substrate.
20. A device, comprising a film of claim 1 , a cathode, and an anode.