Interfacial Charge Transport Enhancement of Liquid-Crystalline Polymer Transistors Enabled by Ionic Polyurethane Dielectric.

In organic field-effect transistors (OFETs) using disordered organic semiconductors, interface traps that hinder efficient charge transport, stability, and device performance are inevitable. Benchmark poly(9,9-dioctylfuorene-co-bithiophene) (F8T2) liquid-crystalline polymer semiconductor has been extensively investigated for organic electronic devices due to its promising combination of charge transport and light emission properties. This study demonstrates that high-capacitance single-layered ionic polyurethane (PU) dielectrics enable enhanced charge transport in F8T2 OFETs. The ionic PU dielectrics are composed of a mild blending of PU ionogel and PU solution, thereby forming a solid-state film with robust interfacial characteristics with semiconductor layer and gate electrode in OFETs and measuring high capacitance values above 10 µF cm-2 owing to the combined dipole polarization and electric double layer formation. The optimized fabricated ionic PU-gated OFETs exhibit a low-voltage operation at -3 V with a remarkable hole mobility of over 5 cm2 V-1 s-1 (average = 2.50 ± 1.18 cm2 V-1 s-1), which is the highest mobility achieved so far for liquid-crystalline F8T2 OFETs. This device also provides excellent bias-stable characteristics in ambient air, exhibiting a negligible threshold voltage shift of -0.03 V in the transfer curves after extended bias stress, with a reduced trap density.

Hole Mobility Enhancement in Benzo[1,2-b:4,5-b']Dithiophene-Based Conjugated Polymer Transistors through Directional Alignment, Perovskite Functionalization and Solid-State Electrolyte Gating.

Tunability in electronic and optical properties has been intensively explored for developing conjugated polymers and their applications in organic and perovskite-based electronics. Particularly, the charge carrier mobility of conjugated polymer semiconductors has been deemed to be a vital figure-of-merit for achieving high-performance organic field-effect transistors (OFETs). In this study, the systematic hole carrier mobility improvement of benzo[1,2-b:4,5-b']dithiophene-based conjugated polymer in perovskite-functionalized organic transistors is demonstrated. In conventional OFETs with a poly(methyl methacrylate) (PMMA) gate dielectric, improvements in hole mobility of 0.019 cm2 V-1 s-1 are measured using an off-center spin-coating technique, which exceeds those of on-center counterparts (0.22 ± 0.07 × 10-2 cm2 V-1 s-1). Furthermore, the mobility drastically increases by adopting solid-state electrolyte gating, corresponding to 2.99 ± 1.03 cm2 V-1 s-1 for the control, and the best hole mobility is 8.03 cm2 V-1 s-1 (average ≈ 6.94 ± 0.59 cm2 V-1 s-1) for perovskite-functionalized OFETs with a high current on/off ratio of >106. The achieved device performance would be attributed to the enhanced film crystallinity and charge carrier density in the hybrid perovskite-functionalized organic transistor channel, resulting from the high-capacitance electrolyte dielectric.

Interfacial Interaction Enables Enhanced Mobility in Hybrid Perovskite-Conjugated Polymer Transistors with High-k Fluorinated Polymer Dielectrics.

The charge carrier mobility of organic field-effect transistors (OFETs) has been remarkably improved through several engineering approaches and techniques by targeting pivotal parts. Herein, an ultrathin perovskite channel layer that boosts the field-effect mobility of conjugated polymer OFETs by forming perovskite-conjugated polymer hybrid semiconducting channel is introduced. The optimized lead-iodide-based perovskite-conjugated polymer hybrid channel transistors show enhanced hole mobility of over 4 cm2  V-1  s-1 (average = 2.10 cm2  V-1  s-1 ) with high reproducibility using a benchmark poly(3-hexylthiophene) (P3HT) polymer and employing high-k fluorinated polymer dielectrics. A significant hole carrier mobility enhancement of ≈200-400% in benzo[1,2-b:4,5:b']dithiophene (BDT)-based conjugated polymers is also demonstrated by exploring certain interactive groups with perovskite. This significant enhancement in the transistor performance is attributed to the increased charge carrier density in the hybrid semiconducting channel and the perovskite-polymer interactions. The findings of this paper demonstrate an exceptional engineering approach for carrier mobility enhancement in hybrid perovskite-conjugated-polymer-based electronic devices.

Configurationally Random Polythiophene for Improved Polymer Ordering and Charge-Transporting Ability.

Random polythiophene polymers are characterized by the arbitrary sequences of monomeric units along polymer backbones. These untailored orientations generally result in the twisting of thiophene rings out of the conjugation planarity in addition to steric repulsions experienced among substituted alkyl chains. These tendencies have limited close polymer packing, which has been detrimental to charge transport in these moieties. To ameliorate charge transport in these classes of polymers, we make use of simple Stille coupling polymerization to synthesize highly random polythiophene polymers. We induced a positive microstructural change between polymer chains by attuning the ratio between alkyl-substituted and nonalkyl-substituted monomer units along the backbones. The optimized random polythiophene was found to have enhanced intermolecular interaction, increased size of crystallites, and stronger tendency to take edge orientation compared with both regiorandom and regioregular poly(3-hexylthiophene) polymers. Incorporation of the optimized random polythiophene as an active material in solid-state electrolyte-gated organic field-effect transistors exhibited better performance than the control device using regioregular poly(3-hexylthiophene), with a high hole mobility up to 4.52 cm2 V-1 s-1 in ambient conditions.

Polymer Electrolyte Blend Gate Dielectrics for High-Performance Ultrathin Organic Transistors: Toward Favorable Polymer Blend Miscibility and Reliability.

We report on systematic mobility enhancements in electrolyte-gated organic field-effect transistors (OFETs) by thinning down the active layer and exploiting polymer solid-state electrolyte gate insulators (SEGIs). The SEGI is composed of homogeneous poly(vinylidene fluoride- co-hexafluoropropylene) [P(VDF-HFP)] polymer solution-ion gel blends of high areal capacitance of >10 µF cm-2 at 1 Hz. By scaling up the poly(3-hexylthiophene) (P3HT) semiconducting layer by 1 order of magnitude (5-50 nm), an ultraviolet photoelectron spectroscopy examination reveals a downward vacuum-level shift generating a substantial hole injection barrier that originates from different interfacial dipole layer formations. The ultrathin (5.1 nm) P3HT FETs outperformed the other devices, exhibiting stable device characteristics with a highest field-effect mobility of >2 cm2 V-1 s-1 (effective mobility of 0.83 ± 0.05 cm2 V-1 s-1), on/off ratio of ∼106, low threshold voltage of <-0.6 V, and low gate-leakage current levels of ∼105 below the on-current levels in 10 µm channel length devices. We observed a positive threshold voltage shift in the P3HT/SEGI FETs with decreasing semiconductor thickness. The aforementioned mobility is at least 10 times greater than that of neat P(VDF-HFP) devices. The significant FET performance is attributed to a better insulator/semiconductor interface, efficient hole injection from the Au electrode resulting in a low contact resistance of <500 Ω cm, and boosted charge-carrier densities in the transistor channel. This work demonstrates an excellent approach for carrier mobility enhancement and reliability assessment in low-voltage-operated electrolyte-gated OFETs.

Difluorobenzothiadiazole and Selenophene-Based Conjugated Polymer Demonstrating an Effective Hole Mobility Exceeding 5 cm2 V-1 s-1 with Solid-State Electrolyte Dielectric.

We report synthesis of a new poly(4-(4,4-bis(2-ethylhexyl)-4 H-silolo[3,2- b:4,5- b']dithiophene-2-yl)-7-(4,4-bis(2-ethylhexyl)-6-(selenophene-2-yl)-4 H-silolo[3,2- b:4,5- b']dithiophene-2-yl)-5,6-difluorobenzo[ c][1,2,5]thiadiazole (PDFDSe) polymer based on planar 4,7-bis(4,4-bis(2-ethylhexyl)-4 H-silolo[3,2- b:4,5- b']dithiophen-2-yl)-5,6-difluorobenzo[ c][1,2,5]thiadiazole (DFD) moieties and selenophene linkages. The planar backboned PDFDSe polymer exhibits highest occupied molecular orbital and lowest unoccupied molecular orbital levels of -5.13 and -3.56 eV, respectively, and generates well-packed highly crystalline states in films with exclusive edge-on orientations. PDFDSe thin film was incorporated as a channel material in top-gate bottom-contact organic thin-film transistor with a solid-state electrolyte gate insulator (SEGI) composed of poly(vinylidene difluoride-trifluoroethylene)/poly(vinylidene fluoride- co-hexafluroropropylene)/1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, which exhibited a remarkably high hole mobility up to µ = 20.3 cm2 V-1 s-1 corresponding to effective hole mobility exceeding 5 cm2 V-1 s-1 and a very low threshold voltage of -1 V. These device characteristics are associated with the high carrier density in the semiconducting channel region, induced by the high capacitance of the SEGI layer. The excellent carrier mobility from the PDFDSe/SEGI device demonstrates a great potential of semiconducting polymer thin-film transistors as electronic components in future electronic applications.

Highly Sensitive Flexible NH3 Sensors Based on Printed Organic Transistors with Fluorinated Conjugated Polymers.

Understanding the sensing mechanism in organic chemical sensors is essential for improving the sensing performance such as detection limit, sensitivity, and other response/recovery time, selectivity, and reversibility for real applications. Here, we report a highly sensitive printed ammonia (NH3) gas sensor based on organic thin film transistors (OTFTs) with fluorinated difluorobenzothiadiazole-dithienosilole polymer (PDFDT). These sensors detected NH3 down to 1 ppm with high sensitivity (up to 56%) using bar-coated ultrathin (<4 nm) PDFDT layers without using any receptor additives. The sensing mechanism was confirmed by cyclic voltammetry, hydrogen/fluorine nuclear magnetic resonance, and UV/visible absorption spectroscopy. PDFDT-NH3 interactions comprise hydrogen bonds and electrostatic interactions between the PDFDT polymer backbone and NH3 gas molecules, thus lowering the highest occupied molecular orbital levels, leading to hole trapping in the OTFT sensors. Additionally, density functional theory calculations show that gaseous NH3 molecules are captured via cooperation of fluorine atoms and dithienosilole units in PDFDT. We verified that incorporation of functional groups that interact with a specific gas molecule in a conjugated polymer is a promising strategy for producing high-performance printed OTFT gas sensors.

Ultrahigh Mobility in Solution-Processed Solid-State Electrolyte-Gated Transistors.

A new concept of a high-capacitance polymeric dielectric based on high-k polymer and ion gel blends is reported. This solid-state electrolyte gate insulator enables remarkable field-effect mobilities exceeding 10 cm2 V-1 s-1 for common polymer and other semiconductor families at VG ≤ 2 V owing to high areal capacitance (>4 µF cm-2 ) from combined polarization of CF interface dipoles and electrical-double-layer formation.

A highly planar fluorinated benzothiadiazole-based conjugated polymer for high-performance organic thin-film transistors.

High-mobility and low-voltage-operated organic field-effect transistors (OFETs) are demonstrated by the design of a new fluorinated benzothiadiazole-based conjugated polymer with fluorinated high-k polymer dielectrics. A record-breaking high hole mobility of 9.0 cm(2) V(-1) s(-1) for benzothiadiazole-based semiconducting polymers is achieved by the excellent planarity of the semiconducting polymer.