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We demonstrate that the transfer characteristics of electrolyte-gated transistors (EGTs) with polythiophene semiconductor channels are a strong function of gate/electrolyte interfacial contact area, i.e., gate size. Polythiophene EGTs with gate/electrolyte areas much larger than the channel/electrolyte areas show a clear peak in the drain current vs gate voltage (ID–VG) behavior, as well as peak voltage hysteresis between the forward and reverse VG sweeps. Polythiophene EGTs with small gate/electrolyte areas, on the other hand, exhibit current plateaus in the ID–VG behavior and a gate-size-dependent hysteresis loop between turn on and off. The qualitatively different transport behaviors are attributed to the relative sizes of the gate/electrolyte and channel/electrolyte interface capacitances, which are proportional to interfacial area. These interfacial capacitances are in series with each other such that the total capacitance of the full gate/electrolyte/channel stack is dominated by the interface with the smallest capacitance or area. For EGTs with large gates, most of the applied VG is dropped at the channel/electrolyte interface, leading to very high charge accumulations, up to ∼0.3 holes per ring (hpr) in the case of polythiophene semiconductors. The large charge density results in sub-band-filling and a marked decrease in hole mobility, giving rise to the peak in ID–VG. For EGTs with small gates, hole accumulation saturates near 0.15 hpr, band-filling does not occur, and hole mobility is maintained at a fixed value, which leads to the ID plateau. Potential drops at the interfaces are confirmed by in situ potential measurements inside a gate/electrolyte/polymer semiconductor stack. Hole accumulations are measured with gate current-gate voltage (IG–VG) measurements acquired simultaneously with the ID–VG characteristics. Overall, our measurements demonstrate that remarkably different ID behavior can be obtained for polythiophene EGTs by controlling the magnitude of the gate-electrolyte interfacial capacitance.
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Sub‐Band Filling and Hole Transport in Polythiophene‐Based Electrolyte‐Gated Transistors: Effect of Side‐Chain Length and Density
The relationship between hole density and conductivity in electrochemically gated polythiophene films is examined. The films are integrated into electrolyte‐gated transistors (EGTs), so that hole accumulations can be electrochemically modulated up to ≈0.4 holes per thiophene ring (hpr). Polythiophenes include poly(3‐alkylthiophenes) (P3ATs) with four different side chain lengths – butyl (P3BT), hexyl (P3HT), octyl (P3OT), or decyl (P3DT) – and poly[2,5‐bis(3‐dodecylthiophen‐2‐yl)thieno[3,2‐b]thiophene] (PBTTT) and poly(3,3′′′‐didodecyl[2,2′:5′,2′′:5′′,2′′′‐quaterthiophene]‐5,5′′′‐diyl) (PQT). Analysis of the drain current – gate voltage (ID–VG) and gate current – gate voltage (IG–VG) characteristics of the EGTs reveals that all six polythiophene semiconductors exhibited reversible conductivity peaks at 0.12 – 0.15 hpr. Conductivity is suppressed beyond ≈0.4 hpr.The maximum carrier mobilities of the P3AT semiconductors increase, and hysteresis of the conductivity peaks decreases, with increasing alkyl side‐chain length. PBTTT and PQT with reduced side chain densities exhibit the largest hysteresis but have higher hole mobilities. The results suggest that at ≈0.4 hpr, a polaronic sub‐band is filled in all cases. Filling of the sub‐band correlates with a collapse in the hole mobility. The side‐chain dependence of the peak conductivity and hysteresis further suggests that Coulombic ion‐carrier interactions are important in these systems. Tailoring ion‐carrier correlations is likely important for further improvements in transport properties of electrochemically doped polythiophenes.
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- Award ID(s):
- 2011401
- PAR ID:
- 10506659
- Publisher / Repository:
- Advanced Functional Materials
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 33
- Issue:
- 37
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1002/adfm.202303700
