The electrochemical doping/dedoping kinetics, and the organic electrochemical transistor (OECT) performance of a series of polythiophene homopolymers with ethylene glycol units in their side chains using both kosmotropic and chaotropic anion solutions were studied. We compare their performance to a reference polymer, the polythiophene derivative with diethylene glycol side chains, poly(3-{[2-(2-methoxyethoxy)ethoxy]methyl}thiophene-2,5-diyl) (P3MEEMT). We find larger OECT material figure of merit, μC *, where μ is the carrier mobility and C * is the volumetric capacitance, and faster doping kinetics with more oxygen atoms on the side chains, and if the oxygen atom is farther from the polythiophene backbone. Replacing the oxygen atom close to the polythiophene backbone with an alkyl unit increases the film π-stacking crystallinity (higher electronic conductivity in the undoped film) but sacrifices the available doping sites (lower volumetric capacitance C * in OECT). We show that this variation in C * is the dominant factor in changing the μC * product for this family of polymers. With more oxygen atoms on the side chain, or with the oxygen atom farther from the polymer backbone, we observe both more passive swelling and higher C *. In addition, we show that, compared to the doping speed, the dedoping speed, as measured via spectroelectrochemistry, is both generally faster and less dependent on ion species or side chain oxygen content. Last, through OECT, electrochemical impedance spectroscopy (EIS) and spectroelectrochemistry measurements, we show that the chaotropic anion PF 6 − facilitates higher doping levels, faster doping kinetics, and lower doping thresholds compared to the kosmotropic anion Cl − , although the exact differences depend on the polymer side chains. Our results highlight the importance of balancing μ and C * when designing molecular structures for OECT active layers.
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The combined influence of polythiophene side chains and electrolyte anions on organic electrochemical transistors
Polythiophenes with differently functionalized side chains (alkyl, oligoethylene oxide, ester, hydroxy, and carboxylic acid) and varied counterions of potassium salt electrolytes were investigated in organic electrochemical transistors (OECTs). In addition, mixed blends were investigated to evaluate any synergistic effects between functionalities. Depending on the functional moiety attached, a large shift to lower potentials of Vth, an increase in drain current, and increase in transconductance can be observed compared to the base combination of alkyl side chain and Cl-. The newly designed and synthesized hydroxy polymer displayed stability to large shifts in VTH, slight increase in drain current, and little or no increase in transconductance when an ionic radius of the dopant is increased until a much larger anion, large polarizability, and low hydration number such as TSFI- was used. The acid-functionalized polymer, on the other hand had the same magnitude in shift with respect to any anion that is larger than Cl-. The polymers were characterized by spectroscopy, x-ray diffraction, thermal analysis, and cyclic voltammetry. This work demonstrates that side-chain engineering can have substantial difference in the level of interaction in the electrolyte which would require tailoring the ion for specific polymer interactions.
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- Award ID(s):
- 1807292
- NSF-PAR ID:
- 10318459
- Date Published:
- Journal Name:
- Electrochemical Science Advances
- ISSN:
- 2698-5977
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Chloride homeostasis is regulated in all cellular compartments. CLC-type channels selectively transport Cl
− across biological membranes. It is proposed that side-chains of pore-lining residues determine Cl− selectivity in CLC-type channels, but their spatial orientation and contributions to selectivity are not conserved. This suggests a possible role for mainchain amides in selectivity. We use nonsense suppression to insert α-hydroxy acids at pore-lining positions in two CLC-type channels, CLC-0 and bCLC-k, thus exchanging peptide-bond amides with ester-bond oxygens which are incapable of hydrogen-bonding. Backbone substitutions functionally degrade inter-anion discrimination in a site-specific manner. The presence of a pore-occupying glutamate side chain modulates these effects. Molecular dynamics simulations show backbone amides determine ion energetics within the bCLC-k pore and how insertion of an α-hydroxy acid alters selectivity. We propose that backbone-ion interactions are determinants of Cl− specificity in CLC channels in a mechanism reminiscent of that described for K+channels. -
null (Ed.)Aims: The aim of the study was to determine whether and to what extent any of a family of amphiphilic heptapeptide synthetic anion transporters (SATs) affected the growth or root morphology of Arabidopsis thaliana. Study Design: A. thaliana plants were grown from seedlings in PNS media in the absence or presence of one of 21 SATs. Place and Duration of Study: Departments of Chemistry & Biochemistry, University of Missouri – St. Louis, 1 University Blvd., St. Louis, MO 63121 U. S. A. The study was conducted 2017-2018. Methodology: Twenty one compounds of the form R2N-COCH2YCH2CO-(Aaa)3Pro(Aaa)3-O(CH2)6CH3 were prepared and studied. The amino acids included Ala, Gly, and Ser. R was normal alkyl having 6, 10, 12, or 18 carbons. Y was methylene, oxygen, sulfur, or absent. The PNS media was infused with various concentrations of the SAT and 21 plants in each group were allowed to grow for 11 days. Overall plant growth and root morphology were visualized and/or measured and the results recorded. Results: A comparison of primary root length and lateral root number revealed that the greatest alterations in lateral root densities were observed for peptide sequences of the type GGGPSGS, whether or not serine was protected by t-butyl. Differences were also observed for these peptide sequences according to the identity of Y in the ~COCH2YCH2CO~ chain. Conclusion: The presence of serine’s oxygen atoms on the C-terminal side of the heptapeptide interact with Cl¯ leading to a change in ion concentrations and alterations in primary root lengths and lateral root densities.more » « less
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Abstract Organic electrochemical transistors (OECTs) operate at very low voltages, transduce ions into electronic signals, and reach extremely large transconductance values, making them ideally suited for bio‐sensing applications. However, despite their promising performance, the dependence of their maximum transconductance on device geometry and applied voltages are not correctly captured by current capacitive device models. Here, current scaling laws are revised in the light of a recently developed 2D device model that adequately accounts for drift and diffusion of ions inside the polymer channel. It is shown that the maximum transconductance of the devices is found at the transition between the depletion and accumulation region of the transistors, which as well provides an explanation for the observed shift of the transconductance peak with geometric dimensions and the drain potential. Overall, the results provide a better understanding of the working mechanisms of OECTs, and facilitate design rules to optimize OECT performance further.
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Abstract 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 (I D–V G) and gate current – gate voltage (I G–V G) 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.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1002/elsa.202100165
