We report the development of redox-active conjugated polymers that have potential applications in electrochemical energy storage. Side chain engineering enables processing of the polymer electrodes ...from solution, stability in aqueous electrolytes and efficient transport of ionic and electronic charge carriers. We synthesized a 3,3′-dialkoxybithiophene homo-polymer (p-type polymer) with glycol side chains and prepared naphthalene-1,4,5,8-tetracarboxylic-diimide-dialkoxybithiophene (NDI-gT2) copolymers (n-type polymer) with either a glycol or zwitterionic side chain on the NDI unit. For the latter, we developed a post-functionalization synthesis to attach the polar zwitterion side chains to the polymer backbone to avoid challenges of purifying polar intermediates. We demonstrate fast and reversible charging of solution processed electrodes for both the p- and n-type polymers in aqueous electrolytes, without using additives or porous scaffolds and for films up to micrometers thick. We apply spectroelectrochemistry as an
in operando
technique to probe the state of charge of the electrodes. This reveals that thin films of the p-type polymer and zwitterion n-type polymer can be charged reversibly with up to two electronic charges per repeat unit (bipolaron formation). We combine thin films of these polymers in a two-electrode cell and demonstrate output voltages of up to 1.4 V with high redox-stability. Our findings demonstrate the potential of functionalizing conjugated polymers with appropriate polar side chains to improve the accessible capacity, and to improve reversibility and rate capabilities of polymer electrodes in aqueous electrolytes.
Conjugated polymers with mixed ionic and electronic transport are essential for developing the complexity and function of electrochemical devices. Current n‐type materials have a narrow scope and low ...performance compared with their p‐type counterparts, requiring new molecular design strategies. This work presents two naphthalene diimide‐bithiophene (NDI‐T2) copolymers functionalized with hybrid alkyl‐glycol side chains, where the naphthalene diimide unit is segregated from the ethylene glycol (EG) units within the side chain by an alkyl spacer. Introduction of hydrophobic propyl and hexyl spacers is investigated as a strategy to minimize detrimental swelling close to the conjugated backbone and balance the mixed conduction properties of n‐type materials in aqueous electrolytes. It is found that both polymers functionalized with alkyl spacers outperform their analogue bearing EG‐only side chains in organic electrochemical transistors (OECTs). The presence of the alkyl spacers also leads to remarkable stability in OECTs, with no decrease in the ON current after 2 h of operation. Through this versatile side chain modification, this work provides a greater understanding of the structure‐property relationships required for n‐type OECT materials operating in aqueous media.
A fundamental study on side chain engineering of n‐type polymers reveals that substitution of polar side chains with hybrid non‐polar/polar ones improves the performance of electrochemical transistors. This study shows that swelling of the active layer must be controlled to guarantee stable device operation during continuous operation.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone ...is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.
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Conjugated polymers achieve redox activity in electrochemical devices by combining redox-active, electronically conducting backbones with ion-transporting side chains that can be tuned for different ...electrolytes. In aqueous electrolytes, redox activity can be accomplished by attaching hydrophilic side chains to the polymer backbone, which enables ionic transport and allows volumetric charging of polymer electrodes. While this approach has been beneficial for achieving fast electrochemical charging in aqueous solutions, little is known about the relationship between water uptake by the polymers during electrochemical charging and the stability and redox potentials of the electrodes, particularly for electron-transporting conjugated polymers. We find that excessive water uptake during the electrochemical charging of polymer electrodes harms the reversibility of electrochemical processes and results in irreversible swelling of the polymer. We show that small changes of the side chain composition can significantly increase the reversibility of the redox behavior of the materials in aqueous electrolytes, improving the capacity of the polymer by more than one order of magnitude. Finally, we show that tuning the local environment of the redox-active polymer by attaching hydrophilic side chains can help to reach high fractions of the theoretical capacity for single-phase electrodes in aqueous electrolytes. Our work shows the importance of chemical design strategies for achieving high electrochemical stability for conjugated polymers in aqueous electrolytes.
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Here, it is investigated whether an energetic cascade between mixed and pure regions assists in suppressing recombination losses in non‐fullerene acceptor (NFA)‐based organic solar cells. The impact ...of polymer‐NFA blend composition upon morphology, energetics, charge carrier recombination kinetics, and photocurrent properties are studied. By changing film composition, morphological structures are varied from consisting of highly intermixed polymer‐NFA phases to consisting of both intermixed and pure phase. Cyclic voltammetry is employed to investigate the impact of blend morphology upon NFA lowest unoccupied molecular orbital (LUMO) level energetics. Transient absorption spectroscopy reveals the importance of an energetic cascade between mixed and pure phases in the electron–hole dynamics in order to well separate spatially localized electron–hole pairs. Raman spectroscopy is used to investigate the origin of energetic shift of NFA LUMO levels. It appears that the increase in NFA electron affinity in pure phases relative to mixed phases is correlated with a transition from a relatively planar backbone structure of NFA in pure, aggregated phases, to a more twisted structure in molecularly mixed phases. The studies focus on addressing whether aggregation‐dependent acceptor LUMO level energetics are a general design requirement for both fullerene and NFAs, and quantifying the magnitude, origin, and impact of such energetic shifts upon device performance.
An energetic cascade between mixed and pure regions assists in suppressing recombination losses in nonfullerene acceptor (NFA)‐based organic solar cells. The impact of polymer–NFA blend composition upon film morphology, energetics, charge carrier recombination kinetics, and photocurrent properties is studied.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
On-site signal amplification for bioelectronic sensing is a desirable approach to improving recorded signal quality and to reducing the burden on signal transmission and back-end electronics. While ...organic electrochemical transistors (OECTs) have been used as local transducers of bioelectronic signals, their current output presents challenges for implementation. OECT-based circuits offer new opportunities for high-performance signal processing. In this work, we introduce an active sensing node based on cofacial vertical OECTs forming an ambipolar complementary inverter. The inverter, which shows a voltage gain of 28, is composed of two OECTs on opposite side walls of a single active area, resulting in a footprint identical to a planar OECT. The inverter is used as an analog voltage preamplifier for recording electrocardiogram signals when biased at the input voltage corresponding to peak gain. We further demonstrate compatibility with nontraditional fabrication methods with potential benefits for rapid prototyping and large-area printed electronics.
Organic semiconductors are being increasingly used for a variety of biological applications, such as biochemical sensors, drug delivery, and neural interfaces. However, the poor adhesion of cells to ...the typically hydrophobic, neutrally charged, and low-surface energy semiconducting thin films limits their use as part of in vitro, cell-integrated bioelectronic devices. In this work, we investigate the influence of lysine side chain units incorporated in a diketopyrrolopyrrole semiconducting polymer on neural cell adhesion and growth and evaluate their function in electrical devices. Synthesis of such biofunctionalized polymers obviates the need for biological coating steps while changing the surface physiochemistry, which makes them promising for applications in bioelectronics.
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With a host of new materials being investigated as active layers in organic electrochemical transistors (OECTs), several advantageous characteristics can be utilized to improve transduction and ...circuit level performance for biosensing applications. Here, the subthreshold region of operation of one recently reported high performing OECT material, poly(2‐(3,3′‐bis(2‐(2‐(2‐methoxyethoxy)ethoxy)ethoxy)‐2,2′‐bithiophen‐5‐yl)thieno3,2‐bthiophene), p(g2T‐TT) is investigated. The material's high subthreshold slope (SS) is exploited for high voltage gain and low power consumption. An ≈5× improvement in voltage gain (AV) for devices engineered for equal output current and 370× lower power consumption in the subthreshold region, in comparison to operation in the higher transconductance (g m), superthreshold region usually reported in the literature, are reported. Electrophysiological sensing is demonstrated using the subthreshold regime of p(g2T‐TT) devices and it is suggested that operation in this regime enables low power, enhanced sensing for a broad range of bioelectronic applications. Finally, the accessibility of the subthreshold regime of p(g2T‐TT) is evaluated in comparison with the prototypical poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), and the role of material design in achieving favorable properties for subthreshold operation is discussed.
Organic electrochemical transistors can achieve subthreshold slopes of 60 mV dec−1. Operation in this regime is shown to provide favorable gain and low power characteristics for sensing circuits. Subthreshold voltage amplification is demonstrated for recording electroencephalography signals.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Electron-transporting (n-type) conjugated polymers have recently been applied in numerous electrochemical applications, where both ion and electron transport are required. Despite continuous efforts ...to improve their performance and stability, n-type conjugated polymers with mixed conduction still lag behind their hole-transporting (p-type) counterparts, limiting the functions of electrochemical devices. In this work, we investigate the effect of enhanced backbone coplanarity on the electrochemical activity and mixed ionic-electronic conduction properties of n-type polymers during operation in aqueous media. Through substitution of the widely employed electron-deficient naphthalene diimide (NDI) unit for the core-extended naphthodithiophene diimide (NDTI) units, the resulting polymer shows a more planar backbone with closer packing, leading to an increase in the electron mobility in organic electrochemical transistors (OECTs) by more than two orders of magnitude. The NDTI-based polymer shows a deep-lying lowest unoccupied molecular orbital level, enabling operation of the OECT closer to 0 V vs Ag/AgCl, where fewer parasitic reactions with molecular oxygen occur. Enhancing the backbone coplanarity also leads to a lower affinity toward water uptake during cycling, resulting in improved stability during continuous electrochemical charging and ON–OFF switching relative to the NDI derivative. Furthermore, the NDTI-based polymer also demonstrates near-perfect shelf-life stability over a month-long test, exhibiting a negligible decrease in both the maximum on-current and transconductance. Our results highlight the importance of polymer backbone design for developing stable, high-performing n-type materials with mixed ionic-electronic conduction in aqueous media.
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Introducing ethylene glycol (EG) side chains to a conjugated polymer backbone is a well-established synthetic strategy for designing organic mixed ion-electron conductors (OMIECs). However, the ...impact that film swelling has on mixed conduction properties has yet to be scoped, particularly for electron-transporting (n-type) OMIECs. Here, the authors investigate the effect of the length of branched EG chains on mixed charge transport of n-type OMIECs based on a naphthalene-1,4,5,8-tetracarboxylic-diimide-bithiophene backbone. Atomic force microscopy (AFM), grazing-incidence wide-angle X-ray scattering (GIWAXS), and scanning tunneling microscopy (STM) are used to establish the similarities between the common-backbone films in dry conditions. Electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) and in situ GIWAXS measurements reveal stark changes in film swelling properties and microstructure during electrochemical doping, depending on the side chain length. It is found that even in the loss of the crystallite content upon contact with the aqueous electrolyte, the films can effectively transport charges and that it is rather the high water content that harms the electronic interconnectivity within the OMIEC films. These results highlight the importance of controlling water uptake in the films to impede charge transport in n-type electrochemical devices.
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