Erratum: N-type organic electrochemical transistors with stability in water

Giovannitti, Alexander; Nielsen, Christian B.; Sbircea, Dan-Tiberiu; Inal, Sahika; Donahue, Mary J.; Niazi, Muhammad Rizwan; Hanifi, David; Amassian, Aram; Malliaras, George G.; Rivnay, Jonathan; McCulloch, Iain

doi:10.1038/ncomms13955

Cited by 12 publications

(15 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To further confirm the enhanced conductivity of dry crystalline P3MEEMT, we fabricated and tested organic field effect transistors (OFETs) and found a higher mobility in the annealed sample (Figure S21). Although initially counterintuitive, this difference in OFET mobility and OECT mobility is similar to findings by Giovannitti et al in which the polymer with greater dry field effect mobility and nearly equivalent volumetric capacitance performed significantly worse as an OECT . Both of these experiments suggest that changes in the polymer in its hydrated or doped state can have a detrimental effect on electronic transport.…”

Section: Resultsmentioning

confidence: 79%

“…OECT performance enhancement using oligoethylene glycol side chains is generalizable to a number of different conjugated backbones, including polythiophene, benzodithiophene, propylenedioxythiophenes, and bithiophene–thienothiophene . Additionally, ethylene glycol side chains have been shown to increase the OECT performance compared to that of their alkyl analogues in n-type polymers based on naphthalene tetracarboxylic diimide. , In each of these instances, the presence of ethylene glycol side chains improves both the steady-state characteristics (transconductance) and the switching kinetics of OECTs. Well-designed polymers now function as single-phase, accumulation-mode OECTs with volumetric capacitances approaching the theoretical limit of approximately 400 F cm –3 in aqueous environments. , …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Polymer Crystallinity Controls Water Uptake in Glycol Side-Chain Polymer Organic Electrochemical Transistors

Flagg¹,

Bischak²,

Onorato³

et al. 2019

J. Am. Chem. Soc.

211

410

View full text Add to dashboard Cite

We study poly(3-{[2-(2-methoxyethoxy)ethoxy]methyl}thiophene-2,5-diyl) (P3MEEMT), a new polythiophene derivative with ethylene glycol-based side chains, as a promising semiconducting polymer for accumulation-mode organic electrochemical transistors (OECTs) with figures of merit comparable to those of state-of-the-art materials. By characterizing the OECT performance of P3MEEMT transistors as a function of the anion, we find that large hydrophobic anions lower the threshold voltage. We find that, compared to poly(3-hexylthiophene-2,5-diyl) (P3HT), P3MEEMT has faster anion injection rates, which we attribute to the hydration of the P3MEEMT crystal lattice. We study P3MEEMT-based OECT and organic field-effect transistor (OFET) performance as a function of film crystallinity and show that changing the crystallinity of the polymer by thermal annealing increases the OFET mobility yet decreases the OECT mobility. We attribute this difference to the fact that, unlike OFETs, OECTs operate in aqueous environments. To probe how hydration affects the operation of OECTs, we investigate the role of water in electrochemical doping using electrochemical quartz microbalance (EQCM) gravimetry. We find that steady-state hydration and hydration dynamics under electrochemical bias differ dramatically between the crystalline and amorphous P3MEEMT films. These results suggest that the presence of water reduces the electronic connectivity between the crystalline regions of P3MEEMT, thus lowering the mobility in solution. Overall, our study highlights the importance of the role of polymer hydration and nanoscale morphology in elucidating design principles for OECT operation.

show abstract

Section: Resultsmentioning

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Polymer Crystallinity Controls Water Uptake in Glycol Side-Chain Polymer Organic Electrochemical Transistors

Flagg¹,

Bischak²,

Onorato³

et al. 2019

J. Am. Chem. Soc.

211

410

View full text Add to dashboard Cite

show abstract

“…Initial work in the mixed conductor field showed that increased swelling in the presence of electrolyte leads to higher ionic conductivity. − Thus, the design of modern organic mixed conductors is largely based upon substituting hydrophilic side chains, which promote hydration and ion transport, onto polymer backbones and small molecules known to have high electronic conductivity. This strategy has proven very successful, as polymers with polar side chains, including alcohols, carboxylic acids, amides, sulfonates, − and most commonly, oligoethylene glycol, − display dramatically enhanced ion transporting properties while maintaining their good electronic properties.…”

mentioning

confidence: 99%

P-Type Electrochemical Doping Can Occur by Cation Expulsion in a High-Performing Polymer for Organic Electrochemical Transistors

Flagg

Bischak

Quezada

et al. 2020

ACS Materials Lett.

View full text Add to dashboard Cite

We investigate the mechanism of ion-dependent charge compensation during electrochemical oxidation (doping) of the model mixed ionic/electronic transporting polythiophene derivative poly(3-{[2-(2-methoxyethoxy)ethoxy]methyl}thiophene-2,5-diyl) (P3MEEMT). Using a combination of electrochemical quartz microbalance gravimetry and glow discharge optical emission spectroscopy, we show that charge compensation during polymer redox processes proceeds via a cation-dependent mechanism. For p-type polymer oxidation in certain electrolytes, charge compensation is achieved by both eventual injection of anions into the film, as well as initial expulsion of cations from the film. We compare doping mechanisms for a variety of electrolyte salts including potassium chloride, tetrabutylammonium chloride, potassium hexafluorophosphate (KPF6), and tetrabutylammonium hexafluorophosphate. For the electrolyte KPF6, both the cations and anions coexist in the water-swelled polymer even prior to application of electrical bias. Our data indicate that electrochemical doping (hole injection into the polymer and ionic charge compensation) proceeds via the following mechanism: (1) hydration of the neutral film by electrolyte (water, cations, anions), (2) cation (K+) expulsion from the film upon initial application of an oxidative bias, and (3) anion injection into the film at higher oxidation/doping levels (>∼2 × 1020/cm3). Understanding the mechanism of charge compensation during the doping process should allow for the design of improved mixed ionic/electronic conductors for use in applications ranging from organic supercapacitors and redox flow batteries to bioelectronic sensors, thermoelectrics, and devices for neuromorphic computing.

show abstract

“…The monomers TDPP(BE) 2 , 3ETGTDPP-Br 2 , BBT(SnBu 3 ) 2 , and NDITEG-Br 2 were synthesized by following procedures reported in the literature. 48,51,52 Methods. Average molecular weights (M w , M n ) were determined by gel permeation chromatography (GPC) against polystyrene standards.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The required four monomers 3TEGTDPP-Br 2 , BBT(SnBu 3 ) 2 , TDPP(BE) 2 and NDITEG-Br 2 were synthesized according to the literature reported procedures. 51,52 The polymer BBT-3TEG-TDPP was obtained with Stille coupling of BBT (SnBu 3 ) 2 and TDPP-3TEG-TDPP by using Pd(PPh 3 ) 4 as a catalyst, whereas polymers TDPP-3TEG-TDPP and P(gNDI-TDPP) were synthesized via Suzuki coupling reaction by using Pd 2 (dba) 3 as the catalyst. The detailed procedures for the synthesis of polymers are described in the Supporting Information.…”

Section: ■ Introductionmentioning

confidence: 99%

Rational Design of Donor–Acceptor Based Semiconducting Copolymers with High Dielectric Constants

et al. 2021

View full text Add to dashboard Cite

The low dielectric constant of organic semiconductors limits the efficiency of organic solar cells (OSCs). In an attempt to improve the dielectric constant of conjugated polymers, we report the synthesis of three semiconducting copolymers by combining the thiophene-substituted diketopyrrolopyrrole (TDPP) monomer with three different monomeric units with varying electron donating/accepting strengths: benzodithiophene (BBT-3TEG-TDPP), TDPP (TDPP-3TEG-TDPP), and naphthalene diimide (P(gNDI-TDPP)). Among the series, BBT-3TEG-TDPP and P(gNDI-TDPP) exhibited the highest dielectric constants (∼5) at 1 MHz frequency, signifying the contribution of dipolar polarization from TEG side-chains. Furthermore, transient absorption spectroscopic studies performed on these polymers indicated low exciton diffusion length as observed in common organic semiconducting polymers. Our findings suggest that utilizing the polar side-chains enhances the dielectric constant in a frequency regime of megahertz. However, it is not sufficient to reduce the Coulombic interaction between hole and electron in excitonic solar cells.

show abstract

Erratum: N-type organic electrochemical transistors with stability in water

Cited by 12 publications

References 0 publications

Polymer Crystallinity Controls Water Uptake in Glycol Side-Chain Polymer Organic Electrochemical Transistors

Polymer Crystallinity Controls Water Uptake in Glycol Side-Chain Polymer Organic Electrochemical Transistors

P-Type Electrochemical Doping Can Occur by Cation Expulsion in a High-Performing Polymer for Organic Electrochemical Transistors

Rational Design of Donor–Acceptor Based Semiconducting Copolymers with High Dielectric Constants

Contact Info

Product

Resources

About