Polymer-Based Thermally Stable Chemiresistive Sensor for Real-Time Monitoring of NO2 Gas Emission.

We present a thermally stable, mechanically compliant, and sensitive polymer-based NO2 gas sensor design. Interconnected nanoscale morphology driven from spinodal decomposition between conjugated polymers tethered with polar side chains and thermally stable matrix polymers offers judicious design of NO2-sensitive and thermally tolerant thin films. The resulting chemiresitive sensors exhibit stable NO2 sensing even at 170 °C over 6 h. Controlling the density of polar side chains along conjugated polymer backbone enables optimal design for coupling high NO2 sensitivity, selectivity, and thermal stability of polymer sensors. Lastly, thermally stable films are used to implement chemiresistive sensors onto flexible and heat-resistant substrates and demonstrate a reliable gas sensing response even after 500 bending cycles at 170 °C. Such unprecedented sensor performance as well as environmental stability are promising for real-time monitoring of gas emission from vehicles and industrial chemical processes.

Molecularly Hybridized Conduction in DPP-Based Donor-Acceptor Copolymers toward High-Performance Iono-Electronics.

Iono-electronics, that is, transducing devices able to translate ionic injection into electrical output, continue to demand a variety of mixed ionic-electronic conductors (MIECs). Though polar sidechains are widely used in designing novel polymer MIECs, it remains unclear to chemists how much balance is needed between the two antagonistic modes of transport (ion permeability and electronic charge transport) to yield high-performance materials. Here, the impact of molecularly hybridizing ion permeability and charge mobility in semiconducting polymers on their performance in electrochemical and synaptic transistors is investigated. A series of diketopyrrolopyrrole (DPP)-based copolymers are employed to demonstrate the multifunctionality attained by controlling the density of polar sidechains along the backbone. Notably, efficient electrochemical signal transduction and reliable synaptic plasticity are demonstrated via controlled ion insertion and retention. The newly designed DPP-based copolymers further demonstrate unprecedented thermal tolerance among organic mixed ionic-electronic conductors, a key property in the manufacturing of organic electronics.

Influence of Alkyl Chain Spacer Length on the Charge Carrier Mobility of Isotactic Poly(N-carbazolylalkyl acrylates).

In the search for semiconducting polymer alternatives to conjugated polymers, stereoregular nonconjugated pendant electroactive polymers (NCPEPs) have recently shown competitive hole mobilities with conjugated polymers and a dramatic increase in mobility relative to atactic analogues. Here we investigate one of the key structural variables of NCPEPs: the flexible alkyl spacer that separates the electroactive pendant from the backbone. We investigate a straightforward postpolymerization functionalization synthetic method to synthesize such polymers with high isotacticity using poly(N-carbazolylalkyl acrylate) as a model system, where the alkyl chain spacer in the NCPEPs is varied from 2 to 12 carbons. We observed that the hole mobility increased from the two-carbon spacer, resulting in the highest mobility upon thermal annealing with a four-carbon spacer for 75% isotactic polymers and with a six-carbon spacer for 87% isotactic polymers. As such, we have demonstrated an important role of the spacer chain in influencing mobility. For all spacer lengths, higher mobilities were measured with the more isotactic polymer. While physical characterization of the largely amorphous polymers yielded little insight into the structure-function relationships, DFT and MD simulations indicated helical structures for the polymers where intermolecular short-range π-stacking is observed and is affected by spacer chain length. This work demonstrates that both the degree of stereoregularity and the spacer chain length play a role in determining the hole mobility in NCPEPs.

Contrasting the Charge Carrier Mobility of Isotactic, Syndiotactic, and Atactic Poly((N-carbazolylethylthio)propyl methacrylate).

Isotactic nonconjugated pendant electroactive polymers (NCPEPs) have recently shown potential to achieve comparable charge carrier mobilities with conjugated polymers. Here we report the broader influence of tacticity in NCPEPs, using poly((N-carbazolylethylthio)propyl methacrylate) (PCzETPMA) as a model polymer. We utilized the thiol-ene reaction as an efficient postpolymerization functionalization method to achieve pendant polymers with high isotacticity and syndiotacticity. We found that a stereoregular isotactic polymer showed ∼100 times increased hole mobility (µh) as compared to both atactic and low molecular weight syndiotactic PCzETPMA, achieving µh of 2.19 × 10-4 cm2 V-1 s-1 after annealing at 120 °C. High molecular weight syndiotactic PCzETPMA gave ∼10 times higher µh than its atactic counterpart, comparable to isotactic PCzETPMA after annealing at 150 °C. Importantly, high molecular weight syndiotactic PCzETPMA showed a dramatic increase in µh to 1.82 × 10-3 cm2 V-1 s-1 when measured after annealing at 210 °C, which surpassed the well-known conjugated polymer poly(3-hexylthiophene) (P3HT) (µh = 4.51 × 10-4 cm2 V-1 s-1). MD simulations indicated short-range π-π stacked ordering in the case of stereoregular isotactic and syndiotactic polymers. This work is the first report of charge carrier mobilities in syndiotactic NCPEPs and demonstrates that the tacticity, annealing conditions, and molecular weight of NCPEPs can strongly affect µh.

Influence of Systematic Incorporation of Conjugation-Break Spacers into Semi-Random Polymers on Mechanical and Electronic Properties.

An extensive family of semi-random polymers was prepared via Stille polycondensation with varying contents of alkyl spacers incorporated into the polymer backbone to serve as a break in conjugation. This family was investigated to determine the effect of alkyl spacer length and percent incorporation on the optical, electronic, and mechanical properties. The optical bandgap was found to steadily increase from 1.53 to 1.70 eV as the amount of spacer was increased from 10 mol percent to 40 mol percent while the length of the spacer had little to no effect. In space charge limited current (SCLC) carrier mobility measurements, hole mobility was found to decrease as the amount of spacer increased but was found to steadily increase as the length of the spacer was increased from 6 to 10 carbons. Mechanical properties were observed by film-on-elastomer and film-on-water measurements, with low elastic moduli and high ductility attributed both to the break in conjugation as well as the semi-random structure of the polymer backbone. Measurements of the mechanical properties using the buckling method revealed elastic moduli between 0.14 and 1.3 GPa, and several polymers, when bonded to an elastomeric substrate, could be stretched beyond 80% strain. These polymers were further tested as free-standing films by obtaining a pull test on the surface of water, where we obtained tensile moduli between 0.13 and 0.75 GPa. These results indicate that semi-random polymers with conjugation-break spacers are promising candidates for further study in flexible electronics.

Converging the Hole Mobility of Poly(2-N-carbazoylethyl acrylate) with Conjugated Polymers by Tuning Isotacticity.

Nonconjugated electroactive polymers (also known as pendant or side-chain electroactive polymers) promise several potential advantages relative to conjugated polymers including enhanced mechanical durability, greater stability and synthesis via living polymerization techniques. However, most previous examples suffer from low charge carrier mobility. Here, using poly(2-N-carbazoylethyl acrylate) (PCzEA) as a model polymer, we investigate the ability of side-chain tacticity to influence hole mobility. Specifically, we investigated polymers with dyad isotacticity (m) ranging from ∼45 to ∼95% synthesized by several methods including free radical polymerization and anionic polymerization. We found that the hole mobility (µh) measured via the space charge limited current (SCLC) technique increased proportionally to the increasing isotacticity from 2.11 × 10-6 cm2 V-1 s-1 (m = 45.5%) to 4.68 × 10-5 cm2 V-1 s-1 (m = 94.7%) in unannealed samples and that mobilities could be boosted as high as 2.74 × 10-4 cm2 V-1 s-1 (m = 94.7%) with thermal annealing, which rivaled the well-known conjugated polymer poly(3-hexylthiophene) (P3HT) (µh = 5.8 × 10-4 cm2 V-1 s-1). As such, we report here clear experimental evidence that control of side chain tacticity can enhance charge carrier mobility in nonconjugated pendant electroactive polymers, converging with mobilities typically only observed in conjugated polymers.