Networks of as-dispersed, polymer-wrapped (6,5) single-walled carbon nanotubes for selective Cu2+ and glyphosate sensing.

Networks of semiconducting single-walled carbon nanotubes (SWNTs) can be used as the transducing layer for sensors based on water-gated transistors. To add specific sensing capabilities, SWNTs are often functionalized with additional moieties or selective membranes are applied, thus increasing the complexity of the fabrication process. Here we demonstrate that drop-cast networks of monochiral (6,5) SWNTs, which are commonly dispersed in organic solvents with the polyfluorene-bipyridine copolymer PFO-BPy, can be employed directly and without additional functionalization or ion-selective membranes to detect Cu2+ ions over a wide range of concentrations in aqueous solutions. The observed voltage shifts of water-gated transistors with these (6,5) SWNT networks directly correlate with the cupric ion concentration. They result from induced n-doping due to the complexation of positive copper ions to the bipyridine units of the wrapping polymer. Furthermore, the competitive binding of Cu2+ to the herbicide glyphosate as well as to biologically relevant pyrophosphates can be used for the direct detection and quantification of these molecules at nano- to micromolar concentrations.

Enhancing Electrochemical Transistors Based on Polymer-Wrapped (6,5) Carbon Nanotube Networks with Ethylene Glycol Side Chains.

Organic electrochemical transistors (ECTs) are an important building block for bioelectronics. To promote the required ion transport through the active layer, state-of-the-art semiconducting polymers feature hydrophilic ethylene glycol side chains that increase the volumetric capacitance and transconductance of the devices. Here, we apply this concept to polymer-wrapped single-walled carbon nanotubes (SWCNTs) as a high-mobility semiconducting material. We replace the polyfluorene copolymer (PFO-BPy), which is used for selectively dispersing semiconducting (6,5) SWCNTs and contains octyl side chains, by an equivalent polymer with tetraethylene glycol side chains. Aerosol-jet printed networks of these SWCNTs are applied as the active layer in water-gated ECTs. These show high hole mobilities (3-15 cm2·V-1·s-1), significantly improved volumetric capacitances and larger transconductances. Thin networks of SWCNTs reach (219 ± 16) F·cm-1·V-1·s-1 as the product of mobility and volumetric capacitance. In situ photoluminescence measurements show more efficient quenching of the near-infrared fluorescence for nanotube networks with hydrophilic glycol side chains compared to those with hydrophobic alkyl side chains, thus corroborating more complete charging under bias. Overall, networks of semiconducting SWCNTs with such tailored wrapping polymers provide excellent device performance. Combined with their inherent mechanical flexibility and durability, they constitute a competitive material for bioelectronics.

Probing Mobile Charge Carriers in Semiconducting Carbon Nanotube Networks by Charge Modulation Spectroscopy.

Solution-processed networks of semiconducting, single-walled carbon nanotubes (SWCNTs) have attracted considerable attention as materials for next-generation electronic devices and circuits. However, the impact of the SWCNT network composition on charge transport on a microscopic level remains an open and complex question. Here, we use charge-modulated absorption and photoluminescence spectroscopy to probe exclusively the mobile charge carriers in monochiral (6,5) and mixed SWCNT network field-effect transistors. Ground-state bleaching and charge-induced trion absorption features as well as exciton quenching are observed depending on applied voltage and modulation frequency. Through correlation of the modulated mobile carrier density and the optical response of the nanotubes, we find that charge transport in mixed SWCNT networks depends strongly on the diameter and thus bandgap of the individual species. Mobile charges are preferentially transported by small bandgap SWCNTs especially at low gate voltages, whereas large bandgap species only start to participate at higher carrier concentrations. Our results demonstrate the excellent suitability of modulation spectroscopy to investigate charge transport in nanotube network transistors and highlight the importance of SWCNT network composition for their performance.

Effect of Crystal Grain Orientation on the Rate of Ionic Transport in Perovskite Polycrystalline Thin Films.

In this work, we examine the effect of microstructure on ion-migration-induced photoluminescence (PL) quenching in methylammonium lead iodide perovskite films. Thin films were fabricated by two methods: spin-coating, which results in randomly oriented perovskite grains, and zone-casting, which results in aligned grains. As an external bias is applied to these films, migration of ions causes a quenching of the PL signal in the vicinity of the anode. The evolution of this PL-quenched zone is less uniform in the spin-coated devices than in the zone-cast ones, suggesting that the relative orientation of the crystal grains plays a significant role in the migration of ions within polycrystalline perovskite. We simulate this effect via a simple Ising model of ionic motion across grains in the perovskite thin film. The results of this simulation align closely with the observed experimental results, further solidifying the correlation between crystal grain orientation and the rate of ionic transport.