A nonintuitive observation of monovalent anion-induced ion current rectification inversion at polyimidazolium brush (PimB)-modified nanopipettes is presented. The rectification inversion degree is strongly dependent on the concentration and species of monovalent anions. For chaotropic anions (for example, ClO ), the rectification inversion is easily observed at a low concentration (5 mm), while there is no rectification inversion observed for kosmotropic anions (Cl ) even at a high concentration (1 m). Moreover, at the specific concentration (for example, 10 mm), the variation of rectification ratio on the type of anions is ranged by Hofmeister series (Cl ≥NO >BF >ClO >PF >Tf N ). Estimation of the electrokinetic charge density (σ ) demonstrates that rectification inversion originates from the charge inversion owing to the over-adsorption of chaotropic monovalent anion. To qualitatively understand this phenomenon, a concentration-dependent adsorption mechanism is proposed.
The exciton effect in two-dimensional (2D) transition metal dichalcogenides (TMDs) plays a dominating role in describing the optical and optoelectronic properties. However, the interplay between the excitons and free carriers has not yet been understood upon photoexcitation in 2D TMDs. Here, we first present a study of the dynamical interplay of excitons and unbound electron–hole pairs using time-resolved terahertz (THz) spectroscopy (TRTS) in a few-layer WS2 laminate. Our experimental results demonstrate that the Auger recombination is observed in the relaxation process of the mobile charge carriers rather than that of excitons upon photoexcitation. The transient complex THz photoconductivity spectroscopy of WS2 is well described by the Drude–Lorentz model of free carriers modulated by the exciton polarization field. Our results provide a comprehensive understanding of nonequilibrium carrier kinetics (both excitons and free carriers) in WS2 laminate, and should be applicable to other 2D systems.
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