Adopting Back Reduction Current as an Additional Output Signal for Achieving Photoelectrochemical Differentiated Detection.

Photoelectrochemical (PEC) sensors are usually based on a single output signal, that is, the photocurrent change caused by the (photoelectro)chemical reaction between target analytes and photoelectrodes. However, the photocurrent may be influenced by redox species other than the target analyte; therefore, modifying the surface of photoelectrodes with probes that selectively bind to the analyte is essential. Moreover, even though various surface modification methods have been developed, distinguishing molecularly similar chemicals using PEC sensing systems remains a significant challenge. To address these selectivity issues, we proposed a photoanode-based PEC sensor that utilizes a cathodic transient current as a second output signal in addition to the photocurrent, which arises from the back reduction of photo-oxidized species. Factors influencing the back reduction were investigated by observing the transient photocurrent of hematite photoanodes in the presence of model redox probes. The chemical environment around the electrode-electrolyte interface was manipulated by altering the electrolyte composition or modifying the electrode surface. The favorable interaction between the electrode surface and redox species led to an increase in the extent of back reduction and the cathodic transient current. In addition, the extent of back reduction also depends on the chemical identity of the redox species, such as the kinetics of subsequent chemical reactions. Therefore, the synergistic combination of the photocurrent and the cathodic transient current enabled the differentiated detection of various catecholamine neurotransmitters with a single pristine photoelectrode, which has never been achieved using traditional PEC methods. Revisiting the transient photocurrent can complement conventional PEC applications and offers possibilities for more effective semiconductor-based applications.

A photoelectrocatalytic system as a reaction platform for selective radical-radical coupling.

The selection of electrode material is a critical factor that determines the selectivity of electrochemical organic reactions. However, the fundamental principles governing this relationship are still largely unexplored. Herein, we demonstrate a photoelectrocatalytic (PEC) system as a promising reaction platform for the selective radical-radical coupling reaction owing to the inherent charge-transfer properties of photoelectrocatalysis. As a model reaction, the radical trifluoromethylation of arenes is shown on hematite photoanodes without employing molecular catalysts. The PEC platform exhibited superior mono- to bis-trifluoromethylated product selectivity compared to conventional electrochemical methods utilizing conducting anodes. Electrochemical and density functional theory (DFT) computational studies revealed that controlling the kinetics of anodic oxidation of aromatic substrates is essential for increasing reaction selectivity. Only the PEC configuration could generate sufficiently high-energy charge carriers with controlled kinetics due to the generation of photovoltage and charge-carrier recombination, which are characteristic features of semiconductor photoelectrodes. This study opens a novel approach towards selective electrochemical organic reactions through understanding the intrinsic physicochemical properties of semiconducting materials.

Retention characteristics of Schottky barrier tunneling transistor-nano floating gate memory with various side walls.

At present, the nano floating gate memory (NFGM) device has shown a great promise as a ultra-dense, high-endurance memory device for low-power applications. As the size of the NFGM reduced, the short channel effect became one of the critical issues in the base Field Effect Transistor (FET). Schottky barrier tunneling transistor (SBTT) can improve the controllability of the short channel effect. In this work, we studied nano floating gate memory based on the SBTT. Erbium silicide was employed instead of the conventional heavily doped S/D. The NFGM device based on the SBTT used Si nanocrystals as charge storages. The subthreshold slope and the threshold voltage of the SBTT-NFGM were 90 mV/dec. and 0.2 V, respectively. The memory window appeared about 4 V after the applied write/erase bias at +/- 11 V for 500 ms. The write/erase speeds of the memory device were 50 ms and 200 ms at +/- 13 V, respectively. We also analyzed the retention characteristics of the Schottky barrier tunneling transistor nonvolatile floating gate memory according to the various side walls.