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Nanostructured electrodes and their flexible integrated systems have great potential for many applications, including electrochemical energy storage, electrocatalysis and solid-state memory devices, given their ability to improve faradaic reaction sites by large surface area. Although many processing techniques have been employed to fabricate nanostructured electrodes onto flexible substrates, these present limitations in terms of achieving flexible electrodes with high mechanical stability. In this study, the adhesion, mechanical properties and flexibility of TiN nanotube arrays on a Pt substrate were improved using a Ti interlayer. Highly ordered and well-aligned TiN nanotube arrays were fabricated on a Pt substrate using a template-assisted method with an anodic aluminum oxide (AAO) template and atomic layer deposition (ALD) system. We show that with the use of a Ti interlayer between the TiN nanotube arrays and Pt substrate, the TiN nanotube arrays could perfectly attach to the Pt substrate without delamination and faceted phenomena. Furthermore, the I-V curve measurements confirmed that the electric contact between the TiN nanotube arrays and substrate for use as an electrode was excellent, and its flexibility was also good for use in flexible electronic devices. Future efforts will be directed toward the fabrication of embedded electrodes in flexible plastic substrates by employing the concepts demonstrated in this study. [ABSTRACT FROM AUTHOR]

In the photoelectrochemical (PEC) water splitting (WS) reactions, a photon is absorbed by a semiconductor, generating electron-hole pairs which are transferred across the semiconductor/electrolyte interface to reduce or oxidize water into oxygen or hydrogen. Catalytic junctions are commonly combined with semiconductor absorbers, providing electrochemically active sites for charge transfer across the interface and increasing the surface band bending to improve the PEC performance. In this review, we focus on transition metal (di)chalcogenide [TM(D)C] catalysts in conjunction with silicon photoelectrode as Earth-abundant materials systems. Surprisingly, there is a limited number of reports in Si/TM(D)C for PEC WS in the literature. We provide almost a complete survey on both layered TMDC and non-layered transition metal dichalcogenides (TMC) co-catalysts on Si photoelectrodes, mainly photocathodes. The mechanisms of the photovoltaic power conversion of silicon devices are summarized with emphasis on the exact role of catalysts. Diverse approaches to the improved PEC performance and the proposed synergetic functions of catalysts on the underlying Si are reviewed. Atomic layer deposition of TM(D)C materials as a new methodology for directly growing them and its implication for low-temperature growth on defect chemistry are featured. The multi-phase TM(D)C overlayers on Si and the operation principles are highlighted. Finally, challenges and directions regarding future research for achieving the theoretical PEC performance of Si-based photoelectrodes are provided. [ABSTRACT FROM AUTHOR]

We describe the direct formation of mixed-phase (1T and 2H) MoS2 layers on Si as a photocathode via atomic layer deposition (ALD) for application in the photoelectrochemical (PEC) reduction of water to hydrogen. Without typical series-metal interfaces between Si and MoS2, our p-Si/SiOx/MoS2 photocathode showed efficient and stable operation in hydrogen evolution reactions (HERs). The resulting performance could be explained by spatially genuine device architectures in three dimensions (i.e., laterally homo and vertically heterojunction structures). The ALD-grown MoS2 overlayer with the mixed-phase 1T and 2H homojunction passivates light absorber and surface states and functions as a monolithic structure for effective charge transport within MoS2. It is also beneficial in the operation of p-i-n heterojunctions with inhomogeneous barrier heights due to the presence of mixed-phase cocatalysts. The effective barrier heights reached up to 0.8 eV with optimized MoS2 thicknesses, leading to a 670 mV photovoltage enhancement without employing buried Si p-n junctions. The fast-transient behaviors via light illumination show that the mixed-phase layered chalcogenides can serve as efficient cocatalysts by depinning the Fermi levels at the interfaces. A long-term operation of ~70 h was also demonstrated in a 0.5 M H2SO4 solution. [ABSTRACT FROM AUTHOR]