Search

Non-equilibrium fractal growth of MoS2 was induced by establishing an extremely Mo rich chemical vapor deposition (CVD) environment using a rapid heating rate in a confined reaction space. In addition, a detailed shape evolution mechanism was suggested based on the results of thermodynamics and kinetics studies. The extremely Mo rich CVD condition allowed various MoS2 flakes to be synthesized with triangular, star-like, and dendrite-like shapes in series, owing to the thermodynamic preference to increase the number of growth directions. Moreover, numerous small triangular crystals led to the formation of MoS2 flakes with jagged edges, probably as a result of the aggressive nucleation triggered by a fast and abundant supply of MoO3−x vapors. Lastly, using the MoS2 flakes with various fractal shapes, a systematic improvement of the hydrogen evolution reaction performance was demonstrated in accordance with the increase in the surrounding edge length. [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]