Few-Layer to Multilayer Germanium(II) Sulfide: Synthesis, Structure, Stability, and Optoelectronics

Abstract

Among 2D/layered semiconductors, group IV monochalcogenides such as SnS(e) and GeS(e) have attracted attention as phosphorene/black phosphorus analogues with anisotropic structures and predicted unusual properties. In contrast to SnS, for which bottom-up synthesis has been reported, few-layer GeS has been realized primarily <i>via</i> exfoliation from bulk crystals. Here, we report the synthesis of large (up to >20 μm), faceted single crystalline GeS flakes with anisotropic properties using a vapor transport process. <i>In situ</i> electron microscopy is used to identify the thermal stability and sublimation pathways, and demonstrates that the GeS flakes are self-encapsulated in a thin, sulfur-rich amorphous GeS_<i>x</i> shell during growth. The shell provides exceptional chemical stability to the layered GeS core. In contrast to exfoliated GeS, which rapidly degrades during exposure to air, the synthesized GeS-GeS_<i>x</i> core-shell structures show no signs of chemical attack and remain unchanged in air for extended time periods. Measurements of the optoelectronic properties by photoluminescence spectroscopy show a tunable bandgap due to out-of-plane quantum confinement in flakes with thickness below 100 nm. Cathodoluminescence (CL) spectroscopy with nanoscale excitation provides evidence for interfacial charge transfer due to a type II heterojunction between the crystalline core and amorphous shell. Measurements by locally excited CL yield a minority carrier (electron) diffusion length in the <i>p</i>-type GeS core <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msup><mml:mrow><mml:mi>l</mml:mi></mml:mrow><mml:mrow><mml:mi>diff</mml:mi></mml:mrow></mml:msup></mml:mrow></mml:math> = 0.27 μm, on par with diffusion lengths in the highest-quality layered chalcogenide semiconductors.