In Situ Growth of GeS Nanowires with Sulfur-Rich Shell for Featured Negative Photoconductivity.

The negative photoconductivity (NPC) effect originating from the surface shell layer has been considered as an efficient approach to improve the performance of optoelectronic nanodevices. However, a scientific design and precise growth of NPC-effect-caused shell during nanowire (NW) growth process for achieving high-performance photodetectors are still lacking. In this work, GeS NWs with a controlled sulfur-rich shell, diameter, and length are successfully prepared by a simple chemical vapor deposition method. As checked by transmission electron microscopy, the thickness of the sulfur-rich shell ranges from 10.5 ± 1.5 to 13.4 ± 2.5 nm by controlling the NW growth time. The composition of the sulfur-rich shell is studied by X-ray photoelectron spectroscopy, showing the decrease of S in the GeSx shell from the surface to core. When configured into the well-known phototransistor, a featured NPC effect is observed, benefiting the high-performance photodetector with high responsivity of 105 A·W-1 and detectivity of 1012 Jones for λ = 405 nm with ultralow intensity of 0.04 mW·cm-2. However, the thicker-shell NW phototransistor shows an unstable photodetector behavior with smaller negative photocurrent because of more hole-trapping states in the thicker shell. All results suggest a careful design and controlled growth of an NPC-effect-caused shell for future optoelectronic applications.