Atomic Layer Deposition of Emerging 2D Semiconductors,
HfS2 and ZrS2, for Optoelectronics
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Posted on 2019-08-12 - 12:40
Semiconducting two-dimensional
(2D) materials are studied intensively
because of their promising performance in diverse applications from
electronics to energy storage and catalysis. Recently, HfS2 and ZrS2 have emerged as potential rivals for the commonly
studied 2D semiconductors such as MoS2 and WSe2, but their use is hindered by the difficulty of producing continuous
films. Herein, we report the first atomic layer deposition (ALD) processes
for HfS2 and ZrS2 using HfCl4 and
ZrCl4 with H2S as the precursors. We demonstrate
the deposition of uniform and continuous films on a range of substrates
with accurately controlled thicknesses ranging from a few monolayers
to tens of nanometers. The use of semiconductor industry-compatible
precursors and temperatures (approximately 400 °C) enables facile
upscaling of the process. The deposited HfS2 and ZrS2 films are crystalline, smooth, and stoichiometric with oxygen
as the main impurity. As an important step toward applications of
HfS2 and ZrS2, we show that their sensitivity
toward oxidation can be overcome by minimizing the impurities in the
reactor and by depositing a protective AlxSiyOz layer
on the top without a vacuum break. Finally, we demonstrate HfS2 and ZrS2 photodetectors exhibiting good performance
and stable operation in ambient conditions. Photoresponsivity comparable
to thin films or even single flakes of HfS2 or ZrS2 deposited at much higher temperatures is achieved, although
the response speed seems to be limited by photogating, as is common
for 2D photodetectors. We expect the first ALD processes for HfS2 and ZrS2 to enable further exploration of these
materials for various semiconductor applications.
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Mattinen, Miika; Popov, Georgi; Vehkamäki, Marko; King, Peter J.; Mizohata, Kenichiro; Jalkanen, Pasi; et al. (2019). Atomic Layer Deposition of Emerging 2D Semiconductors,
HfS2 and ZrS2, for Optoelectronics. ACS Publications. Collection. https://doi.org/10.1021/acs.chemmater.9b01688