TY - JOUR
T1 - Superior Electro-Oxidation and Corrosion Resistance of Monolayer Transition Metal Disulfides
AU - Schulman, Daniel S.
AU - May-Rawding, Dan
AU - Zhang, Fu
AU - Buzzell, Drew
AU - Alem, Nasim
AU - Das, Saptarshi
N1 - Funding Information:
The work of D.S.S. and S.D. was partially supported through Grant ECCS-1640020 from National Science Foundation (NSF) and Contract 2016-NE-2699 from Nanoelectronic Research Corporation. The work of F.Z. and N.A. was partially supported from the National Science Foundation under EFRI 2-DARE awards 1433378.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2018/1/31
Y1 - 2018/1/31
N2 - Physics of monolayer and few-layer transition metal dichalcogenides (TMDs) and chemistry of few-layer TMDs have been well studied in recent years in the context of future electronic, optoelectronic, and energy harvesting applications. However, what has escaped the attention of the scientific community is the unique chemistry of monolayer TMDs. It has been demonstrated that the basal plane of multilayer TMDs is chemically inert, whereas edge sites are chemically active. In this article, we experimentally demonstrate that the edge reactivity of the TMDs can be significantly impeded at the monolayer limit through monolayer/substrate interaction, thus making the monolayers highly resistant to electrooxidation and corrosion. In particular, we found that few-layer flakes of MoS2 and WS2 exfoliated on conductive TiN substrates are readily corroded beyond a certain positive electrode potential, while monolayer remnants are left behind unscathed. The electrooxidation resistance of monolayers was confirmed using a plethora of characterization techniques including atomic force microscope (AFM) imaging, Raman spectroscopy, photoluminescence (PL) mapping, scanning/transmission electron microscope (S/TEM) imaging, and selected area electron diffraction (SAED). It is believed that strong substrate monolayer interaction compared to the relatively weak interlayer van der Waals interaction is responsible for the superior monolayers chemical stability in highly corrosive oxidizing environments. Our findings could pave the way for the implementation of monolayer transition metal disulfides as superior anticorrosion coating which can have a significant socioeconomic impact.
AB - Physics of monolayer and few-layer transition metal dichalcogenides (TMDs) and chemistry of few-layer TMDs have been well studied in recent years in the context of future electronic, optoelectronic, and energy harvesting applications. However, what has escaped the attention of the scientific community is the unique chemistry of monolayer TMDs. It has been demonstrated that the basal plane of multilayer TMDs is chemically inert, whereas edge sites are chemically active. In this article, we experimentally demonstrate that the edge reactivity of the TMDs can be significantly impeded at the monolayer limit through monolayer/substrate interaction, thus making the monolayers highly resistant to electrooxidation and corrosion. In particular, we found that few-layer flakes of MoS2 and WS2 exfoliated on conductive TiN substrates are readily corroded beyond a certain positive electrode potential, while monolayer remnants are left behind unscathed. The electrooxidation resistance of monolayers was confirmed using a plethora of characterization techniques including atomic force microscope (AFM) imaging, Raman spectroscopy, photoluminescence (PL) mapping, scanning/transmission electron microscope (S/TEM) imaging, and selected area electron diffraction (SAED). It is believed that strong substrate monolayer interaction compared to the relatively weak interlayer van der Waals interaction is responsible for the superior monolayers chemical stability in highly corrosive oxidizing environments. Our findings could pave the way for the implementation of monolayer transition metal disulfides as superior anticorrosion coating which can have a significant socioeconomic impact.
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U2 - 10.1021/acsami.7b17660
DO - 10.1021/acsami.7b17660
M3 - Article
C2 - 29278319
AN - SCOPUS:85041434829
SN - 1944-8244
VL - 10
SP - 4285
EP - 4294
JO - ACS Applied Materials and Interfaces
JF - ACS Applied Materials and Interfaces
IS - 4
ER -