Direct atomic layer deposition of ultra-thin $Al_{2}O_{3}$ and $HfO_{2}$ films on gold-supported monolayer $MoS_{2}$

In this paper, the atomic layer deposition (ALD) of ultra-thin films (<4 nm) of $Al_{2}O_{3}$ and $HfO_{2}$ on Au-supported monolayer (1L) $MoS_{2}$ is investigated, providing an insight on the nucleation mechanisms in the early stages of the ALD process. A preliminary multiscale characterization of large area 1L-$MoS_{2}$ exfoliated on sputter-grown Au/Ni films revealed an almost conformal $MoS_{2}$ membrane with the Au topography and the occurrence of strain variations at the nanoscale. Ab-initio DFT calculations of $MoS_{2}$/Au(111) interface showed a significant influence of the Au substrate on the $MoS_{2}$ energy band structure, whereas small differences were accounted for the adsorption of the $H_{2}O$, TMA and TDMAHf precursors. This suggests a crucial role of nanoscale morphological effects, such as local curvature and strain of the $MoS_{2}$ membrane, in the enhanced physisorption of the precursors. Therefore, the nucleation and growth of $Al_{2}O_{3}$ and $HfO_{2}$ films onto 1L-$MoS_{2}$/Au was investigated, by monitoring the surface coverage as a function of the number (N) of ALD cycles, with N from 10 to 120. At low N values, a slower growth rate of the initially formed nuclei was observed for $HfO_{2}$, probably due to the bulky nature of the TDMAHf precursor as compared to TMA. On the other hand, the formation of continuous films was obtained in both cases for N>80 ALD cycles, corresponding to 3.6 nm $Al_{2}O_{3}$ and 3.1 nm $HfO_{2}$. Current mapping by C-AFM showed, for the same applied bias, a uniform insulating behavior of $Al_{2}O_{3}$ and the occurrence of few localized breakdown spots in the case of $HfO_{2}$, associated to less compact films regions. Finally, an increase of the 1L-$MoS_{2}$ tensile strain was observed by Raman mapping after encapsulation with both high-k films, accompanied by a reduction in the PL intensity.
Comment: 26 pages, 9 figures