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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

The integration of two-dimensional $MoS_{2}$ with $GaN$ recently attracted significant interest for future electronic/optoelectronic applications. However, the reported studies have been mainly carried out using heteroepitaxial $GaN$ templates on sapphire substrates, whereas the growth of $MoS_{2}$ on low-dislocation-density bulk GaN can be strategic for the realization of truly vertical devices. In this paper, we report the growth of ultrathin $MoS_{2}$ films, mostly composed by single-layers ($1L$), onto homoepitaxial $n-GaN$ on $n^{+}$ bulk substrates by sulfurization of a pre-deposited $MoO_{x}$ film. Highly uniform and conformal coverage of the $GaN$ surface was demonstrated by atomic force microscopy, while very low tensile strain (0.05%) and a significant $p^{+}$-type doping ($4.5 \times 10^{12} cm^{-2}$) of $1L-MoS_{2}$ was evaluated by Raman mapping. Atomic resolution structural and compositional analyses by aberration-corrected electron microscopy revealed a nearly-ideal van der Waals interface between $MoS_{2}$ and the $Ga$-terminated $GaN$ crystal, where only the topmost $Ga$ atoms are affected by oxidation. Furthermore, the relevant lattice parameters of the $MoS_{2}/GaN$ heterojunction, such as the van der Waals gap, were measured with high precision. Finally, the vertical current injection across this 2D/3D heterojunction has been investigated by nanoscale current-voltage analyses performed by conductive atomic force microscopy, showing a rectifying behavior with an average turn-on voltage $V_{on}=1.7 V$ under forward bias, consistent with the expected band alignment at the interface between $p^{+}$ doped $1L-MoS_{2}$ and $n-GaN$., Comment: 21 pages, 6 figures

The gold-assisted exfoliation is a very effective method to produce large-area ($cm^2$-scale) membranes of molybdenum disulfide ($MoS_2$) for electronics. However, the strong $MoS_2/Au$ interaction, beneficial for the exfoliation process, has a strong impact on the vibrational and light emission properties of $MoS_2$. Here, we report an atomic force microscopy (AFM), micro-Raman ($\mu-R$) and micro-Photoluminescence ($\mu-PL$) investigation of $MoS_2$ with variable thickness exfoliated on Au and subsequently transferred on an $Al_2O_3/Si$ substrate. The $E_{2g}$ - $A_{1g}$ vibrational modes separation $\Delta\mu$ (typically used to estimate $MoS_2$ thickness) exhibits an anomalous large value ($\Delta\mu=21.2 cm^{-1}$) for monolayer (1L) $MoS_2$ on Au as compared to the typical one ($\Delta\mu=18.5 cm^{-1}$) measured on 1L $MoS_2$ on $Al_2O_3/Si$. Such substrate-related differences, explained in terms of tensile strain and p-type doping arising from the $MoS_2/Au$ interaction, were found to gradually decrease while increasing the number of $MoS_2$ layers. Furthermore, $\mu-PL$ spectra for 1L $MoS_2$ on Au exhibit a strong quenching and an overall red-shift of the main emission peak at 1.79 eV, compared to the 1.84 eV peak for 1L $MoS_2$ on $Al_2O_3$. After PL spectra deconvolution, such red shift was explained in terms of a higher trion/exciton intensity ratio, probably due to the higher polarizability of the metal substrate, as well as to the smaller equilibrium distance at $MoS_2/Au$ interface., Comment: 14 pages, 4 figures

Gold-assisted mechanical exfoliation currently represents a promising method to separate ultra-large (cm-scale) transition metal dichalcogenides (TMDs) monolayers (1L) with excellent electronic and optical properties from the parent van der Waals (vdW) crystals. The strong interaction between $Au$ and chalcogen atoms is the key to achieve this nearly perfect 1L exfoliation yield. On the other hand, it may affect significantly the doping and strain of 1L TMDs in contact with Au. In this paper, we systematically investigated the morphology, strain, doping, and electrical properties of large area 1L $MoS_{2}$ exfoliated on ultra-flat $Au$ films ($0.16-0.21 nm$ roughness) and finally transferred to an insulating $Al_{2}O_{3}$ substrate. Raman mapping and correlative analysis of the $E'$ and $A1'$ peaks positions revealed a moderate tensile strain ($0.2\%$) and p-type doping ($n=-0.25 \times 10^{13} cm^{-2}$) of 1L $MoS_{2}$ in contact with $Au$. Nanoscale resolution current mapping and current-voltage (I-V) measurements by conductive atomic force microscopy (C-AFM) showed direct tunnelling across the 1L $MoS_{2}$ on $Au$, with a broad distribution of tunnelling barrier values (from 0.7 to 1.7 eV) consistent with the p-type doping of $MoS_{2}$. After the final transfer of $1L-MoS_{2}$ on $Al_{2}O_{3}/Si$, the strain was converted to compressive ($-0.25\%$). Furthermore, an n-type doping ($n=0.5 \times 10^{13} cm^{-2}$) was deduced by Raman mapping and confirmed by electrical measurements of an $Al_{2}O_{3}/Si$ back-gated 1L $MoS_{2}$ transistor. These results provide a deeper understanding of the $Au$-assisted exfoliation mechanisms and can contribute to its widespread applications for the realization of novel devices and artificial vdW heterostructures

The integration of graphene (Gr) with nitride semiconductors is highly interesting for applications in high-power/high-frequency electronics and optoelectronics. In this work, we demonstrated the direct growth of Gr on Al0.5Ga0.5N/sapphire templates by propane (C3H8) chemical vapor deposition (CVD) at temperature of 1350{\deg}C. After optimization of the C3H8 flow rate, a uniform and conformal Gr coverage was achieved, which proved beneficial to prevent degradation of AlGaN morphology. X-ray photoemission spectroscopy (XPS) revealed Ga loss and partial oxidation of Al in the near-surface AlGaN region. Such chemical modification of a 2 nm thick AlGaN surface region was confirmed by cross-sectional scanning transmission electron microscopy (STEM) combined with electron energy loss spectroscopy (EELS), which also showed the presence of a bilayer of Gr with partial sp2/sp3 hybridization. Raman spectra indicated that the deposited Gr is nanocrystalline (with domain size 7 nm) and compressively strained. A Gr sheet resistance of 15.8 kOhm/sq was evaluated by four-point-probe measurements, consistently with the nanocrystalline nature of these films. Furthermore, nanoscale resolution current mapping by conductive atomic force microscopy (C-AFM) indicated local variations of the Gr carrier density at a mesoscopic scale, which can be ascribed to changes in the charge transfer from the substrate due to local oxidation of AlGaN or to the presence of Gr wrinkles., Comment: 20 pages, 8 figures

In this work, the nucleation and growth mechanism of aluminum oxide (Al2O3) in the early stages of the direct atomic layer deposition (ALD) on monolayer epitaxial graphene (EG) on silicon carbide (4H-SiC) has been investigated by atomic force microscopy (AFM) and Raman spectroscopy. Contrary to what is typically observed for other types of graphene, a large and uniform density of nucleation sites was observed in the case of EG and ascribed to the presence of the buffer layer at EG/SiC interface. The deposition process was characterized by Al2O3 island growth in the very early stages, followed by the formation of a continuous Al2O3 film (2.4 nm thick) after only 40 ALD cycles due to the islands coalescence, and subsequent layer-by-layer growth. Raman spectroscopy analyses showed low impact of the ALD process on the defects density and doping of EG. The EG strain was also almost unaffected by the deposition in the regime of island growth and coalescence, whereas a significant increase was observed after the formation of a compact Al2O3 film. The obtained results can have important implications for device applications of epitaxial graphene requiring the integration of ultra-thin high-k insulators., Comment: 19 pages, 6 figures