Two-dimensional (2D) transition metal dichalcogenides are potential low dissipative semiconductor materials for nanoelectronic devices. Such applications require the deposition of these materials in their crystalline form and with controlled number of monolayers on large area substrates, preferably using growth temperatures compatible with temperature sensitive structures. This paper presents a low temperature Plasma Enhanced Atomic Layer Deposition (PEALD) process for 2D WS2 based on a ternary reaction cycle consisting of consecutive WF6, H2 plasma and H2S reactions. Strongly textured nanocrystalline WS2 is grown at 300 °C. The composition and crystallinity of these layers depends on the PEALD process conditions, as understood by a model for the redox chemistry of this process. The H2 plasma is essential for the deposition of WS2 as it enables the reduction of-W 6+ Fx surface species. Nevertheless, the impact of sub-surface reduction reactions needs to be minimized to obtain WS2 with well-controlled composition (S/W ratio of two).

When two-dimensional (2D) group-VI transition metal dichalcogenides such as tungsten disulfide (WS2) are grown by atomic layer deposition (ALD) for atomic growth control at low deposition temperatures (< 450 °C), they often suffer from a nanocrystalline grain structure limiting the carrier mobility. The crystallinity and monolayer thickness control during ALD of 2D materials is determined by the nucleation mechanism, which is currently not well understood. Here, we propose a qualitative model for the WS2 nucleation behavior on dielectric surfaces during plasma-enhanced (PE-) ALD using WF6, H2 plasma and H2S based on analyses of the morphology of the WS2 crystals. The WS2 crystal grain size increases from ~20 nm to 200 nm by lowering the nucleation density. This is achieved by lowering the precursor adsorption rate on the starting surface using an inherently less reactive starting surface, by decreasing the H2 plasma reactivity, and by enhancing the mobility of the adsorbed species at higher 2 deposition temperature. Since SiO2 is less reactive than Al2O3, and diffusion and crystal ripening is enhanced at higher deposition temperature, WS2 nucleates in an anisotropic island-like growth mode with preferential lateral growth from the WS2 crystal edges. This work emphasizes that increasing the crystal grain size while controlling the basal plane orientation is possible during ALD at low deposition temperatures, based on insight in the nucleation behavior, which is key to advance the field of ALD of 2D materials. Moreover, this work demonstrates the conformal deposition on 3D structures, with WS2 retaining the basal plane orientation along topographic structures.

Revealing defects and inhomogeneities of physical and chemical properties beneath a surface or an interface with in-depth nanometric resolution plays a pivotal role for a high degree of reliability in nanomanufacturing processes and in materials science more generally. (1, 2) Nanoscale noncontact depth profiling of mechanical and optical properties of transparent sub-micrometric low-k material film exhibiting inhomogeneities is here achieved by picosecond acoustics interferometry. On the basis of the optical detection through the time-resolved Brillouin scattering of the propagation of a picosecond acoustic pulse, depth profiles of acoustical velocity and optical refractive index are measured simultaneously with spatial resolution of tens of nanometers. Furthermore, measuring the magnitude of this Brillouin signal provides an original method for depth profiling of photoelastic moduli. This development of a new opto-acoustical nanometrology paves the way for in-depth inspection and for subsurface nanoscale imaging of inorganic- and organic-based materials.

We demonstrate the impact of reducing agents for Chemical Vapor Deposition (CVD) and Atomic Layer Deposition (ALD) of WS2 from WF6 and H2S precursors. Nanocrystalline WS2 layers with a two-dimensional structure can be obtained at low deposition temperatures (300-450 °C) without using a template or anneal.

We achieve depth-profiling of the elasticity of a thin transparent film of a nanoporous low-k material using picosecond acoustic interferometry. The variation in the material properties with depth is extracted from time-resolved femtosecond optical reflectivity measurements. More than 40% of the variation in the longitudinal elastic modulus between the front and the back surfaces of an 800 nm thick nanoporous layer is mapped with a 40 nm spatial resolution. We attribute this variation to the spatially inhomogeneous UV curing of the film during fabrication.

We report a new curing procedure of a plasma enhanced chemical vapor deposited SiCOH glasses for interlayer dielectric applications in microelectronic. It is demonstrated that SiOCH glasses with improved mechanical properties and ultralow dielectric constant can be obtained by controlled decomposition of the porogen molecules used to create nanoscale pores, prior to the UV-hardening step. The Young's modulus ͑YM͒ of conventional SiOCH-based glasses with 32% open porosity hardened with porogen is 4.6 GPa, this value is shown to increase up to 5.2 GPa with even 46% open porosity, when the glasses are hardened after porogen removal. This increase in porosity is accompanied by significant reduction in the dielectric constant from 2.3 to 1.8. The increased YM is related to an enhanced molecular-bridging mechanism when film is hardened without porogen that was explained on the base of percolation of rigidity theory and random network concepts.

The structure, crystallinity and properties of as-deposited two-dimensional (2D) transition metal dichalcogenides are determined by nucleation mechanisms in the deposition process. 2D materials grown by atomic layer deposition (ALD) in absence of a template, are polycrystalline or amorphous. Little is known about their nucleation mechanisms.Therefore, we investigate the nucleation behavior of WS2 during plasma enhanced ALD from WF6, H2 plasma and H2S at 300 °C on amorphous ALD Al2O3 starting surface and on monocrystalline, bulk sapphire. Preferential interaction of the precursors with the Al2O3 starting surface promotes fast closure of the WS2 layer. The WS2 layers are fully continuous at WS2 content corresponding to only 1.2 WS2 monolayers. On amorphous Al2O3, (0002) textured and polycrystalline WS2 layers form with grain size of 5 nm to 20 nm due to high nucleation density (~10 14 nuclei/cm 2 ). The WS2 growth mode changes from 2D (layer-by-layer) growth on the initial Al2O3 surface to threedimensional (Volmer-Weber) growth after WS2 layer closure. Further growth proceeds from both WS2 basal planes in register with the underlying WS2 grain, and from or over grain boundaries of the underlying WS2 layer with different in-plane orientation. In contrast, on monocrystalline sapphire, WS2 crystal grains can locally align along a preferred in-plane orientation. Epitaxial seeding occurs locally albeit a large portion of crystals remain randomly oriented, presumably due to the low deposition temperature.The WS2 sheet resistance is 168 MΩµm suggesting that charge transport in the WS2 layers is limited by grain boundaries.3

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