Tungsten disulfide (WS2) films were grown on c-plane sapphire in a cold-wall gas-source chemical vapor deposition system to ascertain the effect of the chalcogen precursor on the film growth and properties. Tungsten hexacarbonyl (W­(CO)6) was used as the tungsten source, and hydrogen sulfide (H2S) and diethyl sulfide (DES-(C2H5)2S) were the chalcogen sources. The film deposition was studied at different temperatures and chalcogen-to-metal ratios to understand the effect of each chalcogen precursor on the film growth rate, thickness, coverage, photoluminescence, and stoichiometry. Larger lateral growth was observed in films grown with H2S than DES. The reduced lateral growth with DES can be attributed to carbon contamination, which also quenches the photoluminescence. Thermodynamic calculations agreed well with the experimental observations, suggesting formation of WS2 with both sulfur precursors and additional formation of carbon when deposition is done using DES.

Understanding oxidation of layered chalcogenide semiconductors is important for device processing, as oxidation can be both an intentional and unintentional result of processing steps. Here, the authors investigate chemical and morphological changes in mechanically exfoliated few-layer MoS2 in oxidizing and inert environments using different microscopies (optical, scanning electron, and atomic force) and spectroscopy (Raman, x-ray photoelectron, and Auger electron) techniques. The environments studied were oxygen, oxygen and water vapor, argon, argon and water vapor, and ultraviolet-generated ozone at temperatures from 25 to 550 °C. Oxidation at low temperatures resulted in the formation of a condensed molybdenum oxide phase and sulfur trioxide gas. At sufficiently elevated temperatures, all the products of oxidation volatilize, resulting in a vapor-phase etch. The kinetics of oxidation and etching depended upon the annealing gas, temperature, time, and the number of layers of MoS2. Conditions can be selected to create isolated etch pits, smooth oxide layers, oxide islands, or flakes of reduced lateral dimensions (etching from the flakes' edges). These results can provide useful guidance for MoS2 device processing.

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Molybdenum oxide (MoO3) thin films were prepared via Radio Frequency (RF) sputtering at different ambient composition and post-deposition annealing. The effects on the structural, optical, and surface properties of the deposited films were investigated. The ambient oxygen concentration O2/(O2 + Ar) was varied from 10% to 100% at 10 mTorr. Post deposition anneals were performed in Ar at 300–500 °C. The films were analyzed using glancing incidence x-ray diffraction (GIXRD), UV/Vis/NIR spectrophotometry, and x-ray photoelectron spectroscopy (XPS). As-deposited films have amorphous structures, independent of the oxygen partial pressure. Annealing at 300 °C in air resulted in crystallization of the molybdenum oxide films to the monoclinic β-MoO3 phase. Samples annealed at 400 and 500 °C were identified as pure orthorhombic α-MoO3 phase with (020) preferred orientation. High resolution XPS studies showed the presence of Mo6+ (MoO3) and Mo5+ (Mo4O11) oxidation states at the surface of as deposited and low temperature (300 °C) annealed films, and the Mo6+ to Mo5+ did not change much with deposition oxygen partial pressure. Annealing at 400–500 °C suppressed the oxygen deficiency at the surface, resulting in films with composition close to stoichiometric phases. UV/Vis/NIR spectrophotometry revealed that all films have a high optical transmittance (>80%) in the visible range, followed by a steep drop at λ ≈ 400 nm indicating a strong absorption due to band-to-band transition. Increasing the oxygen partial pressure had no significant effect on optical transmittance of the films, and the bandgaps in the range of 2.6 eV to 2.9 eV were obtained. Annealing at 300 °C had a negligible effect on the optical properties of the MoO3 films, but samples annealed at 400 °C and 500 °C exhibited wider bandgaps within the range of 3.1–3.4 eV.