Process-Induced Modulation of Domain Orientations during WS₂ Epitaxy by Metal–Organic Chemical Vapor Deposition on Sapphire

Single monolayers (MLs) of transition metal dichalcogenides (TMDs) like molybdenum disulfide (MoS 2 ) and tungsten disulfide (WS 2 ) are promising semiconductors for next-generation logic devices, photodetectors, and light-emitting diodes. Applications require industry-relevant deposition techniques that form large monocrystalline TMD domains with low defect density. In this work, we study the growth of WS 2 by metal–organic chemical vapor deposition on c-plane sapphire substrates at different temperatures. We investigate the growth phenomena during the initial stages before ML formation and apply the obtained knowledge to design an optimized deposition process. High deposition temperatures (1000 °C) yield a high degree of in-plane crystal orientation but give rise to codeposition of WS 2 and tungsten, presumably due to the fast desorption of sulfur species. The preferred WS 2 domain orientation can be modulated by the process: WS 2 deposition at 850 °C followed by annealing of WS 2 crystals in H 2 S at 1000 °C results mainly in step-edge guided domains, whereas crystal lattice-guided domains are predominant during subsequent deposition at 1000 °C. The optimized three-step process results in a preferential formation of 0 and 60° oriented domains in the closed WS 2 ML, with less than 2% of crystals with different orientations. These presented insights can be used to modulate and optimize the WS 2 structure further toward monocrystalline monolayers.