Metal−organic chemical vapor deposition (MOCVD) is one of the main methodologies used for thin-film fabrication in the semiconductor industry today and is considered one of the most promising routes to achieve large-scale and high-quality 2D transition metal dichalcogenides (TMDCs). However, if special measures are not taken, MOCVD suffers from some serious drawbacks, such as small domain size and carbon contamination, resulting in poor optical and crystal quality, which may inhibit its implementation for the large-scale fabrication of atomic-thin semiconductors. Here we present a growthetch MOCVD (GE-MOCVD) methodology, in which a small amount of water vapor is introduced during the growth, while the precursors are delivered in pulses. The evolution of the growth as a function of the amount of water vapor, the number and type of cycles, and the gas composition is described. We show a significant domain size increase is achieved relative to our conventional process. The improved crystal quality of WS 2 (and WSe 2 ) domains wasis demonstrated by means of Raman spectroscopy, photoluminescence (PL) spectroscopy, and HRTEM studies. Moreover, time-resolved PL studies show very long exciton lifetimes, comparable to those observed in mechanically exfoliated flakes. Thus, the GE-MOCVD approach presented here may facilitate their integration into a wide range of applications.

Conventional epitaxy plays a crucial role in current state-of-the art semiconductor technology, as it provides a path for accurate control at the atomic scale of thin films and nanostructures, to be used as the building blocks in nanoelectronics, optoelectronics, sensors, etc. Four decades ago, the terms "van der Waals" (vdW) and "quasi-vdW (Q-vdW) epitaxy" were coined to explain the oriented growth of vdW layers on 2D and 3D substrates, respectively. The major difference with conventional epitaxy is the weaker interaction between the epi-layer and the epi-substrates. Indeed, research on Q-vdW epitaxial growth of transition metal dichalcogenides (TMDCs) has been intense, with oriented growth of atomically thin semiconductors on sapphire being one of the most studied systems. Nonetheless, there are some striking and not yet understood differences in the literature regarding the orientation registry between the epi-layers and epi-substrate and the interface chemistry. Here we study the growth of WS 2 via a sequential exposure of the metal and the chalcogen precursors in a metal−organic chemical vapor deposition (MOCVD) system, introducing a metal-seeding step prior to the growth. The ability to control the delivery of the precursor made it possible to study the formation of a continuous and apparently ordered WO 3 mono-or few-layer at the surface of a c-plane sapphire. Such an interfacial layer is shown to strongly influence the subsequent quasi-vdW epitaxial growth of the atomically thin semiconductor layers on sapphire. Hence, here we elucidate an epitaxial growth mechanism and demonstrate the robustness of the metal-seeding approach for the oriented formation of other TMDC layers. This work may enable the rational design of vdW and quasi-vdW epitaxial growth on different material systems.

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