Synthesis of Few-Layered Transition-Metal Dichalcogenides by Ion Implantation of Chalcogen and Metal Species into Sapphire.
Romain BudeIvan VerschuerenIleana FloreaJean Luc MauricePierre LegagneuxLino M C PereiraHarsh BanaRenan VillarrealRaoul BlumeAxel Knop-GerickeTravis E JonesDidier PribatPublished in: ACS omega (2023)
The growth of transition-metal dichalcogenides (TMDCs) has been performed so far using most established thin-film growth techniques (e.g., vapor phase transport, chemical vapor deposition, molecular beam epitaxy, etc.). However, because there exists no self-limiting mechanism for the growth of TMDCs, none of these techniques allows precise control of the number of TMDC layers over large substrate areas. Here, we explore the ion implantation of the parent TMDC atoms into a chemically neutral substrate for the synthesis of TMDC films. The idea is that once all of the ion-implanted species have reacted together, the synthesis reaction stops, thereby effectively stopping growth. In other words, even if there is no self-limiting mechanism, growth stops when the nutrients are exhausted. We have co-implanted Mo and S ions into c-oriented sapphire substrates using various doses corresponding to 1- to 5-layer atom counts. We find that the subsurface region of the sapphire substrates is amorphized by the ion implantation process, at least for implanted doses of 2-layer atom counts and over. For all doses, we have observed the formation of MoS 2 material inside the sapphire after postimplantation annealing between 800 and 850 °C. We report that the order of implantation (i.e., whether S or Mo is implanted first) is an important parameter. More precisely, samples for which S is implanted first tend to yield thin crystals with a large lateral extension (more than 200 nm for 5-layer doses) and mainly located at the interface between the amorphized and crystalline sapphire. When Mo is first implanted, the MoS 2 crystals still predominantly appear at the amorphous-crystalline interface (which is much rougher), but they are much thicker, suggesting a different nucleation mechanism.