Epitaxial Growth and Electronic Properties of QuasiFreeStanding Rhombohedral WSe2 Bilayers on Cubic W110

Abstract: Rhombohedral-stacked transition metal dichalcogenides (TMDs) break inversion symmetry between adjacent layers, giving rise to an intrinsic out-of-plane ferroelectric polarization.Controlling the formation of this stacking polytype is therefore essential for harnessing ferroelectric effects in two-dimensional materials. In this work, we demonstrate the epitaxial growth of rhombohedral bilayer tungsten diselenide (3R-WSe2) on a cubic W(110) single crystal by molecular beam epitaxy. We show that selenium passivation of the substrate is key to enable a quasi van der Waals epitaxy effectively suppressing strong interfacial bonding and promoting the growth of quasi free standing bilayer films. The 3R stacking order is confirmed through a combination of Raman spectroscopy and high-resolution angle-resolved photoemission spectroscopy (ARPES), supported by density functional theory (DFT) calculations. ARPES and DFT reveal an indirect-gap electronic structure with the valence-band maximum at the Gamma point, as well as a pronounced spin orbit driven splitting of 520 +- 20 meV at the K point. Analysis of the measured dispersions yields hole effective masses of 0.46 +- 0.04 me and 0.75 +- 0.06 me for the upper and lower valence bands at K point, respectively. These results establish a robust route for synthesizing quasi free standing 3R-WSe2 and provide a platform for exploring the electronic, optical, and ferroelectric functionalities that emerge from inversion symmetry breaking in layered TMDs. Our findings further highlight the potential of cubic substrates for deterministic fabrication of rhombohedral TMD heterostructures and ferroelectric devices at the nanoscale.