Kinetics-controlled epitaxial growth and bipolar transport properties of semimetal Bi4Se3

(Bi2)m(Bi2Se3)n (m, n: integers) compounds with an infinitely adaptive superlattice structure exhibit several fascinating topological phases. Here, we study kinetics-controlled epitaxial growth of Bi4Se3 on mica by co-evaporating Bi and Se using molecular beam epitaxy technique, as well as the transport properties of Bi4Se3. By precisely controlling the beam fluxes of Bi and Se and growth temperature, we can tune the growth modes from van der Waals' condensation to spiral growth, thus achieving single-crystalline Bi4Se3 of dislocation-free microplate or mounded thin-film morphologies. This reflects a transition from near-thermodynamic-equilibrium to non-thermodynamic-equilibrium growth processes of single-crystalline Bi4Se3. Thin-film Bi2+xSe3 (1.7 < x < 2) solid-solution phases consisting of randomly stacked Bi2 and Bi2Se3 units are also prepared as comparative samples. Hall and thermopower properties suggest that the as-grown Bi4Se3 films exhibit semimetallic bipolar conduction behaviors while the Bi2+xSe3 films present typical semiconducting transport characteristics with a n-type polarity. Due to semiconductor band structures, the Bi2+xSe3 films show superior thermopower to that of semimetal Bi4Se3.