Self-organized twist-heterostructures via aligned van der Waals epitaxy and solid-state transformations

Vertical van der Waals (vdW) heterostructures of 2D crystals with defined interlayer twist are of interest for band-structure engineering via twist moiré superlattice potentials. To date, twist-heterostructures have been realized by micromechanical stacking. Direct synthesis is hindered by the tendency toward equilibrium stacking without interlayer twist. Here, we demonstrate that growing a 2D crystal with fixed azimuthal alignment to the substrate followed by transformation of this intermediate enables a potentially scalable synthesis of twisted heterostructures. Microscopy during growth of ultrathin orthorhombic SnS on trigonal SnS₂ shows that vdW epitaxy yields azimuthal order even for non-isotypic 2D crystals. Excess sulfur drives a spontaneous transformation of the few-layer SnS to SnS₂, whose orientation - rotated 30° against the underlying SnS₂ crystal - is defined by the SnS intermediate rather than the substrate. Preferential nucleation of additional SnS on such twisted domains repeats the process, promising the realization of complex twisted stacks by bottom-up synthesis.