Unconventional van der Waals heterostructures beyond stacking

Two-dimensional crystals provide exceptional opportunities for integrating dissimilar materials and forming interfaces where distinct properties and phenomena emerge. To date, research has focused on two basic heterostructure types: vertical van der Waals stacks and laterally joined monolayer crystals with in-plane line interfaces. Much more diverse architectures and interface configurations can be realized in the few-layer and multilayer regime, and if mechanical stacking and single-layer growth are replaced by processes taking advantage of self-organization, conversions between polymorphs, phase separation, strain effects, and shaping into the third dimension. Here, we highlight such opportunities for engineering heterostructures, focusing on group IV chalcogenides, a class of layered semiconductors that lend themselves exceptionally well for exploring novel van der Waals architectures, as well as advanced methods including in situ microscopy during growth and nanometer-scale probes of light-matter interactions. The chosen examples point to fruitful future directions and inspire innovative developments to create unconventional van der Waals heterostructures beyond stacking.