Engineering Heat Transport Across Epitaxial Lattice-Mismatched van der Waals Heterointerfaces

[Image: see text] Artificially engineered 2D materials offer unique physical properties for thermal management, surpassing naturally occurring materials. Here, using van der Waals epitaxy, we demonstrate the ability to engineer extremely insulating thermal metamaterials based on atomically thin lattice-mismatched Bi(2)Se(3)/MoSe(2) superlattices and graphene/PdSe(2) heterostructures with exceptional thermal resistances (70–202 m(2) K/GW) and ultralow cross-plane thermal conductivities (0.012–0.07 W/mK) at room temperature, comparable to those of amorphous materials. Experimental data obtained using frequency-domain thermoreflectance and low-frequency Raman spectroscopy, supported by tight-binding phonon calculations, reveal the impact of lattice mismatch, phonon-interface scattering, size effects, temperature, and interface thermal resistance on cross-plane heat dissipation, uncovering different thermal transport regimes and the dominant role of long-wavelength phonons. Our findings provide essential insights into emerging synthesis and thermal characterization methods and valuable guidance for the development of large-area heteroepitaxial van der Waals films of dissimilar materials with tailored thermal transport characteristics.