Tunable Phonon Polariton Hybridization in a Van der Waals Hetero‐Bicrystal

Phonon polaritons, the hybrid quasiparticles resulting from the coupling of photons and lattice vibrations, have gained significant attention in the field of layered van der Waals heterostructures. Particular interest has been paid to hetero‐bicrystals composed of molybdenum oxide (MoO3) and hexagonal boron nitride (hBN), which feature polariton dispersion tailorable via avoided polariton mode crossings. In this work, the polariton eigenmodes in MoO3‐hBN hetero‐bicrystals self‐assembled on ultrasmooth gold are systematically studied using synchrotron infrared nanospectroscopy. It is experimentally demonstrated that the spectral gap in bicrystal dispersion and corresponding regimes of negative refraction can be tuned by material layer thickness, and these results are quantitatively matched with a simple analytic model. Polaritonic cavity modes and polariton propagation along “forbidden” directions are also investigated in microscale bicrystals, which arise from the finite in‐plane dimension of the synthesized MoO3 micro‐ribbons. The findings shed light on the unique dispersion properties of polaritons in van der Waals heterostructures and pave the way for applications leveraging deeply sub‐wavelength mid‐infrared light‐matter interactions. Van der Waals heterostructures provide unique opportunities for controlling light at the nanoscale. Here, hetero‐bicrystals composed of molybdenum oxide (MoO3) and hexagonal boron nitride (hBN) are studied. These bicrystals feature phonon polaritons, the hybrid quasiparticles resulting from the coupling of photons and lattice vibrations, which show a dispersion tailorable via avoided polariton mode crossings.