Broad‐Spectral‐Range Sustainability and Controllable Excitation of Hyperbolic Phonon Polaritons in α‐MoO3

Hyperbolic phonon polaritons (HPhPs) in orthorhombic-phase molybdenum trioxide ($\alpha$-MoO3) show in-plane hyperbolicity, great wavelength compression and ultra-long lifetime, therefore holding great potential in nanophotonic applications. However, its polaritonic response in the far-infrared (FIR) range has long remained unexplored due to challenges in experimental characterization. Here, using monochromated electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM), we probe HPhPs in $\alpha$-MoO3 in both mid-infrared (MIR) and FIR frequencies and correlate their behaviors with microstructures and orientations. We find that low-structural symmetry leads to various phonon modes and multiple Reststrahlen bands (RBs) over a broad spectral range (over 70 meV) and in different directions (55-63 meV and 119-125 meV along b axis, 68-106 meV along c axis, 101-121 meV along a axis). These HPhPs can be selectively excited by controlling the direction of swift electrons. These findings provide new opportunities in nanophotonic and optoelectronic applications such as directed light propagation, hyperlenses and heat transfer.