Vacancy-Engineered Phonon Polaritons in a van der Waals Crystal.

Sakib, Mashnoon Alam; Hussain, Naveed; Stepanova, Mariia; Harris, William; Bocanegra, Joshua J; Sanchez, Juan Diego; Velez, Camilo; Wu, Ruqian et al. · ACS Nano · 2026

basic_science · Level V

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Abstract

Phonon polaritons (PhPs) in low-symmetry van der Waals (vdW) materials enable deep-subwavelength control of mid-infrared light for nanoscale optics and sensing. However, intrinsically reconfiguring their dispersion without external fields, lithography, or chemical intercalation has remained elusive. Here, we introduce a thermomechanical approach that tunes PhPs in α-molybdenum trioxide (α-MoO<sub>3</sub>) through controlled oxygen vacancy formation and lattice strain. Near-field nanoimaging reveals an average polariton wavevector shift of Δ<i>k</i>/<i>k</i> ≈ 0.13 within the lower Reststrahlen band. Stoichiometric analysis, density functional theory, and finite-difference time-domain simulations indicate vacancy concentrations of 1-2% and ≈-1.2% compressive strain, resulting in a dielectric permittivity modulation of up to ≈15%. Despite these structural perturbations, polariton lifetimes remain high (1.15 ± 0.29 ps). This work offers thermomechanical vacancy engineering as a robust route for reprogrammable polaritonic response in vdW crystals for nonvolatile nanophotonic architectures.