Engineering the Berreman mode in mid-infrared polar materials.

We demonstrate coupling to and control over the broadening and dispersion of a mid-infrared leaky mode, known as the Berreman mode, in samples with different dielectric environments. We fabricate subwavelength films of AlN, a mid-infrared epsilon-near-zero material that supports the Berreman mode, on materials with a weakly negative permittivity, strongly negative permittivity, and positive permittivity. Additionally, we incorporate ultra-thin AlN layers into a GaN/AlN heterostructure, engineering the dielectric environment above and below the AlN. In each of the samples, coupling to the Berreman mode is observed in angle-dependent reflection measurements at wavelengths near the longitudinal optical phonon energy. The measured dispersion of the Berreman mode agrees well with numerical modes. Differences in the dispersion and broadening for the different materials is quantified, including a 13 cm-1 red-shift in the energy of the Berreman mode for the heterostructure sample.

Hafnia (HfO2) nanoparticles as an X-ray contrast agent and mid-infrared biosensor.

The interaction of hafnium oxide (HfO2) nanoparticles (NPs) with X-ray and mid-infrared radiation was investigated to assess the potential as a multifunctional diagnostic probe for X-ray computed tomography (CT) and/or mid-infrared biosensing. HfO2 NPs of controlled size were prepared by a sol-gel process and surface functionalized with polyvinylpyrrolidone, resulting in relatively spherical and monodispersed NPs with a tunable mean diameter in the range of ∼7-31 nm. The X-ray attenuation of HfO2 NPs was measured over 0.5-50 mM concentration and compared with Au NPs and iodine, which are the most prominent X-ray contrast agents currently used in research and clinical diagnostic imaging, respectively. At clinical CT tube potentials >80 kVp, HfO2 NPs exhibited superior or similar X-ray contrast compared to Au NPs, while both exhibited significantly greater X-ray contrast compared to iodine, due to the favorable location of the k-shell absorption edge for hafnium and gold. Moreover, energy-dependent differences in X-ray attenuation enabled simultaneous quantitative molecular imaging of each agent using photon-counting spectral (multi-energy) CT. HfO2 NPs also exhibited a strong mid-infrared absorption in the Reststrahlen band from ∼250-800 cm(-1) and negative permittivity below 695 cm(-1), which can enable development of mid-infrared biosensors and contrast agents, leveraging surface enhanced mid-infrared and/or phonon polariton absorption.