Infrared (IR) glass-ceramics (GCs) hold the potential to dramatically expand the range of optical material solutions available for use in bulk and planar optical systems in the IR. Current material solutions are limited to single- or polycrystalline materials and traditional IR-transparent optical glasses. GCs that can be processed with spatial control and extent of induced crystallization present the opportunity to realize an effective refractive index variation, enabling arbitrary gradient refractive index elements with tailored optical function. This work discusses the role of the parent glass composition and morphology on nanocrystal phase formation in a multicomponent chalcogenide glass. Through a two-step heat treatment protocol, a Ge-As-Pb-Se glass is converted to an optical nanocomposite where the type, volume fraction, and refractive index of the precipitated crystalline phase(s) define the resulting nanocomposite's optical properties. This modification results in a giant variation in infrared Abbe number, the magnitude of which can be tuned with control of crystal phase formation. The impact of these attributes on the GCs' refractive index, transmission, dispersion, and thermo-optic coefficient is discussed. A systematic protocol for engineering homogeneous or gradient changes in optical function is presented and validated through experimental demonstration employing this understanding.

The arsenic (As) to selenium (Se) ratio in AsxSe1-x glasses ranging from x = 0.2 to 0.5 was varied in order to examine the effect of chemical and topological ordering on the glass' thermal transport behavior. The fundamental thermal properties of glass transition temperature (Tg), thermal conductivity (k), and heat capacity (cp) were experimentally measured using differential scanning calorimetry, transient plane source method, and ultrasonic testing. Based on topological constraint theory, inflections in Tg and k were found at the structural coordination number ⟨r⟩ of 2.4, whereas a slight increase in heat capacity (cp) with increasing ⟨r⟩ was observed. A maximum in total thermal conductivity of 0.232 W/m·K was measured for the composition with x = 0.4, which corresponds to the stoichiometric As2Se3. Gas kinetic theory was used to derive an expression for the photon (kp) portion of thermal conductivity, which was calculated by measurements of the glass' absorption coefficient (α) and refractive index (n). Models based on Debye theory were used to derive expressions for specific heat (cv) and the lattice (kl) portion of thermal conductivity. The maximum value for kp was 0.173 W/m·K for the composition with x = 0.2, and a minimum value of 0.144 W/m·K was measured for the composition with x = 0.4. Photonic conduction was found to be the dominant carrier mechanisms in all compositions, comprising 60% to 95% of the measured total thermal conductivity.