A novel photothermal process to spatially modulate the concentration of sub-wavelength, high-index nanocrystals in a multicomponent Ge-As-Pb-Se chalcogenide glass thin film resulting in an optically functional infrared grating is demonstrated. The process results in the formation of an optical nanocomposite possessing ultralow dispersion over unprecedented bandwidth. The spatially tailored index and dispersion modification enables creation of arbitrary refractive index gradients. Sub-bandgap laser exposure generates a Pb-rich amorphous phase transforming on heat treatment to high-index crystal phases. Spatially varying nanocrystal density is controlled by laser dose and is correlated to index change, yielding local index modification to ≈+0.1 in the mid-infrared.

Thermally-induced nucleation and growth of secondary crystalline phases in a parent glass matrix results in the formation of a glass ceramic. Localized, spatial control of the number density and size of the crystal phases formed can yield 'effective' properties defined approximately by the local volume fraction of each phase present. With spatial control of crystal phase formation, the resulting optical nanocomposite exhibits gradients in physical properties including gradient refractive index (GRIN) profiles. Micro-structural changes quantified via Raman spectroscopy and X-ray diffraction have been correlated to calculated and measured refractive index modification verifying formation of an effective refractive index, n eff , with the formation of nanocrystal phases created through thermal heat treatment in a multi-component chalcogenide glass. These findings have been used to define experimental laser irradiation conditions required to induce the conversion from glass to glass ceramic, verified using simulations to model the thermal profiles needed to substantiate the gradient in nanocrystal formation. Pre-nucleated glass underwent spatially varying nanocrystal growth using bandgap laser heating, where the laser beam's thermal profile yielded a gradient in both resulting crystal phase formation and refractive index. The changes in the nanocomposite's micro-Raman signature have been quantified and correlated to crystal phases formed, the material's index change and the resulting GRIN profile. A flat, threedimensional (3D) GRIN nanocomposite focusing element created through use of this approach, is demonstrated.

Refractive index modification in glass or crystalline materials typically involves conversion of state (amorphous to crystalline or crystalline to amorphous) through a homogeneous, external stimulus such as laser-or current-induced heating, melting, or localized (resonant) bond modification. With the exception of traditional phase change materials that exploit reversibility, usually at high speeds and over multiple cycles, localized patterning of the refractive index is most frequently employed to induce a complete change of phase to enable the creation of embedded or surface optical structures. The present effort employs a novel, laser-induced vitrification (LIV) process developed to spatially modify the refractive index in a fully homogeneous glass ceramic material. Such processing leads to a local re-vitrification of the pre-existing nanocrystalline microstructure within the material to realize spatially-defined, refractive index profiles. Post-processing refractive index modification on the order of ∆n ~-0.062 was realized in a partially crystallized, multicomponent chalcogenide glass ceramic nanocomposite, subjected to bandgap laser exposure. Spatially-varied phase modification in the lateral and axial directions within a bulk glass ceramic is quantified and the optical function of the resulting structure is demonstrated in the formation of an infrared grating. The underlying mechanism associated with the resulting local refractive index modification is explained through quantification of the multi-phase material attributes including parent glass properties, crystal phase identity and phase fraction as determined through micro-XRD and electron microscopic analysis. This correlation validates the proposed mechanism associated with the modification. A threshold power density for LIV in the starting glass ceramic has been determined based on exposure conditions and material attributes.

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.

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