Synthesis of Deuterated and Sulfurated Polymers by Inverse Vulcanization: Engineering Infrared Transparency via Deuteration.

The synthesis of deuterated, sulfurated, proton-free, glassy polymers offers a route to optical polymers for infrared (IR) optics, specifically for midwave IR (MWIR) photonic devices. Deuterated polymers have been utilized to enhance neutron cross-sectional contrast with proteo polymers for morphological neutron scattering measurements but have found limited utility for other applications. We report the synthesis of perdeuterated d14-(1,3-diisopropenylbenzene) with over 99% levels of deuteration and the preparation of proton-free, perdeuterated poly(sulfur-random-d14-(1,3-diisopropenylbenzene)) (poly(S-r-d14-DIB)) via inverse vulcanization with elemental sulfur. Detailed structural analysis and quantum computational calculations of these reactions demonstrate significant kinetic isotope effects, which alter mechanistic pathways to form different copolymer microstructures for deutero vs proteo poly(S-r-DIB). This design also allows for molecular engineering of MWIR transparency by shifting C-H bond vibrations around 3.3 µm/3000 cm-1 observed in proteo poly(S-r-DIB) to 4.2 µm/2200 cm-1. Furthermore, the fabrication of thin-film MWIR optical gratings made from molding of deuterated-sulfurated, proton-free poly(S-r-d14-DIB) is demonstrated; operation of these gratings at 3.39 µm is achieved successfully, while the proteo poly(S-r-DIB) gratings are opaque at these wavelengths, highlighting the promise of MWIR sensors and compact spectrometers from these materials.

Photo-Crosslinkable Inorganic/Organic Sulfur Polymers.

Inverse vulcanization techniques are used to fabricate thermodynamically stable, sulfur polymers. Sulfur-based polymers exhibit higher refractive indices and improved transparency in the mid-wave infrared region compared with most organic polymers. Herein, the postsynthetic modification of sulfur polymers created via inverse vulcanization to generate novel, inorganic/organic photoresists is discussed. Amine-containing sulfur resins are postfunctionalized with cross-linkable alkynes. The sulfur-based materials undergo rapid photo-crosslinking to generate patternable films within 10 min under UV irradiation (365 nm). The development of these resins enables sulfur polymers to be utilized in processes where spatial and hierarchical control is necessary. The generation of this class of materials also expands on sulfur-based organic polymer systems with optical applications.

Infrared Fingerprint Engineering: A Molecular-Design Approach to Long-Wave Infrared Transparency with Polymeric Materials.

Optical technologies in the long-wave infrared (LWIR) spectrum (7-14 µm) offer important advantages for high-resolution thermal imaging in near or complete darkness. The use of polymeric transmissive materials for IR imaging offers numerous cost and processing advantages but suffers from inferior optical properties in the LWIR spectrum. A major challenge in the design of LWIR-transparent organic materials is that nearly all organic molecules absorb in this spectral window which lies within the so-called IR-fingerprint region. We report on a new molecular-design approach to prepare high refractive index polymers with enhanced LWIR transparency. Computational methods were used to accelerate the design of novel molecules and polymers. Using this approach, we have prepared chalcogenide hybrid inorganic/organic polymers (CHIPs) with enhanced LWIR transparency and thermomechanical properties via inverse vulcanization of elemental sulfur with new organic co-monomers.

Recent Advances in Electro-Optic Response of Polymer-Stabilized Cholesteric Liquid Crystals.

Cholesteric liquid crystals (CLC) are molecules that can self-assemble into helicoidal superstructures exhibiting circularly polarized reflection. The facile self-assembly and resulting optical properties makes CLCs a promising technology for an array of industrial applications, including reflective displays, tunable mirror-less lasers, optical storage, tunable color filters, and smart windows. The helicoidal structure of CLC can be stabilized via in situ photopolymerization of liquid crystal monomers in a CLC mixture, resulting in polymer-stabilized CLCs (PSCLCs). PSCLCs exhibit a dynamic optical response that can be induced by external stimuli, including electric fields, heat, and light. In this review, we discuss the electro-optic response and potential mechanism of PSCLCs reported over the past decade. Multiple electro-optic responses in PSCLCs with negative or positive dielectric anisotropy have been identified, including bandwidth broadening, red and blue tuning, and switching the reflection notch when an electric field is applied. The reconfigurable optical response of PSCLCs with positive dielectric anisotropy is also discussed. That is, red tuning (or broadening) by applying a DC field and switching by applying an AC field were both observed for the first time in a PSCLC sample. Finally, we discuss the potential mechanism for the dynamic response in PSCLCs.