Tetracyanomethane, C(CN)4, is a tetrahedral molecule containing a central sp3 carbon that is coordinated by reactive nitrile groups that could potentially transform to an extended CN network with a significant fraction of sp3 carbon. High-purity C(CN)4 was synthesized, and its physiochemical behavior was studied using in situ synchrotron angle-dispersive powder X-ray diffraction (PXRD) and Raman and infrared (IR) spectroscopies in a diamond anvil cell (DAC) up to 21 GPa. The pressure dependence of the fundamental vibrational modes associated with the molecular solid was determined, and some low-frequency Raman modes are reported for the first time. Crystalline molecular C(CN)4 starts to polymerize above ∼7 GPa and transforms into an interconnected disordered network, which is recoverable to ambient conditions. The results demonstrate feasibility for the pressure-induced polymerization of molecules with premeditated functionality.

We report experimental analysis of optical fibers thermally poled over long lengths using novel types of internal liquid electrodes to generate effective second-order nonlinearities. Our analysis includes transmission losses, depletion region formation, SHG at telecom pump wavelengths.

Dicyanoacetylene (C4N2) is an unusual energetic molecule with alternating triple and single bonds (think miniature, nitrogen-capped carbyne), which represents an interesting starting point for the transformation into extended carbon nitrogen solids. While pressure-induced polymerization has been documented for a wide variety of related molecular solids, precise mechanistic details of reaction pathways are often poorly understood and the characterization of recovered products is typically incomplete. Here, we study the highpressure behavior of C4N2 and demonstrate polymerization into a disordered carbon nitrogen network that is recoverable to ambient conditions. The reaction proceeds via activation of linear molecules into buckled molecular chains, which spontaneously assemble into a polycyclic network that lacks long-range order. The recovered product was characterized using a variety of optical spectroscopies, X-ray methods, and theoretical simulations and is described as a predominately sp(2) network comprising "pyrrolic" and "pyridinic" rings with an overall tendency toward a two-dimensional structure. This understanding offers valuable mechanistic insights into design guidelines for next-generation carbon nitride materials with unique structures and compositions.

The high-pressure behavior of lithium dicyanamide (LiN(CN)2) was studied with in situ Raman and infrared (IR) spectroscopies, and synchrotron angle-dispersive powder X-ray diffraction (PXRD) in a diamond anvil cell (DAC) to 22 GPa. The fundamental vibrational modes associated with molecular units were assigned using a combination of experimental data and density functional perturbation theory. Some low-frequency modes were observed for the first time. On the basis of spectroscopic and diffraction data, we suggest a polymorphic phase transformation at ∼8 GPa, wherein dicyanamide ions remain as discrete molecular species. Above ca. 18 GPa, dicyanamide units polymerize, forming a largely disordered network, and the extent of polymerization may be increased by annealing at elevated temperature. The polymerized product consists of tricyanomelaminate-like groups containing sp2-hybidized carbon-nitrogen bonds and exhibits a visible absorption edge near 540 nm. The product is recoverable to ambient conditions but is not stable in air/moisture.

A technique has been developed to generate stable Ar plasmas at atmospheric pressure inside of a quartz capillary tube. The microwave plasma in the capillary tube is produced by utilizing a single mode resonant circular cavity applicator with 2.45 GHz frequency excitation. The plasma can be confined or fully exposed outside the cavity as plasma jets depending on the operating conditions. The profile of the plasma front has been characterized as a conical tip or split branching jet plume. The measured discharge length and the power density of the plasma range from 6 to 10 cm and 35 to 75 W · cm -3 , respectively. Addition of CH 4 into the Ar plasma results in an increase in the abundances of excited CN and C 2 carbon radicals and a concomitant decrease in the intensity of the Ar emission.

Materials exhibiting electronic phase transitions have attracted widespread attention. By switching between metallic and insulating states under external stimuli, the accompanying changes in the electrical and optical properties can be harnessed in novel electronic and optical applications. In this work, a laterally confined conductive pattern is inscribed into an otherwise insulating VO2 thin film using ultraviolet light, inducing an almost four orders of magnitude decrease in electrical resistivity of the exposed area. The metallic imprint remains in VO2 after ultraviolet light exposure and can be completely erased by a short low temperature anneal. The ability to optically pattern confined metallic structures provides new opportunities for reconfigurable photonic and plasmonic structures, as well as re‐writable electric circuitry.

A novel selective filling technique has been developed for the patterning of semiconductor materials in microstructured optical fibers (MOFs) based on waveguide curing of epoxy filled capillary holes. The technique is compatible with the high pressures required for the semiconductor deposition and allows for quick and convenient selective filling, or coating, of complex designs in a range of MOF hole sizes and spacings. A variety of semiconductor filled MOFs have been demonstrated including the patterning of different materials within selected holes. The ability to selectively fill MOFs with multiple semiconductor materials is a step towards developing arrays of both passive and active all-fiber optoelectronic devices.