A polymerization methodology is reported using sulfur monochloride (S 2 Cl 2 ) as an alternative feedstock for polymeric materials. S 2 Cl 2 is an inexpensive petrochemical derived from elemental sulfur (S 8 ) but has numerous advantages as a reactive monomer for polymerization vs S 8 . This new process, termed sulfenyl chloride inverse vulcanization, exploits the high reactivity and miscibility of S 2 Cl 2 with a broad range of allylic monomers to prepare soluble, high molar-mass linear polymers, segmented block copolymers, and crosslinked thermosets with greater synthetic precision than achieved using classical inverse vulcanization. This step-growth addition polymerization also allows for preparation of a new class of thiol-free, inexpensive, highly optically transparent thermosets (α = 0.045 cm −1 at 1310 nm), which exhibit among the best optical transparency and low birefringence relative to commodity optical polymers, while possessing a higher refractive index (n > 1.6) in the visible and near-infrared spectra. The fabrication of large-sized optical components is also demonstrated.

fabrication techniques for device fabrication in contrast to inorganic counterpart materials, such as silicon (Si) and silicon nitride (SiN). As a result, optical polymers are increasingly seen as cost-effective solutions for manufacturing photonic devices in high volume. Despite these numerous processing advantages, optical polymer materials for integrated photonics remain limited relative to inorganic materials with respect to critical optical properties, especially refractive index (n, or RI). The vast majority of current optical polymers have a refractive index ranging between 1.3-1.6 at telecom wavelengths, which is significantly lower than the RI values of SiN, lithium niobate (n ≈ 2.0-2.2), or higher RI materials such as Si, [9,10] indium phosphide, or germanium (n ≈ 3.5-4.0). Because of these dramatically lower RI values, on-chip integrated photonic components, such as waveguides or ring resonators fabricated using optical polymers require much larger feature sizes beyond what is tenable for numerous on-chip device systems and preclude the fabrication of curved features with tight bend radii which are essential integrated optical elements. With an ever-increasing demand for high density integrated optical circuitry, the large areal footprint of state-of-the-art polymer devices due to limited RI contrast remains a critical limitation toward realizing all-polymer photonic circuits for high density interconnects and integration. Hence, there is a compelling technological need for high RI polymers (n >> 1.6 at telecom at 1310 and 1550 nm) that are amenable to thin film processing and high throughput nano/ microfabrication techniques (e.g., photolithography). There are a handful of inorganic materials, such as Hydex glass [11,12] and silicon oxynitride (SiON), [13] which have been studied to create inexpensive, earth-abundant inorganic materials that achieve RI values ranging from n = 1.6-2.0 at telecom wavelengths. Furthermore, recent work on solution-processable chalcogenide glasses (ChGs) has been explored to create thin films and integrated photonic components, such as single-mode waveguides in the mid-wave infrared (MWIR), which exploit the high RI and high transparency ChGs. [14][15][16][17] However, fabrication processes for these materials remain non-trivial, requiring multi-step high temperature methods, or the use of unconventional toxic solvents which has limited wide-scale deployment. Numerous Optical polymer-based integrated photonic devices are gaining interest for applications in optical packaging, biosensing, and augmented/virtual reality (AR/VR). The low refractive index of conventional organic polymers has been a barrier to realizing dense, low footprint photonic devices. The fabrication and characterization of integrated photonic devices using a new class of high refractive index polymers, chalcogenide hybrid inorganic/organic polymers (CHIPs), which possess high refractive indices and lower optical losses compared to traditional hydrocarbon-based polymers, are reported. These optical polyme...

We present a proof of concept for tunable plasmon resonance frequencies in a core shell nano-architectured hybrid metal-semiconductor multilayer structure, with Ag as the active shell and ITO as the dielectric modulation media. Our method relies on the collective change in the dielectric function within the metal semiconductor interface to control the surface. Here we report fabrication and optical spectroscopy studies of large-area, nanostructured, hybrid silver and indium tin oxide (ITO) structures, with feature sizes below 100 nm and a controlled surface architecture. The optical and electrical properties of these core shell electrodes, including the surface plasmon frequency, can be tuned by suitably changing the order and thickness of the dielectric layers. By varying the dimensions of the nanopillars, the surface plasmon wavelength of the nanopillar Ag can be tuned from 650 to 690 nm. Adding layers of ITO to the structure further shifts the resonance wavelength toward the IR region and, depending on the sequence and thickness of the layers within the structure, we show that such structures can be applied in sensing devices including enhancing silicon as a photodetection material.