Enhanced third harmonic generation by organic materials on high-Q plasmonic photonic crystals

The enhanced optical nonlinearity enabled by localized plasmonic fields has been well studied for all-optical switching processing (AOSP) devices for future optical communication systems. In this work, plasmonic photonic crystals with a nonlinear polycarbonate/polymethine blend cladding layer are designed to enhance the third harmonic generation (THG) at the telecom wavelengths (~1550 nm). Due to the presence of he two-dimensional (2-D) gold nano-patch arrays with improved Q-factor and high local fields, more than 20 × of enhanced THG signals in the hybrid organic-plasmonic nanostructure are experimentally observed. The enhanced THG in the hybrid organic-plasmonic materials suggested that such extraordinary nonlinear effects can be used for AOSP devices and wavelength conversion.This is the publisher’s final pdf. The published article is copyrighted by the Optical Society of America and can be found at: http://www.opticsinfobase.org/oe/home.cfm

Quasi-three-level Model Applied to Measured Spectra of Nonlinear Absorption and Refraction in Organic Molecules

Materials with a large nonlinear refractive index (2) and relatively small linear and nonlinear absorption losses, namely, two-photon absorption (2PA, of coefficient 2), have long been sought after for applications such as all-optical switching (AOS). Here we experimentally determine the linear and 2PA properties of several organic molecules, which we approximate as centrosymmetric, and use a simplified essential-state model (quasi-three-level model) to predict the dispersion of 2. We then compare these predictions with experimental measurements of 2 and find good agreement. Here “quasi”-three-level means using a single one-photon allowed intermediate state and multiple (here two) two-photon allowed states. This also allows predictions of the figure-of-merit (FOM), defined as the ratio of nonlinear refractive phase shift to the 2PA fractional loss, that determines the viability for such molecules to be used in device applications. The model predicts that the optimized wavelength range for a large FOM lies near the short wavelength linear absorption edge for cyanine-like dyes where the magnitude of 2 is quite large. However, 2PA bands lying close to the linear absorption edge in certain classes of molecules can greatly reduce this FOM. We identify two molecules having a large FOM for AOS. We note that the FOM is often defined as the ratio of real to imaginary parts of the third-order susceptibility ((3)) with multiple processes leading to both components. As explained later in this paper, such definitions require care to only include the 2PA contribution to the imaginary part of (3) in regions of transparency.Abstract © 2016 Optical Society of Americ

Tunable Surface Modification of Mesoporous Carbon Nanoparticles for Polysulfide Trapping in Lithium-Sulfur Batteries

Lithium-Sulfur (LiS) batteries are a front runner for next-generation secondary battery systems. This is partially due to the low cost, relative abundance, and environmentally benign nature of their active materials, but arguably most important is the order of magnitude increase in theoretical specific capacity of LiS cells compared to current state of the art lithium-metal oxide systems (~1,600 mAhg-1 vs ~160mAhg-1, respectively). Despite these inherent benefits, the commercialization of LiS systems has been impeded by a rapid loss of capacity upon repeated cycling due to the complexities of lithiation and delithiation at the carbon/sulfur composite cathode. During discharge, elemental sulfur is sequentially reduced to lithium sulfide following the reaction S8 + 16Li+ + 16e-→ 8Li2S, where intermediates Li2S(8-2) are formed, their length depending on depth of discharge. Long-chain lithium polysulfides (LiPS), Li2S(8-4) are highly soluble in organic electrolytes and, once solvated, will migrate to the lithium metal anode. This leads to permanent capacity loss and internal shorting via lithium polysulfide redox shuttling. To combat this limitation, extensive efforts have been focused on trapping long-chain LiPS by both: 1. physically confining them in mesoporous carbons, and 2. chemically inducing electrostatic attractions with electron rich heteroatoms on the cathode. In this work we not only aim to find synergy between these two approaches, but also investigate the potential for doubling the binding energy of electrostatic interactions by covalent tethering of long chain LiPS to the cathode surface via reversible di-sulfide bonding. Through a highly tunable one-step reaction, we functionalize mesoporous carbon surfaces with aromatic small molecules using in-situ generation of diazonium radicals. The flexibility of our approach allows for the introduction of a wide variety of surface functionality, and thus a platform to broaden our understanding of cathode/electrolyte interactions. Our current progress focuses on the spectroscopic, physical, and electrochemical characterization of a thiophenol terminated carbon. Through this work we have demonstrated not only successful modification of carbon particles, but an ability to control the density of modifier groups on the surface. In conjunction with finding an optimal concentration of surface modifiers, we investigate the role of modifiers and carbon pore size in modulating the kinetics and capacity retention of LiS cells. By optimizing pore-size and modifier concentration, we have drastically increased the cycle life of our devices, which maintain &gt;900 mAhg-1 over 150+ cycles at 0.1C. We hypothesize that the mechanism responsible for this improvement is a reversible covalent interaction based on electrochemical measurements, which indicate a concentration-dependent shift toward solid-phase reaction pathways. </jats:p

Nonlinear Spectra/Dispersion Of Quinolinium Dyes Using Dual-Arm Z-Scan

We report two-photon absorption spectra and nonlinear refraction dispersion of a new series of quinolinium heptamethine cyanine dyes measured using our dual-arm Z-scan and fit of spectra and dispersion with an essential-state model. © 2013 The Optical Society