Experimental and First-Principles Spectroscopy of Cu₂SrSnS₄ and Cu₂BaSnS₄ Photoabsorbers

Cu2BaSnS4 (CBTS) and Cu2SrSnS4 (CSTS) semiconductors have been recently proposed as potential wide band gap photovoltaic absorbers. Although several measurements indicate that they are less affected by band tailing than their parent compound Cu2ZnSnS4, their photovoltaic efficiencies are still low. To identify possible issues, we characterize CBTS and CSTS in parallel by a variety of spectroscopic methods complemented by first-principles calculations. Two main problems are identified in both materials. The first is the existence of deep defect transitions in low-temperature photoluminescence, pointing to a high density of bulk recombination centers. The second is their low electron affinity, which emphasizes the need for an alternative heterojunction partner and electron contact. We also find a tendency for downward band bending at the surface of both materials. In CBTS, this effect is sufficiently large to cause carrier-type inversion, which may enhance carrier separation and mitigate interface recombination. Optical absorption at room temperature is exciton-enhanced in both CBTS and CSTS. Deconvolution of excitonic effects yields band gaps that are about 100 meV higher than previous estimates based on Tauc plots. Although the two investigated materials are remarkably similar in an idealized, defect-free picture, the present work points to CBTS as a more promising absorber than CSTS for tandem photovoltaics

Localized Surface Plasmon Resonance Biosensing with Large Area of Gold Nanoholes Fabricated by Nanosphere Lithography

Localized surface plasmon resonance (LSPR) has been extensively studied as potential chemical and biological sensing platform due to its high sensitivity to local refractive index change induced by molecule adsorbate. Previous experiments have demonstrated the LSPR generated by gold nanoholes and its biosensing. Here, we realize large uniform area of nanoholes on scale of cm2 on glass substrate by nanosphere lithography which is essential for mass production. The morphology of the nanoholes is characterized using scanning electron microscope and atomic force microscope. The LSPR sensitivity of the nanoholes to local refractive index is measured to be 36 nm/RIU. However, the chip has demonstrated high sensitivity and specificity in biosensing: bovine serum albumin adsorption is detected with LSPR peak redshift of 27 nm, and biotin-streptavidin immunoassay renders a LSPR redshift of 11 nm. This work forms a foundation toward the cost-effective, high-throughput, reliable and robust chip-based LSPR biosensor

Sensitivity of Localized Surface Plasmon Resonances to Bulk and Local Changes in the Optical Environment

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C copyright © 2009 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jp810322qSingle rod-shaped and disk-shaped gold nanoparticles with sizes ranging from 60 to 162 nm were analyzed using dark-field scattering spectroscopy. The sensitivity of the localized surface plasmon resonance (LSPR) of each nanoparticle to both a bulk and a local change in the refractive index of the environment was obtained by monitoring the change in the spectral position of the LSPR. It was found that the rods were more sensitive to changes in both the local environment and the bulk environment, in particular rods with a length > 110 nm. This behavior was confirmed by finite element modeling of the structures that clearly indicated a saturation of the relative wavelength shift for the disks as the diameter increased whereas the sensitivity of the rods continued to increase linearly with increasing length. This disparity in the behavior of the two types of nanoparticle may in part be attributed to two principal effects associated with the presence of the substrate: first, that the proportion of the surface area of the nanoparticle in contact with the substrate is larger for the disk than for the rod; second, that the LSPR electromagnetic field is more concentrated within the superstrate for the rod compared to the disk. Further analysis of data obtained from modeling a changing local environment indicates that, although the rods are more sensitive, both rods and disks exhibit a similar field confinement

Explosive and chemical threat detection by surface-enhanced Raman scattering: A review

Acts of terror and warfare threats are challenging tasks for defense agencies around the world and of growing importance to security conscious policy makers and the general public. Explosives and chemical warfare agents are two of the major concerns in this context, as illustrated by the recent Boston Marathon bombing and nerve gas attacks on civilians in the Middle East. To prevent such tragic disasters, security personnel must be able to find, identify and deactivate the threats at multiple locations and levels. This involves major technical and practical challenges, such as detection of ultra-low quantities of hazardous compounds at remote locations for anti-terror purposes and monitoring of environmental sanitation of dumped or left behind toxic substances and explosives. Surface-enhanced Raman scattering (SERS) is one of todays most interesting and rapidly developing methods for label-free ultrasensitive vibrational "fingerprinting" of a variety of molecular compounds. Performance highlights include atto-molar detection of TNT and DNT explosives, a sensitivity that few, if any, other technique can compete with. Moreover, instrumentation needed for SERS analysis are becoming progressively better, smaller and cheaper, and can today be acquired for a retail price close to 10,000 US$. This contribution aims to give a comprehensive overview of SERS as a technique for detection of explosives and chemical threats. We discuss the prospects of SERS becoming a major tool for convenient in-situ threat identification and we summarize existing SERS detection methods and substrates with particular focus on ultra-sensitive real-time detection. General concepts, detection capabilities and perspectives are discussed in order to guide potential users of the technique for homeland security and anti-warfare purposes. (C) 2015 Elsevier B.V. All rights reserved

SERS and Raman studies of UV-Induced Modification of Graphene/DNA Interface

The peculiar properties of the graphene/DNA interface show interesting trends under irradiation, which is promising for the realization of sensors with superior performances for a wide range of applications. In this frame, hybrid nanomaterials based on the assembly of DNA and graphene nanoplatelets (GNP) have been used for the real time detection of UV radiation, and are expected to be useful to monitor the biological damage induced by UV in Earth and space environment