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Title: The Influence of Nonlocal Metal–Dielectric Environments on Physical and Chemical Processes

Journal Article · · Accounts of Chemical Research

Plasmonic nanolayers and laminar metallic/dielectric multilayers were originally developed for optical cloaking applications and lensing applications that could potentially image objects whose size was below the diffraction limit. These assemblies were initially formed from gold or silver nanorods grown within an alumina mesh. However, more recently, assemblies with similar properties have also been prepared by sequential thin-layer deposition of alternating layers of gold and magnesium fluoride (MgF2). These metal/dielectric composite materials enable control of the dielectric constant in the directions perpendicular to the layers and balance the real and imaginary dielectric constants of the assembly such that the speed and the amplitude of the waves traveling through the assembly are not attenuated. In this Account, we will also focus on a few of the applications ranging from surface wetting to fluorescence quenching to enhancement of photochemical reactions. First, we will share an introduction to processes used to create these materials, which are combinations of low refractive index metals and transparent higher index materials arranged in a scalable repeating fashion. Two fabrication methods were employed: an electrochemical deposition of Ag nanorods into an anodized alumina matrix which produced materials with an anisotropic negative refractive index material within the plane of the film and lamellar metal/dielectric layers in which the negative index perpendicular to the growth direction. These alternating layers of plasmonic metals and dielectric materials were ultimately chosen to prepare films for further testing, because of their relative ease of fabrication. We will continue with a discussion of a few of the applications of both of these nonlocal dielectric composite materials including more specialized plasmonic, composite, and hyperbolic metamaterials including fluorescence quenching, photochemical reactions, and surface wetting. In each of these applications, the unique response caused by the enhancement of the electric field and the interface between hyperbolic materials and plasmonic materials as they interact photophysically with their near neighbors is presented. In each of the applications, the enhanced electric field extends from the composite substrate layer to interact with its near neighbors and beyond. Furthermore, the presence of this extended interaction can be observed in the form of decreased emission lifetime, enhancement of photochemical reaction rates, and changes in the surface energies measured by contact angle goniometry. In this Account, all of these situations will be addressed. Finally, we will conclude with a summary and vision for the future as well as a discussion of the unique challenges and opportunities available as research active faculty at an HBCU.

Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); US Army Research Office (ARO); National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR)
Grant/Contract Number:
AC52-07NA27344; DMR 1205457; DMR 0611430; DGE 0966188; FA9550-09-1-0456; FA9550-14-1-0221; W911NF-14-1-0639; DMR 1120923; EEC-0228390; 50342-PH-MUR
OSTI ID:
2203353
Report Number(s):
LLNL-JRNL-855882; 1083887
Journal Information:
Accounts of Chemical Research, Vol. 56, Issue 11; ISSN 0001-4842
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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