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Published December 16, 2013 | Supplemental Material
Journal Article Open

Doped Nanocrystals as Plasmonic Probes of Redox Chemistry

Abstract

The use of nanostructured probes for chemical sensing has opened up the ability to detect ultra-low analyte volumes and achieve nanoscale spatial resolution. Metal nanoparticles exhibiting localized surface plasmon resonances (LSPRs) have been at the forefront of this research1–5 for two reasons: 1) LSPR scattering can be routinely measured from single nanoparticle probes and 2) the frequency of the LSPR band is highly sensitive to the local refractive index (nm) around the nanoparticle as per the resonance condition: εᵣ(ω) = 2nₘ² where εᵣ is the real part of the metal dielectric function as a function of optical frequency ω. Analytes, which induce a change in the local refractive index around the nanoparticle, are detected by shifts in the frequency of the LSPR scattering band. The method, while powerful, is limited: chemical events, which do not involve a large enough change in refractive index, go undetected.

Additional Information

© 2013 WILEY-VCH. Issue Online: 17 December 2013. Version of Record online: 23 October 2013. Manuscript received: 30 April 2013. This article also appears in: Paul Alivisatos: Priestley Medalist 2021. Work by P.K.J. and S.L.W. on oxidation/reduction chemistry of nanocrystals and their plasmonic/structural characterization was supported by the Dupont Young Professor Award (P.K.J.). Simulations were supported by a National Science Foundation Graduate Research Fellowship awarded to J.F. under Grant No. DGE-1144245 and an IACAT fellowship to P.K.J. Work on methods of nanocrystal doping was supported by the Physical Chemistry of Inorganic Nanostructures Program, KC3103, Director, Office of Science, Office of Basic Energy Sciences, of the United States Department of Energy under contract DE-AC02-05CH11231 and a graduate fellowship awarded to K.M. from the Department of Energy Office of Science Graduate Fellowship Program (DOE SCGF), made possible in part by the American Recovery and Reinvestment Act of 2009, administered by ORISE-ORAU under contract no. DE-AC05-06OR23100. Electrical characterization by J.H.E. was supported by Self-Assembly of Organic/Inorganic Nanocomposite Materials (Grant DE-AC02-05CH11231 to A.P.A.). We thank Jessy Rivest for CdS nanorod samples.

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