TY - JOUR T1 - Plasmonic Enhancement of Nonradiative Charge Carrier Relaxation and Proposed Effects from Enhanced Radiative Electronic Processes in Semiconductor-Gold Core-Shell Nanorod Arrays JF - Journal of Physical Chemistry C Y1 - 2011 A1 - Dreaden, Erik A1 - Neretina, Svetlana A1 - Qian, Wei A1 - El-Sayed, Mostafa A A1 - Hughes, Robert A A1 - Preston, John S A1 - Mascher, Peter AB - Plasmonic field enhancement of nonradiative exciton relaxation rates in vertically aligned arrays of high aspect ratio CdTe-Au core-shell nanorods was investigated by transient absorption spectroscopy, computational electromagnetics, and kinetic modeling. Increasing shell thickness in the high aspect ratio nanorods was found to result in dramatic differences in polarization-dependent nonradiative exciton relaxation rates, which we attribute to differing mechanisms of plasmonic field enhancement associated with predominant ground- or excited-state absorption processes. These results are compared with previous investigations of low aspect ratio CdTe-Au core-shell nanorods, and overall conclusions regarding plasmonic enhancement of nonradiative relaxation rates in this system are presented. We propose that when the resonantly coupled dipolar plasmon field of the shell is polarized parallel to the ground-state absorption transition moment of the core, Auger recombination dominates carrier relaxation and slower second-order decay kinetics are observed. When contributions of the resonantly coupled plasmon field are nondipolar or orthogonal to the ground-state absorption transition moment of the core, excited-state absorption processes are believed to dominate and increasingly rapid first-order relaxation kinetics are observed. We find that these processes can vary greatly, depending on shell thickness and the orientation of the array, but are insensitive to aspect ratio. These investigations have significant implications in the design of photovoltaic and optoelectronic devices incorporating anisotropic plasmonic elements. VL - 115 SN - 1932-7447 N1 - Dreaden, Erik C. Neretina, Svetlana Qian, Wei El-Sayed, Mostafa A. Hughes, Robert A. Preston, John S. Mascher, Peter M3 - 10.1021/jp112129k ER - TY - JOUR T1 - The Dependence of the Plasmon Field Induced Nonradiative Electronic Relaxation Mechanisms on the Gold Shell Thickness in Vertically Aligned CdTe-Au Core-Shell Nanorods JF - Nano Letters Y1 - 2009 A1 - Neretina, Svetlana A1 - Dreaden, Erik A1 - Qian, Wei A1 - El-Sayed, Mostafa A A1 - Hughes, Robert A A1 - Preston, John S A1 - Mascher, Peter AB - The dependence of the plasmon field enhancement of the nonradiative relaxation rate of the band gap electrons in vertically aligned CdTe-Au core-shell nanorods on the plasmonic gold nanoshell thickness is examined. Increasing the thickness of the gold nanoshell from 15 to 26 nm is found to change the decay curve from being nonexponential and anisotropic to one that is fully exponential and isotropic (i.e., independent of the nanorod orientation with respect to the exciting light polarization direction). Analysis of the kinetics of the possible electronic relaxation enhancement mechanisms is carried out, and DDA simulated properties of the induced plasmonic field of the thin and thick gold nanoshells are determined. On the basis of the conclusions of these treatments and the experimental results, it is concluded that by increasing the nanoshell thickness the relaxation processes evolve from multiple enhancement mechanisms, dominated by highly anisotropic Auger processes, to mechanism(s) involving first-order excited electron ejection process(es). The former is shown to give rise to nonexponential anisotropic decays in the dipolar plasmon field of the thin nanoshell, while the latter exhibits an exponential isotropic decay in the unpolarized plasmonic field of the thick nanoshell. VL - 9 SN - 1530-6984 N1 - Neretina, Svetlana Dreaden, Erik C. Qian, Wei El-Sayed, Mostafa A. Hughes, Robert A. Preston, John S. Mascher, Peter M3 - 10.1021/nl901960w ER - TY - JOUR T1 - Exciton Lifetime Tuning by Changing the Plasmon Field Orientation with Respect to the Exciton Transition Moment Direction: CdTe-Au Core-Shell Nanorods JF - Nano Letters Y1 - 2009 A1 - Neretina, Svetlana A1 - Qian, Wei A1 - Dreaden, Erik A1 - El-Sayed, Mostafa A A1 - Hughes, Robert A A1 - Preston, John S A1 - Mascher, Peter AB - We studied the anisotropy of the influence of plasmonic fields, arising from the optical excitation of a gold nanoshell plasmon absorption at 770 nm, on the lifetime of the bandgap state of the CdTe core in vertically aligned CdTe-Au core-shell nanorods. The previously observed decrease in the lifetime was studied as a function of the tilt angle between the long axis of the nanorod and the electric field polarization direction of the plasmon inducing exciting light. It is observed that the strongest enhancement to the exciton relaxation rate occurs when the two axes are parallel to one another. These results are discussed in terms of the coupling between the exciton transition moment of the CdTe rod and the electric field polarization direction of the gold nanoshell plasmon at 770 nm, which was determined from theoretical modeling based on the discrete dipole approximation. VL - 9 SN - 1530-6984 N1 - Neretina, Svetlana Qian, Wei Dreaden, Erik C. El-Sayed, Mostafa A. Hughes, Robert A. Preston, John S. Mascher, Peter M3 - 10.1021/nl900183m ER - TY - JOUR T1 - Plasmon Field Effects on the Nonradiative Relaxation of Hot Electrons in an Electronically Quantized System: CdTe−Au Core−Shell Nanowires JF - Nano Letters Y1 - 2008 A1 - Neretina, Svetlana A1 - Qian, Wei A1 - Dreaden, Erik A1 - El-Sayed, Mostafa A A1 - Hughes, Robert A A1 - Preston, John S A1 - Mascher, Peter AB - The intense electromagnetic fields of plasmonic nanoparticles, resulting from the excitation of their localized surface plasmon oscillations, are known to enhance radiative processes. Their effect on the nonradiative electronic processes, however, is not as well-documented. Here, we report on the enhancement of the nonradiative electronic relaxation rates in CdTe nanowires upon the addition of a thin gold nanoshell, especially at excitation energies overlapping with those of the surface plasmon oscillations. Some possible mechanisms by which localized surface plasmon fields can enhance nonradiative relaxation processes of any quantized electronic excitations are proposed.The intense electromagnetic fields of plasmonic nanoparticles, resulting from the excitation of their localized surface plasmon oscillations, are known to enhance radiative processes. Their effect on the nonradiative electronic processes, however, is not as well-documented. Here, we report on the enhancement of the nonradiative electronic relaxation rates in CdTe nanowires upon the addition of a thin gold nanoshell, especially at excitation energies overlapping with those of the surface plasmon oscillations. Some possible mechanisms by which localized surface plasmon fields can enhance nonradiative relaxation processes of any quantized electronic excitations are proposed. PB - American Chemical Society VL - 8 SN - 1530-6984 UR - http://dx.doi.org/10.1021/nl801303g CP - 8 N1 - doi: 10.1021/nl801303g J1 - Nano Lett. M3 - 10.1021/nl801303g ER -