Uv vis book

Challa S S R Kumar Editor UV-VIS and Photoluminescence Spectroscopy for Nanomaterials Characterization UV-VIS and Photoluminescence Spectroscopy for Nanomaterials Characterization Challa S.S.R Kumar Editor UV-VIS and Photoluminescence Spectroscopy for Nanomaterials Characterization With 278 Figures and Tables Editor Challa S.S.R Kumar Center for Advanced Microstructures and Devices Baton Rouge, LA, USA ISBN 978-3-642-27593-7 ISBN 978-3-642-27594-4 (eBook) DOI 10.1007/978-3-642-27594-4 Springer Heidelberg New York Dordrecht London Library of Congress Control Number: 2013930307 # Springer-Verlag Berlin Heidelberg 2013 This work is subject to copyright All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed Exempted from this legal reservation are brief excerpts in connection with reviews or scholarly analysis or material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work Duplication of this publication or parts thereof is permitted only under the provisions of the Copyright Law of the Publisher’s location, in its current version, and permission for use must always be obtained from Springer Permissions for use may be obtained through RightsLink at the Copyright Clearance Center Violations are liable to prosecution under the respective Copyright Law The use of general descriptive names, registered names, trademarks, service marks, etc in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use While the advice and information in this book are believed to be true and accurate at the date of publication, neither the authors nor the editors nor the publisher can accept any legal responsibility for any errors or omissions that may be made The publisher makes no warranty, express or implied, with respect to the material contained herein Printed on acid-free paper Springer is part of Springer Science + Business Media (www.springer.com) Editor-in-Chief Challa S.S.R Kumar Center for Advanced Microstructures and Devices Baton Rouge, LA USA v Contents Geometrically Tunable Optical Properties of Metal Nanoparticles Hao Jing, Li Zhang, and Hui Wang Optical Properties of Metallic Semishells: Breaking the Symmetry of Plasmonic Nanoshells Jian Ye and Pol Van Dorpe 75 Exploiting the Tunable Optical Response of Metallic Nanoshells Ovidio Pen˜a-Rodrı´guez and Umapada Pal 99 UV-Vis Spectroscopy for Characterization of Metal Nanoparticles Formed from Reduction of Metal Ions During Ultrasonic Irradiation Kenji Okitsu 151 Size-Dependent Optical Properties of Metallic Nanostructures Lucı´a B Scaffardi, Daniel C Schinca, Marcelo Lester, Fabia´n A Videla, Jesica M J Santilla´n, and Ricardo M Abraham Ekeroth 179 Modeling and Optical Characterization of the Localized Surface Plasmon Resonances of Tailored Metal Nanoparticles J Toudert 231 Tailoring the Optical Properties of Silver Nanomaterials for Diagnostic Applications Jae-Seung Lee 287 Optical Properties of Oxide Films Dispersed with Nanometal Particles Moriaki Wakaki and Eisuke Yokoyama 311 Optical Properties of Silicon Nanowires Michael M Adachi, Mohammedreza Khorasaninejad, Simarjeet S Saini, and Karim S Karim 357 vii viii Contents 10 Optical Properties of Oxide Nanomaterials A B Djurisˇic´, X Y Chen, J A Zapien, Y H Leung, and A M C Ng 11 UV-VIS Spectroscopy/Photoluminescence for Characterization of Silica Coated Core-shell Nanomaterials Masih Darbandi 431 Optical and Excitonic Properties of Crystalline ZnS Nanowires Rui Chen, Dehui Li, Qihua Xiong, and Handong Sun 453 13 Optical Properties of Nanocomposites Timothy O’Connor and Mikhail Zamkov 485 14 Biomedical and Biochemical Tools of F€ orster Resonance Energy Transfer Enabled by Colloidal Quantum Dot Nanocrystals for Life Sciences ă zg Urartu O ur Sáafak Sáeker and Hilmi Volkan Demir 12 15 Probing Photoluminescence Dynamics in Colloidal Semiconductor Nanocrystal/Fullerene Heterodimers with Single Molecule Spectroscopy Zhihua Xu and Mircea Cotlet Index 387 531 561 591 List of Contributors Michael M Adachi Department of Electrical and Computer Engineering, University of Waterloo, Waterloo, ON, Canada X Y Chen Department of Physics, The University of Hong Kong, Pokfulam Road, Hong Kong Rui Chen Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore Mircea Cotlet Brookhaven National Laboratory, Upton, NY, USA Masih Darbandi Faculty of Physics and Center for Nanointegration DuisburgEssen (CeNIDE), University of Duisburg-Essen, Duisburg, Germany Hilmi Volkan Demir Department of Electrical and Electronics Engineering, Department of Physics and UNAM—Institute of Materials Science and Nanotechnology, Bilkent University, Ankara, Turkey Luminous! Centre of Excellence for Semiconductor Lighting and Displays, School of Electrical and Electronic Engineering, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore A B Djurisˇic´ Department of Physics, The University of Hong Kong, Pokfulam Road, Hong Kong ´ ptica de So´lidos-Elfo, Centro de Ricardo M Abraham Ekeroth Grupo de O Investigaciones en Fı´sica e Ingenierı´a del Centro de la Provincia de Buenos Aires – Instituto de Fı´sica Arroyo Seco, Facultad de Ciencias Exactas, Universidad Nacional del Centro de la Provincia de Buenos Aires, Buenos Aires, Argentina Consejo Nacional de Investigaciones Cientı´ficas y Te´cnicas CONICET, Buenos Aires, Argentina Hao Jing Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC, USA Karim S Karim Department of Electrical and Computer Engineering, University of Waterloo, Waterloo, ON, Canada ix a 30 b 30 PL (counts) Photoluminescence Dynamics in Colloidal Semiconductor Nanocrystals PL (counts) 15 20 10 0 20 40 Time (s) 60 579 20 10 0 100 200 Occurrence 300 PL Lifetime (ns) c 40 30 20 10 0 12 PL Intensity (103 counts) Fig 15.12 PL intensity trajectory (a), PL intensity histogram (b), and correlations of PL intensity versus PL lifetime (c) for a single QD isomer exhibiting multi-state blinking behavior 5.4 Photoinduced Electron Transfer Single molecule spectroscopy (SMS) is a powerful method to unveil the inhomogeneous dynamics of CT obscured by ensemble-averaging, and it has been successfully applied to a variety of systems including organic donor-bridge-acceptor systems, dyes adsorbed on TiO2 or proteins [25, 61, 76, 78–80] A limited number of SMS studies address charge transfer between QDs and acceptor materials, such as TiO2 or an ensemble of dyes adsorbed on a QD [59, 71, 81] The QD-bridge-FMH heterodimers fabricated by the surface-based assembly procedure reported in the previous paragraph provide a model system for the single molecule exploration of photoinduced electron transfer between QDs and electron acceptors, which is an essential process in QD-based solar cells By varying the linker length and the QD size, it is possible to control the rate and the magnitude of fluctuations of the photoinduced electron transfer at the level of individual dimer, and with SMS, it is possible on the other hand to unveil both static and dynamic heterogeneity in ET, as will be shown below Representative PL intensity and PL lifetime trajectories of a single QD605 isomer and of single DBA heterodimers of the type QD605-16AHT-FMH, 580 Z Xu and M Cotlet 30 20 20 10 10 20 40 Time (s) 60 PL intensity PL lifetime 25 20 20 15 15 10 10 5 20 40 Time (s) 60 d 15 10 5 20 40 Time (s) 60 PL intensity PL lifetime 15 10 10 5 20 40 Time (s) PL lifetime (ns) 10 PL lifetime (ns) PL intensity PL lifetime PL intensity (Counts/ms) c PL intensity (Counts/ms) 25 PL lifetime (ns) 30 PL intensity (Counts/ms) b PL intensity PL lifetime 40 PL lifetime (ns) PL intensity (Counts/ms) a 60 Fig 15.13 Single molecule trajectories of the PL intensity (black) and lifetime (red) measured from (a) QD605 isomer and from dimers, (b) QD605-16AHT-FMH, (c) QD605-11AUT-FMH and (d), QD605-6AHT-FMH (reproduced from reference [21]) QD605-11AUT-FMH, and QD605-6AHT-FMH are shown in Fig 15.13 The PL intensity trajectory of a QD605 isomer shows the typical “on-off” blinking, similar to that depicted in Fig 15.9 – a behavior that can be regarded as a signature for the presence of a single emitting nanocrystal The corresponding PL lifetime fluctuates in time and in correlation with the PL intensity, that is, high intensity states tend to exhibit longer PL lifetime, suggesting variations in the nonradiative recombination rate [56] The PL intensity and lifetime trajectories of QD-FMH dimers also show correlated fluctuations, but the corresponding PL intensity and lifetime values are suppressed when compared to that of the QD605 isomer, suggesting enhanced nonradiative recombination due to photoinduced electron transfer from QD to FMH Compared to the QD isomer, the dimers exhibit different blinking dynamics, as discussed in the previous paragraph: the PL intensity distributes continuously between “on” and “off” states, suggesting inhomogeneous electron transfer between QD and FMH The inhomogeneity of ET in QD-FMH dimers is better seen in the PL lifetime histograms from Fig 15.14 that were constructed from PL lifetime trajectories measured from each 50 individual QD605 isomers (Fig 15.13a) and from each 50 individual QD605-FMH dimers of a given linker length (Fig 15.14b–d) For QD605 isomers, the lifetimes distribute symmetrically around 20 ns with a standard 15 Photoluminescence Dynamics in Colloidal Semiconductor Nanocrystals a 1.0 581 b Probability 0.8 0.6 0.4 0.2 0.0 c 1.0 d Probability 0.8 0.6 0.4 0.2 0.0 20 Lifetime (ns) 40 20 Lifetime (ns) 40 Fig 15.14 Histograms of single molecule PL lifetimes constructed from each 50 individual trajectories measured from (a) QD605 isomers, from dimers, (b) QD605-16AHT-FMH, (c) QD605-11AUT-FMH, (d) QD605-6AHT-FMH (reproduced from reference [21]) deviation s6.5 ns For dimers, the lifetime histograms are asymmetric and with peak values diminished to ns (s6.7 ns) for QD605-16AHT-FMH, ns (s5.9 ns) for QD605-11AUT-FMH, and ns (s4.4 ns) for QD605-6AHT-FMH, indicating enhanced electron transfer rate and suppressed ET fluctuation with reducing linker length As a comparison, the PL lifetime histogram constructed from 50 individual QD isomers spin-coated on top of an FMH thin film, a condition where QD and FMH are not linked by a molecular bridge, is shown in Fig 15.15 This histogram features a peak at 20 ns and a rather wide standard deviation (s7.6 ns) compared to those of the heterodimers (Fig 15.14b–d) However, it is rather similar to PL lifetime distributions observed for QDs deposited on TiO2 film [59] This suggests that the dimer structure significantly reduces the magnitude of fluctuations of ET between QD and FMH The inhomogeneity of electron transfer in QD-FMH dimers leads to a distribution of PL lifetimes and ET rates seen here as static heterogeneity The linker length effect on electron transfer rate kET can be calculated from the intensity-weighted average PL 582 Z Xu and M Cotlet Fig 15.15 Histograms of single molecule PL lifetimes constructed from each 50 individual trajectories measured from QD605 isomers spincoated on a FMH film (reproduced in part from reference [21]) 1.0 Probability 0.8 0.6 0.4 0.2 0.0 20 Lifetime (ns) 40 lifetime, tav for QD-FMH dimers from the lifetime histograms from Fig 15.14b–d The average PL lifetime tav of QDs and QD-FMH dimers was calculated using P t tav ¼ Pi i j aj t j (15.6) where is the occurrence probability of lifetime ti in the PL lifetime histogram The average ET rate kET for QD-FMH dimers can then be calculated based on kET ẳ 1=tav  kR ỵ kNR ị (15.7) where kR and kNR are the radiative and nonradiative recombination rates for QD isomers, which can be calculated using the average PL lifetime estimated for QD isomers We found that the average ET rate exhibits an exponential dependence on ˚ 1, linker length as shown in Fig 15.16, with an attenuation coefficient b0.1 A calculated from ln kET ¼ ln k0  bR, with R linker length For organic only DBA systems with flexible alkane bridges, bulk measurements in solution reported ˚ 1 [66] For QD-FMH dimers, a small b might indicate collapsed/folded b0.8 A aminoalkanethiol linkers due to the solvent-free environment in which the single molecule experiments were performed The electron transfer is not only influenced by the D-A electronic coupling, but also by the driving force (energy band offset) between D and A moieties The unique size-dependent energy bandgap of QDs provides another effective 15 Photoluminescence Dynamics in Colloidal Semiconductor Nanocrystals Fig 15.16 Electron transfer rate, kET versus linker length, R, calculated for QD605FMH dimmers on the basis of single molecule experiments (reproduced in part from reference [21]) 583 In (KET) 18.0 17.5 17.0 10 15 20 R (A) way to control single molecule ET in QD-FMH dimers By decreasing the QD’s core size from 4.4 to 2.5 nm, the conduction band is expected to be uplifted by around 0.2 eV [29], resulting in an increase of the ET driving force PL lifetime histograms constructed from trajectories corresponding to 50 each individual QD isomers and 50 each individual QD-16AHT-FMH dimers with QDs of different colors (sizes), namely, QD605 (core size 4.5 nm), QD565 (3.2 nm), and QD525 (2.5 nm), are shown in Fig 15.16ac–c, respectively Figure 15.18 shows the average ET rate versus QD’s core size calculated based on the histograms from Fig 15.17a–c The ET rate increases from 2.2  107 s1 for QD605-16AHT-FMH to 4.9  108 s1 for QD525-16AHT-FMH, consistent with the size-dependent ET observed from CdSe QDs to TiO2 [32] One interesting phenomenon associated with the size-dependent ET rate is that ET fluctuations are suppressed in dimers with smaller QD size The standard deviation of the PL lifetime is 6.7 ns for QD605-16AHT-FMH, 1.4 ns for QD565-16AHT-FMH, and 0.8 ns for QD525-16AHT-FMH, respectively This suppression of ET fluctuation in dimers with smaller QD size leads to stable charge generation rate which can have a positive impact on the application of these dimers in molecular electronics The time scale of ET fluctuations in QD-FMH dimers can be unraveled by using a photon-by-photon analysis method capable of probing fluctuations in single molecule lifetimes from as short as few microseconds, up to seconds [27, 78] As described in previous paragraphs, the photon-by-photon method does this by computing autocorrelations of the PL lifetimes (ACPLs) measured from a single molecule on a photon-by-photon basis (see detailed description in previous paragraph) Typical ACPLs for a single QD isomer and a QD-FMH dimer are shown in Fig 15.19, and they can be roughly described by a single exponent decay (Fig 15.19a) 584 Occurrence a 100 QD605 QD605-16AHT-FMH 80 60 40 20 0 10 20 30 40 Lifetime (ns) 50 60 b 100 Occurrence Fig 15.17 Histograms of single molecule PL lifetimes constructed from each 50 individual trajectories measured from QD isomers and QD-FMH dimers using QDs of different sizes: (a) QD605 isomer (red) and QD605-16AHT-FMH dimer (black); (b) QD565 isomer (orange) and QD565-16AHTFMH dimer (black); (c) QD525 isomer (green) and QD525-16AHT-FMH dimer (black) (reproduced from reference [21]) Z Xu and M Cotlet QD565 QD565-16AHT-FMH 80 60 40 20 0 10 20 30 40 Lifetime (ns) 50 60 Occurrence c 100 QD525 QD525-16AHT-FMH 80 60 40 20 0 10 20 30 40 Lifetime (ns) 50 60 and a biexponent decay (Fig 15.19b), respectively Fluctuations in the PL lifetime of individual QDs isomers have been previously explained by invoking dynamic distribution of the charge trap state [56, 82] The variation in the trap state not only leads to fluctuations in the nonradiative recombination rate, but also to variations in the QD’s electronic states, as manifested by spectral diffusion [64] – a phenomenon that could influence the electron transfer to FMH Therefore, the long time decay (after 10 ms) of the ACPLs of QD isomer and QD-FMH dimer can be attributed to fluctuations of the charge trapping state in QDs, consistent with recent findings that spectral diffusion dynamics of single QDs is slower than 10 ms [83] In this assumption, it is understandable the observation of suppressed ET fluctuations in dimers with smaller QD sizes, because these dimers have larger ET driving force and hence will be less prone to fluctuation of the electronic states of the QD Compared to a QD isomer, the ACPLs of QD-FMH dimers exhibit a significant decay before 10 ms These fast ET fluctuations might be due to the complicated thermally induced molecular motions, similar to that previously reported for organic DBA systems [65, 66] We observed that reducing linker length in dimer results in suppression of ET fluctuations, which indicates that linker motion plays an important role for defining and controlling the magnitude of ET fluctuation 15 Photoluminescence Dynamics in Colloidal Semiconductor Nanocrystals Fig 15.18 Electron transfer rate versus QD core size calculated for QD-FMH dimers on the basis of single molecule experiments (reproduced from reference [21]) 585 KET (S−1) 109 108 107 25 b 1.0 0.8 0.6 0.6 0.4 0.2 0.0 0.0 101 102 103 Time lag (ms) 104 45 50 0.4 0.2 10−1 10−0 35 40 Diameter (A) 1.0 0.8 ACPL ACPL a 30 10−1 10−0 101 102 103 Time lag (ms) 104 Fig 15.19 Photon-by-photon autocorrelations of PL lifetimes (ACPLs) measured from individual (a) QD605 isomer and (b) QD605-16AHT-FMH dimer Shown in red are single exponential (panel a, 572 ms) and biexponential (panel b, 25 ms, 1,490 ms) decay fits (reproduced from reference [21]) Conclusion and Future Perspective We have successfully fabricated a series of donor-bridge-acceptor heterodimers composed of core/shell CdSe/ZnS quantum dots and fullerene FMH via a novel surface-based stepwise self-assembly approach The QD-FMH heterodimers exhibit controlled electron transfer properties, including controlled ET rate and reduced ET rate fluctuation when compared to similar components assembled 586 Z Xu and M Cotlet without a molecular linker A thorough comparison of the single molecule spectroscopic behavior of the QD-FMH heterodimer and QD isomers has provided deeper insight into the PL blinking mechanism of core/shell QDs For example, by comparing the PL blinking characteristics between QDs and QD-FMH dimers with varying interparticle linker length, we found that external charge traps that are properly coupled to the excited state of a QD have a significant effect on the QD’s PL blinking dynamics Charge transfer followed by charge recombination between a QD and an external trap leads to a quasi-continuous distribution of the on-states and an early cutoff of P(ton) and P(toff) distributions from an inverse power-law behavior This multistate blinking was also observed in some 10 % of the probed QD isomers and attributed to trap-induced charge transfer/recombination with traps supposedly in the form of defects located at the QD surface An evaluation of the blinking dynamics of QD isomers and QD-FMH dimers in view of the diffusion-controlled ET model suggests the need to refine such models addressing the presence of not only long-lived shallow traps but also short-lived deep ones Single molecule spectroscopic characterization of the electron transfer in QD-FMH dimers not only revealed the linker length and QD size effect on the average ET rate, but unveiled the static and dynamic inhomogeneity of ET, otherwise obscured in ensemble-averaged experiments We have successfully identified two distinct ET fluctuation regimes that were attributed to variation of the trap state in the QDs and to molecular motions within dimers Reducing linker length and QD size has been found to limit fluctuations of ET in these dimers With excellent, sizedependent light absorption properties conferred by the incorporated QDs, the DBA dimers are promising power generating units for molecular electronics While we and others have found that PL blinking behavior of individual quantum dots is closely related to photoinduced charge transfer, further experimental and theoretical investigations are needed to understand the exact relationship, which is of significant importance for the widespread applications of quantum dots Acknowledgments We would like to thank Dr H.L Wang from Los Alamos National Laboratory in New Mexico for providing the fullerene compound and our colleagues from Brookhaven National Laboratory, Dr M Sfeir for helping with transient absorption experiments and Drs M Hybertsen and Q Wu for helpful discussions and suggestions in connection with some of the data reported here We also thank the Office of Science of the United States Department of 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130(17):5632–5633 82 Verberk R, van Oijen AM, Orrit M (2002) Simple model for the power-law blinking of single semiconductor nanocrystals Phys Rev B 66(23):233202 83 Marshall LF et al (2010) Extracting spectral dynamics from single chromophores in solution Phys Rev Lett 105(5):053005 Index A Absorption, 358–360, 362–367, 369, 370, 372–377, 380, 381 Absorption and scattering, 232, 234, 235, 262 cross sections, 235 Absorption spectroscopy, 394, 407 Absorption to scattering ratio, 123 Active hybrid systems, 274 Ag and Cu nanorods, 20 Ag core-Ag2O shell Nps, 220 Ag dielectric function, 190 Aggregates of gold nanoparticles, 348, 349 Ag nanoclusters, 165, 166 Ag nanocubes, 48, 50, 51, 53, 329, 330 2D Ag nanoparticle arrays, 57 Ag nanoparticle chains, 56 Ag nanoparticles, 14, 53, 55–57, 164–166 Ag nanoprisms, 45–47 Ag nanorods, 329, 330 Ag nanospheres, 14, 53 AgNO3, 329 Alexa Fluor 633, 539 Alloy nanospheres, 5, 16 Alternative plasmonic metals, 273 Anisotropic AgNPs, 290 Anisotropic nanoparticle shapes, 251 Anisotropic structures, Antibonding, 84, 89–91 Antibunching, 565, 571 Arrays of nanoparticles, 236 Artifacts, 388, 391, 393, 395, 397, 417, 419 Aspect ratio, 170, 171 Assembling, 237 Au-Ag alloy films, 16 Au-Ag alloy nanoparticles, 16, 17 Au, Ag, and Cu nanospheres, 14 Au-Ag bimetallic nanoparticles Au-Ag core-shell particles, 17 Au and Ag nanoprisms, 46 Au dielectric function, 190 Au nanocup, 39, 41 Au nanoparticles, 160–162, 169–171 Au nanorods, 9, 20–28, 43, 153, 169–172 Au nanoshell heptamer cluster, 55 Au nanosphere, 3, 7, 11, 21, 25, 37, 53, 57 Au3+ reduction, 156 Au2S-Au nanoshells, 29 Auto-organization, 237 B Bacteriorhodopsin (bR), 550 BDAC-CTAB binary surfactant, 22 BEM See Boundary element method (BEM) Bimetallic nanoparticles of Au/Pd, 169 Bimetallic nanospheres, 15–17 Bioconjugation, 432 Biomedical imaging, 60 Bio-sensing, 133–135 Bipods, 48 Bipyramids and decahedra, 48 Blinking dynamics, 562, 573, 578, 586 Bonding, 84 Bottom-up method, 314 Boundary element method (BEM), 9, 10, 264, 265 Bound electron contributions (Bulk) bulk, 180, 182–184, 186–196, 207, 212–214 multiple transitions, 193–197 single transition, 191–193 Bruggeman, D.A.G., 312, 339–343, 347–351 Bruggeman model, 341, 347–351 Bubble temperature, 154–156, 173 Bulk See Bound electron contributions (Bulk) C Cadmium selenide (CdSe), 562 Cadmium sulfide (CdS), 562 591 592 Capping agent, 328, 334 Carbon nanoparticle (CNP), 94, 95 Carrier dynamics, 472–473 Cathodoluminescence, 389–394, 403–417 Cavitation bubbles, 153–156 Cavitation phenomenon, 152, 173 CdSe/ZnS QD, 563, 567 CdTe, 535, 536, 539, 544, 550 Cetyltrimethylammonium bromide (CTAB), 17, 21–23, 49 Chemical effects of cavitation, 155 Classical calculations, 19 Classical electromagnetic theory, 9, 20, 31, 58 Classical Mie scattering theory, 33 Clausius-Mossotti equation, 341 Cleaving enzyme, 544 CNP See Carbon nanoparticle (CNP) Coefficients an and bn, 108, 110 Coherent potential model, 341 Colloidal Au nanorods, 20, 21 Colloidal semiconductor nanocrystals, 561–586 Colorimetric detection, 299, 300, 305 Complex dielectric function, 186, 189, 210 Composite materials, 314, 316, 340, 342, 343 Constitutive parameters, 180, 182, 207, 216, 222 Cooperative interactions, 292 Core-shell, 250, 252, 274, 486, 489–494, 497–500, 507, 508, 518–520 CdSe/ZnS quantum dots (QDs), 563, 564, 566, 585 heterostructured bimetallic nanoparticles, 16, 17 quantum dot (QD), 562 silver-silver oxide, 219 structures, 101, 109 Critical points, 117 Cross sections, 105, 107, 108, 111, 134 CTAB See Cetyltrimethylammonium bromide (CTAB) Cu dielectric function, 190, 207 Cyclic disulflde, 296, 297 Cy5-labeled DNA, 542 Cy photothermal therapy, 4, 28, 60 D Damping constant, 118, 186, 188, 191, 194, 196 Dark-field microscope, 7, 24 Dark-field microscopy, 7, 8, 52, 239, 266 DBA heterodimers, 563, 564 Index DCET See Diffusion-controlled electron transfer (DCET) DCN See Double concentric nanoshells (DCN) DDA See Discrete dipole approximation (DDA) Defect emission, 388, 389, 393, 404–406, 408–410, 412–415, 417, 419 Dehybridization, 289, 303 Density functional theory (DFT), 10 Depolarization electric field, 323 Depolarization factor N, 324, 326, 344, 345 Depolarization field, 319, 324 DFT See Density functional theory (DFT) Dielectric functions, 105, 106, 116–119, 180, 182, 185–197, 201, 204, 205, 207, 210, 212–214, 218, 222, 317–320, 325, 343 of copper, 195, 197 of metals, 185–197 Differential equation (Diff.), 350, 351 Differential near-field scanning optical microscopy (DNSOM), Diffusion-controlled electron transfer (DCET), 576, 578, 586 Dimer, 235–238, 250, 265, 269–274 Dipolar dimer modes, 269 Dipolar plasmon resonance, 241, 244, 245, 247, 249, 262, 266, 267, 270, 271 Dipole moment, 318, 321–325, 338 Discrete dipole approximation (DDA), 9, 10, 18, 45, 51, 134, 235, 241, 249, 264–266, 271, 330, 332, 335, 336, 338, 350 Dispersion relation, 321 Distance-dependent optical properties, 299, 305 Dithiothreitol, 292 DNA-AgNW conjugates, 302, 303 DNA aptamers, 542–544 DNA DNA, 542 DNA protein, 542 DNA-silver nanocube conjugates, 305 DNA-silver nanoprism conjugates, 298, 299 DNA small molecule, 542 DNA-spherical silver nanoparticle conjugates, 296 DNSOM See Differential near-field scanning optical microscopy (DNSOM) Dodecanethiol (DT), 348 Donor-acceptor (DA) charge transfer systems, 563 Doped semiconductor nanoparticles, 12, 13 Double concentric nanoshells (DCN), 113, 121 Drude dielectric function, 33 Index Drude model, 14, 191, 317–320, 326 Drude sommerfeld model, 187 Dry etching, 78–80, 93 DT See Dodecanethiol (DT) Duplex formation, 289 Dye-sensitized cells, 563 Dynamic depolarization, 262, 264, 265 E EBID See Electron beam-induced deposition (EBID) EBL See Electron-beam lithography (EBL) EDC chemistry, 541 EELS See Electron energy loss spectroscopy (EELS) Effective medium approximation (EMA), 339–344 Effective medium modeling, 251–261 Effective polarizability tensor, 250 Efficiency factors, 108 EFTEM See Energy-filtered transmission electron microscope (EFTEM) EG See Ethylene glycol (EG) Eigenmodes, 320 Electric dipole mode, 92 Electroluminescence, 389–394, 403–417 Electromagnetic field, 85, 90, 92, 93 Electromagnetic responses of infinitely long nanowires, 206–207 Electron beam etching, 78 Electron beam-induced deposition (EBID), 94, 95 Electron-beam lithography (EBL), 23, 236, 238, 239 Electron energy loss spectroscopy (EELS), 8, Electronic interband transitions, 191 Electron mean free path, 188 Electron transfer donor-bridge-acceptor (DBA) heterodimers, 563 Electrostatic interaction, 536–537, 544, 553 Ellipsoidal Au nanoparticles, 19 Ellipsoidal nanoparticles, 18 Ellipsometry, 240, 251, 252, 254, 258, 260 EMA See Effective medium approximation (EMA) Encapsulation, 432, 435, 437, 439–442, 446–447 Energy bands of noble metals, 191 Energy bands of solid metals, 187 Energy-filtered transmission electron microscope (EFTEM), Estrogen receptor, 539 593 ET fluctuations, 581, 583, 584, 586 Ethylene glycol (EG), 328, 329, 334 Exciton, 486, 488, 489, 491–495, 497, 498, 500–512, 514–515, 520, 521 Excitonic property, 453–479 Exciton-phonon interaction, 454, 462, 467–472, 478 Exciton-plasmon, 507, 509, 510, 514, 521 Experimental bulk dielectric function, 190, 192 Extinction cross-section, 180, 181, 197, 199, 201, 205, 207, 208, 210–213, 238 Extinction spectroscopy, 180, 182–184, 218, 219 F Fabrication, 184, 185, 208, 218 Fano resonances, 54, 55, 102, 140, 141, 271 Far field coupling, 268 FDTD See Finite difference time-domain (FDTD) FEM See Finite element method (FEM) Femto-second laser near-field ablation, 239 Femto-second transient absorption, 500, 510 Fermi energy distribution function, 194 Finite difference time-domain (FDTD), 9, 10, 31, 38, 39, 83, 84, 89, 94, 95, 114, 116, 235, 264–266, 269, 271 Finite element method (FEM), 9, 10, 235, 264, 265 Finite-size effects, 235, 244–245 Fluorescence lifetime, 538, 551, 554 Fluorescence resonance energy transfer (FRET), 54 FMH See Fullerene-malonic acid-hexadduct (FMH) Focused ion beam (FIB) lithography, 23 Forster resonance energy transfer, 551 Forward scattering theorem, 200 Fragmentation process, 185 Free electrons, 191, 194–196, 201, 207, 216 contribution, 186–189, 192, 218 metal, 187 FRET See Fluorescence resonance energy transfer (FRET) Fullerene-malonic acid-hexadduct (FMH), 563, 564, 573, 574, 578, 585 Functionalization, 432, 444–446 G Gans theory, 18, 19 Ga2O3, 412, 413