Photoluminescence of Gold Nanorods: Purcell Effect Enhanced Emission from Hot Carriers.

We demonstrate, experimentally and theoretically, that the photon emission from gold nanorods can be viewed as a Purcell effect enhanced radiative recombination of hot carriers. By correlating the single-particle photoluminescence spectra and quantum yields of gold nanorods measured for five different excitation wavelengths and varied excitation powers, we illustrate the effects of hot carrier distributions evolving through interband and intraband transitions and the photonic density of states on the nanorod photoluminescence. Our model, using only one fixed input parameter, describes quantitatively both emission from interband recombination and the main photoluminescence peak coinciding with the longitudinal surface plasmon resonance.

[1]  Gregory V Hartland,et al.  Optical studies of dynamics in noble metal nanostructures. , 2011, Chemical reviews.

[2]  Paul V. Ruijgrok,et al.  Room-Temperature Detection of a Single Molecule’s Absorption by Photothermal Contrast , 2010, Science.

[3]  Stephan Link,et al.  One-Photon Plasmon Luminescence and Its Application to Correlation Spectroscopy as a Probe for Rotational and Translational Dynamics of Gold Nanorods , 2011 .

[4]  C. D'Andrea,et al.  Time-Resolved Photoluminescence in Gold Nanoantennas , 2016 .

[5]  G. Wiederrecht,et al.  Anomalous ultrafast dynamics of hot plasmonic electrons in nanostructures with hot spots. , 2015, Nature nanotechnology.

[6]  Hangqi Zhao,et al.  Distinguishing between plasmon-induced and photoexcited carriers in a device geometry , 2015, Nature Communications.

[7]  Peter Nordlander,et al.  Plasmon-induced hot carriers in metallic nanoparticles. , 2014, ACS nano.

[8]  Matthew Pelton,et al.  Modified spontaneous emission in nanophotonic structures , 2015, Nature Photonics.

[9]  Lukas Novotny,et al.  Continuum generation from single gold nanostructures through near-field mediated intraband transitions , 2003 .

[10]  R. Frontiera,et al.  Ultrafast Surface-Enhanced Raman Probing of the Role of Hot Electrons in Plasmon-Driven Chemistry. , 2016, The journal of physical chemistry letters.

[11]  Erik Dujardin,et al.  Tailoring and imaging the plasmonic local density of states in crystalline nanoprisms. , 2013, Nature materials.

[12]  Ravishankar Sundararaman,et al.  Theoretical predictions for hot-carrier generation from surface plasmon decay , 2014, Nature Communications.

[13]  Lijun Wu,et al.  Comparison of photoluminescence quantum yield of single gold nanobipyramids and gold nanorods. , 2015, ACS nano.

[14]  Mohammad M. Shahjamali,et al.  Influence of Surfactant Bilayers on the Refractive Index Sensitivity and Catalytic Properties of Anisotropic Gold Nanoparticles. , 2016, Small.

[15]  H. Atwater,et al.  Plasmoelectric potentials in metal nanostructures , 2014, Science.

[16]  Jun Liu,et al.  Relaxation of Plasmon-Induced Hot Carriers , 2017 .

[17]  Naomi J. Halas,et al.  Photodetection with Active Optical Antennas , 2011, Science.

[18]  Jeremy J. Baumberg,et al.  Demonstrating Photoluminescence from Au is Electronic Inelastic Light Scattering of a Plasmonic Metal: The Origin of SERS Backgrounds , 2015, Nano letters.

[19]  Stephan Link,et al.  Optical characterization of single plasmonic nanoparticles. , 2015, Chemical Society reviews.

[20]  S. Linic,et al.  Tuning Selectivity in Propylene Epoxidation by Plasmon Mediated Photo-Switching of Cu Oxidation State , 2013, Science.

[21]  Takuya Iida,et al.  Anomalous optical selection rule of an organic molecule controlled by extremely localized light field , 2011 .

[22]  T. Shahbazyan.  Theory of plasmon-enhanced metal photoluminescence. , 2012, Nano letters.

[23]  R. Rosei,et al.  Splitting of the interband absorption edge in Au , 1975 .

[24]  Mostafa A. El-Sayed,et al.  Electron dynamics in gold and gold–silver alloy nanoparticles: The influence of a nonequilibrium electron distribution and the size dependence of the electron–phonon relaxation , 1999 .

[25]  Sun,et al.  Femtosecond-tunable measurement of electron thermalization in gold. , 1994, Physical review. B, Condensed matter.

[26]  Daniel Kleppner,et al.  Cavity quantum electrodynamics , 1986 .

[27]  R. Baer,et al.  Near-field manipulation of spectroscopic selection rules on the nanoscale , 2012, Proceedings of the National Academy of Sciences.

[28]  F. Aryasetiawan,et al.  Corrected local-density approximation band structures, linear-response dielectric functions, and quasiparticle lifetimes in noble metals , 2001 .

[29]  M. Kociak,et al.  Link between Cathodoluminescence and Electron Energy Loss Spectroscopy and the Radiative and Full Electromagnetic Local Density of States , 2015 .

[30]  W. Pfeiffer,et al.  Electron dynamics in supported metal nanoparticles: relaxation and charge transfer studied by time-resolved photoemission , 2004 .

[31]  J. Dionne,et al.  Hot-Carrier-Mediated Photon Upconversion in Metal-Decorated Quantum Wells. , 2017, Nano letters.

[32]  Hajime Ishihara,et al.  Selection-rule breakdown in plasmon-induced electronic excitation of an isolated single-walled carbon nanotube , 2013, Nature Photonics.

[33]  R. Rosei,et al.  Splitting of the interband absorption edge in Au: Temperature dependence. , 1975 .

[34]  Jan Mertens,et al.  How Light Is Emitted by Plasmonic Metals. , 2017, Nano letters.

[35]  G. Gerber,et al.  Surface plasmon dynamics in silver nanoparticles studied by femtosecond time-resolved photoemission. , 2000, Physical review letters.

[36]  E. Knoesel,et al.  Ultrafast dynamics of hot electrons and holes in copper: Excitation, energy relaxation, and transport effects , 1998 .

[37]  M. El-Sayed,et al.  The `lightning' gold nanorods: fluorescence enhancement of over a million compared to the gold metal , 2000 .

[38]  N. D. Fatti,et al.  Nonequilibrium Electron Interactions in Metal Films , 1998, 0709.0815.

[39]  Hailong Hu,et al.  Plasmon-modulated photoluminescence of individual gold nanostructures. , 2012, ACS nano.

[40]  G. Meister,et al.  New lifetime estimates for d-band holes at noble metal surfaces , 1999 .

[41]  Thomas A. Klar,et al.  Anticorrelation of Photoluminescence from Gold Nanoparticle Dimers with Hot-Spot Intensity , 2016, Nano letters.

[42]  Mustafa Yorulmaz,et al.  Luminescence quantum yield of single gold nanorods. , 2012, Nano letters.

[43]  Theodore Goodson,et al.  Femtosecond excitation dynamics in gold nanospheres and nanorods , 2005 .

[44]  A. Mooradian,et al.  Photoluminescence of Metals , 1969 .

[45]  T. Majima,et al.  Nanoplasmonic Photoluminescence Spectroscopy at Single-Particle Level: Sensing for Ethanol Oxidation. , 2016, Angewandte Chemie.

[46]  Kenji Setoura,et al.  Optical Scattering Spectral Thermometry and Refractometry of a Single Gold Nanoparticle under CW Laser Excitation , 2012 .

[47]  Ulrich Hohenester,et al.  MNPBEM - A Matlab toolbox for the simulation of plasmonic nanoparticles , 2011, Comput. Phys. Commun..

[48]  Theodore Goodson,et al.  Relative enhancement of ultrafast emission in gold nanorods , 2002 .

[49]  Hiromi Okamoto,et al.  Plasmon mode imaging of single gold nanorods. , 2004, Journal of the American Chemical Society.

[50]  V. Zhukov,et al.  Lifetimes of d holes in Cu and Au: Full-potential LMTO approach , 2003 .

[51]  Keyu Xia,et al.  Luminescence quantum yields of gold nanoparticles varying with excitation wavelengths. , 2016, Nanoscale.

[52]  Shen,et al.  Photoinduced luminescence from the noble metals and its enhancement on roughened surfaces. , 1986, Physical review. B, Condensed matter.

[53]  Jun Yi,et al.  Intraband Hot-Electron Photoluminescence from Single Silver Nanorods , 2016 .

[54]  Gyoujin Cho,et al.  Femtosecond Emission Studies on Gold Nanoparticles , 2002 .

[55]  C. Schönenberger,et al.  Additional peak appearing in the one-photon luminescence of single gold nanorods. , 2016, Optics letters.

[56]  R. Marcus,et al.  Time-dependent fluorescence spectra of large molecules in polar solvents , 1998 .

[57]  Adnan,et al.  Fluorescence Efficiency of Rhodamine 6G Doped PMMA , 2010 .

[58]  C. Murray,et al.  Using binary surfactant mixtures to simultaneously improve the dimensional tunability and monodispersity in the seeded growth of gold nanorods. , 2013, Nano letters.

[59]  Stephan Link,et al.  Photoluminescence of a Plasmonic Molecule. , 2015, ACS nano.

[60]  Martin Moskovits,et al.  An autonomous photosynthetic device in which all charge carriers derive from surface plasmons. , 2013, Nature nanotechnology.

[61]  B. Valeur.  Characteristics of Fluorescence Emission , 2001 .

[62]  Stephan Link,et al.  Plasmon emission quantum yield of single gold nanorods as a function of aspect ratio. , 2012, ACS nano.

[63]  Wei Wang,et al.  Resonant secondary light emission from plasmonic Au nanostructures at high electron temperatures created by pulsed-laser excitation , 2014, Proceedings of the National Academy of Sciences.

[64]  Thomas A. Klar,et al.  Plasmon emission in photoexcited gold nanoparticles , 2004 .

[65]  V. A. Apkarian,et al.  Observation and analysis of Fano-like lineshapes in the Raman spectra of molecules adsorbed at metal interfaces , 2015, 1509.03906.

[66]  J. Simon.  Time-resolved studies of solvation in polar media , 1988 .