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Fundamentals & applications of Lecture 2/2 plasmonics Svetlana V. Boriskina Overview: lecture 2 • Recap of Lecture 1 • Refractive index sensing • SP-induced nanoscale optical forces – Optical trapping & manipulation of nano-objects • • • • • Fluorescence & Raman spectroscopy Plasmonics for photovoltaics Hydrodynamic design of plasmonic components Magnetic effects Thermal effects: – Plasmonic heating – Near-field heat transfer via SPP waves • Plasmonic photosensitization of materials • Further reading & software packages • Omitted topics S.V. Boriskina, 2012 Drude-Lorentz-Sommerfeld theory Plasma frequency Drude permittivity function: p2 ne2 0me ( ) 1 p2 Image credit: Wikipedia ( 2 i ) Collision frequency 1 v l electron velocity S.V. Boriskina, 2012 mean free path Recap of Lecture 1: Propagating waves Frequency Plane wave transverse Bulk plasmon longitudinal photon Dispersion equation kx c ω d p p plasmon 1 d metals: ne 2 10eV k 1 2 2 1 2 p p x p c 0 me semicond.: p 0.5eV Surface plasmon p TM: E=(Ex,0,Ez) 1 d S.V. Boriskina, 2012 (Quasi) particle polariton = photon + k x m d c m d plasmon 12 kx(ω) High DOS, high localization Recap of Lecture 1: Localized plasmons Scattering response quadrupole E dipole Near-field patterns --+++ Lowest-energy modes Movie: http://juluribk.com dimer heptamer Plasmonic molecules Plasmonic antenna array S.V. Boriskina, 2012 λ High DOS, high localization Plasmonic atom Schematic dipoles Plasmons interactions with matter • Optical – Extreme light focusing/localization (sub-resolution imaging, photovoltaics) – Strong sensitivity to environmental changes (sensing) – Amplification of weak molecular signals (fluorescence, Raman scattering, absorption, circular dichroism) • Electronic – Enhancement of catalytic reactions – Plasmonic photosensitization of materials • Mechanical – Mechanical manipulation of nanoobjects • Thermal – Selective heating of nanoscale areas – Enhanced near-field heat transfer S.V. Boriskina, 2012 SP-enhanced sensing LSP sensors SPP sensors McFarland, A.D. & R.P. Van Duyne, Nano Lett. 2003. 3(8): p. 1057-1062. Sensor figure of merit (FoM): Sensitivity http://www.bio-sensors.net Requirements: • High sensitivity • High spectral resolution • Compact S.V. Boriskina, 2012 design FoM n Resonance linewidth FOM enhancement & miniaturization • Fano resonances in plasmonic molecules Mirin, N.A., K. Bao, & P. Nordlander, J. Phys. Chem. A, 2009. 113(16): p. 4028-4034. S.V. Boriskina, 2012 Towards single-molecule sensitivity Hybrid modes in optoplasmonic molecules: S.V. Boriskina, 2012 Santiago-Cordoba, M.A. et al, Appl. Phys. Lett., 2011. 99: p. 073701. Also: Boriskina, S.V. & B.M. Reinhard, Opt. Express, 2011. 19(22): 22305-22315; Ahn, W. et al, ACS Nano, 2012. 6(1): 951-960. Raman spectroscopy Rayleigh scattering Dipole moment induced by light: E0 cos(0t ) polarizability tensor (q) 0 q q Raman scattering vibrational coordinate q q0 cos(mt ) cos(0 m )t E0 cos(0t ) q0 E0 cos ( ) t q 0 m Rayleigh IR ~ 6 d particle size 4 S.V. Boriskina, 2012 hν0 hν0 Raman (Stokes & anti-Stokes) hν0 νm - molecular fingerprint excited hν0 virtual (induced dipole) hνm 3 I Ram ~ 10 I R a very weak effect! h(ν0 ± νm) Rayleigh vibrat. ground Stokes Raman Raman – Nobel Prize in 1930 Surface enhanced Raman spectroscopy (SERS) ERam ~ R g g E0 E-field enhancement @ ν0 @ the molecule position! E-field enhancement @ (ν0 –νm) High field localization enables SERS fingerprinting of single molecules R6G molecules on Ag nanoparticles Nie, S. & S.R. Emory, Science, 1997. 275(5303): 1102-1106. Fleischman M,et al Chem. Phys. Lett. 1974; 26: 123. S.V. Boriskina, Jeanmaire DL, 2012 Duyne RPV. J. Electroanal. Chem. 1977; 84: 1. Review: Moskovits, M., J. Raman Spectr., 2005. 36(6-7): p. 485-496 +references therein Single molecule delivery to the SP hot spot • super-hydrophobic delivery: De Angelis, F., et al. Nat Photon. 5(11): p. 682-687. S.V. Boriskina, 2012 Single molecule delivery to the SP hot spot • Optical trapping: Gradient force Dissipative force F U FD I 0n ( ' G " kG ) c 0 The probability to find a molecule @ r : Intensity enhancement P ( r,U ) µ P0 ( r) exp {- U(r) kBT } Optical potential Stable trapping: U (r) kBT 10 Review: Juan, M.L. et al, Nat Photon, 2011. 5(6): p. 349-356 S.V. Boriskina, 2012 L. Novotny, et al, Phys. Rev. Lett. 79 (4), 645 (1997); H. Xu and M. Käll, Phys. Rev. Lett. 89 (24), 246802 (2002). SP-enhanced fluorescence Fluorescence Fluorescence rate of a dipole with moment μ: f exc r ( r nr ) excitation rate radiative rate Excitation rate: exc μ E(rm , exc ) 2 hνexc hνf non-radiative rate (resistive heating) Spacer is needed to avoid quenching Fermi’s golden rule: 2 2 ( r nr ) μ (rm , f ) 3 0 Local density of states The emission intensity affected by both the excitation & emission modification S.V. Boriskina, 2012 Anger, P., P. Bharadwaj & L. Novotny, Phys. Rev. Lett., 2006. 96(11): p. 113002 SP-enhanced fluorescence ( r nr ) Single-molecule fluorescence 2 2 μ (rm , f ) 3 0 Emission spectrum shaping by the high-LDOS nanoparticle resonances Kinkhabwala, A., et al. Nature Photon., 2009. 3(11): p. 654-657. Russell, K.J., et al., Nat Photon, 2012. advance online publication. S.V. Boriskina, 2012 See also a review: Ming, T., et al., J. Phys. Chem. Lett. 3(2): p. 191-202 (2012). Plasmonic solar cells optical absorption c-Si: 250 - 700 μm a-Si: 0.1 – 0.3 μm charge carrier diffusion H. Atwater & A. Polman, Nature Mater. 2010 Electronic/photonic lengths mismatch S.V. Boriskina, 2012 Efficient nanoscale light trapping increase of the local density of optical states in a certain frequency range Callahan et al, Nano Lett. 2012 scattering field enhancement waveguiding Atwater & Polman, Nature Mater. 2010 S.V. Boriskina, 2012 How can a particle absorb more than the light C.F. Bohren, Am J. Phys. 1983, 51(4), p.326 incident upon it? S 1 2 Re E H Poynting vector determines electromagnetic power flow W. Ahn, S.V. Boriskina, et al, Nano Lett. 12, 219-227 (2012) extinction cross-section S.V. Boriskina, 2012 powerflow saddle point Optical energy flows in the direction of the phase change v g k group velocity phase saddle phase vortex flow saddle flow vortex Local topological features (sources, saddle points, vortices & sinks) define phase landscape that governs optical power flow S.V. Boriskina, 2012 W. Ahn, et al, Nano Lett. 12, 219-227 (2012) vortex nanogear transmission Reconfigurable vortex transmissions S.V. Boriskina, 2012 S.V. Boriskina & B.M. Reinhard, Nanoscale, 4, 76-90, 2012 Reconfigurable vortex transmissions: vortex nanogates ‘… the title is straight out of Enterprise's engineering room’ NextBigFuture.com SciTech forum S.V. Boriskina, 2012 Physical picture behind vortex nanogate Hydrodynamic design of SP components Electromagnetics Fluid dynamics ? Maxwell’s equations: E H 0 Gauss’ law Gauss’ law for magnetism E H t H J Ε t Faraday’s law Ampere’s law Navier-Stokes equations: t ( v) 0 Continuity (mass conservation) equation v t ( v ) v p T f Momentum conservation equation + boundary conditions S.V. Boriskina, 2012 fluid density flow velocity Hydrodynamic form of Maxwell’s equations Madelung transformation: (r ) k02 (r ) E(r, t ) U(r) expi((r) t ) ‘Photon fluid’ density: material loss or gain ‘mass’ conservation: (r) I (r) | U(r) |2 (r ) v(r ) (r ) (r ) ‘Photon fluid’ velocity: momentum conservation: v (r ) v(r) v(r) V (r) Q(r) convective term • steady state flow • local convective acceleration possible • fluid flux (the momentum density): S.V. Boriskina, 2012 S 1 (20) (r)v(r) external potential created by the nanostructure V (r) k 02 2 1 (r) S.V. Boriskina & B.M. Reinhard, Nanoscale, 4, 76-90, 2012 Hydrodynamic form of Maxwell’s equations Vortex generates a velocity field: v(r) v(r) V (r) Q(r) S.V. Boriskina, 2012 S.V. Boriskina & B.M. Reinhard, Nanoscale, 4, 76-90, 2012 Energy flows in plasmonic nanostructures Stockman’s nanolens: Li, K., M.I. Stockman, & D.J. Bergman, Phys. Rev. Lett., 2003. 91(22): p. 227402. S.V. Boriskina & Reinhard, Nanoscale, 4, 76-90, 2012 Surface plasmon polariton wave: S.V. Boriskina, 2012 Magnetic SP effects coil magnet Plasmonic nanostructures built from nonmagnetic materials can exhibit effective magnetic permeability E H t Split-ring resonator: Image: http://www.ndt-ed.org/ double-negative metamaterials effective permeability Pendry, J.B. et al, IEEE Trans. Microw. Theory Tech., 47(11), p.2075, 1999 rotating currents in the rings induce magnetic flux S.V. Boriskina, 2012 Shelby, R.A., et al Science, 2001. 292(5514): p. 77-79. Magnetic SP effects in nanoparticle clusters E H t Anti-ferromagnetic response: charge density: Magnetic dipole induced magnetic moments: Liu, N., et al., Nano Letters, 2011. 12(1): p. 364-369. dx dy Ag 2r k Electric z yfield intensity: x E Magnetic field distribution: Fan, J.A., et al. Science, 2010. 328(5982): p. 1135-1138. S.V. Boriskina, 2012 S.V. Boriskina, in Plasmonics in metal nanostructures: Theory & applications ( Shahbazyan & Stockman eds.) Springer, 2012 Thermal SP effects cancer treatment Electric field to heat: T t ~ j(r, t ) E(r, t ) temperature dissipation of optical energy Chen, J., et al. Small, 2010. 6(7): p. 811-817. nanopatterning Govorov A.O. & Richardson, Nano Today, 2007. 2(1) 30-38 Atanasov, P.A., et al., Int. J. Nanopart. 2010. 3(3): p. 206-219. S.V. Boriskina, 2012 Thermal SP effects Heat to electric field: E(r, ) i0 G(x, x' , ) j(x' , )dx' V ~ DOS fluctuating currents Near-field heat transfer: (cold, T2) d (hot, T1) High SPP-induced DOS results in the near-field coherence e.g., Narayanaswamy, A. & G. Chen, Appl. Phys. Lett. 2003. 82(20): p. 3544-3546; Fu, C.J. & W.C. Tan, J. Quant. Spectr. Radiat. Transf. 2009. 110(12): p. 1027-1036; Rousseau, E., et al. Nat Photon, 2009. 3(9): p. 514-517; Volokitin, A.I. & B.N.J. Persson. Rev. Mod. Phys., 2007. 79(4): p. 1291-1329 S.V. Boriskina, 2012 Plasmonic photosensitization of semiconductors Knight, M.W., et al., Science. 332(6030): p. 702-704. • hot electrons can tunnel from metal nanoantennas into semiconductor • photon detection at energies below the semiconductor band gap Theoretical prediction: Shalaev, V.M., et al., Phys. Rev. B, S.V. Boriskina, 2012 1996. 53(17): p. 11388-11402. Plasmonic enhancement of photocurrent in graphene: in silicon: Xu, G., et al (2012), Adv. Mater., 24: OP71–OP76 Mubeen, S., et al., Nano Letters. 11(12): p. 5548-5552. Echtermeyer, T.J., et al. 2012, Nature Commun. 2: p. 458. S.V. Boriskina, 2012 Books & review articles on plasmonics: • Lal, S., S. Link, and N.J. Halas, Nano-optics from sensing to waveguiding. Nat Photon, 2007. 1(11): p. 641-648 • Halas, N.J., et al., Plasmons in strongly coupled metallic nanostructures. Chem. Rev., 2011. 111(6): p. 3913-3961 • Schuller, J.A., et al., Plasmonics for extreme light concentration and manipulation. Nature Mater., 2010. 9(3): p. 193-204 • Stockman, M.I., Nanoplasmonics: past, present, and glimpse into future. Opt. Express. 2011, 19(22): p. 22029-22106 • Maier, SA, Plasmonics: Fundamentals and Applications, Springer, NY, 2007 • Novotny, L., and B. Hecht. Principles of Nano-Optics, Cambridge University Press, 2006 This list is by no means complete … S.V. Boriskina, 2012 Commercial & free software • Lumerical FDTD Solutions http://www.lumerical.com/tcad-products/fdtd/ • COMSOL Multiphysics® (FEM) http://www.comsol.com/products/multiphysics/ • MEEP (FDTD) http://ab-initio.mit.edu/wiki/index.php/Meep • DDSCAT (discrete dipole approximation) http://www.astro.princeton.edu/~draine/DDSCAT.html • A collection of free software (including Mie theory methods) http://www.scattport.org/index.php/light-scattering-software S.V. Boriskina, 2012 Topics I had to omit due to the lack of time Plasmonic cloaking: New Journal of Physics, Focus Issue on 'Cloaking and Transformation Optics', Guest Editors: Ulf Leonhardt and David R. Smith, Vol. 10, Nov 2008. Non-local response: A.D. Boardman, Electromagnetic Surface Modes, Ch. Hydrodynamic Theory of Plasmon–polaritons on Plane Surfaces, John Wiley & Sons Ltd., 1982. Resonant energy transfer & ‘dark’ plasmonic nanocircuits: Andrew, P. and W.L. Barnes, Energy Transfer Across a Metal Film Mediated by Surface Plasmon Polaritons. Science, 2004. 306(5698): p. 1002-1005 Akimov, A.V., et al., Generation of single optical plasmons in metallic nanowires coupled to quantum dots. Nature, 2007. 450(7168): p. 402-406. Boriskina, S.V. and B.M. Reinhard, Spectrally and spatially configurable superlenses for optoplasmonic nanocircuits. Proc. Natl. Acad. Sci. USA, 2011. 108(8): p. 3147-3151. Spasers: Stockman, M.I., Spasers explained. Nat Photon, 2008. 2(6): p. 327-329. Plasmonic particles on demand: Luther, J.M., et al., Localized surface plasmon resonances arising from free carriers in doped quantum dots. Nat Mater, 2011. 10(5): p. 361-366. finally, Metamaterials is a huge area in itself – could be a separate class S.V. Boriskina, 2012