ECE280: Nano-Plasmonics and Its Applications. Week8

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1 ECE280: Nano-Plasmonics and Its Applications Week8 Surface Enhanced Raman Scattering (SERS) and Surface Plasmon Amplification by Stimulated Emission of Radiation (SPASER)

2 Raman Scattering Chandrasekhara Venkata Raman 1928 Raman observed spectrally shifted lines in the scattering spectrum. The frequency shift is independent of the excitation frequency. Rayleight scattering Raman received the Nobel Prize in 1930

3 Raman Scattering Raman scattering on vibrational / rotational states of molecules

4 SERS Raman scattering is an extremely inefficient process with scattering cross sections (~10-30 cm 2 /molecule) approximately 14 orders of magnitude smaller than the absorption cross sections (~10-16 cm 2 /molecule) of fluorescent dye molecules. To achieve single-molecule sensitivity, the normal Raman scattering efficiency must be enhanced fold or more.

5 Surface Enhanced Raman Scattering Theoretical explanations for SERS A. Electromagnetic field enhancement mechanism EM G SERS (,) r v excitation of surface plasmon tends to form localized hot spots the magnitude of enhancement ~ times for single colloidal silver, and ~10 8 for the gap between two coupled particles = E(,) rv E inc( v) 4 B. Chemical enhancement due to specific interactions, forming charge-transfer complexes the magnitude of chemical enhancement ~ times

6 SERS Fig. 1. Single Ag nanoparticles imaged with evanescent -wave excitation. Total internal reflection of the laser beam at the glass-liquid interface was used to reduce the laser scattering background. The instrument setup for evanescent-wave microscopy was adapted from Funatsu et al. The images were directly recorded on color photographic film (ASA-1600) with a 30-s exposure by a Nikon 35-mm camera attached to the microscope. (A) Unfiltered photograph showing scattered laser light from all particles immobilized on a polylysine-coated surface. (B) Filtered photographs taken from a blank Ag colloid sample (incubated with 1 mm NaCl and no R6G analyte molecules). (C) and (D) Filtered photographs taken from a Ag colloid sample incubated with M R6G. These images were selected to show at least one Raman scattering particle. Different areas of the cover slip were rapidly screened, and most fields of view did not contain visible particles. (E) Filtered photograph taken from Ag colloid incubated with M R6G. (F) Filtered photograph taken from Ag colloid incubated with MR6G. A highperformance bandpass filter was used to remove the scattered laser light and to pass Stokes-shifted Raman signals from 540 to 580 nm (920 to 2200 cm21). Continuous-wave excitation at nm was provided by an Ar ion laser. The total laser power at the sample was 10 mw. Note the color differences between the scattered laser light in (A) and the red-shifted light in (C) through (F).

7 SERS SERS can be much stronger than normal fluorescence of molecules scattering cross-section can be in creased by a factor of 10 14

8 One Example

9 SERS

10 Other Plasmonic Structures

11 Other Plasmonic Structures Dendritic Gold Substrates Nano-Burger

12 Raman Imaging Chemical Imaging with a Raman Atomic-Force Microscope

13 Further Reading Reference 1. A quick overview of surface-enhanced Raman spectroscopy 2. Raman spectroscopy and related optical techniques 3. Introduction to plasmons and plasmonics 4. SERS enhancement factors and related topics 5. Calculations of electromagnetic enhancements 6. EM enhancements and plasmon resonances: examples and discussion 7. Metallic colloids and other SERS substrates 8. Recent developments A. Density functional theory (DFT) calculations for Raman spectroscopy B. The bond-polarizability model C. A brief overview of Maxwell's equations in media D. Lorentz model of the atomic/molecular polarizability E. Dielectric function of gold and silver F. Plane waves and planar interfaces G. Ellipsoids in the electrostatic approximation H. Mie theory and its implementation

14 ECE280: Nano-Plasmonics and Its Applications Surface Plasmon Amplification by Stimulated Emission of Radiation (SPASER)

15 E-M M wave at the interface ε > 0, ε < 0 Case 4: 1 2 and ε 1+ ε 2 < 0 We have: kx 1 ω εε = = c ε1+ ε2 1 2 real number 2 ω ε 1 kz1 = i = imaginary number c ε1+ ε ω ε 2 kz2 = i = imaginary number c ε1+ ε2 ε 2 <0 Media 2 Media 1 ε 1 >0 k z2 k z1 k x2 k x1 z x EM wave propagates in x direction, but exponentially decays away from the interface! This is called the surface plasma. SPs propagates in x direction, and also decays in x direction that is determined by the metal loss. Introduce gain in dielectrics?

16 Metal / Gain Interface ε 2 <0 k z2 Media 2 ε 1 =ε 1 +iε 1 (with negative ε 1 representing gain) ε 2 =ε 2 +iε 2 k z k x2 K x E z k x1 ε 1 >0 k z1 Gain Media Media 1 SPs: bound to the interface Im(k z1 )>0

17 Metal / Gain Interface =0

18 Experiments M M -1

19 Experiments -- 2

20 A maximum signal enhancement of 50% (1.73 db) was recorded at a higher pump power of 266 mw

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