SURFACE ENHANCED RAMAN SCATTERING

- Revati Muttur

OUTLINE
1. 2.

Scattering Raman scattering

Basics Rayleigh and Raman scattering Raman spectroscopy

3.

4.

5. 6.

SERS History Enhancement Mechanism SERS Substrates Applications Single Molecule SERS Nanofiber based SERS-active substrate Raman vs IR Spectrography TERS

SCATTERING

Scattering is a general physical process where some forms of radiation, such as light, sound, or moving particles, are forced to deviate from a straight trajectory by one or more localized non-uniformities in the medium through which they pass. Light scattering is a form of scattering in which light is the form of propagating energy which is scattered. Light scattering can be thought of as the deflection of a ray from a straight path, for example by irregularities in the propagation medium, particles, or in the interface between two media.

http://www.tutorvista.com/content/physics/physics-iv/optics/light-scattering.php

RAMAN SCATTERING

Raman scattering or Raman effect is named after Sir Chandrasekhara Venkata Rman, an Indian physicist He was the recipient of the Nobel Prize for Physics in 1930 for the discovery that when light traverses a transparent material, some of the light that is deflected changes in wavelength.
http://en.wikipedia.org/wiki/C._V._Raman

RAMAN SCATTERING- BASICS

The energy (E) is equal to Plancks constant (h) multiplied by the frequency (v) of the light

E hv
A c v

The wavelength of the light is equal to the speed of light divided by the frequency. The wavenumber (a) is equal to the frequency divided by the speed of light, or the inverse of the wavelength. av 1 c A

Typically, when light is incident on a molecule, it interacts only with the electron cloud surrounding the molecule, and there is only a tiny energy interaction between the electrons and the incident light.
This interaction being unstable, molecule quickly returns back to its original state, and the light is scattered at its original wavelength and frequency.

RAYLEIGH AND RAMAN SCATTERING

http://www.doitpoms.ac.uk/tlplib/raman/raman_scattering.php

RAMAN SPECTROSCOPY

http://www.grin.com/en/doc/244450/identification-of-neuroblastoma-and-its-prognostic-markers-using-raman

SURFACE ENHANCED RAMAN SCATTERING- HISTORY

SERS from pyridine adsorbed on electrochemically roughened silver was produced by Martin Fleischman and coworkers in 1974 They justified the large signal that they saw simply as a matter of the number of molecules that were scattering on the surface and did not recognize that there was a major enhancement effect In 1977 two groups independently noted that the concentration of scattering species could not account for the enhanced signal and each proposed a mechanism for the observed enhancement

SURFACE ENHANCED RAMAN SCATTERING

(i) An increased Raman signal appears due to magnification of both incident and Raman-scattered field, known as electromagnetic enhancement
(ii) chemical or electronic enhancement due to the increase of Raman cross-section when the molecule or lattice is in contact with metal nanostructures

ENHANCEMENT MECHANISMS

Since Raman intensity of a molecule or a crystal is proportional to the incident electromagnetic field, the enhancement factor (EF) of each molecule or crystal is described by EF t | E ( w) |2 | E ( w ') |2 where E() represents the electric-field enhancement factor at excitation source frequency of , and E() gives the EF of the Raman scattering fields at Stokes shifted frequency of The magnitude of enhancement is approximately |E()| 4, when = The enhancement deteriorates by a fraction of [r/(r +d)] 12, for a single molecule, is at a distance d from the surface of a metal sphere of radius r

ENHANCEMENT MECHANISMS

Chemical enhancement is another mechanism that is responsible for the SERS effect, in which the polarizability of a molecule adsorbed on a metal surface is enhanced When a photon impinges onto a metal, electron in the metal is excited and moves into electron affinity levels of the molecule adsorbed on the metal Hence, relaxation of the molecule follows a different new equilibrium, unlike the normal route of the same molecule without any metallic contact The molecule may stay in the new excited vibrational state, even after the excited electron moves back to the metal and combines with a metal hole, rendering a Raman-scattered photon Charge transfer can take place between the metal and absorbate and thus, chemical enhancement is realized and lead to SERS enhancement

ENHANCEMENT MECHANISMS

Earliest experiments reported enhancement factors of 104 to 106 Electromagnetic and electronic effects account for the observed 1014 enhancement Large enhancement is related to metal nanostructures specific morphologies Electromagnetic contribution accounts for bulk of the enhancement

SERS SUBSTRATES

The enhancement results from the amplification of the light by the excitation of Localized Surface Plasmon Resonances (LSPRs) This light concentration occurs preferentially in the gaps, crevices, or sharp features of plasmonic materials, which are traditionally noble and coinage metals with nanoscale features The success of SERS is highly dependent on the interaction between adsorbed molecules and the surface of plasmonic nanostructures, often the classic SERS substrates of gold (Au), silver (Ag), or copper (Cu) In general, Au and Ag are most often used as SERS substrates because they are air stable materials, while Cu is more reactive All three metals have LSPRs that cover most of the visible and near infrared wavelength range, where most Raman measurements occur, also making them convenient to use

SERS SUBSTRATES

Materials today, Jan-Feb 2012. Volume 15

SINGLE MOLECULE SERS

For Raman cross section of 10-29 cm2, large number of molecules required to convert enough laser photons to Raman photons For example, from 100mW laser light focused to 1um2 , single molecule photon scatters only 10-4 photons/second One would have to wait more than an hour for a single Raman photon which made single-molecule Raman spectroscopy a science fiction By virtue of extremely high enhancement factors in SERS, insight into individual molecules intrinsic vibrational properties can be obtained

SINGLE MOLECULE SERS

Microscope attachment used to focus near-IR laser light on small volume of solution containing silver nanoclusters Raman-scattered light channeled to spectrometer Molecules dilute enough to ensure no more than one molecule is in focus at a time

Physics Today, November 2007

SINGLE MOLECULE SERS

When average number of target molecules in scattering volume approaches one or fewer, Gaussian distribution of Raman intensities changes to Poisson distribution Poisson statistics imply uniform enhancement factors for all target molecules

Physics Today, November 2007

NANOFIBER-BASED SERS-ACTIVE SUBSTRATES

Oxygen plasma bombardment is usually utilized to remove used photoresist masks or residual photoresist After a long enough period of bombardment the surface of the substrates is very clean and smooth For photoresist of SU-8, the nanoresidues aggregate to form nanofibers, which can stand upright on the substrates. Since the dimensions of the nanofibers and the space between each of them are within a nanoscale range, it is possible to utilize them as SERS-active substrates.

NANOFIBER-BASED SERS-ACTIVE SUBSTRATES

NANOFIBER-BASED SERS-ACTIVE SUBSTRATES

a. Top view of large area of nanofibres

b. 45 view of nanofires

Haiyang Mao; Yulong Zhang; Wengang Wu; Chenyang Xue; Nano/Micro Engineered and Molecular Systems (NEMS), 2010 5th IEEE International Conference on , vol., no., pp.993-996, 20-23 Jan. 2010

RAMAN vs IR SPECTROSCOPY
RAMAN SPECTROSCOPY

IR SPECROSCOPY

It is due to the scattering light by the vibrating molecules. Polarizability of the molecule will decide whether the Raman spectra will be observed or not It can be recorded only in one exposure As Raman lines are weaker in intensity concentrated solution must be used to increase the intensity of Raman lines

It is the result of absorption of light by vibrating molecule The presence of permanent dipole moment in a molecule is the criterion of I.R. spectra It required at least two separate runs with different prisms to cover the whole region of I.R This condition is not rigid

TIP-ENHANCED RAMAN SCATTERING

Tip-enhanced Raman scattering (TERS) implemented as a scanning probe method, providing optical nanometer spatial resolution Here, rather than relying on the field enhancement of stationary nanoparticles, a plasmon resonance located at the apex of a noble metal scanning probe tip is utilized The inherent flexibility of a scanning probe system affords the freedom for spatially resolved spectroscopic probing and imaging of surface analytes
http://www.zenobi.ethz.ch/raman.html http://www.horiba.com/fr/scientific/products/raman-spectroscopy/raman-systems/hybrid-raman/raman-afm/ters

QUESTIONS?