Surface-Enhanced Raman Spectroscopy

PRESENTED BY
MD AMANULLAH SAIFEE
DEPARTMENT OF PHYSICS
JAMIA MILLIA ISLAMIA
 Spectroscopy

 Spectroscopy is the study of interaction of electromagnetic radiation with matter. Spectroscopic methods can be
based on phenomena of emission, absorption, fluorescence or scattering.

 What is Raman Effect?

Raman scattering or Raman effect is the inelastic scattering of photons from an atom or a molecule. This effect was
discovered by the famous Indian physicist C V Raman in the year 1928. In general, most photons are elastically
scattered from an atom or a molecule, with the scattered photons having the same energy and wavelength as the incident
photons. This phenomenon is known as ‘Rayleigh scattering’ and it accounts for the blue color of the sky. However, a
small fraction (1×10–7) of the scattered photons have a frequency different from the incident photons.
 Raman scattering

 Scattering of light by molecules can be elastic, Rayleigh scattering, or inelastic, Raman scattering. In
the elastic case, the photon’s energy and the state of the molecule after the scattering events are
unchanged. Hence, Rayleigh scattered light does not contain much information on the structure of
molecular states. In inelastic scattering, the frequency of photons of monochromatic light changes
upon interaction with the vibrational states, or modes, of a molecule.

In Raman scattering, two inelastic processes can occur:

 This shift provides information about vibrational, rotational, and other low frequency transitions in
molecules. Raman spectroscopy can be used to study solid, liquid, and gaseous samples.
• Energy level diagram for
Rayleigh and Raman
scattering
 Surface-enhanced Raman spectroscopy

 One of the limitations of the Raman effect is that it is a very weak phenomenon. About one in 107 photons
undergo Raman scattering. Therefore the Raman signal is very low from low concentrations of the analyte or
poor Raman scatterers. Sometimes the high fluorescence from the molecule obscures the Raman signals.
Surface enhanced Raman spectroscopy (SERS) is all about amplifying Raman signals from molecules, by
several orders of magnitude.

 SERS is a technique where molecules undergo much higher scattering efficiencies when adsorbed on metal
colloidal nanoparticles or rough metal surfaces.

 Surface-enhanced Raman scattering (SERS) exploits the capability of metallic nanostructures to concentrate
electromagnetic energy via optical modes called surface plasmons (SPs)
 SERS mechanisms

 With respect to the ordinary Raman spectroscopy, the main outcome of SERS is the gigantic enhanced Raman intensity in the level
of several orders of magnitude, which is widely agreed mainly from the joint contribution of electromagnetic and chemical
mechanisms.
 The classical theory of Raman scattering establishes that a molecule under an oscillating incident electric field may experience an
induced polarization and emit scattered light at a Raman-shifted (𝑃0) frequency (𝜔𝑅). The magnitude of depends on the Raman
polarizability of the electrons in the molecule and the strength of the incoming 𝑃0 (𝛼0R ) electromagnetic radiation 𝐸0 (with a
frequency of 𝜔0), as follows:

 Qualitatively, 𝛼0R represents the change in the electron cloud during the molecular vibration, and the Raman scattering involves the
interaction between two basic elements: a molecule and an incoming radiation. On the other hand, for SERS to occur, it requires
the presence of metallic nanostructures. Therefore, a complete description of SERS involves the interaction among light,
molecule, and metallic nanostructure.
 When a metal nanostructure is irradiated with incoming light (𝐸0), the conductive electrons are delocalized
into collective oscillations, which generate an EM field around the interface formed by the metal
nanostructure and the dielectric environment. The frequency of such electron oscillations depends on the
density of electrons, the effective electron mass, and the shape and size of the charge distribution. If the
frequency of the incoming radiation (𝜔0) is resonant with that of the electron oscillation, the excitation process
is referred as surface plasmon resonance (SPR). SPR can either propagate as a longitudinal wave at extended
metal surfaces or remain highly localized on places such as edges, tips, or crevices of the interface between
the metallic surface and the dielectric, corresponding to surface plasmon polaritons (SPPs) and localized
surface plasmon resonance (LSPR), respectively.
 Generally, the local EM field (𝐸𝐿𝑜𝑐) associated with the LSPR is higher in magnitude than the incident EM
field, which results in the enhancement of the EM field in SERS by a factor of
𝐺𝑒𝑥 = [𝐸𝑙𝑜𝑐(𝜔0)/𝐸0(𝜔0)]2
 A minor change in the local field enhancement can lead to significant variation in SERS enhancement. Moreover,
when two nanoparticles are spaced 1 nm apart, the plasmons of the two nanoparticles can couple with each other. In
this case, the SERS signal of one molecule can be enhanced by as high as 9 to 12 orders of magnitude when it is
placed in the 1 nm3 volume of the gap between the two nanoparticles (the so-called hot spot), and it may decay
quickly with increasing distance from the hot spot.

 The chemical mechanism encompasses effects that result from molecular adsorptions and lead to the modification
of 𝛼0R as a result of either chemical complexation, or charge transfer and charge transfer resonance.
 Key factors to boost SERS

 Estimation of SERS enhancement factors:

SERS Enhancement factor (EF) is an essential parameter for evaluating the analytical performance of a SERS
substrate, and it is defined as the ratio of SERS intensity contributed by each surface molecule to the ordinary
Raman intensity contributed by each free molecule. EF is normally estimated by the average SERS enhancement.

where ISERS and IRS are the SERS and ordinary Raman intensities, respectively, which can be obtained
experimentally. NSERS and NRS are the numbers of molecules probed by SERS and ordinary Raman.
 Selection of materials for SERS substrates.
Any material supporting plasmon activity at the excitation wavelength can serve as a SERS substrate, as long as
it shows good chemical stability of materials in the applied environment.

Gold, silver and copper are the most commonly used materials for SERS substrates with the outstanding SERS
enhancement. Silver can be used for excitation over the whole visible to near infrared region, whereas gold and
copper are used for the red and near infrared regions. Silver has a higher plasmon quality than that of gold and
copper, and gold has a much better chemical stability. In some specific applications such as catalysis and
electrochemistry, transition metals like platinum, palladium, iron, nickel and their alloys with a low SERS
enhancement have to be used.
 Raman vs SERS…

 In standard Raman spectroscopy, a laser source is directly focused on to a sample (Fig. a). The bonds of the
analyte scatter the laser light, and the inelastically scattered light is gathered and processed into a Raman
spectrum.
 Two significant Raman Spectroscopy limitations: 1) the intrinsic insensitivity of Raman, as only ~1 in
106 incident photons are Raman scattered; and 2) fluorescence emission interference, which is associated
with the excitation wavelength and the nature of the analyte molecule used.
The arrows in Fig. b are shown in bold to demonstrate this increase in magnitude. Theoretically,
this mechanism can account for signal enhancement by factors as great as 10 11
The standard Raman spectrum for fentanyl contains considerably more peaks than the relative SERS
spectrum. The SERS bands are also visibly wider than the standard Raman bands.
The main features of SERS technique are summarized briefly as follows:

 It is a highly surface-sensitive, non-destructive and in situ vibrational spectroscopic technique.

 SERS occurs when target molecules are brought within a few nanometers of the surface of
SERS active substrates of different morphologies.
 It has extremely high spatial resolution. The enhancement range is several nanometers,
effective for one or several molecular layers close to the SERS active substrate.
 SERS activity strongly depends on the nature of metal and surface roughness. Therefore,
SERS active substrate fabrication is a very important field in SERS research. The two most
common SERS active substrates are metal colloids of coinage metals of Au, Ag and Cu
obtained from chemical reduction, and the metal electrode surfaces roughened by one or more
electrochemical oxidation–reduction cycles. The recent advancement of nanotechnology has
been utilized to fabricate various nanostructures from nanoparticles to nanowires, which can be
used as SERS active substrates.
Thank You