LangmuirBlodgettSilverNanowireMonolayersfor

MolecularSensingUsingSurfaceEnhancedRaman
Spectroscopy

Submittedby
PrasannaKumarSiddireddy
MohammadSaquibAlam
SanchitaDhas

DepartmentofPhysics
IITBombay

IntroductiontoSERS

Smekal theoretically predicted inelastic light scattering in 1923. Raman and Krishnan first
experimentally observed the phenomenon and reported in their 1928 Nature paper that the
inelastic scattering effectwascharacterizedbyitsfeeblenessincomparisonwiththeordinary
scattering. This feeble phenomenon is now known as Raman scattering. The change in
wavelength that is observed when a photon undergoes Raman scattering is attributed to the
excitation (or relaxation) of vibrational modes of a molecule. Because different functional
groups have differentcharacteristic vibrationalenergies,everymoleculehasauniqueRaman
spectrum.

In accordance with the Raman selection rule, the molecular polarizability changes as the
molecular vibrations displace the constituent atoms from their equilibrium positions. The
intensity of Raman scattering is proportional to the magnitude of the change in molecular
polarizability. Thus, aromatic molecules exhibit more intense Raman scatteringthanaliphatic
molecules. Even so, Raman scattering cross sections are typically 14 orders of magnitude
smaller than those of fluorescence therefore, the Raman signal is still several orders of
magnitude weaker than the fluorescence emission in most cases. Becauseof the inherently
small intensity of the Raman signal, the sensitivity limits of available detectors, and the
intensity of the excitation sources, the applicability of Raman scattering was restricted for
many years. However, its utility as an analytical technique improved with the advent of the
laserandtheevolutionofphotondetectiontechnology.

In 1977,JeanmaireandVanDuynedemonstratedthatthemagnitudeoftheRaman scattering
signal can be greatly enhanced when the scatterer is placed on or near a roughened
noblemetal substrate. Strong electromagnetic fields are generated when the localized
surface plasmon resonance (LSPR) of nanoscale roughness features on a silver, gold, or
copper substrate is excited by visible light. When the Raman scatterer is subjected to these
intensified electromagnetic fields, the magnitude of the induced dipole increases, and
accordingly, the intensity of the inelastic scattering increases. This enhanced scattering
process is known as surface enhanced Raman (SER) scatteringa term that emphasizes
thekeyroleofthenoblemetalsubstrateinthisphenomenon.

FundamentaltheoryofSERS

The mechanism of SERS enhancement remains an active research topic. There are two
primary theories and while their mechanisms differ substantially, distinguishing them
experimentally has not been straightforward. The electromagnetic theory posits the
excitation of localized surface plasmons, while the chemical theory proposesthe formation
of chargetransfer complexes. The chemical theory applies only for speciesthathaveformed
a chemical bond withthesurface,soitcannotexplainthe observedsignalenhancementinall
cases, whereas the electromagnetic theory can apply even in those cases where the
specimenisphysisorbedonlytothesurface.

Thechemicalmechanism:
In the chemical mechanism, is thought to contribute an averageenhancementfactorof100,
a chargetransfer state is created between the metal and adsorbate molecules. In a manner
analogous to that observed in resonance Raman spectroscopy, the existence of this
chargetransfer state increases the probability of a Raman transition byproviding a pathway
for resonant excitation. This mechanism issitespecificandanalytedependent.Themolecule
must be directly adsorbed to the roughened surface to experience the chemical
enhancement.

Fig1.SERSPhenomenon

Theelectromagneticenhancement:

To understand the electromagnetic enhancement, one must consider the size, shape, and
material of the nanoscale roughness features. These characteristics determine theresonant
frequency of the conduction electrons in a metallic nanostructure. When electromagnetic
radiation with the same frequency is incident upon the nanostructure, the electric field of the
radiation drivesthe conduction electronsintocollectiveoscillation.ExcitationoftheLSPRhas
two consequences: selective absorption and scattering of the resonant electromagnetic
radiation, and generation of large electromagnetic fields at the surface of the roughness
feature. Electromagnetic enhancement relies on Ramanactive molecules being confined
within these electromagnetic fields and contributes an average enhancement factor of
10,000.

The simple example of an isolated sphere, with a quasi static description of the incident
electromagneticfield,hasbeenusedtoderivetheproportionality

in which E is the electric field magnitude at the surface of the sphere, E0 isthe incident field
magnitude, m is the wavelengthdependent dielectric constant of the metal composing the
sphere, and 0 is the dielectric constant of the local environment around the sphere. This
relation reveals that when m = 20, which can be achieved for silver and gold at certain
wavelengths in the visibleand nearIR,themagnitudeoftheelectricfieldatthesurfaceofthe
sphere becomes very large. This field enhancement is induced by satisfying the LSPR
condition. Maximization of these cross sections at resonant wavelengths yields the
spectroscopicsignatureofexcitingtheLocalisedSurfaceplasmonresonance(LSPR).

Technique

Objective:
Application of SERS for detection of trace chemical components used in warfare fornational
andglobalsecurity.

Techniqueused:
LangmuirBlodgett technique was usedto assemble monolayers of aligned silver nanowires
that are 50 nm in diameter and 23 m in length. These nanowires possess pentagonal
crosssections and pyramidal tips. They are closepacked and are aligned parallel to each
other. The resulting nanowire monolayers served as excellent substrates for
surfaceenhanced Raman spectroscopy (SERS) with large electromagnetic field
enhancementfactors(2105for2,4dinitrotoluene).[2]

ExperimentalProcedure:
Silver nanowires were prepared using poly vinyl pyrrolidone(PVP)asthecappingagent.The
samples were purifiedtoremovesphericalnanoparticles. Theresultingnanowiresareuniform
in both diameter and aspect ratio. After functionalizing with 1hexadecanethiol ligands, the
wires were rendered hydrophobic and redispersed in chloroform. An important feature of
these nanowires is their pentagonal crosssections. In addition, these wires possess
pentagonal pyramidal ends with vertices as sharp as 2 nm. The noncircular crosssections
and sharp wire tips might haveimportant consequences for molecular sensing using surface
enhancedRamanspectroscopy.

The nanowires were then dispersed onto a water surface of the LangmuirBlodgett trough.
The displacement of the PVP capping agents with thiol ligands is critical in rendering the
nanowire surface hydrophobic as well as preventing aggregation. Theassembly processisa
microscopic version of logsonariver. At this stage, the surface pressure is zero and the
nanowires are randomly oriented. The water surface is essentially transparent. When the
nanowires were compressed, thesurface pressure increased.Aboveacertaincriticalsurface
pressure, the monolayer underwent a Mottinsulatortometal transition, aspreviouslyseenin
LangmuirBlodgettmonolayers ofsphericalAgnanocrystals.Thistransitionisindicatedbythe
appearance of a metallic sheen on the nanowire monolayer surface.Thefinalalignedareais
limitedonlybytheamountofinitialmaterialusedforthecompression.

Most importantly, the compressed silver nanowire monolayer exhibits remarkable alignment
parallel to the trough barrier. The nanowires are aligned sidebyside over large areas,
resembling a nematic twodimensionalordering of a liquid crystal.Thislargescaledirectional
ordering was also verifiedby imaging the sample under an opticalmicroscopeequippedwith
acrosspolarizer.

This large area of nanowire alignment enabled the fabrication of highdensity nanoscale
interconnects, sensor arrays, as well as multilayer structures via a layerbylayer transfer
approach. These monolayers can be readily transferred to any desired substrate, including
silicon wafers, glass slides, and polymer substrates. LangmuirBlodgett approach is a very
powerfultechniquefortheorganizationofanisotropicbuildingblocksintofunctional nanoscale
assemblieswithunprecedentedlyhighpackingdensity.

Significantly, these aligned nanowire monolayers can bereadily used as surface enhanced
Raman spectroscopy(SERS) substrates for molecular sensing with high sensitivity and
specificity. These metallic layers areexpectedtoexhibitgiantlocal electromagnetic(EM)field
enhancement,particularlyfornanowireswithsharptipsandnoncircularcrosssections.

Theenhancementfactor(EF)wascalculatedaccordingtothefollowingexpression:
EF=[ISERS]/[IRaman][Mb]/[Mads]
where Mb istheconcentrationofmoleculesinthebulksample andMadsistheconcentrationof
adsorbed molecules. ISERS and IRaman are intensities in the SER and Raman spectrum,
respectively. This enhancementcan be attributed to increasedlocalopticalfieldsneartheAg
surfaceduetotheexcitationofsurfaceplasmonresonances.

Fig2.SERS spectrum of 2,4DNT on the thiolcapped Ag nanowire monolayers after incubation for 10minin 102M
2,4DNT/MeOH solution.Thespectrumwasrecordedusing25mWof532nmlaserlight.Theacquisition timewas 10
s.[2]

The observedlarge enhancementfactorssuggestthatthesemonolayerscanindeedserve as

robust solid substrates for carryingoutmolecularsensingwithhighsensitivityandspecificity.
The capability of nanowire substrates for the detection of 2,4dinitrotoluene(2,4DNT), the
most common nitroaromatic compound for detecting buried landmines and other explosives
wasdemonstrated.

SERS spectrum of 2,4DNT absorbed on the thiolcapped Ag nanowire monolayers. TheNO

2 stretching mode at 1348 cm1thekeyvibrationalmodefortheanalysisof2,4DNTisclearly
displayed and wellseparated from the surfactantrelated Raman bands at 1295 and 1435
cm1. A sensitivity of approximately 0.7 pg, assuming a monolayer coverage for2,4DNTand
an area of 45 2 per adsorbate. An EF of 2 105 was calculated for the vibration mode at
1348cm1.

Commentonthistechnique

The LangmuirBlodgett technique used to assemble monolayers of aligned silver nanowires

appears to have severaladvantages. We see that we can completely reproduce the method
in a laboratory to obtain the substrate for carrying out the SERS. When this substrate is
applied to detect 2,4DMT which is usually found near the proximity of landmineswehavea
sharppeakinthespectrumwhichgivesusanindicationaboutthepresenceofalandmine.

References

1) Haynes, Christy L., Adam D. McFarland, and Richard P. Van Duyne.

"SurfaceenhancedRamanspectroscopy."AnalyticalChemistry77.17(2005):338A.

2) Tao, Andrea, et al. "LangmuirBlodgett silver nanowire monolayers for molecular

sensing using surfaceenhanced Raman spectroscopy." Nano Letters 3.9 (2003):
12291233.