Surface-Enhanced Raman Scattering

(SERS)
Enhancement
Factor (EF)

SERS
=
Raman

= E
Chemical

Raman
Scattering
( 0 vib)

Electromagnetic

Laser
Excitation
( 0 )

Haynes, McFarland, and Van Duyne, Anal. Chem.,77, 338A-346A (2005).

SERS Enhancement Mechanisms

Chemical Mechanism:
Laser excites (a) new electronic states arising from
chemisorption or (b) shifted or broadened adsorbate
electronic states yielding a resonance condition.
Short range (1-5 )
No roughness requirement
Contributes EF ~ 102 104
Electromagnetic Mechanism:
LSPR induces large electromagnetic fields at roughened
metal surface where molecules are adsorbed.
Long range (2-4 nm)
Affected by all factors determining LSPR
Contributes EF > 104

Localized Surface Plasmon Resonance

Non-resonant

Resonant

1) Resonant is absorbed
2) EM fields localized at nanoparticle surface

Noble Metal Nanoparticles

heat or

sonication
Metal Salt
Reducing Agent
Capping Agent

Metal Colloids
coated with
Reducing Agent/Capping Agent

Aged
Metal Colloids

Noble Metal Nanoparticles

Master
Au_1spin_5min_7500xg.Master.Absorbance
Au_3spin_5min_7500xg.Master.Absorbance

Absorbance
0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0
400

500

600

Wavelength (nm)

700

800

D = 24.8 4.1 nm50 nm

Nanostructured Substrates

http://pubs.acs.org/cgi-bin/article.cgi/ancham-a/0000/77/i17/pdf/905feature_vanduyne.pdf

Localized Surface Plasmon Resonance

The resonance results in (1) wavelength-selective

extinction and (2) enhanced EM fields at the surface.
Spectral location of the LSPR is dependent upon particle
size, shape, composition, and dielectric environment.

24 Na m
Extinction
ln(10)
2

3/ 2

2
2
( R 2 m ) I

Field Enhancement by Metallic Spheres #1

When a metallic sphere is subject to an external electric field,
E0, the field outside the sphere is given by the following
equation:
$

E out E z$ E z 3z ( z z$ xx$ y $y )
0
0
3
5
r
r

where the polarizability of the sphere is

ga 3

where a is the sphere radius and

in out
g
in 2 out

The condition for achieving the greatest external field strength

occurs when the denominator in the above equation is
large.

Beyond Metallic Spheres

For spheroidal particles, the expression for g becomes:

in out
g
in out
where is a variable that is calculated based on the aspect
ratio of the particle. The table below lists for a few
different aspect ratios.
Aspect Ratio

2:1

4.76

3:1

8.20

4:1

12.26

5:1

16.91

Spectroscopic Consequences of Field Enhancement

The SERS enhancement is determined by

manner:

g in the following

2
'2
Eout
Eout
2
' 2
EF
16 g g
4
E0

The magnitude of the extinction and scattering cross sections

are also related to g :

ext Im( g )
scat g

Resonant Rayleigh Scattering

Light that is elastically scattered due to the LSPR can be used
as an in situ monitor of nanoparticle optical properties.

20 m

The primary benefit of scattering spectroscopy is that

the single-to-noise ratio is much higher than
extinction spectroscopy when examining single
nanoparticles.

LSPR Dielectric Response

100

A
510.2

588.0
574.2

600.8
611.9

600

60

max (nm)

Intensity

80

640

40

B
max= 203.1*RI + 306.5

560

520

20

480

0
450

500

550
600
650
Wavelength (nm)

700

1.2
1.4
Refractive Index

1.6

Blue = N2 (1.000), Green = Methanol (1.329), Red = 1-Propanol

(1.385), Purple = Chloroform (1.446), Orange = Benzene (1.501)

Single Nanoparticle Sensing Proof of Concept

Wide-field Image

Biosensing with Single Nanoparticles

http://relic.bio.anl.gov

Streptavidin:
60kDa Tetrameric Protein
~4 nm x 4 nm x 5nm

Biotin:
Vitamin H
Ka = 1014 M-1

Biosensing with Single Nanoparticles

Monitoring Biotin-Streptavidin Binding with Single Nanoparticles
1200
508.0

520.7

Intensity

800

= +12.7 nm
max
max = +12.7 nm

400

Conc
Conc==10
10nM
nM SA
SA
0
450

500

550

Wavelength (nm)

600

~700
~700SA
SAmolecules
molecules

Comparison of Unenhanced and Enhanced

Raman Spectra

Relationship between the LSPR and Laser

Wavelength

max ==690
690nm
nm
max
-1
1575
1575cm
cm-1band
band

NN==13
13points
points
Range
Range==475
475700
700
nm
nm
High
High==662
662nm
nm
7
EF
EF==1.9
1.9xx10
107

Locating Landmines with SERS

Roughened Au

ex = 785 nm

Sylvia, J. M. et al. Anal. Chem. 2000, 72,5834.

Locating Landmines with SERS

115 mW
30 sec

TNT
DNT
DNB

Sylvia, J. M. et al. Anal. Chem. 2000, 72,5834.

Are you getting the concept?

Why hasnt surface-enhanced Raman replaced normal
Raman completely? In other words, why would someone
do a normal Raman scattering experiment?

Partition Layers to Detect Non-Traditional

Analytes with SERS Kyle Bantz

Partitioning PCBs

Are you getting the concept?

Kyle fabricates a new Ag SERS substrate and wants to calculate the EF.
She doses the substrate with benzenethiol (packing density = 6.8 x 10 14
molecules/cm2), and measures the spectrum with a laser spot size of
1.26 mm2. The intensity of the 1000 cm-1 shift ring breathing stretch is
35793 adus. For her standard, she puts undiluted benzenethiol ( =
1.073 g/cm3) into a cuvette with a known probe volume of 0.00413 mL
and measures a 1000 cm-1 shift band intensity of 36364 adus. What is
the EF (assuming that the laser power and collection time were the
same for both measurements)?

Single Molecule SERS

EF=
1014-1015 !

S. Nie, et. al. Science 1997, 275, 1102-1106 K. Kneipp, et. al. Phys. Rev. Lett. 1997, 78, 1667-1670

Hyper Raman and Surface-Enhanced

Hyper Raman Spectroscopy
With focused, pulsed laser, you can induce a nonlinear interaction:
r 1 r r 1 r r r
ind E E E E E E ...

2
6
Incident: 0
Scattered: 20, 20 1
Selection Rules:
All IR active modes are also hyper-Raman active
Some hyper-Raman active modes are neither IR
or Raman active

Coherent Anti-Stokes Raman

Phase-match p and s in a four wave mixing process:

ind

r 1 r r 1 r r r
E E E E E E ...

2
6
Incident: p, s
Scattered: 2p - s

ICARS ~ Ip2Is
Large signal when:
p-s =

CARS Advantage:
The AS signal beam is spatially and temporally removed
from the fluorescence signal.