Raman Spectroscopy

: An Analytical Technique
Raman Effect

Rayleigh scattering - same v

Stokes scattering - less v

Antistokes scattering - higher v

Scattering of light with change in colour (frequency)
E
incident
(v)

Rayleigh
Antistokes
Stokes
RAMAN SPECTRUM OF MOLECULES





Cause of Raman scattering
Vibrational excitation
Rotational excitation
Electronic excitation
Magnetic excitation

Inelastic Scattering Process
inc
inc
scatt
scatt
Stokes Antistokes
E
i
E
f
E
i
E
f
Total dipole moment
E
0
p
~
+ =
Permanent dipole
moment
Induced dipole
moment
o: polarizability -depends on symmetry of the molecule
The classical description (by Placek)
Assuming
incident frequency is far off electronic resonance frequency
q
n
: normal coordinate
of nuclear displacement
..... q
q

(0) (q)
....... q
q

(0)
n
0
Q
1 n
n
ij
ij ij
Q
1 n
n
0
n
+
|
|
.
|

\
|
c
c
+ =
+
|
|
.
|

\
|
c
c
+ =

=
=
Assuming normal coordinate of the vibrating molecule as
t) cos( q (t) q
n
0
n n
=
)t] Cos( )t [Cos( q
q

E
2
1
t) Cos( q
q

t) Cos( E (0) p
n n n0
0
Q
1 n
n
ij
0
n n
0
Q
1 n
n
n 0 ij 0
+ +
|
|
.
|

\
|
c
c
+
|
|
.
|

\
|
c
c
+ + =

=
=
Rayleigh scattering
Infrared scattering
Raman scattering
Raman scattering rule



In order to be Raman active an internal motion of the molecule
(rotation or vibration) must cause some change in a component
of the molecular polarizibility.

Change in magnitude and direction of polarizibility ellipsoid

Crystal symmetry + symmetry properties of elementary
excitation

0
0
=
c
c
|
|
|
.
|

\
|
q
o
Example
Linear molecule : CO
2
R
IR
IR
R
R
IR
0
q

0, =
c
c
=
0
q

=
c
c
0
q

=
c
c
0
q
=
c
co
0
q
=
c
co
0
q
=
c
co
Mutual selection rule between IR and Raman spectroscopy
Center of inversion :
Raman active IR inactive
Lack of center of inversion
Both Raman and IR active
IMPORTANT :Symmetry of vibration
Eg. A molecule has C
3v
symmetry
Character Table
C
3v
E 2C
3
3
ov
Activity
A
1
A
2
E
1 1 1
2 1 -1
2 -1 0
Z
R
z
(x,y)
(R
x
,R
y
)
x
2
+y
2
+z
2

(x
2
-y
2
,xy)
(xz,yz)
IR, Raman
IR
IR, Raman
Example
Linear molecule
Raman IR

=0

Yes

No

= 0

No

Yes

=0

No

Yes
0
|
|
|
.
|

\
|
c
o c
Non-Linear molecule
Raman IR

= 0

Yes

Yes

= 0

Yes

Yes

=0

Yes

Yes
0
|
|
|
.
|

\
|
c
o c
R
xx
R
xz

R
yx
R
yy

R
zx

R
zy

R
zz

R
yz

Non-zero components are determined from crystal
symmetry (Raman tensor determines the selection rule)
for symmetric vibration : a diagonal
R
xy
R
=
Polarization effect on Raman scattering
e
(i)
: unit polarization vector of incident light
e
(s)
: ,, of scattered light
where
a tensor of rank two
2
2
(i) k
ji
(s)
(i) (s)
s
.e .R e
q.e
q

. e I

|
|
.
|

\
|
c
c

k
ji
R q
q

=
|
|
.
|

\
|
c
c
Breathing mode
Bending mode
Kekule mode
Raman spectrum of Benzene
500 600 700 800 900 1000 1100 1200 1300
2000
4000
6000
8000
10000
12000
Bend mode
Kekule Mode
Breathing mode
I
n
t
e
n
s
i
t
y

a
.
u
.
Raman shift (cm
-1
)
Raman scattering: an example of forced oscillation
Forced oscillator with damping
resistance force is proportional to speed :
dx
c
dt
2
2
( )
d x dx
m c kx F t
dt dt
+ + =
Equation of motion
( ) ( )
2
2
0

i t i t
F
i x i x x e e
m
e e
e e e
(
+ + =

In complex method
For convenience:
c m =
Also, k=me
0
2
( )
2 2
0

F
x
m i e e e
=
+
Solution of damped harmonic motion
Define
( )
2 2
0
1
R
m i e e e
=
+
R F x

=
( )
0

i
i
F e Fe
u
u

+
= =
0
cos( ) x F t e u = + +
( )
0
Re of

i t
i t
F F e
Fe
e
e
+
=
=
0
2 2 2 2 2
0
( )
F
x
m e e e
=
+
Maximum amplitude at
2
2
0
2

e e =
) (
tan
) ( sin cos
1
) (
1 1 1
2 2
0
2 2
0
2 2
0
e e
e
u
e e e u

e e e

u
u

=
+ =
+ =
|
|
.
|

\
|
= =

m i m
i
i m e
e R
i
i
Somnath Bharadwaj and Pratik Khastgir, Department of Physics and Meteorology, IIT Kharagpur, 721 302 India
http://www.cts.iitkgp.ernet.in/~phy1/
Amplitude and Phase (again)
-
2

SB
u
0
F
f
m
=
Average energy of the oscillator
*

2
k
E xx =
( )( )
( )
2
2 2 2 2 2
0 0
2
2 2 2 2 2
0
1
1
m i i
m

e e e e e e
e e e
=
+
=
(
+
(

Plot of
2
vs e (near resonance)

e
0

2
e
Intensity of Raman scattering
| |
|
\ .
ij
ij,k
k
q=0

=
q
R ij,k
P = E
o
ij,k
is the polarizibility tensor of third rank
for first order Raman
scattering
4
2
s
S ij,k q
4
3h Ld
I = (n +1)
c
Intensity of the first order Raman scattering (Stokes)
L: sample length along light wavevector
: crystal density
n
q
: occupation number of phonons
dO: detector solid angle
Raman scattering by crystal
Linear chain of diatomic molecule
Optical mode
Acoustic mode
Phonon dispersion
relation
Raman scattering by phonon : quantum unit of lattice vibration

p atoms per primitive cell : total 3p modes (3 acoustic+3p-3 optical)
Very weak process

Conservation of momentum

0 q k k
ph
s
i
~ =
~10
5
cm
-
1

<< First BZ Boundary
i
k
Microscopic theory of Raman spectroscopy
Scattering of excited
electrons by phonons
Scattering of hole
by phonons
(1) Interaction of incident photon with an electron
(2) Interaction of electron/hole/exciton with phonon
(3) Recombination of electron-hole pair

Probability of scattering per unit time
)
S I
( e e e c
n
i
: number of incident photons
0 : number of scattered photons
n
0
: number of optic phonons
Initial state
a and b : complete sets of intermediate sets
2
0
0 1
0
1 1
2 1
6


> >< >< + <
=
s
k ,
i
k b , a
)
I b
)(
I
a
(
g ; n ;
, i
n
ER
H b
EL
H a a
ER
H g ; n ; ,
i
n
e e e e
t
t
Raman scattering cross-section
m: effective mass of electron
d: lattice constant
M: reduce mass of lattice atom
R
ij
k
: Raman tensor
i: incident light polarization
j: scattered light polarization
k: phonon polarization
R has same property as o
( )
( )( )

(
(

+

=

i q i
y
0
x

z
0
q s i
x
yz
....

p p
V
1
, , R
Phonon deformation pot.
Momentum
matrix element
(

+ +
+
=
2
z
xy
2
y
zx
2
x
yz
i q
4 2 4 3
q s
4
R R R
Mc d m 4
1)Ld V(n e
I

) , , ( R ) , , ( R
q q s q i
x
zy q s i
x
yz
+ + =
What we measure in Raman spectroscopy





q s i
q s i
k k k

=
=
Change in incident photon energy (in cm
-1
) : Raman shift
Energy and wavevector conservation lead to
Raman spectrum of Silicon
Phonon dispersion curve
and density of states
of Silicon
What information does a Raman spectrum provide?
Qualitative and quantitative
information :

- Intensity : proportional to
concentration

- Peak position : chemical
species, symmetry

- Shift in position : stress,
Temperature effect

- Width : structural disorder


Band position
Band Position
shift
I
n
t
e
n
s
i
t
y

Band
Width
Raman shift
Ion irradiated semiconductors

A: 265 cm
-1
(TO)
B: 292 cm
-1
(LO)
C: 182 cm
-1
(2TA)
Crystalline phonon modes
A
B
A
B
C
Amorphization of a crystal

1. Continuous random network (CRN)
Amorophous mode:
a measure of phonon density of states




( ) [ ( , ) 1] ( ) /
b b
b
I C n T D e e e e = +

RAMAN VIBRATIONAL STUDIES OF TRANSIENT ANNEALING OF GaAs

AMORPHOUS
THIN FILMS
J. Sapriel et al, JOURNAL DE PHYSIQUE
Colloque C5, supplkment au n04, Tome 45, avril 1984 page C5-75

RAMAN-SCATTERING SELECTION-RULE BREAKING AND THE DENSITY
QF STATES IN AMORPHOUS MATERIALSReuben Shuker and Robert W.
Gammon, PRL, Vol. 25, p. 222
D(e):vibrational density of states
C: coupling of vibrational modes
with radiation
n(e)+1: Bose Einstein factor
Increasing
Laser
Radiation
power
2. Medium range ordering (MRO) cannot be directly visualized
either by high resolution transmission electron microscopy or by
atomic force microscopy.

Manifestation of excess vibrational states (D(e)) over the prediction
of Debye model.
consensus that the boson peak is a manifestation of some sort of
disorder (medium range ordering in the system)
D: ~ 124 cm
-1
(Boson mode MRO)
265 cm
-1
(TO)
292 cm
-1
(LO)
250 cm
-1
(CRN mode)
150 cm
-1
(Boson mode)
Crystalline phonon modes
amorphous phonon modes
Graphene
Allotropes of carbon
Phonon dispersion and electronic band
structure of a single graphite layer.
A.C Ferrari and J. Robertson
PHYSICAL REVIEW B
VOLUME 61, Page 14095
Raman spectrum of graphite
Graphene
Energy bands near the Fermi level in graphene.
System performances to discuss
Spectrometer performance
Spectral resolution
Spectral Range
Low frequency capability
Mapping
reliability , stability ( Process/Industrial)

Samples characteristics
On situ or Ex-situ measurements
Volumes to analyze ( macro, micro, nano)
Type of samples ( liquids , solids , films , powders , .)
Specific conditions ( temperature , pressure , electrical field,
Coupling with other techniques

What do we need to make a Raman measurement ?
Laser
Sample
Filter
Grating
Detector
Rejection filter
(A way of removing the
scattered light that is not
shifted( changed in colour).
(A way of focussing the laser onto
the sample and then collecting the
Raman scatter.)
Sampling optics
Monochromatic Light source
typically a laser
Spectrometer and detector
(often a single grating spectrometer
and CCD detector.)
Raman Units are defined Av=v
laser
v
Raman

where v=1/
Horizontal lines indicate
range for a full Raman
spectrum

v
24 22 20 18 16 14 12 10 x10
3
cm-1
500 625 800 1000 nm
Ar HeNe
Nd:Yag
HeCd Diode
N
d
:
Y
a
g
/
2

ov/o
200nm 25cm
-1
/
300 11
400 6.25
500 4
600 2.8
700 2
800 1.6
900 1.1
1000 1
With a multichannel detector :
- Single wavelength filters :Notch Holographic or Edge
Single Stage Raman Systems

- Tunable filters :Double subtractive monochromators
Triple Stage Raman Spectrographs

With a monochannel detector :
-Double or triple additive monochromators

How to filter the Rayleigh scattering in
Raman systems ?
2 ways depending on the type of detector which is
used
Filtering performance of a Super Notch+ filter
and a Double Subtractive Monochromator
3000
2000
1000
0
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
-10 -5 0 5 10 15 20 25
Wavenumber (cm-1)
50000
40000
30000
20000
10000
0
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)

0 50 100 150 200 250 300 350
wavenumber (cm
-1
)
Notch Filter
subtractive double monochromator
3000
2000
1000
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)

-10 -5 0 5 10 15 20 25
wavenumber (cm
-1
)
0
M
1
M
2
G

CCD
Single monochromator as spectrograph
Schematic of Raman spectrometer
B: Plasma filter
C: Right angel prism
D: Focusing & collection lens
G: Dispersive Grating


Configuration : Subtractive Triple Spectograph
Polychromatic Radiation

Grating 1
Grating 2
Grating 3
Entrance slit S
1

Intermediate slit
S
i1/2

1

2

Intermediate slit
S
i2/3
CCD Detector

1

2

Subtractive mode
Configuration

1

2

Raman Basics: Laser Choice
The choice of laser will influence
different parameters:
Signal Intensity: (1/)
4
rule applies to
Raman intensity.
Probing volume: spot size and material
penetration depth.
Fluorescence: may overflow Raman
signal.
Enhancement: some bounds only react
strongly at a certain wavelength.
Coverage range and Resolution: grating
dispersion varies along the spectral range.
0,001
0,01
0,1
1
10
100
200 300 400 500 600 700 800 900
P
e
n
e
t
r
a
t
i
o
n

d
e
p
t
h

(

m
)
Wavelength (nm)
Silicium
Wavelength Influence on the depth penetration:
Analysis of a 1 m thickness film of Si
70
Ge
30
deposited on Silicon

ex
penetration
633nm 10 m
532nm 1500
350nm 150

70000
60000
50000
40000
30000
20000
10000
0
100 200 300 400 500 600 700
Using short wavelengths, the
Raman signal of the film is
increased compared to the
signal of the substrate
100x I
6000
5000
4000
3000
2000
1000
0
200 300 400 500 600
200x I
Substrate
Film
25000
20000
15000
10000
5000
0
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
500 1000 1500 2000 2500 3000
Wavenumber (cm-1)
35000
30000
25000
20000
15000
10000
5000
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
500 1000 1500 2000 2500 3000
Wavenumber (cm-1)
70000
60000
50000
40000
30000
20000
10000
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
500 1000 1500 2000 2500 3000
Wavenumber (cm-1)
A careful and adequate choice of the
laser wavelength enables to
counteract the emission of
fluorescence
633 nm
785 nm
532 nm
Multiple Laser Excitation Advantage
(coloured polymer spectra)
When high resolution is advantageous ?
When the widths of
the Raman band are
close to or narrower
than the bandpass of
spectrometer high
resolution, it is
advantageous.
If Raman bands are
very large , no
advantage
300 nm : 62.1 cm
-1
/mm
1577.34 in 1024 pixel*
1.54 cm
-1
per pixel
Resolution ~ 4.5 cm
-1
800 nm : 0.56 cm
-1
/mm
14.22 in 1024 pixel*
0.01 cm
-1
per pixel
Resolution ~ 0.03 cm
-1
300 nm : 20.7 cm
-1
/mm
525.78 in 1024 pixel*
0.51 cm
-1
per pixel
Resolution ~ 1.5 cm
-1
800 nm : 0.19 cm
-1
/mm
4.83 in 1024 pixel
0.005 cm
-1
per pixel*
Resolution ~ 0.015 cm
-1
Triple subtractive
Triple additive
* CCD chip of 2.54 cm

No. of pixel (1024256)
Quantum efficiency
Dark noise
Read out noise
ADC speed
Cooling
Image travel down the chip to the read out register as it reads
pixel by pixel and passed it to AD converter and ultimately is
reconstructed on the screen
CCD camera specifications
Triple subtractive configuration : higher throughput


Triple additive configuration : for a very high spectral resolution (< 0.15 cm
-
1
). With a multiple stage instrument , this performance is obtained configuring
them so that their dispersions are added

Choose the correct configuration