Raman spectroscopy 1/20

Riichiro Saito
Department of Physics
National Taiwan Norma University
2024.3.11-5.9

明白了
Hom
e
s
！
work
 2/20

Raman Tensor
What is WavePlate
 3/20
Q10 (again). What is Raman tensor?
• Raman tensor is 3x3 matrix that describes the scattering
Scattered light 𝑷 𝑠
exp {− 𝑖 𝜈𝑡 } anti-Stokes Raman scattering
Incident light 𝑷 𝑖 exp { −𝑖( 𝜔+𝜈) 𝑡 }
𝐸 0 𝑃 exp {𝑖𝑘𝑟 −𝑖 𝜔 𝑡 } Rayleigh scattering
exp {− 𝑖 𝜔 𝑡 } exp {− 𝑖 𝜔 𝑡 }
Stokes Raman scattering
𝑅𝜈 exp { −𝑖(𝜔 −𝜈)𝑡 }
phonon mode
Electric field of light Scattered light
Raman tensor
=

( )
𝑬 =𝐸 0 𝑷 exp { 𝑖𝑘𝑟 −𝑖 𝜔 𝑡 } 𝑥 2
𝑥𝑦 𝑥𝑧
𝑅𝜈 = 𝑥𝑦 𝑦2 𝑦𝑧 Raman intensity

()
𝑎
𝑧𝑥 𝑦𝑧 𝑧2 ∗ 2
𝐼 ∝∨𝑷 𝑅𝜈 𝑷 𝑖 |
Polarization vector 𝑷= 𝑏
𝑐 𝑠
 4/20
Q13 (again). How do we find Raman active modes ?
( )
𝑥2 𝑥𝑦 𝑥𝑧
2
𝑅𝜈 = 𝑥𝑦 𝑦 𝑦𝑧
Raman active modes behaves quadratic functions 2
𝑧𝑥 𝑦𝑧 𝑧
Ex. Character table of the D6h symmetry (graphene)

o d es
t i v e m
a n a c
Ram x , y, z
n ct io n of
a t i c f u
r
Quad
 5/20
Q15 (again). How do we make Raman tensor ?
( )
𝑥2 𝑥𝑦 𝑥𝑧
Raman tensor has a symmetry of the phonon mode 𝑅𝜈 = 𝑥𝑦 𝑦
2
𝑦𝑧
2
𝑧𝑥 𝑦𝑧 𝑧
Ex. Character table of the D6h symmetry (graphene)

Raman active modes of D6h are

𝐴1 𝑔 , 𝐸1 𝑔 , 𝐸2 𝑔 Practice
2 2 2 Obtain in
𝐴1 𝑔 ( 𝑥𝑅+ 𝑦 ) 𝐴1 𝑔𝑅
(𝑧 ) that gives non-zero
( ) ( )
𝑎 0 0 0 0 0
𝐴 1 𝑔= 0 𝑎 0 ¿ 𝐴 1 𝑔= 0 0 ¿
¿
0 0 0 ¿
0
0
0 𝑐 Raman intensity
𝐸1 𝑔 ( 𝑥𝑧𝑅) 𝐸1 𝑔 ( 𝑦𝑧 ) for
𝑅
( ) ( )
0 0 𝑏 0 0 0
𝐸1 𝑔= 0 0 0 ¿ 𝐸1 𝑔= 0 0 𝑑 ¿
¿ ¿
𝑏 0 0 0 𝑑 0
𝐸 2 𝑔 ( 𝑥 2 − 𝑦 2) 𝐸 2 𝑔 ( 𝑥𝑦 )
𝑅 𝑅
( ) ( )
𝑒 0 0 0 𝑓 0
𝐸 2𝑔 = 0 −𝑒 0 ¿ 𝐸 2𝑔 = 𝑓 0 0 ¿
¿ ¿
0 0 0 0 0 0
 6/20
Q16(again) Only back scattering?
D4h
Most experiment setup is
back scattering

We can set
right angle scattering
general angle !!

D4h
 7/20
Q20. How do we select
• Incident laser light is linearly polarized,
• half-wave plate () rotates
• half-wave plate has the fast and slow axes
slow
rotates
𝑃𝐿
slow 𝜃𝜃 by
𝑃𝑖 𝑃𝐿 𝑃𝐿
𝑃𝑖
Rota
Adjust to fast te ha
plate lf-wave 𝜃
the slow axis by fast

half-wave plate () When we rotate half-wave plate

() by , rotates by
 8/20
Q21. What is half-wave plate ()?
• Birefringent material has two refraction indices
• wavelength : velocity

Green: slow Exit

Blue: fast

Entrance
Green: same direction
Blue: opposite direction
𝑃𝐿
𝑃𝑖
half-wave plate ()
 9/20
Q22. How do we select
• Linear polarizer select
• By rotating , maximum intensity
𝑃𝑠
cut 2
𝐼 ∝ cos 𝛼
𝑃 𝑜𝑢𝑡 𝜃

𝑃 𝑜𝑢𝑡
𝑃𝑠
𝑃𝑠 select

𝑃 𝑜𝑢𝑡

Linear polarizer
 10/20
Q23. Polarized Raman spectra 𝑃𝑠
𝑃 𝑜𝑢𝑡
• By rotating of linear polarizer,
• We plot intensity as a function of

cut
𝛼 𝐼 ∝|𝑃 𝑠 ∙ 𝑅∙ 𝑃 𝑖|
† 2

()
1
𝑃 𝑜𝑢𝑡 𝑃 𝑖= 0
0
𝑃𝑠 select

( )
cos 𝛼
𝑃 𝑠 = sin 𝛼
2 0
Linear polarizer 𝐼 ∝ cos 𝛼
 11/20
Q24. How to calculate Polarized Raman spectra 𝑃𝑠

𝐼 ∝|𝑃 𝑠 ∙ 𝑅∙ 𝑃 𝑖|
† 2
𝑃 𝑜𝑢𝑡

()
1 𝑅
( )
𝑎 0 0
𝑃 𝑖= 0 𝐴 1 𝑔= 0 𝑎 0 ¿
¿
0 0 0 0

𝛼
( )
cos 𝛼 𝑅
( )
𝑒 0 0
𝑃 𝑠 = sin 𝛼 𝐸 2𝑔 = 0 −𝑒 0 ¿
0 ¿
0 0 0

Practice
Obtain for A1g and E2g modes as a function of following
geometry. What is a good gerometry for observing the
polarized Raman spectra for the phonon modes?
(1) (3)
 12/20

Helicity-dependent Raman spectroscopy

using circularly-polarized light

+ℏ −ℏ

−2 ℏ
 13/20
Q25. What is circularly polarized light?
“spin” angular momentum of circularly polarized light
Left-handed () Right-handed () Linear

Polarization of light
the Jones vector
Helicity
(angular momentum)

𝑷𝑥 𝑷 𝑦
lightfield
Electric
𝑦 𝜎 +¿ ¿
𝑧 𝑥
P rop aga
tion
Directio
n of ligh
t
=
 14/20

Q26 How to make circularly polarized light (CPL)?

• quater-wave plate () : after passing , we get CPL

= + 45 degree → left-handed CPL ()

= - 45 degree → right-handed CPL ()
𝜎 +¿ 𝜎 − slow
slow
𝑃𝑖
𝑃𝑖
fast fast

quater-wave plate () quater-wave plate ()

 15/20
Q27 Raman intensity using circularly polarize light?
𝐸=𝐸 0 𝑷 exp { 𝑖𝑘𝑟 −𝑖 𝜔 𝑡 } scattered incident
• Circularly polarized light 𝑧 𝑠 𝑖
Polarization vector 𝑥 𝑷𝑠 𝑷𝑖
∗ 𝑷
2 𝑦
𝐼 ∝∨𝑷 𝑅𝜈 𝑷 𝑖 | () ( )
1 1
+¿ = 𝑖 , 𝑷 −= −𝑖 ¿
𝑠 0 0

• Helicity conserved Raman mode

𝑠 𝑖
( ) 𝑧
𝑎 0 0
2 2
Ex. 𝐴 1 𝑔 ( 𝑥 + 𝑦 ) 𝑅 𝐴 1 𝑔= 0
0
𝑎
0
0
0
𝑥 𝑷 +¿¿ 𝑷 +¿¿
= 𝑦
𝐴 1 𝑔 ( 𝑥 2+ 𝑦 2 )
=
Helicity of light
does not change!

Helicity-conserved Raman scattering

 16/20
Q28 What is helicity changing mode?
• Helicity changing Raman mode scattered incident
𝑧 𝑠 𝑖
𝑅
𝑥 𝑷𝑠 𝑷𝑖
( )
𝑒 0 0
𝐸 2𝑔 ( 𝑥 − 𝑦 )= 0
2 2
−𝑒 0 ¿
¿
0 0 0 𝑦
=
∗ 2
𝐼 ∝∨𝑷 𝑅𝜈 𝑷 𝑖 | 𝑠
=
𝑧 𝑠 𝑖 Circularly polarized right
𝑥 𝑷 − 𝑷 +¿¿ 𝑷
() ( )
1 1

( ) 𝑦
0 𝑓 0 +¿ = 𝑖 , 𝑷 −= −𝑖 ¿
𝐸 2 𝑔 (𝑥𝑦) 𝑅 𝐸 2𝑔 ( 𝑥𝑦)= 𝑓 0 0 0 0

0 0 0
= 𝐸 2 𝑔 ( 𝑥 2 − 𝑦 2)
Helicity of light change!
=
 17/20

Q29 How to measure Raman by CPL?

1. Sample is set on y-z plane.
2. Set slow axis of to
LP
3. Rotate to y axis by
4. Set slow axis of to
𝑃𝑖 5. Set of LP to
6. Rotate by to get
7. Rotate LP for polarized Raman

• → helicity-conserved
• → helicity-changed
 18/20

Q30 How to calculate polarized Raman?

• Obtain 2nd rank tensor to connect to vector (the Johns vector)
1. (1,1,0) to (1, i, 0) (
2. (0,0,1) to for propagating direction.
3. Rotate by for (0,0,1) for propagating direction.
4. Make a new problem by selecting wave plate.
LP
• Obtain the formula of polarized Raman intensity
• as a function of
• for a phonon mode (please select) 𝑃𝑖
• for rotating = (please select)
• Plot the calculated intensity in the polar plot.