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Nano-photonics
-Raman Spectroscopy
2
Outline
- Raman effect and Raman Spectroscopy;

- Near-field Scanning Optical Microscopy (NSOM);

- Near-field Raman Spectroscopy;

- Physical Review Letter Paper.


3
Raman Spectroscopy
Raman Effect : 1928 by C.V. Raman (Nobel 1930)

--Inelastic light scattering by optical phonons in materials, or more generally by other elementary
excitations (e.g. magnons, electronic excitations, etc).

Simple model: harmonic crystal
--Collection of normal modes of lattice vibrations,

--Phonons, Quasi-particles,

Conservation Laws ( space-time symmetries )

1) Energy: + : anti-stokes
(one phonon process) - : stokes (creation)
Note that stokes usually much stronger!
2) Momentum:

Comments:
~ a few eV, Debye ~0.01 eV
( ) k
i

e
)
2
1
) ( ( ) ( + k n k
i i
e
) (k
i L S
e e e =
} { G k nq q n
L S

+ =
G q q
S L
<< ,
L S
e e , D
e
4

-Conclusion
1) collect information on and q, q obtain information on
2) sharp peaks on Raman Spectrum one-phonon process (1st-order Born Expansion)
broad background higher-order, multi-phonon processes

-Notes:
1) No translation symmetry (solutions, alloys, glass): RS density of states of particular excitations
2) Quantum Wells, QWs, QDs: k in some directions, (perpendicular to size quantization)
3) Absorbing medium: k is complex.



Spontaneous and stimulated Raman scattering
-Spontaneous process, weak, -Stimulated, strong


Model by Hellwarth et. al 1963
Probability /time for photon to emit into stokes mode: (Einstein)
Stimulated Raman gain:

Briefly explain why stimulated RS is much stronger (exponential )
S L,
e ) (k
i
e
dt
dm
m Dm P
S
S L
= + ) 1 (
|
-1 6
cm 10 ~ . /

vol o
c Dnm G
L
/ =
) Im( ) Im(
S L
q q k + ~ A
5
Stimulated RS described thru. nonlinear polarization (Garmire,1963)



Langevin Equation in Statistical


Describing harmonic oscillator under external field.

NL polarization: (stokes) 3rd-order

Stokes-Anti stokes coupling:
Assumptions: isotropic; slowly-varying-amplitude; non-depleted pump approximation




Phase-matching in the second term

These basic models for Raman effects are employed to explain spectroscopic properties of samples.


Raman Spectroscopy:
-Inelastic collision:
light loses ( or gains) energy due to vibration energy-level change in sample

-Chance of photons interaction is small (~1 in million),
usually counts Raman scattered photons instead of measuring intensity on a DC meter.

-Raman-active
Polarizability changes as the molecules move during the vibrations
m t F q
dt
dq
dt
q d
/ ) ( 2
2
2
2
= + +
u
e
z k k i
a L F
z ik
s L R s
NL
a L s
e A A e A A P
) 2 ( 2
2
) (
-
+ = _ _ e
z k k k i
a s s s
s a S L
e A A
dz
dA
) 2 ( -
+ = k o
z k k k i
s a a a
a a S L
e A A
dz
dA
) 2 ( -
+ = k o
6

Apparatus for Raman Spectroscopy:
-A large (~1m) grating spectrometer is to measure the
small color changes.
Great care must be taken to exact the signal in the presence of the large
Raman-scattered light

-Detection for low light levels
(1) photon counting commonly involved (2) Dark-counts, (Above: Raman Spectra of KTP)


-Light source: Laser












(Schematic setup ref. to NCSU optics group)
C

45
7
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Applications of Raman Spectroscopy
Raman Spectroscopy is a method of determining modes of molecular motions, especially
vibrations. It is predominantly applicable to the qualitative and quantitative analyses of
covalently bonded molecules.

Extra:
-Identification of phases (mineral inclusions, composition of the gas phase inclusions)
-Anions in the fluid phase (OH-, HS-, etc.)
-Identification of crystalline polymorphs (Sillimanite, Kyanite, andalusite, etc.)

-Measurement of mid-range order of solids
-Measurement of stress

-High-pressure and High-temperature in situ studies
-Phase transition and order-disorder transitions in minerals (quartz, graphite)
-Water content of silicate glasses and minerals
-Speciation of water in glasses



To visit caltech webpage: mineral.gps.caltech.edu Mineral Spectroscopy Server.
9
Near-field Scanning Optical Microscopy
First proposed by Synge, S. H. in 1928 about his basic ideas of
designing sub-wavelength aperture scanned in the near-field of
sample, raster scanned images, piezoelectric position control,
opaque (metal) coatings to confine optical field,

NSOM( or SNOM, European name)

-The interaction of light with sample close to a metal aperture, which
constrains the lateral extent of light. The aperture is held in place in
a manner similar to those used for other scanning probes.

Advantages of near-field interactions:
Improved spatial resolution,

Surface enhancement,
Combined topography,
Low sensitivity (small cross section) incoherent in
conventional Raman SERS( surface enhanced Raman
Scattering)

(Graphs ref. to Hallens group at North Carolina State University)
) Sin( 2 o

n
10
NSOM Image Theory (Paesler, <Near-field Optics>)
Optical Field detected at distance Z be written in terms of F.T.
of the field at z=0,






Now consider








-To examine how (4.4) and (4.6) behave with regards to delivering
spatial information detected at z=Z (far-field), considering
(4.4) ) 0 , ( ) , (
i.e. , / over integrate to need only field far For
(4.3) ) 0 , ( ) , (
2
2
) ( 2 2
) ( 2 2
2 / 1 2 2
2 / 1 2 2
= = =
s
= = =
}
}
+


+


C
C
Z i
x
x i
x
Z i
x
x i
x
x x
x x
e z F e d Z z x f
c k
e z F e d Z z x f
t
e
t
e
o o t to
o o t to
o o
e
o o
c c << = Z by recaptured is (4.3) Eqn. Then , z
frequency spatial one with ), ( ) 0 , ( K K E z F
x o x
= = o o o
) 6 . 4 ( }
) ) sin((
) 0 , (
{ ) , ( : field far Now
) ( ) , ( aperture, at taking Then
2 " 2 "
2 2
2
"
"
" 2 "
2
2
) ( 2 2

=
= =
= =


}
}
c o o t to
t
e
t
e
c o o t to
o o
o o
o o
o
e
c
x x
x x
e
w
z F e d
e e d Z z x f
x
rect z x f
x x
x x
x
x i
x
C
C
Z i x i
x
11
Continued:






Notes: (4.8) fulfills all our notions about far-field microscope and its inability
to carry information beyond certain spatial frequency

(4.9) integral doesnt vanish for , such that high-frequency
elements still contribute to the signal arriving at z=Z (far field).

(4.9) collapses to (4.8) when w (aperture width) is large, i.e.



In the near-field, evanescent terms must be taken into account, due to the convolution of the tip and
the sample.
) 8 . 4 ( / for 0,
/ for ) , ( ) 4 . 4 .(
2 2
2 2
> =
< = =

C K
C K e e E Z z x f Eqn
Z K i Kx i
o
e
e
o t t
(4.9)
) sin(
) , ( ) 6 . 4 .(
2
2
) ( 2 2 2
2 2 2 2

= =
}


C
C x
x
Z i x i
x
K i
o
K
w K
e e d e E Z z x f Eqn
x x t
e
t
e
c o o t to c o t
o
o
o
C K / e >
) (
) sin(
K
K
w K
x
x
x

o o
o
o
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Ultrasensitive Raman Spectroscopy and SERS
Advantages of Raman Spectroscopy:

1) provide extremely rich information on molecular vibrations, and material structures
2) No special requirements for sample preparations in contrast with IR spectroscopy
3) Can be applied non-invasively under almost any ambient condition.

Disadvantages:
extremely small cross section, Low sensitivity

SERS: Surface Enhanced Raman Scattering
Discovered in 1977, Jeanmire et al. & Albrecht et al.

--Strongly increased Raman signals from molecules attached to metal nanostructures
--SERS active substrates: metallic structures with size about 10--100 nm (e.g. colloidal Ag, Au)


General contributions:
1)Electromagnetic field enhancement
2) Chemical first layer effect
molecule cm / 10
2 30
now realizable t enhancemen total 10
14
>
R
L s
NI I o u u ) ( ) ( : al Convention =
R
SERS s L L SERS
A A I N I o u u u
2 2
"
) ( ) ( ) ( : SERS =
13

1) Electromagnetic field enhancement

Excitations of EM resonances: Surface Plasmon

For isolated metallic Ag particles, enhancement is


(2) Chemical first layer effect
Electronic interaction between molecule and metal

Mechanism--Dynamic charge transfer
(1) Photon annihilation, and excitation of electron into a hot electron in metallic cluster;
(2) Transfer of hot electron into the LUMO of the molecule (molecular vibrations involved);
(3) Transfer of hot electron from LUMO back into metal (with changed electronic state);
(4) Electron returns to initial state, and stokes and/or anti stokes photons created.

Extra Notes:
(1) Excitations are not homogeneous Existence of hot spots and hot electrons. (Improvement: Tip-Enhanced SERS)
Normally

(2) Vibrational population pumping by SERS balances stokes and anti-stokes ratio




(3) Developing stable SERS-active substrates: Ag films made by vapor deposition, Ag and Au colloidal particles self
assembled, colloidal metallic particles in hydrosols

(4) Strong fluctuations in single-molecule SERS signals appear due to Brownian motion of metallic particles in and out of
the probing volume
) / exp( /
1
T k n I I
B as L
SERS SERS
s
SERS
a
v t o + =
N N % 01 . 0
"
s
molecule cm
SERS
/ 10
2 16
~ o
laser excitation the of density flux photon :
state al vibration excited 1st the of lifetime :
1
L
n
t
cally theoreti 10 10
7 6

) ( ), (
S L
A A u u
14






Experimental Set-up for single-molecule SERS. Insert shows an electron micrograph of typical SERS-active colloidal clusters
(Adapted from K. Kneipp, Bioimaging 1998,6, 104-106 )
15

Applications:
1) Trace analysis down to approximately 100 molecule detection limit
Potential in environmental, biomedical, pharmaceutical researches
(Feature article: J.J. Laserna et al., Analytica Chimica Acta, 283,607-622,1993)

2) Raman detection of single molecules:


(To see last page)
3) DNA sequencing
The nucleotide bases show well-distinguished SERS spectra
(Feature article: K. Kneipp et al., Phys. Rev. E, 57, 6281, 1998)


____________________________________________________________________________
Screening of single molecules in extremely small volumes using a combination of scanning near-field
microscopy and SERS promises exciting opportunities for future developments of microinstrumentation for
detection and identification of single-molecules in small volumes on the order of atto-liters.
--Kneipp et al. Chem. Rev.99, 2957,1999



--If more interested in theoretical details, please refer to Surface Enhanced Raman Scattering, R. K. Chang, ed.,1982
detection molecule - single for allows / 10 * 4 lly Theoretica
2 18
molecule cm

16
Near-Field Raman and Various Combinations




(ABOVE and RIGHT: P.G. Gucciadi SILC-Net School, May 2002)


Comparison:
(1) Illumination
(2) Resolution
(3) simultaneous topographic image and Raman scattering image
(3) Selection Rules and Rayleigh Tail (Next page)
(4) Surface Enhancement Effect (Next page)
Incident Light
Far Field Microscopy
Sample Surface
C
o
l
l
e
c
t
i
o
n

O
p
t
i
c
s
Screen
Diffraction
Spot

17

(Potassium titanyl phosphate (KTP), H.D. Hallen et al. SPIE Proceedings 3467 (1998))


Feature Articles
P. G. Gucciardi, et al. " Optical Near-Field Raman imaging with sub-diffraction resolution ", Applied Optics
in press (June 2003).

C.L. Jahncke, et al, Proc. of the 7th International Conf. on near-field optics, NFO-7, August 2002, P.142
18

More evolvements:

(1) Micro-Raman (Far-field)
--1960s, Intensive Laser input, and output collected by a microscope

(2) Nano-Raman
--1990s, Similar to SNOM, but output is directed to a spectroscopy
before being analyzed

(3) Tip-Enhanced SERS Raman:
--A laser scanning con-focal microscope and an AFM capable of both tip and
sample scanning.













Cresyl blue SERS spectra. Adapted from Stckle et al., Chem. Phys. Lett. 2000, 318, 131.
19
One Example: Near-field Raman of SWNT
(Hartschuh et al., P.R.L.,9, 95503,(2003))
Technique: Tip-enhanced SERS (Silver tip is raster scanned over sample surface)
Object: single-wall nanotube (SWNT)
**The 1st paper to show SWNT was detected optically with <30 nm resolution in Raman Spectroscopy


Experimental Setup:
(1) Optical microscopy with x, y scan stage;
(2) Laser beam is focused on sample surface, polarized along tip axis
(3) Sharp Ag tip (10-15 nm in radius) positioned near the focus of laser beam and above sample about 1 nm (sensitive! )
(4) Raman scattering is collected with same objective, transmitted by beam-splitter and filtered by a long pass filter
(5) Signals are detected by either a combination of a spectrograph and a thermoelectrically cooled CCD or by a
narrow band-pass filter (FWHM=10 nm) centered at 760 or 700 nm followed by a photon
counting avalanche photo-diode


Two different types of SWNTs

(1) SWNT bundles grown by CVD on substrate
(2) Purified SWNTs with diameter 1.0-1.8 nm produced by arc-discharge
W nm 100 30 , 633 =
2
SiO
20

Fig 2 Simultaneous near-field Raman image (a) and topographic image
(b) of SWNT grown by CVD. The Raman image is acquired by detecting
Intensity of the G band upon laser excitation at 633 nm. Cross sections
are taken along the indicated dashed line in (c) Raman image and
(d) topographic image. The height of individual tubes is about 1.4 nm.
Vertical units are photon counts / second

-Resolution of SERS-Raman is better
than topographic image

-No Raman scattering signal is detected
from humidity related circular features
present in the topographic image.

-Vertically and horizontally oriented SWNTs are
observed in Raman image with similar signal
intensities even if laser is z-polarized (right above).
(different from far field Raman, right)

21
Fig (3) (a) dependence of Raman scattering strength of G band on the longitudinal
separation ( ) between a single SWNT and the tip. The solid line is an exponential
fit with a decay length of 11nm. The signal is normalized with the far-field signal.
(b) Scanning electron microscopy of a sharp Ag tip fabricated by focused ion beam
milling.


-Fig. (3) demonstrates enhanced field confinement
in longitudinal direction.

--Tip is positioned above one SWNT and Raman scattering strength is recorded as function
of . The curve is fitted with exponential and normalized with Raman strength without
Ag tip. 11nm fit is consistent with 10-15nm tip radius.
--High experimental enhancement is 1000, compared with theoretical )


Fig (4) (a) Three-dimensional topographic image of a SWNT grown by Arc-discharge. The
3 bumps with height 5 nm are presumably enclosed Ni/Y catalyst particles and indicate the
initial point of growth.
(b) Near field Raman spectra detected at the marked positions 1 to 4 in (a).
The spectra is offset for clarity.

1) G band at 1596 nm^(-1) is not shifted V.S.G band at 2619 is shifted to 2610 and double
peaked

2)


Explanation: Variations in Raman spectrum reflect changes in the molecular structure
caused by external stress, catalyst particles, or local defect, etc.
Z A
4 point and 0.7 to 2 and 1 points at 1.3 from goes
'
G
G
Z A
7
10 >