ptl spectroscopy lecture 2 · a. marcano o., j. ojeda and n. melikechi, “absorpti on spectra of...
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1
Photothermal SpectroscopyLecture 2 - Applications
Aristides Marcano Olaizola (PhD)Research ProfessorDepartment of Physics and EngineeringDelaware State University, US
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Outlook
1. Optical characterization of matter.2. The place of photothermal spectroscopy3. Achromatic character of the mode-
mismatched configuration.4. NIR Photothermal spectroscopy5. Photothermal-absorbance-fluorescence
spectrophotometer.6. Photothermal spectroscopy of
fluorescence and scattering samples.7. Perspectives.
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Material samples exhibit generally more than one type of effect upon interaction with light
Transmitted lightIncident light
Reflected light
Scattered light
Absorption of lightPhotoacoustic effectsPhotothermal effectsPhotomechanical effectsPhotochemical effectsLuminescence
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)()( RsThFTo PPPPPP
From the energy conservation law we obtain
sP
TP
oP Incident power
Transmitted power
FP Power used for fluorescence
Power degraded into heat ThPScattered power
RP Reflected power
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)(
)(
o
T
PPT Transmittance
)(log)( TA Absorbance
)(
)(
o
F
PPF Fluorescence excitation
spectrum
)(
)(
o
R
PPR Reflectance
)(
)(
o
Th
PPPT Photothermal spectrum
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-40 -20 0 20 40-0.15
-0.10
-0.05
0.00
0.05
Mode-mismatched
Mode-matchedT
L si
gnal
Sample position (cm)
o=-0.1, p=632 nm, e=750 nm, L=200 cm, D=0.001491 cm2/s,t=10 s, zp=0.2 cm for mode-matched scheme and zp=2000 cm formode-mismatched scheme.
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D
Ampl.
Sample
Exc
itatio
n la
ser
M1M2
F
A
Osc.
L1
L2
L3
L4
Prob
ela
ser
B z
Ch
Marcano O. A. and N. Melikechi, App. Spectros. 61, 659-664 (2007).
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-20 -10 0 10 20-0.06
-0.03
0.00
0.03
Mode-mismatched
Mode-matchedT
L si
gnal
Sample position (cm)
Experimental Z-scan of 1-cm cell containing distilled water measuredunder the mode-matched (open stars) and mode-mismatched (solidsquares) schemes.
p=632 nm, e=807 nm
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700 800 900 10000.0
0.2
0.4 Mode-mismatched
Mode-matched
Abs
orpt
ion
(cm
-1)
Wavelength (nm)PTL spectra of distilled water measured using the mode-matched (large open stars) andmode-mismatched (large crossed circles) experimental configurations. Results ofprevious reports on water absorption of different authors have been included (smallsymbols).
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Ultrasensitive spectroscopy of water
R. A. Cruz, A. Marcano O., C. Jacinto, and T. Catunda, “Ultra-sensitive Thermal Lens Spectroscopy of Water”, Opt. Lett. 34 (12), 1882-1884 (June 15, 2009).
High precision values of absorption of water in the 300-500 nm spectral region
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700 800 900 10000.0
0.3
0.6 Comparison of TL spectrum with absorbance speof distilled water measured by other authors
TL spectrum
Pope and Fry
Palmer and Willians
Abs
orpt
ion
coef
ficie
nt (c
m-1)
Wavelength (nm)
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700 800 9000.00
0.05
0.10
0.15A
bsor
banc
e
Wavelength (nm)
Ethanol TL
Cary absorbance measurement
NIR spectroscopy of Ethanol
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700 750 800 850 900 9500.0
0.1
0.2
0.3
Abs
orba
nce
Wavelength (nm)
PTL Methanol cell 1 mm
Cary absorbance
NIR of Methanol
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Nd:YAG OPO
He-Ne
M1
M2
D1 D2 D3
BS1
L1 Sample BS2
F1M3
L2
D4
Laser based PTL, absorbance ,and fluorescence excitation spectrophotometer.J. Hung, A. Marcano O., J. Castillo, J. Gonzalez, V. Piscitelli, A. Reyes and A. Fernandez, “Thermal lensing and absorbance spectra of a fluorescent dye”, Chem. Phys. Lett. 386, 206-210
A
L3
F2
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Figure 2. Hung et al.
450 475 500 525 550 5750,00
0,01
0,02
0,03
Abs
olut
e va
lues
F(e)
1-T(e)
ATh(e)
Wavelength (nm)
. Absorbance (crossed circles), fluorescence excitation (crossed stars) and TL spectra (solidtriangles) of a 5 10-6 M ethanol solution of Rhodamine 6G. The solid line is the absorbancespectrum of the same sample obtained using a spectrophotometer.
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Figure 3. Hung et al.
475 500 525 5500,000
0,006
0,012
F(e)
1-T(e)
ATh(e)
Abs
olut
e va
lues
Wavelength (nm)Absorbance (crossed circles), fluorescence excitation (crossed stars) and TL spectra (solid triangles) of the same sample of previous slide after adding of the quencher (KI).
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475 500 525 5500,0
0,5
1,0
With quencher
No quencherFl
uore
scen
ce Q
uant
um Y
ield
Wavelength (nm)
Fluorescence quantum yield spectrum of the 5 10-6 M ethanol solution of Rhodamine 6G in presence of high fluorescence and in the presence of fluorescence quenching.
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He-NeL1L2
M1
S
M2
D Ch
XeLamp
A
M3
IFSL3 L4
B
White light photothermal lens spectrophotometer
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PTL spectrum of a non-fluorescent dye
400 500 600 7000
50
100
150
Wavelength (nm)
Mol
ar e
xtin
ctio
n co
effic
ient
(mM
-1 c
m-1)
0.0
0.4
0.8
ATL ()
PTL spectrum of 0.125 mM solution of Malachite green in ethanol. There is coincidence with the absorbance spectrum.A. Marcano O., J. Ojeda and N. Melikechi, “Absorption spectra of dye solutions measured using a white-light thermal lens spectrophotometer”, Appl. Spectros. 60 (5), 560-563 (2006).
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PTL of a fluorescent dye
400 450 500 550 6000
50
100
Wavelength (nm)
Mol
ar e
xtin
ctio
n co
effic
ient
(mM
-1 c
m-1)
0.0
0.1
0.2
0.3
ATL ()
PTL and absorbance spectra of a 50 mM solution of R6G in ethanol.
Because of fluorescence both spectra are different. This property of PTL spectroscopy can be used for measuring the quantum yield of fluorescence
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Quantum yield of fluorescence
450 500 550 6000.0
0.5
1.0
F
Wavelength (nm)
)L)(exp(1/)(A1 TLFF
L ︶︵
︶︵ATL
PTL absorbance
absorbance
FAverage wavelength of fluorescence
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400 500 600 7000.0
5.0x104
1.0x105
1.5x105
Ext
inct
ion
(cm
-1/M
)Wavelength (nm)
Malachite Green Oxalate
400 500 600 7000.0
5.0x104
1.0x105
1.5x105
Ext
inct
ion
(cm
-1/M
)
Wavelength (nm)
Malachite Green Oxalatea b
a- PTL and extinction spectra of Malachite Green Oxalate with nopolystyrene microbeads added; b- PTL and extinction spectra of MalachiteGreen Oxalate containing polystyrene microbeads at concentration of0.005% by weight. The standard deviation is estimated averaging over 5different experiments.
PTL spectroscopy of scattering samplesA. Marcano O., S. Alvarado, J. Meng, D. Caballero, E. Marin and R. Edziah, Applied Spectroscopy, 68 (6), 680‐685, June 2014. DOI: 10.1366/13‐07385.
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a
500 600 7000.0
0.5
1.0N
orm
aliz
ed P
TL
Sig
nal
Wavelength (nm)
Methylene Blue
b
400 500 600 7000.0
0.5
1.0
0.0017 %
Nor
mal
ized
Ext
inct
ion
Wavelength (nm)
Methylene Blue
0
0.005 %
a - Normalized PTL spectra of Nile Blue with polystyrene microbeads added atconcentration of 0 (crossed circles), 0.0017% (stars) and 0.005% (crossed squares)by weight; b- Normalized extinction spectra of Nile Blue containing polystyrenemicrobeads at concentration of 0, 0.0017% and 0.005% by weight as indicated. Thestandard deviation is estimated averaging over 5 different experiments.
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400 500 600 7000.0
0.5
1.0
Scat
teri
ng Q
uant
um Y
ield
Wavelength (nm)
Malachite Green
500 600 700
0.0
0.5
1.0
Scat
teri
ng Q
uant
um Y
ield
Wavelength (nm)
Methylene Blue
a b
a- Scattering quantum yield of the Malachite Green Oxalate sample with addedpolystyrene microparticles at 0.005 % concentration by weight; b- Scatteringquantum yield of the Nyle Blue sample with added polystyrene microparticles at0.005 % by weight. The standard deviation is estimated averaging over 5 differentexperiments.
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400 500 600 700109
1010
1011
Ext
inct
ion
coef
ficie
nt (c
m-1
/M)
Wavelength (nm)
Au nanoparticles
Extinction (solid line) and PTL (crossed circles) spectra of a solution of 50-nmdiameter gold nanoparticles at concentration of 1 mg/mL. The standard deviationis estimated averaging over 5 different experiments.
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400 500 600 7000.0
0.5
1.0
Scat
teri
ng Q
uant
um Y
ield
Wavelength (nm)
Malachite Green
500 600 700
0.0
0.5
1.0
Scat
teri
ng Q
uant
um Y
ield
Wavelength (nm)
Methylene Blue
a b
a- Scattering quantum yield of the Malachite Green Oxalate sample with addedpolystyrene microparticles at 0.005 % concentration by weight; b- Scatteringquantum yield of the Nyle Blue sample with added polystyrene microparticles at0.005 % by weight. The standard deviation is estimated averaging over 5 differentexperiments.
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400 500 600 7000.01
0.1
1
10E
xtin
ctio
n co
effic
ient
(A.U
.)
Wavelength (nm)
Blood
a b
400 500 600 700
0.0
0.5
1.0
Scat
teri
ng Q
uant
um Y
ield
Wavelength (nm)
Blood
a- Extinction (solid line) and PTL (crossed circles) spectra of a blood sample; b-Scattering quantum yield of the same blood sample. The standard deviation is estimated averaging over 5 different experiments.
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Photothermal mirror effect
Nanometric bump
Excitation light
Reflected light
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Xe lamp
He-NeCoCh
D1
SF
L1 L2B
M1
M2
D2
A
Pre-AmplOsc.
White-light photothermal mirror spectrophotometer
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The signal is defined as
o
o
TTTS
)()(
T() is the transmission through the aperture of the probe light in the presence of the pump beam.
To is the transmission through the aperture of the probe light in the absence of the pump beam.
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)()()( PKS
A model based on the simultaneous resolution of the thermo-elastic deformation of the surface and thermal diffusivity equation predicts that
)( is the fraction of absorbed energy used to generate heat
)(P is the power of the pump light
K is a proportionality coefficient that does not depend on
)( PTM spectrum
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PTM (black crossed squares) and absorbance (red crossed circles) of a glass plate
400 500 600 7000
3
6 AbsorbanceA
bsor
banc
e an
d PT
M
Wavelength (nm)
Small dark glass plate 2 mm
PTM
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400 500 600 7000.0
0.2
0.4
0.6
0.8
PT
M
Wavelength (nm)
Ag plate no plasma
PTM spectra of a film made using the deposits from a silver nanoparticle solution
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400 500 600 7000
2
4
6
8PT
M S
igna
l (A
rb. U
nits
)
Wavelength (nm)
Dy2TiO5
PTM spectrum of the dysprosium titanate sample
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Conclusions
Photothermal spectroscopy (PT) is a new spectroscopic method that measures the ability of matter to produce heat following the absorption of light.
PT spectra and absorbance spectra coincide for samples with 100 % thermal yield.
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Advantages
• High sensitive• Universality (any sample, any spectral region).• Scattering and fluorescence free• Only visible sensor technology required (no IR or UV sensors needed)• Remote sample analysis possible• Traditional and modern light source technology can be adapted.• Low cost.
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Light Sources for PT Spectroscopy
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Arc lamps
http://zeiss‐campus.magnet.fsu.edu/print/lightsources/xenonarc‐print.htm
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High Intensity Tunable Light Source
22K$ www.newport.com
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White Leds
10$ on ebay
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The Argon laser
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NIR lasers (MIRA 900)Fs and CW modes700-1050 nm
Vantage tunable diode
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Spectra Physics Velocity™ Widely Tunable Lasers
Tunable diodes
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Laser supercontinuum – good option for phototohermalspectroscopy
http://www.nktphotonics.com/