Photothermal Spectroscopy Lecture 2 - Applications Aristides Marcano Olaizola (PhD) Research Professor Department of Physics and Engineering Delaware State University, US 1
Outlook 1. Optical characterization of matter. 2. The place of photothermal spectroscopy 3. Achromatic character of the modemismatched configuration. 4. NIR Photothermal spectroscopy 5. Photothermal-absorbance-fluorescence spectrophotometer. 6. Photothermal spectroscopy of fluorescence and scattering samples. 7. Perspectives.
Material samples exhibit generally more than one type of effect upon interaction with light Scattered light Incident light Transmitted light Reflected light Absorption of light Photoacoustic effects Photothermal effects Photomechanical effects Photochemical effects Luminescence
From the energy conservation law we obtain P o P P P P ( ) P ( ) T F Th s R Po Incident power P T PF Transmitted power Power used for fluorescence P Th P s Power degraded into heat Scattered power PR Reflected power
) ( ) ( o T P P T Transmittance ) ( log ) ( T A Absorbance ) ( ) ( o F P P F Fluorescence excitation spectrum ) ( ) ( o R P P R Reflectance ) ( ) ( o Th P P PT Photothermal spectrum
0.05 Mode-matched TL signal 0.00-0.05-0.10-0.15 Mode-mismatched -40-20 0 20 40 Sample position (cm) o =-0.1, p =632 nm, e =750 nm, L=200 cm, D=0.001491 cm 2 /s, t=10 s, z p =0.2 cm for mode-matched scheme and z p =2000 cm for mode-mismatched scheme.
Excitation laser Probe laser L1 Osc. Ampl. D L 2 A Ch L 3 L 4 Sample F M M 2 1 B z Marcano O. A. and N. Melikechi, App. Spectros. 61, 659-664 (2007).
0.03 Mode-matched TL signal 0.00-0.03 Modemismatched p =632 nm, e =807 nm -0.06-20 -10 0 10 20 Sample position (cm) Experimental Z-scan of 1-cm cell containing distilled water measured under the mode-matched (open stars) and mode-mismatched (solid squares) schemes.
Absorption (cm -1 ) 0.4 Mode-mismatched 0.2 Mode-matched 0.0 700 800 900 1000 PTL spectra of distilled water measured using the mode-matched (large open stars) and mode-mismatched (large crossed circles) experimental configurations. Results of previous reports on water absorption of different authors have been included (small symbols).
Ultrasensitive spectroscopy of water High precision values of absorption of water in the 300-500 nm spectral region 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).
Absorption coefficient (cm -1 ) 0.6 Comparison of TL spectrum with absorbance spe of distilled water measured by other authors 0.3 Pope and Fry Palmer and Willians TL spectrum 0.0 700 800 900 1000
0.15 NIR spectroscopy of Ethanol Absorbance 0.10 0.05 Ethanol TL Cary absorbance measurement 0.00 700 800 900
NIR of Methanol Absorbance 0.3 0.2 0.1 PTL Methanol cell 1 mm Cary absorbance 0.0 700 750 800 850 900 950
Nd:YAG OPO M1 D1 D2 D3 M2 BS 1 L2 F1 L3 M3 L1 Sample BS 2 He- Ne F2 A 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
. Absorbance (crossed circles), fluorescence excitation (crossed stars) and TL spectra (solid triangles) of a 5 10-6 M ethanol solution of Rhodamine 6G. The solid line is the absorbance spectrum of the same sample obtained using a spectrophotometer. 0,03 1-T( e ) Absolute values 0,02 0,01 F( e ) A Th ( e ) 0,00 Figure 2. Hung et al. 450 475 500 525 550 575
1-T( e ) Absolute values 0,012 0,006 A Th ( e ) F( e ) 0,000 475 500 525 550 Absorbance (crossed circles), fluorescence excitation (crossed stars) and TL spectra (solid triangles) Figure 3. of Hung the et al. same sample of previous slide after adding of the quencher (KI).
Fluorescence Quantum Yield 1,0 0,5 0,0 No quencher With quencher 475 500 525 550 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.
White light photothermal lens spectrophotometer L 2 L 1 M 1 He-Ne M 2 A S B IFS L 3 L 4 Xe Lamp D M 3 Ch
PTL spectrum of a non-fluorescent dye Molar extinction coefficient (mm -1 cm -1 ) 150 100 50 0 0.8 0.4 0.0 400 500 600 700 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 whitelight thermal lens spectrophotometer, Appl. Spectros. 60 (5), 560-563 (2006).
PTL of a fluorescent dye Molar extinction coefficient (mm -1 cm -1 ) 100 50 0.3 0.2 0.1 0 0.0 400 450 500 550 600 PTL and absorbance spectra of a 50 mm solution of R6G in ethanol. ATL () Because of fluorescence both spectra are different. This property of PTL spectroscopy can be used for measuring the quantum yield of fluorescence
AT(L())Quantum yield of fluorescence F A ( ) / 1 exp( ( )L) F 1 TL 1.0 F 0.5 PTL absorbance 0.0 450 500 550 600 LabsorbanceF Average wavelength of fluorescence
PTL spectroscopy of scattering samples A. 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. Extinction (cm -1 /M) 1.5x10 5 1.0x10 5 5.0x10 4 a Malachite Green Oxalate Extinction (cm -1 /M) 1.5x10 5 1.0x10 5 5.0x10 4 b Malachite Green Oxalate 0.0 400 500 600 700 0.0 400 500 600 700 a- PTL and extinction spectra of Malachite Green Oxalate with no polystyrene microbeads added; b- PTL and extinction spectra of Malachite Green Oxalate containing polystyrene microbeads at concentration of 0.005% by weight. The standard deviation is estimated averaging over 5 different experiments.
Normalized PTL Signal 1.0 0.5 0.0 a Methylene Blue 500 600 700 Normalized Extinction 1.0 0.5 b Methylene Blue 0.005 % 0.0017 % 0 0.0 400 500 600 700 a - Normalized PTL spectra of Nile Blue with polystyrene microbeads added at concentration of 0 (crossed circles), 0.0017% (stars) and 0.005% (crossed squares) by weight; b- Normalized extinction spectra of Nile Blue containing polystyrene microbeads at concentration of 0, 0.0017% and 0.005% by weight as indicated. The standard deviation is estimated averaging over 5 different experiments.
a b Scattering Quantum Yield 1.0 0.5 0.0 Malachite Green 400 500 600 700 Scattering Quantum Yield 1.0 0.5 0.0 Methylene Blue 500 600 700 a- Scattering quantum yield of the Malachite Green Oxalate sample with added polystyrene microparticles at 0.005 % concentration by weight; b- Scattering quantum yield of the Nyle Blue sample with added polystyrene microparticles at 0.005 % by weight. The standard deviation is estimated averaging over 5 different experiments.
Extinction coefficient (cm -1 /M) 10 11 10 10 10 9 Au nanoparticles 400 500 600 700 Extinction (solid line) and PTL (crossed circles) spectra of a solution of 50-nm diameter gold nanoparticles at concentration of 1 mg/ml. The standard deviation is estimated averaging over 5 different experiments.
a b Scattering Quantum Yield 1.0 0.5 0.0 Malachite Green 400 500 600 700 Scattering Quantum Yield 1.0 0.5 0.0 Methylene Blue 500 600 700 a- Scattering quantum yield of the Malachite Green Oxalate sample with added polystyrene microparticles at 0.005 % concentration by weight; b- Scattering quantum yield of the Nyle Blue sample with added polystyrene microparticles at 0.005 % by weight. The standard deviation is estimated averaging over 5 different experiments.
Extinction coefficient (A.U.) 10 1 0.1 0.01 a Blood 400 500 600 700 Scattering Quantum Yield 1.0 0.5 0.0 b Blood 400 500 600 700 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.
Photothermal mirror effect Excitation light Reflected light Nanometric bump
White-light photothermal mirror spectrophotometer Ch M 1 Co He-Ne Xe lamp B L 1 L 2 F S A D 1 M 2 D 2 Osc. Pre-Ampl
The signal is defined as S ( ) T ( ) T o T o T() is the transmission through the aperture of the probe light in the presence of the pump beam. T o is the transmission through the aperture of the probe light in the absence of the pump beam.
A model based on the simultaneous resolution of the thermoelastic deformation of the surface and thermal diffusivity equation predicts that S( ) K P( ) ( ) () P() K is the fraction of absorbed energy used to generate heat is the power of the pump light is a proportionality coefficient that does not depend on () PTM spectrum
Absorbance and PTM Small dark glass plate 2 mm 6 Absorbance 3 PTM 0 400 500 600 700 PTM (black crossed squares) and absorbance (red crossed circles) of a glass plate
PTM 0.8 0.6 0.4 Ag plate no plasma 0.2 0.0 400 500 600 700 PTM spectra of a film made using the deposits from a silver nanoparticle solution
PTM Signal (Arb. Units) 8 6 4 2 0 Dy 2 TiO 5 400 500 600 700 PTM spectrum of the dysprosium titanate sample
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.
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.
Light Sources for PT Spectroscopy
Arc lamps http://zeiss campus.magnet.fsu.edu/print/lightsources/xenonarc print.htm
High Intensity Tunable Light Source 22K$ www.newport.com
White Leds 10$ on ebay
The Argon laser
NIR lasers (MIRA 900) Fs and CW modes 700-1050 nm Vantage tunable diode
Tunable diodes Spectra Physics Velocity Widely Tunable Lasers
Laser supercontinuum good option for phototohermal spectroscopy http://www.nktphotonics.com/