High sensitivity Thermal Lens spectroscopy / Espectroscopia de lente térmica de alta sensibilidade

AUTOR(ES)
DATA DE PUBLICAÇÃO

2008

RESUMO

The efficiency of conventional transmission methods used to measure absorption of hightransparent materials is usually limited by light scattering and reflection. On the other hand, Thermal Lens spectroscopy is insensible to such phenomena and has been widely applied to determinate low optical absorptions. In this thesis, we have studied a recently developed dualbeam (continuous wave - cw) Thermal Lens configuration as well as its practical applications. This configuration optimizes the technique and significantly improves the measurement sensitivity. Some computational calculations and experimental tests of this approach were carried out. The results were compared with those obtained using a traditional configuration, named Mode-mismatched Dual-beam Thermal Lens. Several applications were made for liquids and solids. As a result, we obtained the absorption spectrum for pure water in the range of 350 to 528 nm, which indicated a minimal value of approximately 1,5 • 10-5 cm-1 around 380 nm, that is lower than those found in literature. Absorption coefficients as small as 2 • 10-7 cm-1, can be measured for water, using 1W of excitation power, with this optimized configuration. We have estimated a detection limit of ~ 6 • 10-9 cm-1 (P = 1 W) for CCl4 solvent, which corresponds (to the best of our knowledge) to the smallest value found in the literature for liquids using cw laser. With regard to the chemical trace analysis, the detection limit was ~ 40 ppb (ng/mL) at 514 nm for Cr (III) in aqueous solutions, which is nearly half of the maximum desired Cr (III) concentration in drinking and natural waters. Some preliminary results for the temperature coefficient of the optical path length (ds/dT) were obtained at solids with different geometries. For the fused-silica (vitreous quartz) Suprasil, we have determined an upper limit for the absorption coefficient, whose values, 1 • 10-6 cm-1 at 493 nm, and 1 • 10-5 cm-1 at 355 nm, also are lower than the values found in literature in this spectrum region. The high sensitivity of the technique allowed us to measure the absorption (at 1064 nm) of matrices of Nd3+ doped laser materials: (1,8 ± 0,1) • 10-3 cm-1 for Q-98 glass (Kigre), and (5 ± 1) • 10-4 cm-1 for Nd:YAG crystal. We carried out as well measurements of fluorescence quantum yield of semiconductor nanocrystals (CdSe/ZnS) suspended in THF and toluene solvents, whose result was approximately 5 times more accurate than that obtained with the conventional fluorescence technique. The main advantages of the optimized configuration are: a simple experimental procedure, a good accuracy for thermal diffusivity measurements, and most important the high sensitivity of the technique. The drawbacks are: a longer time of measurements, and the requirement of larger samples.

ASSUNTO(S)

linear absorption coefficient lowabsorption. coeficiente de absorção linear thermal lens high sensitivity spectroscopy baixas absorções espectroscopia de alta sensibilidade lente térmica

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