Thermal lens spectrometry under excitation of a divergent pump beam

Thermal lens spectrometry (TLS) under excitation of a divergent pump beam is discussed in both conventional and microscopic TLS instruments. A refined thermal lens (TL) model was proposed for calculating the TL signal of a “finite TL element.” Experiments as well as comparison with numerical simulations demonstrated that the effective sample length for a certain pump beam profile was about six times the confocal distance of the pump beam for laser-excited case and 1.5 mm for incoherent light source-excited case. For laser-excited conventional TLS instrument or thermal lens microscope (TLM), an empirical formula of the optimum pump beam waist radius for maximum detection sensitivity was obtained at a given sample length. At larger pump beam waist radius of 7 μm, the TL signal was found 2.5 times lower compared to the diffraction limit; however, the resulting two orders of magnitude lower power density in the sample could be quite desirable for the detection of photolabile analytes. By investigating the influence of a finite TL element on the TL signal, we found that an optimal distance between the probe beam waist and the sample was needed to assure the maximum detection sensitivity and good response linearity. Under the optimal detection scheme, limit of detection of the laser-excited TLM at 4 mW power was evaluated to be 8.6 × 10^?9 M for 100-μm-thick ferroin solution, corresponding to an absorbance of 9.5 × 10^?7 absorbance units.