Ricchiuti, G., Dabrowska, A., Pinto, D., Ramer, G., & Lendl, B. (2022, June 0). A Dual-beam Photothermal Mach-Zehnder Interferometer Employing an External Cavity Quantum Cascade Laser for Detection of Water Traces in Organic Solvents [Poster Presentation]. Analytica, Munich, Germany.
We present a first photothermal mid-IR spectroscopy setup for liquids on the example
of sensitive detection of water traces in organic solvents (ethanol and chloroform) and
as a most difficult application in aircraft’s jet fuel. Classical absorption spectroscopy
based on Lambert-Beer´s law relies on detection of minute differences in light intensity.
However, as absorbance does not scale with laser power it does not fully benefit from
quantum cascade lasers’ (QCLs) high power and brilliance. [1] At the contrary,
photothermal spectroscopy (PTS) is an indirect detection approach where the
generated analytical signal is directly proportional to the applied laser power.
Increasing the power means that the sensitivity is enhanced, too.
In PTS the sample is illuminated by a pulsed mid-IR excitation source causing a
periodical heating and cooling of the sample. The resulting photo-induced thermal
gradient ΔT can be probed as a consequent refractive index change (Δn) by means of
a second laser source, a so called “probe laser”. The challenge lies in detecting the
smallest Δn. To do that, we use an interferometric approach. In particular, our latest
generation liquid PTS IR sensor consists of a Mach-Zehnder Interferometer (MZI) able
to sense sub-nm phase shifts Δφ between its two arms. In detail, we use a HeNe probe
laser and an external cavity (EC)-QCL pump laser tuneable from 1730 to 1565 cm-1.
The stability and linearity of our system are ensured by temperature stabilization and
holding the MZI in its quadrature point using a PID controlled piezo electric transducer
(PZT) glued directly on a mirror in one arm of the MZI. Some of the relevant obtained
results are reported in Fig. 1. Achieved limits of detection are in the low ppm region.
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Projekttitel:
European Joint Doctorate Programme on Optical Sensing using Advanced Photo-Induced Effects: 860808 (European Commission)
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Weitere Information:
Mid-infrared (mid-IR) spectroscopy is a versatile analytical technique that allows for qualitative and quantitative analysis. It is based on probing highly selective rotational and vibrational transitions of analyte molecules present in gases, liquids and solids. Classical absorption spectroscopy based on Lambert-Beer´s law relies on detection of minute differences in light intensity. However, as absorbance does not scale with laser power it does not fully benefit from quantum cascade lasers’ (QCLs) high power and brilliance. [2] At the contrary, photothermal spectroscopy (PTS) is an indirect detection approach where the generated analytical signal is directly proportional to the applied laser power. [3] In this work, we present a photothermal mid-IR spectroscopy setup that achieves low-ppm range limits of detection for water in organic solvents (ethanol and chloroform) and as a most difficult application in aircraft’s jet fuel. The device has been calibrated and validated against coulometric Karl Fischer titration (KF) and is shown to have comparable performance and sensitivity. In contrast to KF, the spectroscopic nature of the sensor allows to gain additional information on the analyte and works reagent-free.