Andreas Genner

Time-resolved spectral characterization of ring cavity surface emitting and ridge-type distributed feedback quantum cascade lasers by step-scan FT-IR spectroscopy.

We present the time-resolved comparison of pulsed 2nd order ring cavity surface emitting (RCSE) quantum cascade lasers (QCLs) and pulsed 1st order ridge-type distributed feedback (DFB) QCLs using a step-scan Fourier transform infrared (FT-IR) spectrometer. Laser devices were part of QCL arrays and fabricated from the same laser material. Required grating periods were adjusted to account for the grating order. The step-scan technique provided a spectral resolution of 0.1 cm(-1) and a time resolution of 2 ns. As a result, it was possible to gain information about the tuning behavior and potential mode-hops of the investigated lasers. Different cavity-lengths were compared, including 0.9 mm and 3.2 mm long ridge-type and 0.97 mm (circumference) ring-type cavities. RCSE QCLs were found to have improved emission properties in terms of line-stability, tuning rate and maximum emission time compared to ridge-type lasers.

Highly reproducible SERS detection in sequential injection analysis: Real time preparation and application of photo-reduced silver substrate in a moving flow-cell

This paper reports an improved way for performing highly reproducible surface enhanced Raman scattering of different analytes using an automated flow system. The method uses a confocal Raman microscope to prepare SERS active silver spots on the window of a flow cell by photo-reduction of silver nitrate in the presence of citrate. Placement of the flow cell on an automated x and y stages of the Raman microscope allows to prepare a fresh spot for every new measurement. This procedure thus efficiently avoids any carry over effects which might result from adsorption of the analyte on the SERS active material and enables highly reproducible SERS measurements. For reproducible liquid handling the used sequential injection analysis system as well as the Raman microscope was operated by the flexible LabVIEW based software ATLAS developed in our group. Quantitative aspects were investigated using Cu(PAR)2 as a model analyte. Concentration down to 5×10(-6) M provided clear SERS spectra, a linear concentration dependence of the SERS intensities at 1333 cm(-1) was obtained from 5×10(-5) to 1×10(-3) with a correlation coefficient r=0.999. The coefficient of variation of the method Vxo was found to be 5.6% and the calculated limit of detection 1.7×10(-5) M. The results demonstrate the potential of SERS spectroscopy to be used as a molecular specific detector in aqueous flow systems.

Application of a ring cavity surface emitting quantum cascade laser (RCSE-QCL) on the measurement of H 2 S in a CH 4 matrix for process analytics.

The present work reports on the first application of a ring-cavity-surface-emitting quantum-cascade laser (RCSE-QCL) for sensitive gas measurements. RCSE-QCLs are promising candidates for optical gas-sensing due to their single-mode, mode-hop-free and narrow-band emission characteristics along with their broad spectral coverage. The time resolved down-chirp of the RCSE-QCL in the 1227-1236 cm-1 (8.15-8.09 µm) spectral range was investigated using a step-scan FT-IR spectrometer (Bruker Vertex 80v) with 2 ns time and 0.1 cm-1 spectral resolution. The pulse repetition rate was set between 20 and 200 kHz and the laser device was cooled to 15-17°C. Employing 300 ns pulses a spectrum of ~1.5 cm-1 could be recorded. Under these laser operation conditions and a gas pressure of 1000 mbar a limit of detection (3σ) of 1.5 ppmv for hydrogen sulfide (H2S) in nitrogen was achieved using a 100 m Herriott cell and a thermoelectric cooled MCT detector for absorption measurements. Using 3 µs long pulses enabled to further extend the spectral bandwidth to 8.5 cm-1. Based on this increased spectral coverage and employing reduced pressure conditions (50 mbar) multiple peaks of the target analyte H2S as well as methane (CH4) could be examined within one single pulse.

Measures for optimizing pulsed EC-QC laser spectroscopy of liquids and application to multi-analyte blood analysis

We employed a broadly tunable pulsed external cavity (EC)-QC laser with a spectral tuning range from 1030 cm-1 to 1230 cm-1 and a tuning speed of 166 cm-1/s for direct absorption spectroscopy of aqueous solutions. The laser offered spectral power densities of up to four orders of magnitude higher than available with a conventional FTIR spectrometer. Therefore, a portable demonstration system with a large optical path length transmission flow cell (165 μm) could be realized preventing clogging of the flow cell. In pulsed mode an EC-QC laser provides significantly higher peak power levels than in continuous-wave mode, but pulse-to-pulse intensity variations, intra-pulse mode hops and mechanical imperfections of the scanning mechanism significantly impair the quality of resulting absorbance spectra. This article reports on measures which we found appropriate to reduce the initially high noise level of EC-QC laser absorbance spectra. These measures include a spectral self-referencing algorithm that makes use of the inherent structure of the EC-QC lasers gain curve to correct laser instabilities, as well as Fourier filtering, among others. This enabled us to derive infrared spectra which were finally useful for quantitative analysis in blood plasma samples. Finally, with the appropriate measures in place and using partial least squares regression analysis it was possible to simultaneously quantify 6 blood analytes from a single physical measurement of a 200 μL blood sample. This proves the potential of EC-QC lasers for practical application in clinical point of care analysis.

Clinical application of a mid-infrared Quantum Cascade Laser based sensor for multianalyte detection in human blood plasma

A portable point-of-care sensor employing a broadly tunable External Cavity Quantum Cascade Laser was applied for clinical multianalyte detection in human blood plasma. Glucose, triglyzerides, total protein, albumin, cholesterol and fibrinogen could be succesfully quantified.