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This paper describes the first implementation of terahertz (THz) quantum cascade lasers for high-resolution absorption spectroscopy on plasmas. Absolute densities of ground state atomic oxygen were directly obtained by using the fine structure transition at approximately 4.75 THz. Measurements were performed on a low-pressure capacitively coupled radio frequency oxygen discharge. The detection limit in this arrangement was found to be 2 × 10 13 cm−3, while the measurement accuracy was within 5%, as demonstrated by reference measurements of a well-defined ammonia transition. The results show that the presented method is well suited to measure atomic oxygen densities, and it closes the THz gap for quantitative atomic density measurements in harsh environments such as plasmas.

Sensitive trace gas detection plays an important role in current challenges occurring in areas such as industrial process control and environmental monitoring. In particular, for medical breath analysis and for the detection of illegal substances, e.g., drugs and explosives, a selective and sensitive detection of trace gases in real-time is required. We report on a compact and transportable multi-component system (RES-Q-Trace) for molecular trace gas detection based on cavity-enhanced techniques in the mid-infrared (MIR). The RES-Q-Trace system can operate four independent continuous wave quantum or interband cascade lasers each combined with an optical cavity. Twice the method of off-axis cavity-enhanced absorption spectroscopy (OA-CEAS) was used, twice the method of optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS), respectively. Multi-functional software has been implemented (i) for the general system control, (ii) to drive the four different laser sources and (iii) to analyze the detector signals for concentration determination of several molecular species. For the validation of the versatility and the performance of the RES-Q-Trace instrument the species NO, N2O, CH4, C2H4 and C3H6O, with relevance in the fields of breath gas analysis and the detection of explosives have been monitored in the MIR with detection limits at atmospheric pressure in the ppb and ppt range.

Applying quantum cascade laser absorption spectroscopy a correlation could be demonstrated between the concentration of the etching products SiF4 and CO and the etching rate of ultra-low-k SiCOH in a low-pressure rf plasma containing CF4.

Plasmas in interaction with surfaces are of key importance in a wide range of applications, which include materials technology, microelectronics, environmental issues, and biomedicine. The intense use of plasma technological processes demands proper plasma diagnostic techniques for monitoring, controlling and optimization purposes in industrial environments. In particular, for the improvement of the efficiency of a production process, in situ diagnostic techniques with online capabilities are favorable. From the middle of the last decade a variety of phenomena in molecular non-equilibrium plasmas in which many short-lived and stable species are produced have been successfully studied with quantum cascade laser absorption spectroscopy (QCLAS) in the mid-infrared spectral range. It has been possible to determine absolute concentrations of species, temperatures, degrees of dissociation, dynamics of reaction processes and phenomena involving plasma-surface interactions using spectroscopy, thereby providing a link with chemical and kinetic modelling of the plasma. Since quantum cascade lasers (QCLs) emit near room temperature, i.e., without the need of cryogenic cooling, very compact and robust spectroscopic instruments can be designed. This has stimulated the adaptation of infrared spectroscopic techniques to industrial requirements. Recent applications of infrared absorption spectroscopy using QCLs for in situ monitoring of plasma processes in industrial environments are reviewed. Examples which emphasize the capabilities of QCLAS as plasma diagnostic technique in industrial plasma processes will be given. (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

To improve the efficiency of many industrial plasma processes, more insight into the plasma chemistry is required. Therefore, the detection and quantitative measurement of important species is a major challenge. We will discuss examples of species detection applying laser-based diagnostics in the mid-infrared using quantum cascade lasers (QCLs) and interband cascade lasers (ICLs). A further increase in sensitivity to detection limits of ppm down to ppt levels can be achieved by combining the lasers with cavity enhanced techniques. We present results of an ICL coupled to a V-shaped optical cavity in an optical feedback cavity enhanced absorption spectroscopy (OF-CEAS) experiment.

We report on recent progress applying quantum cascade laser based optical feedback cavity-enhanced absorption spectroscopy in sensing atmospheric methane in the mid-infrared spectral range. An instrument has been built employing a common V-shaped cavity with a powerful continuous-wave distributed feedback quantum cascade laser. The spectrometer has a noise equivalent absorption coefficient of 3.6 ×10−9 cm−1 Hz−1/2 (1σ) for a spectral scan of CH4 at 7.39 µm. From an Allan-Werle analysis of the optical power transmitted by the evacuated cavity a detection limit of 39 parts per trillion of CH4 at atmospheric pressure within 50 s acquisition time was found.

Low-pressure rf plasmas have been applied for etching of ultra-low-k SiCOH wafers using an Oxford Plasmalab System 100. In pure CF4 plasmas, SiCOH layers have been etched for different power values. Using quantum cascade laser absorption spectroscopy in the mid-infrared spectral range, the correlation of online and in situ measured concentrations of two etching products, CO and SiF4, with the ex situ determined etching rates has been studied. The concentration of SiF4 was found to range between 0.6 and 1.4 × 1013 molecules cm−3. In contrast the concentrations of CO were measured to be only about 50 % of the SiF4 density with 7 × 1012 molecules cm−3 in maximum. The production rate of SiF4, determined from the time behavior of its concentration after plasma ignition, was found to be between 1 and 5 × 1012 cm−3 s−1. The etching rates varied between 2 and 7 nm s−1. Both parameters increase nearly linearly with the applied rf power. It was found that for power values of up to 1.1 kW, the etching rate depends nearly linearly on the in situ monitored concentrations of both etching products. Therefore, the concentration of the etching products can be directly used as a measure of the etching rate.

Chemical sensing using mid-infrared laser absorption spectroscopy coupled with cavity-enhanced absorption spectroscopy in the molecular fingerprint region from 3 to 20 µm is a powerful diagnostic tool achieving detection limits well below ppm level.

We report on sensitive detection of atmospheric methane employing quantum cascade laser based optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS). An instrument has been built utilizing a continuous-wave distributed feedback quantum cascade laser (cw-QCL) with a V-shaped cavity, a common arrangement that reduces feedback to the laser from non-resonant reflections. The spectrometer has a noise equivalent absorption coefficient of 3.6 × 10-9 cm-1 Hz-1/2 for a spectral scan of CH4 at 7.39 μm. From an Allan-Werle analysis a detection limit of 39 parts per trillion of CH4 at atmospheric pressure within 50 s acquisition time was found.

Trace gas sensing in the mid-infrared using quantum cascade lasers (QCLs) promises high specificity and sensitivity. We report on the performance of a simple cavity enhanced absorption spectroscopy (CEAS) sensor using a continuous wave external-cavity QCL at 7.4 μm. A noise-equivalent absorption coefficient αmin of 2.6 × 10–8 cm–1 in 625 s was achieved, which corresponds to a detection limit of 6 ± 1 ppb of CH4 in 15 millibars air for the R(3) transition at 1327.074 cm–1. This is the highest value of noise-equivalent absorption and among the longest effective path length (1780 m) reported to date with QCL-based CEAS.

Three continuous wave external cavity quantum cascade lasers (EC-QCLs) operating between 1305 and 2260 cm−1 (4.42–7.66 µm) have been tested as radiation sources for an absorption spectrometer focused on the analysis of physical and chemical phenomena in molecular plasmas. Based on the wide spectral tunability of EC-QCLs, multiple species detection has become feasible and is demonstrated in a study of low-pressure Ar/N2 microwave plasmas containing methane as a hydrocarbon precursor. Using the direct absorption technique, the evolution of the concentrations of CH4, C2H2, HCN and H2O has been monitored depending on the discharge conditions at a pressure of p = 0.5 mbar and at a frequency of f = 2.45 GHz in a planar microwave plasma reactor. The concentrations were found to be in the range of 1011–1014 molecules cm−3. In addition, based on the analysis of the line profile of selected absorption lines, the gas temperature Tg has been calculated in dependence on the discharge power. Tg increased with the power values and was in the range between 400 and 700 K. Further, in a pure He/Ar microwave plasma, the wavelength modulation spectroscopy technique has been applied for the sensitive detection of transient plasma species with absorbencies down to 10−5. The typical spectral line width of an EC-QCL under the study was found to be in the range 24 to 38 MHz depending (i) on the chopping technique used and (ii) on a single or averaged measurement approach. Further, different methods for the modulation and tuning of the laser radiation have been tested. Varying the power values of an EC-QCL between 0.1 and 154 mW for direct absorption measurements under low pressure conditions, no saturation effects in determining the concentrations of methane, acetylene and carbon monoxide could be found under the experimental conditions used, i.e. for lines with line strengths between 10−19 and 10−22 cm molecule−1.