J Röpcke

Applications of quantum cascade lasers in plasma diagnostics: a review

Over the past few years mid-infrared absorption spectroscopy based on quantum cascade lasers operating over the region from 3 to 12 µm and called quantum cascade laser absorption spectroscopy or QCLAS has progressed considerably as a powerful diagnostic technique for in situ studies of the fundamental physics and chemistry of molecular plasmas. The increasing interest in processing plasmas containing hydrocarbons, fluorocarbons, nitrogen oxides and organo-silicon compounds has led to further applications of QCLAS because most of these compounds and their decomposition products are infrared active. QCLAS provides a means of determining the absolute concentrations of the ground states of stable and transient molecular species at time resolutions below a microsecond, which is of particular importance for the investigation of reaction kinetics and dynamics. Information about gas temperature and population densities can also be derived from QCLAS measurements. Since plasmas with molecular feed gases are used in many applications such as thin film deposition, semiconductor processing, surface activation and cleaning, and materials and waste treatment, this has stimulated the adaptation of QCLAS techniques to industrial requirements including the development of new diagnostic equipment. The recent availability of external cavity (EC) QCLs offers a further new option for multi-component detection. The aim of this paper is fourfold: (i) to briefly review spectroscopic issues arising from applying pulsed QCLs, (ii) to report on recent achievements in our understanding of molecular phenomena in plasmas and at surfaces, (iii) to describe the current status of industrial process monitoring in the mid-infrared and (iv) to discuss the potential of advanced instrumentation based on EC-QCLs for plasma diagnostics.

Modeling of microwave discharges of H2 admixed with CH4 for diamond deposition

Microwave discharges of H2 admixed with CH4 in a moderate-pressure quartz bell jar reactor used for diamond deposition are studied numerically. Special attention was devoted to high-power densities which provide the most effective way for producing high-quality diamond films. First, a one-dimensional radial model describing the coupled phenomena of chemistry, energy transfer, as well as species and energy transport along the reactor’s radial coordinate was developed. Species densities predicted with the model were compared with measurements with infrared tunable diode laser spectroscopy, resulting in validation of the model. Second, a one-dimensional axial model was used to describe the plasma flow along the reactor axis in a region between the reactor end wall and the substrate surface. This model was particularly useful for studying the plasma behavior in the vicinity of the substrate surface, where thermal and composition gradients are large. Both the radial and axial transport models are based on the ...

Application of mid-infrared tuneable diode laser absorption spectroscopy to plasma diagnostics: a review

Within the last decade mid-infrared absorption spectroscopy over a region from 3 to 17?m and based on tuneable lead salt diode lasers, often called tuneable diode laser absorption spectroscopy or TDLAS, has progressed considerably as a powerful diagnostic technique for in situ studies of the fundamental physics and chemistry in molecular plasmas. The increasing interest in processing plasmas containing hydrocarbons, fluorocarbons, organo-silicon and boron compounds has led to further applications of TDLAS because most of these compounds and their decomposition products are infrared active. TDLAS provides a means of determining the absolute concentrations of the ground states of stable and transient molecular species, which is of particular importance for the investigation of reaction kinetic phenomena. Information about gas temperature and population densities can also be derived from TDLAS measurements. A variety of free radicals and molecular ions have been detected by TDLAS. Since plasmas with molecular feed gases are used in many applications such as thin film deposition, semiconductor processing, surface activation and cleaning, and materials and waste treatment, this has stimulated the adaptation of infrared spectroscopic techniques to industrial requirements. The recent development of quantum cascade lasers (QCLs) offers an attractive new option for the monitoring and control of industrial plasma processes. The aim of the present paper is threefold: (i) to review recent achievements in our understanding of molecular phenomena in plasmas, (ii) to report on selected studies of the spectroscopic properties and kinetic behaviour of radicals and (iii) to describe the current status of advanced instrumentation for TDLAS in the mid-infrared.

Spectroscopic diagnostics and modeling of Ar∕H2∕CH4 microwave discharges used for nanocrystalline diamond deposition

In this paper Ar∕H2∕CH4 microwave discharges used for nanocrystalline diamond chemical vapor deposition in a bell-jar cavity reactor were characterized by both experimental and modeling investigations. Discharges containing 1% CH4 and H2 percentages ranging between 2% and 7% were analyzed as a function of the input microwave power under a pressure of 200mbar. Emission spectroscopy and broadband absorption spectroscopy were carried out in the UV-visible spectral range in order to estimate the gas temperature and the C2 density within the plasma. Infrared tunable diode laser absorption spectroscopy was achieved in order to measure the mole fractions of carbon-containing species such as CH4, C2H2, and C2H6. A thermochemical model was developed and used in order to estimate the discharge composition, the gas temperature, and the average electron energy in the frame of a quasihomogeneous plasma assumption. Experiments and calculations yielded consistent results with respect to plasma temperature and compositio...

Trace gas measurements using optically resonant cavities and quantum cascade lasers operating at room temperature

Achieving the high sensitivity necessary for trace gas detection in the midinfrared molecular fingerprint region generally requires long absorption path lengths. In addition, for wider application, especially for field measurements, compact and cryogen free spectrometers are definitely preferable. An alternative approach to conventional linear absorption spectroscopy employing multiple pass cells for achieving high sensitivity is to combine a high finesse cavity with thermoelectrically (TE) cooled quantum cascade lasers (QCLs) and detectors. We have investigated the sensitivity limits of an entirely TE cooled system equipped with an ∼0.5 m long cavity having a small sample volume of 0.3 l. With this spectrometer cavity enhanced absorption spectroscopy employing a continuous wave QCL emitting at 7.66 μm yielded path lengths of 1080 m and a noise equivalent absorption of 2×10−7 cm−1 Hz−1/2. The molecular concentration detection limit with a 20 s integration time was found to be 6×108 molecules/cm3 for N2O a...

Detailed study of the plasma-activated catalytic generation of ammonia in N2-H2 plasmas

We investigated the efficiency and formation mechanism of ammonia generation in recombining plasmas generated from mixtures of N2 and H2 under various plasma conditions. In contrast to the Haber-Bosch process, in which the molecules are dissociated on a catalytic surface, under these plasma conditions the precursor molecules, N2 and H2, are already dissociated in the gas phase. Surfaces are thus exposed to large fluxes of atomic N and H radicals. The ammonia production turns out to be strongly dependent on the fluxes of atomic N and H radicals to the surface. By optimizing the atomic N and H fluxes to the surface using an atomic nitrogen and hydrogen source ammonia can be formed efficiently, i.e., more than 10% of the total background pressure is measured to be ammonia. The results obtained show a strong similarity with results reported in literature, which were explained by the production of ammonia at the surface by stepwise addition reactions between adsorbed nitrogen and hydrogen containing radicals a...

On NOx production and volatile organic compound removal in a pulsed microwave discharge in air

The production of NO and NO2 and the removal of 3-pentanone, as an example for volatile organic compounds (VOCs), in a pulsed microwave discharge in air, near atmospheric pressure has been studied. The influence of changing the pulse duration from 25 to 500 µs and of the pulse repetition rate from 10 to 500 Hz is reported. At a relatively high pressure of p = 800 mbar, plasma ignition is achieved by inserting BaTiO3 pellets inside the microwave excitator. The concentrations of NO and NO2 have been monitored by infrared tunable diode laser absorption spectroscopy. It was found that their concentrations increase monotonically with the average power injected into the plasma. Further, the efficiency of the pulsed microwave discharge for VOC oxidation, in this case of 1400 ppm of 3-pentanone in dry air, has been studied. The VOC removal efficiency has been determined using gas chromatography. The oxidative efficiency of the discharge was found to increase linearly with the pulse repetition rate as well as with the pulse duration, the power duty cycle ratio being the key parameter.

Sensitive trace gas detection with cavity enhanced absorption spectroscopy using a continuous wave external-cavity quantum cascade laser

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.

Diagnostic studies of H2?Ar?N2 microwave plasmas containing methane or methanol using tunable infrared diode laser absorption spectroscopy

Tunable infrared diode laser absorption spectroscopy has been used to detect the methyl radical and nine stable molecules, CH4, CH3OH, C2H2, C2H4, C2H6, NH3, HCN, CH2O and C2N2, in H2–Ar–N2 microwave plasmas containing up to 7% of methane or methanol, under both flowing and static conditions. The degree of dissociation of the hydrocarbon precursor molecules varied between 20% and 97%. The methyl radical concentration was found to be in the range 1012–1013 molecules cm−3. By analysing the temporal development of the molecular concentrations under static conditions it was found that HCN and NH3 are the final products of plasma chemical conversion. The fragmentation rates of methane and methanol (RF(CH4) = (2–7) × 1015 molecules J−1, RF(CH3OH) = (6–9) × 1015 molecules J−1) and the respective conversion rates to methane, hydrogen cyanide and ammonia (RCmax(CH4) = 1.2 × 1015 molecules J−1, RCmax(HCN) = 1.3 × 1015 molecules J−1, RCmax(NH3) = 1 × 1014 molecules J−1) have been determined for different hydrogen to nitrogen concentration ratios. An extensive model of the chemical reactions involved in the H2–N2–Ar–CH4 plasma has been developed. Model calculations were performed by including 22 species, 145 chemical reactions and appropriate electron impact dissociation rate coefficients. The results of the model calculations showed satisfactory agreement between calculated and measured concentrations. The most likely main chemical pathways involved in these plasmas are discussed and an appropriate reaction scheme is proposed.

TRIPLE Q: A three channel quantum cascade laser absorption spectrometer for fast multiple species concentration measurements

A compact and transportable three channel quantum cascade laser system (TRIPLE Q) based on mid-infrared absorption spectroscopy has been developed for time-resolved plasma diagnostics. The TRIPLE Q spectrometer encompasses three independently controlled quantum cascade lasers (QCLs), which can be used for chemical sensing, particularly for gas phase analysis of plasmas. All three QCLs are operated in the intra-pulse mode with typical pulse lengths of the order of 150 ns. Using a multiplexed detection, a time resolution shorter than 1 μs can be achieved. Hence, the spectrometer is well suited to study kinetic processes of multiple infrared active compounds in reactive plasmas. A special data processing and analysis technique has been established to account for time jitter effects of the infrared emission of the QCLs. The performance of the TRIPLE Q system has been validated in pulsed direct current plasmas containing N(2)O/air and NO(2)/air.