CH4 and C2H2 molecules (and their interconversion) in hydrocarbon/rare gas/H2 gas mixtures in a microwave reactor used for plasma enhanced diamond chemical vapor deposition (CVD) have been investigated by line-of-sight infrared absorption spectroscopy in the wavenumber range of 1276.5−1273.1 cm−1 using a quantum cascade laser spectrometer. Parameters explored include process conditions [pressure, input power, source hydrocarbon, rare gas (Ar or Ne), input gas mixing ratio], height (z) above the substrate, and time (t) after addition of hydrocarbon to a pre-existing Ar/H2 plasma. The line integrated absorptions so obtained have been converted to species number densities by reference to the companion two-dimensional (r,z) modeling of the CVD reactor described in Mankelevich et al. [J. Appl. Phys. 104, 113304 (2008)] . The gas temperature distribution within the reactor ensures that the measured absorptions are dominated by CH4 and C2H2 molecules in the cool periphery of the reactor. Nonetheless, the measurements prove to be of enormous value in testing, tensioning, and confirming the model predictions. Under standard process conditions, the study confirms that all hydrocarbon source gases investigated (methane, acetylene, ethane, propyne, propane, and butane) are converted into a mixture dominated by CH4 and C2H2. The interconversion between these two species is highly dependent on the local gas temperature and the H atom number density, and thus on position within the reactor. CH4→C2H2 conversion occurs most efficiently in an annular shell around the central plasma (characterized by 1400

In many examples of the use of mid-infrared quantum cascade (QC) lasers for gas detection or process monitoring, an assumption is made that their use is an obvious extension of tuneable diode laser spectroscopy. We wish to show that making such an assumption is not necessarily justified when the frequency sweep rate is rapid, as is down-chirped QC laser infrared radiation. This is demonstrated via a series of experiments designed to investigate the physics of the interaction of chirped infrared laser radiation with low pressure gases. The unusual signals, which characterise the rapid passage of the down-chirped radiation through a low pressure gas, are due to two main effects, the laser sweep rate, and the long path length of the refocusing cells used. The sweep rate of the laser frequency may be faster than the inter-molecular collision frequency, allowing the build up of a strong molecular alignment within the gas. The long optical path lengths in the refocusing absorption cells, used to facilitate sensitive detection of trace gases, allow the build up of a large macroscopic polarisation within the gas cell. We give examples of this behaviour in molecules with large transition dipole moments, ammonia and nitrous oxide, and with a very small one (OCO)-O-18-C-12-O-16. We also outline the use of Maxwell-Bloch calculations to investigate the origins of this behaviour, and hence to define operating conditions where the concentration of trace molecules may be determined

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Intrapulse quantum cascade laser spectrometers are able to produce both saturation and molecular alignment of the gas sample. This is due to the rapid sweep of the radiation through the absorption features. The intrapulse time domain spectra closely resemble those recorded in coherent optical nutation experiments. In the present paper, the frequency down-chirped technique is employed to investigate the nitrous oxide-foreign gas collisions. We have demonstrated that the measurements may be characterized by the induced polarization dominated and collision dominated measurement limits. The first of these is directly related to the time dependence of the long range collision cross sections. Among the collisional partners considered, carbon dioxide shows a very unusual behavior of rapid polarization damping, resulting in the production of symmetrical line shapes at very low gas buffer pressures. In the collision dominated regime, the pressure broadening parameters, which we have derived, are comparable at slow chirp rates, with those derived from other experimental methods. By comparing the pressure broadening coefficients of Ar, N(2), and CO(2) with those of He, making use of the chirp rate independence of the pressure broadening by helium, we have shown that at higher chirp rates there is clear evidence of the chirp-rate dependence of the pressure broadening parameters of N(2) and CO(2).

In-flight measurements of ambient methane, nitrous oxide and water have been made using frequency down-chirped radiation from a compact, pulsed, quantum-cascade laser spectrometer. In three flights from Oxford airport in October 2006 the variations of the concentration of these three trace gases could be measured and related to possible sources in the flight path