Thomas G. Spence

Optical diagnostics of atmospheric pressure air plasmas

Atmospheric pressure air plasmas are often thought to be in local thermodynamic equilibrium owing to fast interspecies collisional exchange at high pressure. This assumption cannot be relied upon, particularly with respect to optical diagnostics. Velocity gradients in flowing plasmas and/or elevated electron temperatures created by electrical discharges can result in large departures from chemical and thermal equilibrium. This paper reviews diagnostic techniques based on optical emission spectroscopy and cavity ring-down spectroscopy that we have found useful for making temperature and concentration measurements in atmospheric pressure plasmas under conditions ranging from thermal and chemical equilibrium to thermochemical nonequilibrium.

Photoacoustic spectroscopy using quantum-cascade lasers

Photoacoustic spectra of ammonia and water vapor were recorded by use of a continuous-wave quantum-cascade distributed-feedback (QC-DFB) laser at 8.5 mum with a 16-mW power output. The gases were flowed through a cell that was resonant at 1.6 kHz, and the QC-DFB source was temperature tuned over 35 nm for generation of spectra or was temperature stabilized on an absorption feature peak to permit real-time concentration measurements. A detection limit of 100 parts in 10(9) by volume ammonia at standard temperature and pressure was obtained for a 1-Hz bandwidth in a measurement time of 10 min.

A laser-locked cavity ring-down spectrometer employing an analog detection scheme

A system is described that employs a diode-pumped Nd:YAG continuous-wave laser source servolocked to a three-mirror optical cavity and an analog detection circuit that extracts the ring-down rate from the exponentially decaying ring-down waveform. This scheme improves on traditional cavity ring-down spectroscopy setups by increasing signal acquisition rates to tens of kilohertz and reducing measurement noise sources. For example, an absorption spectrum of a weak CO2 transition at 1064 nm is obtained in less than 10 s at a spectral resolution of 75 kHz employing a cavity with an empty-cavity ring-down decay lifetime of 2.8 μs and a total roundtrip path length of 42 cm. The analog detection system enables laser frequency scan rates greater than 500 MHz/s. The long-term sensitivity of this system is 8.8×10−12 cm−1 Hz−1/2 and the short-term sensitivity is 1.0×10−12 cm−1 Hz−1/2.

Cavity ringdown spectroscopy using mid-infrared quantum-cascade lasers.

Cavity ringdown spectra of ammonia at 10 parts in 10(9) by volume (ppbv) and higher concentrations were recorded by use of a 16-mW continuous-wave quantum-casacde distributed-feedback laser at 8.5 mum whose wavelength was continuously temperature tuned over 15 nm. A sensitivity (noise-equivalent absorbance) of 3.4x10(-9) cm(-1) Hz(-1/2) was achieved for ammonia in nitrogen at standard temperature and pressure, which corresponds to a detection limit of 0.25 ppbv.

Pulse-stacked cavity ring-down spectroscopy

Pulse stacking, or synchronous pumping, is a novel approach that offers important advantages in cavity ring-down spectroscopy. Using an ultrashort pulse, high repetition rate laser source we have shown that it is possible to resonantly stack pulses in a high finesse cavity, significantly enhancing the decay wave forms obtained when the laser source is abruptly terminated. We have achieved signal-to-noise ratio improvements of several orders of magnitude compared to single pulse injection systems, demonstrating a sensitivity of 2×10−9 cm−1 at 5.38 μm.

Optical heterodyne detection in cavity ring-down spectroscopy

Abstract Polarization-selective optical heterodyne detection is shown to enhance the practical sensitivity of cavity ring-down spectroscopy. Initial experiments demonstrate a signal-to-noise ratio above 31 dB. Minor improvements should yield shot-noise-limited operation.

Frequency-switched heterodyne cavity ringdown spectroscopy

When the frequency of light coupled into a cavity is suddenly shifted, the radiation emanating from the input port of the previously excited cavity can beat with the reflection of the frequency-shifted input on the surface of a photodetector. When the beat frequency is stable, the time decay of the resulting optical heterodyne signal can be used to measure intracavity absorption spectra with near quantum-limited sensitivity.

Pulsed quantum cascade laser-based CRDS substance detection: real-time detection of TNT

This paper presents experimental results from a pulsed quantum cascade laser based cavity ringdown spectrometer used as a high-throughput detection system. The results were obtained from an optical cavity with 99.8% input and output coupling mirrors that was rapidly swept (0.2s to 7s sweep times) between 1582.25 cm(-1) (6.3201μm) and 1697.00 cm(-1) (5.8928μm). The spectrometer was able to monitor gas species over the pressure range 585 torr to 1μtorr, and the analysis involves a new digital data processing system that optimises the processing speed and minimises the data storage requirements. In this approach we show that is it not necessary to make direct measurements of the ringdown time of the cavity to obtain the system dynamics. Furthermore, we show that correct data processing is crucial for the ultimate implementation of a wideband IR spectrometer that covers a range similar to that of commercial Fourier transform infrared instruments.

Frequency domain analysis for laser-locked cavity ringdown spectroscopy

In this paper we report on the development of a Fourier-transform based signal processing method for laser-locked Continuous Wave Cavity Ringdown Spectroscopy (CWCRDS). Rather than analysing single ringdowns, as is the norm in traditional methods, we amplitude modulate the incident light, and analyse the entire waveform output of the optical cavity; our method has more in common with Cavity Attenuated Phase Shift Spectroscopy than with traditional data analysis methods. We have compared our method to Levenburg-Marquardt non linear least squares fitting, and have found that, for signals with a noise level typical of that from a locked CWCRDS instrument, our method has a comparable accuracy and comparable or higher precision. Moreover, the analysis time is approximately 500 times faster (normalised to the same number of time domain points). Our method allows us to analyse any number of periods of the ringdown waveform at once: this allows the method to be optimised for speed and precision for a given spectrometer.

Real-time FPGA data collection of pulsed-laser cavity ringdown signals

This paper presents results from a pulsed-laser cavity ring-down spectrometer with novel field programable gate array real-time data collection. We show both theoretically and experimentally that the data extraction can be achieved from a single cavity ringdown event, and that the absorbance can be determined without the need to fit the ringdown time explicitly. This methodology could potentially provide data acquisition rate up to 1 MHz, with the accuracy and precision comparable to nonlinear least squares fitting algorithms.