Toni Laurila

Cavity enhanced absorption spectroscopy of multiple trace gas species using a supercontinuum radiation source

Supercontinuum radiation sources are attractive for spectroscopic applications owing to their broad wavelength coverage, which enables spectral signatures of multiple species to be detected simultaneously. Here we report the first use of a supercontinuum radiation source for broadband trace gas detection using a cavity enhanced absorption technique. Spectra were recorded at bandwidths of up to 100 nm, encompassing multiple absorption bands of H(2)O, O(2) and O(2)-O(2). The same instrument was also used to make quantitative measurements of NO(2) and NO(3). For NO(3) a detection limit of 3 parts-per-trillion in 2 s was achieved, which corresponds to an effective 3sigma sensitivity of 2.4 x 10(-9) cm(-1)Hz(-1/2). Our results demonstrate that a conceptually simple and robust instrument is capable of highly sensitive broadband absorption measurements.

Following interfacial kinetics in real time using broadband evanescent wave cavity-enhanced absorption spectroscopy: a comparison of light-emitting diodes and supercontinuum sources

A white light-emitting diode (LED) with emission between 420 and 700 nm and a supercontinuum (SC) source with emission between 450 and 2500 nm have been compared for use in evanescent wave broadband cavity-enhanced absorption spectroscopy (EW-BB-CEAS). The method is calibrated using a dye with known absorbance. While the LED is more economic as an excitation source, the SC source is superior both in terms of baseline noise (noise equivalent absorbances lower than 10(-5) compared to 10(-4) absorbance units (a.u.)) and accuracy of the measurement; these baseline noise levels are comparable to evanescent wave cavity ringdown spectroscopy (EW-CRDS) studies while the accessible spectral region of EW-BB-CEAS is much larger (420-750 nm in this study, compared to several tens of nanometres for EW-CRDS). The improvements afforded by the use of an SC source in combination with a high sensitivity detector are demonstrated in the broadband detection of electrogenerated Ir(IV) complexes in a thin-layer electrochemical cell arrangement. Excellent signal to noise is achieved with 10 micros signal accumulation times at a repetition rate of 600 Hz, easily fast enough to follow, in real time, solution kinetics and interfacial processes.

Cavity Enhanced Spectroscopy of High-Temperature H2O in the Near-Infrared Using a Supercontinuum Light Source:

In this paper we demonstrate how broadband cavity enhanced absorption spectroscopy (CEAS) with supercontinuum (SC) radiation in the near-infrared spectral range can be used as a sensitive, multiplexed, and simple tool to probe gas-phase species in high-temperature environments. Near-infrared SC radiation is generated by pumping a standard single-mode fiber with a picosecond fiber laser. Standard low reflectivity mirrors are used for the cavity and an optical spectrum analyzer is used for the detection of gas-phase species in combustion. The method is demonstrated by measuring flame generated H2O in the 1500 to 1550 nm region and room-temperature CO2 between 1520 nm and 1660 nm. The broadband nature of the technique permits hundreds of rotational features to be recorded, giving good potential to unravel complex, convoluted spectra. We discuss practical issues concerning the implementation of the technique and present a straightforward method for calibration of the CEAS system via a cavity ringdown measurement. Despite the large spectral variation of SC radiation from pulse to pulse, it is shown that SC sources can offer good stability for CEAS where a large number of SC pulses are typically averaged.

Sensitive Method for the Kinetic Measurement of Trace Species in Liquids Using Cavity Enhanced Absorption Spectroscopy with Broad Bandwidth Supercontinuum Radiation

A novel spectrometer for the rapid and sensitive detection of liquid phase analytes at trace concentrations is presented. Broad bandwidth supercontinuum radiation was coupled into a linear optical cavity incorporating an intracavity liquid-sample cuvette. Cavity enhanced absorption spectra of trace species covering more than 300 nm were acquired on time scales of milliseconds. Single shot acquisition times of 10-50 ms are demonstrated here. The effective absorption path length exceeds 2 m in sample volumes measuring 2.7 mL. A key feature of the instrument is that it can be calibrated using cavity ring-down spectroscopy without the requirement of changing the optical alignment. The sensitivity of the instrument is exemplified by measurements of trace concentrations of dye molecules and nickel sulfate dissolved in water. A minimum detectable absorption coefficient of 9.1 x 10(-7) cm(-1) Hz(-1/2) at 550 nm was obtained. The capability to capture broad bandwidth absorption spectra on short time scales permits kinetic studies of liquid phase reactions. We demonstrate this by recording the oscillatory behavior of a Belousov-Zhabotinsky reaction.

Periodic interactions between solitons and dispersive waves during the generation of non-coherent supercontinuum radiation

We present a numerical study of interactions between dispersive waves (DWs) and solitons during supercontinuum generation in photonic crystal fibers pumped with picosecond laser pulses. We show how the soliton-induced trapping potential evolves along the fiber and affects the dynamics of a DW-soliton pair. Individual frequency components of the DW periodically interact with the soliton resulting in stepwise frequency blue shifts. In contrast, the ensemble blue shifts of all frequency components in the DW appear to be quasi-continuous. The step size of frequency up-conversion and the temporal separation between subsequent soliton-DW interactions are governed by the potential well which confines the soliton-DW pair and which changes in time.

Phase-sensitive method for background-compensated photoacoustic detection of NO2 using high-power LEDs

A photoacoustic (PA) sensor has been developed for the detection of nitrogen dioxide (NO(2)). Ten amplitude-modulated high-power light emitting diodes (LEDs), emitting a total optical power of 9 W at 453 nm, are used to excite the photoacoustic signal in NO(2). The LEDs are attached to the circumference of a cylindrical PA cell. The induced longitudinal acoustics waves are detected using two electromechanical film stacks, located at the ends of the cell. Background signal cancelation is achieved by using phase-sensitive detection of the difference signal of the two pressure transducers. The phase-sensitive approach allows for improved dynamic range and sensitivity. A detection limit of 10 parts per billion by volume was achieved for flowing NO(2) gas sample in an acquisition time of 2.1 s, corresponding to a minimum detectable absorption coefficient of 1.6 × 10(-7) cm(-1) Hz(-1/2). The developed sensor has potential for compact, light-weight, and low-cost measurement of NO(2).

Long distance active hyperspectral sensing using high-power near-infrared supercontinuum light source.

A hyperspectral remote sensing instrument employing a novel near-infrared supercontinuum light source has been developed for active illumination and identification of targets. The supercontinuum is generated in a standard normal dispersion multi-mode fiber and has 16 W total optical output power covering 1000 nm to 2300 nm spectral range. A commercial 256-channel infrared spectrometer was used for broadband infrared detection. The feasibility of the presented hyperspectral measurement approach was investigated both indoors and in the field. Reflection spectra from several diffusive targets were successfully measured and a measurement range of 1.5 km was demonstrated.

Incoherent broadband cavity enhanced absorption spectroscopy using supercontinuum and superluminescent diode sources

We investigate incoherent broadband cavity enhanced absorption spectroscopy using a tailored supercontinuum source. By tailoring the supercontinuum spectrum to match the high reflectivity bandwidth of the mirrors, we achieve an unprecedented spectral brightness of more than 7 dBm/nm at wavelengths where the effective absorption path length in the cavity exceeds 40 km. We demonstrate the potential of the source in spectrally broadband measurement of weak overtone transitions of carbon dioxide and methane in the near-infrared 1590 nm - 1700 nm range and evaluate its performance against that of a typical superluminescent diode source. Minimum detectable absorption coefficients (3σ) of 2.2 × 10(-9) cm(-1) and 6.2 × 10(-9) cm(-1) are obtained with the supercontinuum and the superluminescent diode sources, respectively. We further develop a spectral fitting method based on differential optical absorption spectroscopy to fully and properly account for the combined effect of absorption line saturation and limited spectral resolution of the detection. The method allows to cope with high dynamic range of absorption features typical of real-world multi-component measurements.

Development of broadband cavity ring-down spectroscopy for biomedical diagnostics of liquid analytes.

We present a spectrometer for sensitive absorption measurements in liquids across broad spectral bandwidths. The spectrometer combines the unique spectral properties of incoherent supercontinuum light sources with the advantages of cavity ring-down spectroscopy, which is a self-calibrating technique. A custom-built avalanche photodiode array is used for detection, permitting the simultaneous measurement of ring-down times for up to 64 different spectral components at nanosecond temporal resolution. The minimum detectable absorption coefficient was measured to be 3.2 × 10(-6) cm(-1) Hz(-1/2) at 527 nm. We show that the spectrometer is capable of recording spectral differences in trace levels of blood before and after hemolysis.

An adaptive filter for studying the life cycle of optical rogue waves

We present an adaptive numerical filter for analyzing fiber-length dependent properties of optical rogue waves, which are highly intense and extremely red-shifted solitons that arise during supercontinuum generation in photonic crystal fiber. We use this filter to study a data set of 1000 simulated supercontinuum pulses, produced from 5 ps pump pulses containing random noise. Optical rogue waves arise in different supercontinuum pulses at various positions along the fiber, and exhibit a lifecycle: their intensity peaks over a finite range of fiber length before declining slowly.