Intracavity laser absorption spectroscopy: Performance and advantages for energy science

Abstract

Meeting the demands of sustainable energy economy requires diagnostics of the chemical processes surrounding future fuels and contemporary combustion applications. Pioneered in 1970, Intracavity Laser Absorption Spectroscopy (ICAS) has evolved to be a powerful instrument in the toolbox of combustion diagnostics. It owes its ultra-high sensitivity to the enhancement of the effective absorption pathlength by placing the absorber inside the cavity of a broadband laser. In this review we introduce the complementary strengths of ICAS to other methods: ultra-high sensitivity to narrowband absorption alongside the immunity to broadband losses, multiplexed detection and (µs-scale)-temporal resolution. We outline the basic concepts and features of ICAS, focusing on the laser dynamics regime where an absorbing sample in the laser resonator yields the well-known Lambert-Beer law. We chart the progress made over the years in visible (dye-jet laser) and near infrared (fiber laser) ICAS speciation in flames, by highlighting case studies where species like long considered "hard-to detect" ¹CH₂ and HCO radicals, along with O-atoms, C₂, NH₂, HNO, CN, and HCN were measured, as well as thermometry and speciation applications demonstrated in shock tubes, flow-cells and flames based on (stationary or time-resolved) measurements of multicomponent spectral matrices containing lines of CH₄, C₂H₂, CO₂, CO, OH and H₂O. We highlight the contributions of ICAS in gas-phase nanomaterial synthesis, exemplified in prototypical iron-doped flames and discuss prospective applications in spray-flame pyrolysis and metal-powder combustion. Finally, we present advances in the development of lasing media based on Cr²⁺ and Fe²⁺-doped chalcogenide crystals and fluoride crystals doped with trivalent lanthanides, that meet the (ICAS-specific) requirement associated with the necessity to have a gain media lasing directly in the desired wavelength range, and therefore to expand this technique into the important mid-infrared and ultraviolet spectral ranges.