Parts-per-trillion sensitivity for trace-moisture detection using wavelength-meter-controlled cavity ring-down spectroscopy

We introduced frequency-control and temperature-control systems in wavelength-meter-controlled cavity ring-down spectroscopy. The frequency-control system shifted the wavelength of the probe laser from 1393 nm to 696.5 nm where no strong absorption lines of water exist, and therefore, it could avoid measurement errors in laser frequency due to residual moisture in the built-in Fizeau interferometer of a wavelength meter. We verified the hypothesis that the nonuniform reflectivity of the mirror surface contributes to fluctuations in the ring-down time observed with multi-transverse-mode CRDS signals. The fluctuations due to this effect were greatly suppressed by the temperature-control system. Using this system, we could improve the minimum detectable absorption coefficient by three times on average and also improve the experimental standard deviations of the averages by nine times compared with those without the system. We measured near-infrared spectra of residual moisture in dry nitrogen at an approximately 1 nmol/mol (1 ppb) level and performed least-squares fitting of the averaged spectrum. The standard deviation of the residuals of the fitting was 6.6 × 10−12 cm−1, corresponding to a mole fraction of water of 6.3 pmol/mol (6.3 ppt).