Approaching the transit time limit for high-precision spectroscopy on metastable CO around 6 µm.

As molecular spectroscopy makes its comeback to the limelight of fundamental sciences, scientists need ever better coherent light sources and diagnostic methods. Of particular importance for molecular spectroscopy is the mid infrared spectral region, where strong and narrow ro-vibrational excitations have their fundamental transition frequencies. Unfortunately, much technology in some portions of this spectral region is still rather pioneering. Here we present a high-resolution spectroscopy experiment, based on a molecular beam setup, which pushes the measured linewidth close to the transit time limit, on the order of 100 kHz. Moreover, we discuss the issue of frequency-noise characterization and the linewidth measurement of the ultrastable infrared laser used in the experiment.

Measuring molecular frequencies in the 1-10 µm range at 11-digits accuracy.

High-resolution spectroscopy in the 1-10 µm region has never been fully tackled for the lack of widely-tunable and practical light sources. Indeed, all solutions proposed thus far suffer from at least one of three issues: they are feasible only in a narrow spectral range; the power available for spectroscopy is limited; the frequency accuracy is poor. Here, we present a setup for high-resolution spectroscopy, whose approach can be applied in the whole 1-10 µm range. It combines the power of quantum cascade lasers (QCLs) and the accuracy achievable by difference frequency generation using an orientation patterned GaP crystal. The frequency is measured against a primary frequency standard using the Italian metrological fibre link network. We demonstrate the performance of the setup by measuring a vibrational transition in a highly-excited metastable state of CO around 6 µm with 11 digits of precision.

Widely-tunable mid-infrared fiber-coupled quartz-enhanced photoacoustic sensor for environmental monitoring.

A compact widely-tunable fiber-coupled sensor for trace gas detection of hydrogen sulfide (H2S) in the mid infrared is reported. The sensor is based on an external-cavity quantum cascade laser (EC-QCL) tunable between 7.6 and 8.3 µm wavelengths coupled into a single-mode hollow-core waveguide. Quartz-enhanced photoacoustic spectroscopy has been selected as detecting technique. The fiber coupling system converts the astigmatic beam exiting the laser into a TEM(00) mode. During a full laser scan, we observed no misalignment between the optical beam and the tuning fork, thus making our system applicable for multi-gas or broad absorber detections. The sensor has been tested on N2:H2S gas mixtures. The minimum detectable H2S concentration is 450 ppb in ~3 s integration time, which is the best value till now reported in literature for H2S optical sensors.

Intrinsic stability of quantum cascade lasers against optical feedback.

We study the time dependence of the optical power emitted by terahertz and mid-IR quantum cascade lasers in presence of optical reinjection and demonstrate unprecedented continuous wave (CW) emission stability for strong feedback. We show that the absence of coherence collapse or other CW instabilities typical of diode lasers is inherently associated with the high value of the photon to carrier lifetime ratio and the negligible linewidth enhancement factor of quantum cascade lasers.

Subkilohertz linewidth room-temperature mid-infrared quantum cascade laser using a molecular sub-Doppler reference.

We report on the narrowing of a room-temperature mid-IR quantum cascade laser by frequency locking it to a CO2 sub-Doppler transition obtained by polarization spectroscopy. A locking bandwidth of 250 kHz has been achieved. The laser linewidth is narrowed by more than two orders of magnitude below 1 kHz, and its absolute frequency is stabilized at the same level.

Direct link of a mid-infrared QCL to a frequency comb by optical injection.

A narrow-linewidth comb-linked nonlinear source is used as master radiation to injection lock a room-temperature mid-infrared quantum cascade laser (QCL). This process leads to a direct lock of the QCL to the optical frequency comb, providing the unique features of narrow linewidth, absolute frequency, higher output power, and wide mode-hop-free tunability. The QCL reproduces the injected radiation within more than 94%, with a reduction of the frequency-noise spectral density by 3 to 4 orders of magnitude up to about 100 kHz, and a linewidth narrowing from a few MHz to 20 kHz.

Measuring frequency noise and intrinsic linewidth of a room-temperature DFB quantum cascade laser.

The frequency-noise power spectral density of a room-temperature distributed-feedback quantum cascade laser emitting at λ = 4.36 µm has been measured. An intrinsic linewidth value of 260 Hz is retrieved, in reasonable agreement with theoretical calculations. A noise reduction of about a factor 200 in most of the frequency interval is also found, with respect to a cryogenic laser at the same wavelength. A quantitative treatment shows that it can be explained by a temperature-dependent mechanism governing the transport processes in resonant tunnelling devices. This confirms the predominant effect of the heterostructure in determining shape and magnitude of the frequency noise spectrum in QCLs.

Molecular gas sensing below parts per trillion: radiocarbon-dioxide optical detection.

Radiocarbon ((14)C) concentrations at a 43 parts-per-quadrillion level are measured by using saturated-absorption cavity ringdown spectroscopy by exciting radiocarbon-dioxide ((14)C(16)O(2)) molecules at the 4.5 µm wavelength. The ultimate sensitivity limits of molecular trace gas sensing are pushed down to attobar pressures using a comb-assisted absorption spectroscopy setup. Such a result represents the lowest pressure ever detected for a gas of simple molecules. The unique sensitivity, the wide dynamic range, the compactness, and the relatively low cost of this table-top setup open new perspectives for ^{14}C-tracing applications, such as radiocarbon dating, biomedicine, or environmental and earth sciences. The detection of other very rare molecules can be pursued as well thanks to the wide and continuous mid-IR spectral coverage of the described setup.

Ti:sapphire laser intracavity difference-frequency generation of 30 mW cw radiation around 4.5 µm.

A cw mid-IR coherent source based on difference-frequency generation is designed and characterized. For mid-IR generation, a periodically poled MgO:LiNbO(3) crystal is placed inside a compact Ti:sapphire laser cavity. This provides high-power pump radiation for the nonlinear process. Optical injection by an external-cavity diode laser ensures single-frequency operation of the Ti:sapphire laser, while signal radiation is provided by a fiber-amplified Nd:YAG laser. Mid-IR radiation can be generated with 3850-4540 nm tuning range, narrow linewidth, Cs-standard traceability, and TEM(00) spatial mode. 30 mW power is obtained at 4510 nm.

Saturated-absorption cavity ring-down spectroscopy.

We report on a novel approach to cavity ring-down spectroscopy with the sample gas in saturated-absorption regime. This technique allows us to decouple and simultaneously retrieve the empty-cavity background and absorption signal, by means of a theoretical model that we developed and tested. The high sensitivity and frequency precision for spectroscopic applications are exploited to measure, for the first time, the hyperfine structure of an excited vibrational state of 17O12C16O in natural abundance with an accuracy of a few parts in 10{-11}.

Observing the intrinsic linewidth of a quantum-cascade laser: beyond the Schawlow-Townes limit.

A comprehensive investigation of the frequency-noise spectral density of a free-running midinfrared quantum-cascade laser is presented for the first time. It provides direct evidence of the leveling of this noise down to a white-noise plateau, corresponding to an intrinsic linewidth of a few hundred hertz. The experiment is in agreement with the most recent theory on the fundamental mechanism of line broadening in quantum-cascade lasers, which provides a new insight into the Schawlow-Townes formula and predicts a narrowing beyond the limit set by the radiative lifetime of the upper level.

Doppler-free polarization spectroscopy with a quantum cascade laser at 4.3 microm.

We report on what we believe to be the first Doppler-free polarization spectroscopy with a quantum cascade laser. A hot-band CO(2) transition around 4.3 microm wavelength has been used to test the potential of the technique for high-resolution spectroscopy and wide-bandwidth quantum cascade laser frequency stabilization.

Lamb-dip-locked quantum cascade laser for comb-referenced IR absolute frequency measurements.

The frequency of a DFB quantum cascade laser (QCL) emitting at 4.3 microm has been long-term stabilized to the Lamb-dip center of a CO2 ro-vibrational transition by means of first-derivative locking to the saturated absorption signal. Thanks to the non-linear sum-frequency generation (SFG) process with a fiber-amplified Nd:YAG laser, the QCL mid-infrared (IR) radiation has been linked to an optical frequency-comb synthesizer (OFCS) and its absolute frequency counted with a kHz-level precision and an overall uncertainty of 75 kHz.

Frequency-comb-referenced quantum-cascade laser at 4.4 microm.

We report what we believe to be the first absolute frequency measurement performed using a quantum-cascade laser (QCL) referenced to an optical frequency comb synthesizer (OFCS). A QCL at 4.43 microm has been used for producing near-infrared radiation at 858 nm by means of sum-frequency generation with a Nd:YAG source in a periodically poled lithium niobate nonlinear crystal. The absolute frequency of the QCL source has been measured by detecting the beat note between the sum frequency and a diode laser at the same wavelength, while both the Nd:YAG and the diode laser were referenced to the OFCS. Doppler-broadened line profiles of (13)CO(2) molecular transitions have been recorded with such an absolute frequency reference.