High frequency modulation and (quasi) single-sideband emission of mid-infrared ring and ridge quantum cascade lasers.

We investigate the high frequency modulation characteristics of mid-infrared surface-emitting ring and edge-emitting ridge quantum cascade lasers (QCLs). In particular, a detailed comparison between circular ring devices and ridge-QCLs from the same laser material, which have a linear waveguide in a "Fabry-Pérot (FP) type" cavity, reveals distinct similarities and differences. Both device types are single-mode emitting, based on either 2 nd- (ring-QCL) or 1 st-order (ridge-QCL) distributed feedback (DFB) gratings with an emission wavelength around 7.56 µm. Their modulation characteristics are investigated in the frequency-domain using an optical frequency-to-amplitude conversion technique based on the ro-vibrational absorptions of CH 4. We observe that the amplitude of frequency tuning Δf over intensity modulation index m as function of the modulation frequency behaves similarly for both types of devices, while the ring-QCLs typically show higher values. The frequency-to-intensity modulation (FM-IM) phase shift shows a decrease starting from ∼72 ∘ at a modulation frequency of 800 kHz to about 0 ∘ at 160 MHz. In addition, we also observe a quasi single-sideband (qSSB) regime for modulation frequencies above 100 MHz, which is identified by a vanishing -1 st-order sideband for both devices. This special FM-state can be observed in DFB QCLs and is in strong contrast to the behavior of regular DFB diode lasers, which do not achieve any significant sideband suppression. By analyzing these important high frequency characteristics of ring-QCLs and comparing them to ridge DFB-QCLs, it shows the potential of intersubband devices for applications in e.g. novel spectroscopic techniques and highly-integrated and high-bitrate free-space data communication. In addition, the obtained results close an existing gap in literature for high frequency modulation characteristics of QCLs.

Pore Size-Dependent Structure of Confined Water in Mesoporous Silica Films from Water Adsorption/Desorption Using ATR-FTIR Spectroscopy.

The local structure of water on chemically and structurally different surfaces is a subject of ongoing research. In particular, confined spaces as found in mesoporous silica have a pronounced effect on the interplay between the adsorbate-adsorbate and adsorbate-surface interactions. Mid-infrared spectroscopy is ideally suited to quantitatively and qualitatively study such systems as the probed molecular vibrations are highly sensitive to intermolecular interactions. Here, the quantity and structure of water adsorbed from the gas phase into silica mesopores at different water vapor pressures was monitored using mid-infrared attenuated total reflection (ATR) spectroscopy. Germanium ATR crystals were coated with different mesoporous silica films prepared by evaporation-induced self-assembly. Quantitative analysis of the water bending vibration at 1640 cm-1 at varying vapor pressure allows for retrieving porosity and pore size distribution of the mesoporous films. The results were in excellent agreement with those obtained from ellipsometric porosimetry. In addition, different degrees of hydrogen bonding of water as reflected in the band position and shape of the stretching vibrations (3000-3800 cm-1) were analyzed and attributed to high-density, unordered bulk, low-density, and surface-induced ordered water. Thereby, the progression of surface-induced ordered water and bulk water as a function of water vapor pressure was studied for different pore sizes. Small pores of 5 nm diameter showed a number of two-ordered monolayers, whereas for pores >12 nm diameter, the number of ordered monolayers is significantly larger and agrees with the number observed on planar SiO2 surfaces.

Mid-infrared sensing of CO at saturated absorption conditions using intracavity quartz-enhanced photoacoustic spectroscopy.

The sensitivity of quartz-enhanced photoacoustic spectroscopy (QEPAS) can be drastically increased using the power enhancement in high-finesse cavities. Here, low noise resonant power enhancement to 6.3 W was achieved in a linear Brewster window cavity by exploiting optical feedback locking of a quantum cascade laser. The high intracavity intensity of up to 73 W mm-2 in between the prongs of a custom tuning fork resulted in strong optical saturation of CO at 4.59 µm. Saturated absorption is discussed theoretically and experimentally for photoacoustic measurements in general and intracavity QEPAS (I-QEPAS) in particular. The saturation intensity of CO's R9 transition was retrieved from power-dependent I-QEPAS signals. This allowed for sensing CO independently from varying degrees of saturation caused by absorption induced changes of intracavity power. Figures of merit of the I-QEPAS setup for sensing of CO and H2O are compared to standard wavelength modulation QEPAS without cavity enhancement. For H2O, the sensitivity was increased by a factor of 230, practically identical to the power enhancement, while the sensitivity gain for CO detection was limited to 57 by optical saturation.

Frequency-locked cavity ring-down Faraday rotation spectroscopy.

Cavity ring-down Faraday rotation spectroscopy (CRD-FRS) is a technique for trace gas measurements of paramagnetic species that retrieves the molecular concentration from the polarization rotation measured as the difference between simultaneously recorded ring-down times of two orthogonal polarization states. The differential measurement is inherently insensitive to nonabsorber related losses, which makes off-resonance measurements redundant. We exploit this unique property by actively line-locking to a molecular transition for calibration-free trace gas concentration retrieval. In addition, we enhance the effective duty-cycle of the system by implementing a Pound-Drever-Hall laser lock to the cavity resonance, which allows for ring-down rates of up to 9 kHz. The system performance is demonstrated by measurements of trace oxygen with a minimum detection limit at the ppmv/√Hz-level.

Heterodyne Phase-Sensitive Dispersion Spectroscopy in the Mid-Infrared with a Quantum Cascade Laser.

Molecular dispersion spectroscopy encompasses a group of spectroscopic techniques for gas analysis that retrieve the characteristics of the sample from the measurement of the profile of its refractive index in the vicinity of molecular resonances. This approach, which is in clear contrast to traditional methods based on the detection of absorption, provides inherent immunity to power fluctuations, calibration-free operation, and an output that is linearly dependent on gas concentration. Heterodyne phase-sensitive dispersion spectroscopy (HPSDS) is a very recently proposed technique for molecular dispersion spectroscopy based on tunable lasers that is characterized by a very simple architecture in which data processing and concentration retrieval are straightforward. Different HPSDS implementations have been experimentally validated in the near-IR. Here, we present the first demonstration of HPSDS in the mid-IR using a directly modulated quantum cascade laser for the measurement of CO. The setup is put under test to characterize its response to changing concentrations, pressures, and levels of optical intensity on the detector, and the limit of detection is estimated. Besides this, an experimental comparison with wavelength modulation spectroscopy with second-harmonic detection (2f-WMS) is performed and discussed in detail in order to offer a clear view of the benefits and drawbacks that HPSDS can provide over what we could consider the reference method for gas analysis based on tunable laser spectroscopy.

Dual-comb spectroscopy of ammonia formation in non-thermal plasmas.

Plasma-activated chemical transformations promise the efficient synthesis of salient chemical products. However, the reaction pathways that lead to desirable products are often unknown, and key quantum-state-resolved information regarding the involved molecular species is lacking. Here we use quantum cascade laser dual-comb spectroscopy (QCL-DCS) to probe plasma-activated NH3 generation with rotational and vibrational state resolution, quantifying state-specific number densities via broadband spectral analysis. The measurements reveal unique translational, rotational and vibrational temperatures for NH3 products, indicative of a highly reactive, non-thermal environment. Ultimately, we postulate on the energy transfer mechanisms that explain trends in temperatures and number densities observed for NH3 generated in low-pressure nitrogen-hydrogen (N2-H2) plasmas.

Mid-infrared intracavity quartz-enhanced photoacoustic spectroscopy with pptv - Level sensitivity using a T-shaped custom tuning fork.

Resonant optical power buildup inside a high finesse cavity is exploited to boost the sensitivity in quartz-enhanced photoacoustic spectroscopy (QEPAS) for CO, N2O and H2O detection, operating at a wavelength of 4.59 µm. A quartz tuning fork with T-shaped prongs optimized for QEPAS has been employed. Exploiting the high signal-to-noise ratio attainable with this tuning fork together with an optical power amplification of ~100 enabled by efficient optical feedback locking, limits of detection (3σ, 10 s integration) of 260 ppt and 750 ppt for CO and N2O have been reached.

External Cavity Quantum Cascade Laser-Based Mid-Infrared Dispersion Spectroscopy for Qualitative and Quantitative Analysis of Liquid-Phase Samples.

Acquisition of classical absorption spectra of liquids in the mid-IR range with quantum cascade lasers (QCLs) is often limited in sensitivity by noise from the laser source. Alternatively, measurement of molecular dispersion (i.e., refractive index) spectra poses an experimental approach that is immune to intensity fluctuations and further offers a direct relationship between the recorded signal and the sample concentration. In this work, we present an external cavity quantum cascade laser (EC-QCL) based Mach-Zehnder interferometer setup to determine dispersion spectra of liquid samples. We present two approaches for acquisition of refractive index spectra and compare the qualitative experimental results. Furthermore, the performance for quantitative analysis is evaluated. Finally, multivariate analysis of a spectrally complex mixture comprising three different sugars is performed. The obtained figures of merit by partial least squares (PLS) regression modelling compare well with standard absorption spectroscopy, demonstrating the potential of the introduced dispersion spectroscopic method for quantitative chemical analysis.