Gapless tuning of quantum cascade laser frequency combs with external cavity optical feedback.

We present the operation of quantum cascade laser frequency combs in an external cavity configuration. Experimental observations show dependence of comb repetition rate and optical spectrum on the external cavity length. The low phase-noise comb regime is extended to a broader range of bias currents, enabling gapless frequency tuning of the comb modes. Dual-comb measurements also confirm improved comb stability in the presence of unwanted optical feedback when operating in an external cavity configuration. These observations indicate that aside from the continuing efforts to assure low and uniform dispersion characteristics of quantum cascade laser frequency combs, the proposed simple approach of adding a broadband external cavity can significantly enhance operation of sub-optimal devices for spectroscopic applications.

Label-Free Autofluorescence-Detected Mid-Infrared Photothermal Microscopy of Pharmaceutical Materials.

Label-free autofluorescence-detected photothermal mid-IR (AF-PTIR) microscopy is demonstrated experimentally and applied to test the distribution of active pharmaceutical ingredients (APIs) in a mixture containing representative pharmaceutical excipients. Two-photon excited UV-fluorescence (TPE-UVF) supports autofluorescence of native aromatic moieties using visible-light optics. Thermal modulation of the fluorescence quantum yield serves to report on infrared absorption, enabling infrared spectroscopy in the fingerprint region with a spatial resolution dictated by fluorescence. AF-PTIR provides high selectivity and sensitivity in image contrast for aromatic APIs, complementing broadly applicable optical photothermal IR (O-PTIR) microscopy based on photothermal modulation of refractive index/scattering. Mapping the API distribution is critical in designing processes for powdered dosage form manufacturing, with high spatial variance potentially producing variability in both delivered dosage and product efficacy. The ubiquity of aromatic moieties within API candidates suggests the viability of AF-PTIR in combination with O-PTIR to improve the confidence of chemical classification in spatially heterogeneous dosage forms.

Time-resolved HO2 detection with Faraday rotation spectroscopy in a photolysis reactor.

Faraday rotation spectroscopy (FRS) employs the Faraday effect to detect Zeeman splitting in the presence of a magnetic field. In this article, we present system design and implementation of radical sensing in a photolysis reactor using FRS. High sensitivity (100 ppb) and time resolved in situ HO2 detection is enabled with a digitally balanced acquisition scheme. Specific advantages of employing FRS for sensing in such dynamic environments are examined and rigorously compared to the more established conventional laser absorption spectroscopy (LAS). Experimental results show that FRS enables HO2 detection when LAS is deficient, and FRS compares favorably in terms of precision when LAS is applicable. The immunity of FRS to spectral interferences such as absorption of hydrocarbons and other diamagnetic species absorption and optical fringing are highlighted in comparison to LAS.

Dynamic computational optical fringe mitigation in tunable laser absorption spectroscopy.

In optical spectroscopic systems where unwanted optical scattering cannot be eliminated, Fabry-Pérot etalons cause unpredictable changes in the spectral background. Frequent system calibration is then required to maintain the desired measurement accuracy, which presents a major limitation to the spectrometer. We introduce a computational approach to mitigate the adverse effects of optical fringing without hardware modifications. Motivated by experimental observations of complicated fringe behaviors, we simplify the problem by decomposing the fringe background into component etalons that can be addressed according to their individual characteristics. The effectiveness of the proposed method is demonstrated on a silicon photonic methane sensor, where accurate measurements of methane concentration are obtained from spectral data strongly affected by optical fringes.

Adaptive thermal stabilization of an integrated photonic spectrometer using parasitic interference fringes.

Parasitic fringe drift from unwanted scatterings limits the long-term stability of waveguide-based optical spectrometers. Yet their spectral features provide relevant information that can be used to improve performance of the spectrometer. We show that fringe drift can be extracted and utilized to perform accurate thermal stabilization, especially in the case of integrated waveguide sensors. In this Letter, effective stabilization of a methane silicon photonic sensor is demonstrated, and significant reduction in fringe noise is clearly observed.

Field Deployment of a Portable Optical Spectrometer for Methane Fugitive Emissions Monitoring on Oil and Gas Well Pads.

We present field deployment results of a portable optical absorption spectrometer for localization and quantification of fugitive methane (CH4) emissions. Our near-infrared sensor targets the 2ν3 R(4) CH4 transition at 6057.1 cm-1 (1651 nm) via line-scanned tunable diode-laser absorption spectroscopy (TDLAS), with Allan deviation analysis yielding a normalized 2.0 ppmv∙Hz-1/2 sensitivity (4.5 × 10-6 Hz-1/2 noise-equivalent absorption) over 5 cm open-path length. Controlled CH4 leak experiments are performed at the METEC CSU engineering facility, where concurrent deployment of our TDLAS and a customized volatile organic compound (VOC) sensor demonstrates good linear correlation (R2 = 0.74) over high-flow (>60 SCFH) CH4 releases spanning 4.4 h. In conjunction with simultaneous wind velocity measurements, the leak angle-of-arrival (AOA) is ascertained via correlation of CH4 concentration and wind angle, demonstrating the efficacy of single-sensor line-of-sight (LOS) determination of leak sources. Source magnitude estimation based on a Gaussian plume model is demonstrated, with good correspondence (R2 = 0.74) between calculated and measured release rates.

Third-harmonic-generation of a diode laser for quantum control of beryllium ions.

We generate coherent ultraviolet radiation at 313 nm as the third harmonic of an external-cavity diode laser. We use this radiation for laser cooling of trapped beryllium atomic ions and sympathetic cooling of co-trapped beryllium-hydride molecular ions. An LBO crystal in an enhancement cavity generates the second harmonic, and a BBO crystal in a doubly resonant enhancement cavity mixes this second harmonic with the fundamental to produce the third harmonic. Each enhancement cavity is preceded by a tapered amplifier to increase the fundamental light. The 36-mW output power of this all-semiconductor-gain system will enable quantum control of the beryllium ions' motion.