Quartz-Enhanced Photoacoustic Sensor Based on a Multi-Laser Source for In-Sequence Detection of NO2, SO2, and NH3.

In this work, we report on the implementation of a multi-quantum cascade laser (QCL) module as an innovative light source for quartz-enhanced photoacoustic spectroscopy (QEPAS) sensing. The source is composed of three different QCLs coupled with a dichroitic beam combiner module that provides an overlapping collimated beam output for all three QCLs. The 3λ-QCL QEPAS sensor was tested for detection of NO2, SO2, and NH3 in sequence in a laboratory environment. Sensitivities of 19.99 mV/ppm, 19.39 mV/ppm, and 73.99 mV/ppm were reached for NO2, SO2, and NH3 gas detection, respectively, with ultimate detection limits of 9 ppb, 9.3 ppb, and 2.4 ppb for these three gases, respectively, at an integration time of 100 ms. The detection limits were well below the values of typical natural abundance of NO2, SO2, and NH3 in air.

Extraction-Dominated Temperature Degradation of Population Inversion in Terahertz Quantum Cascade Lasers.

Degraded population inversion (PI) at elevated temperature, regarded as an important temperature degradation factor in terahertz quantum cascade lasers (THz QCL), has hindered the widespread use of these devices. Herein, the mechanism of the temperature degradation of PI is investigated microscopically. It is demonstrated that the limited extraction efficiency of the extraction system dominates the decrease of PI at elevated temperatures. To be specific, the increased temperature brings about intense thermally activated longitudinal optical phonon scattering, leading to large amounts of electrons scattering to lower level state. In this case, the resonant-phonon extraction system is incapable of depleting all the electrons from lower level states. So even though the resonant-tunneling injection seems efficient enough to compensate the electron runoff at the upper state, the electron density at lower level state increases and the overall PI turns out lower. In addition, it is found that strong electron-ionized donor separation at high temperature can induce level misalignment, which can stagger the optimal conditions of injection and extraction. Also, the extraction efficiency gets lower as the extraction system requires accurate coupling between several energy levels.

Self-Pulsations in Terahertz Quantum Cascade Lasers under Strong Optical Feedback: The Effect of Multiple Reflections in the External Cavity.

We have recently reported the self-pulsation phenomenon under strong optical feedback in terahertz (THz) quantum cascade lasers (QCLs). One important issue, however, we left open: the effect of multiple round trips in the external cavity on the laser response to feedback. Our current analysis also casts additional light on the phenomenon of self-pulsations. Using only one external cavity round trip (ECRT) in the model has been the common approach following the seminal paper by Lang-Kobayashi in 1980. However, the conditions under which the Lang-Kobayashi model, in its original single-ECRT formulation, is applicable has been rarely explored. In this work, we investigate the self-pulsation phenomenon under multiple ECRTs. We found that the self-pulsation waveform changes when considering more than one ECRT. This we attribute to the combined effect of the extended external cavity length and the frequency modulation of the pulsation frequency by the optical feedback. Our findings add to the understanding of the optical feedback dynamics under multiple ECRTs and provide a pathway for selecting the appropriate numerical model to study the optical feedback dynamics in THz QCLs and semiconductor lasers in general.

Preclassification of Broadband and Sparse Infrared Data by Multiplicative Signal Correction Approach.

Preclassification of raw infrared spectra has often been neglected in scientific literature. Separating spectra of low spectral quality, due to low signal-to-noise ratio, presence of artifacts, and low analyte presence, is crucial for accurate model development. Furthermore, it is very important for sparse data, where it becomes challenging to visually inspect spectra of different natures. Hence, a preclassification approach to separate infrared spectra for sparse data is needed. In this study, we propose a preclassification approach based on Multiplicative Signal Correction (MSC). The MSC approach was applied on human and the bovine knee cartilage broadband Fourier Transform Infrared (FTIR) spectra and on a sparse data subset comprising of only seven wavelengths. The goal of the preclassification was to separate spectra with analyte-rich signals (i.e., cartilage) from spectra with analyte-poor (and high-matrix) signals (i.e., water). The human datasets 1 and 2 contained 814 and 815 spectra, while the bovine dataset contained 396 spectra. A pure water spectrum was used as a reference spectrum in the MSC approach. A threshold for the root mean square error (RMSE) was used to separate cartilage from water spectra for broadband and the sparse spectral data. Additionally, standard noise-to-ratio and principle component analysis were applied on broadband spectra. The fully automated MSC preclassification approach, using water as reference spectrum, performed as well as the manual visual inspection. Moreover, it enabled not only separation of cartilage from water spectra in broadband spectral datasets, but also in sparse datasets where manual visual inspection cannot be applied.

Preprocessing Strategies for Sparse Infrared Spectroscopy: A Case Study on Cartilage Diagnostics.

The aim of the study was to optimize preprocessing of sparse infrared spectral data. The sparse data were obtained by reducing broadband Fourier transform infrared attenuated total reflectance spectra of bovine and human cartilage, as well as of simulated spectral data, comprising several thousand spectral variables into datasets comprising only seven spectral variables. Different preprocessing approaches were compared, including simple baseline correction and normalization procedures, and model-based preprocessing, such as multiplicative signal correction (MSC). The optimal preprocessing was selected based on the quality of classification models established by partial least squares discriminant analysis for discriminating healthy and damaged cartilage samples. The best results for the sparse data were obtained by preprocessing using a baseline offset correction at 1800 cm-1, followed by peak normalization at 850 cm-1 and preprocessing by MSC.

Data Link with a High-Power Pulsed Quantum Cascade Laser Operating at the Wavelength of 4.5 µm.

This article is a short study of the application of high-power quantum cascade lasers and photodetectors in medium-infrared optical wireless communications (OWC). The link range is mainly determined by the transmitted beam parameters and the performance of the light sensor. The light power and the photodetector noise directly determine the signal-to-noise power ratio. This ratio could be maximized in the case of minimizing the radiation losses caused by atmospheric attenuation. It can be obtained by applying both radiation sources and sensors operated in the medium infrared range decreasing the effects of absorption, scattering or scintillation, beam spreading, and beam wandering. The development of a new class of laser sources based on quantum cascade structures becomes a prospective alternative. Regarding the literature, there are descriptions of some preliminary research applying these lasers in data transmission. To provide a high data transfer rate, continuous wave (cw) lasers are commonly used. However, they are characterized by low power (a few tens of mWatts) limiting their link range. Also, only a few high-power pulsed lasers (a few hundreds of mWatts) were tested. Due to their limited pulse duty cycle, the obtained modulation bandwidth was lower than 1 MHz. The main goal of this study is to experimentally determine the capabilities of the currently developed state-of-the-art high-power pulsed quantum cascade (QC) lasers and photodetectors in OWC systems. Finally, the data link range using optical pulses of a QC laser of ~2 W, operated at the wavelength of ~4.5 µm, is discussed.

Advances in Mid-Infrared Spectroscopy-Based Sensing Techniques for Exhaled Breath Diagnostics.

Human exhaled breath consists of more than 3000 volatile organic compounds, many of which are relevant biomarkers for various diseases. Although gas chromatography has been the gold standard for volatile organic compound (VOC) detection in exhaled breath, recent developments in mid-infrared (MIR) laser spectroscopy have led to the promise of compact point-of-care (POC) optical instruments enabling even single breath diagnostics. In this review, we discuss the evolution of MIR sensing technologies with a special focus on photoacoustic spectroscopy, and its application in exhaled breath biomarker detection. While mid-infrared point-of-care instrumentation promises high sensitivity and inherent molecular selectivity, the lack of standardization of the various techniques has to be overcome for translating these techniques into more widespread real-time clinical use.

A New Quantum Cascade IR-Laser Online Detector: Chemical-Sensitive Size-Exclusion Chromatography Measurement at Unprecedented Low Levels.

Online chemically sensitive detectors for size exclusion chromatography (SEC) through coupled setups based on infrared (IR) (or NMR) spectrometers present new possibilities through unprecedented levels of polymer detail with respect to molecular weight and chemical composition. Herein, a new external cavity quantum cascade laser (EC-QCL) mid-IR spectrometer as a chemically sensitive online detector for SEC is custom-designed, built, and tested. This unique spectrometer features multiple broadly tunable EC-QCL sources, which can be operated in continuous wave and pulsed mode, accompanied with balanced liquid nitrogen cooled mercury cadmium telluride (MCT) detectors and a new custom-built transmission flow cell. Automated data analysis is done with a self-written MATLAB code. The limit of detection (LOD) is measured online, coupled with SEC chromatography, where on average, one carbonyl functionality in 530 000 g mol-1 at chromatographic conditions for SEC could be detected. It is possible to detect 0.46 µg (LOD) PMMA, which is approximately a factor of 30 lower than that reported for SEC-Fourier transform infrared.

Infrared Spectroscopy with a Fiber-Coupled Quantum Cascade Laser for Attenuated Total Reflection Measurements Towards Biomedical Applications.

The development of rapid and accurate biomedical laser spectroscopy systems in the mid-infrared has been enabled by the commercial availability of external-cavity quantum cascade lasers (EC-QCLs). EC-QCLs are a preferable alternative to benchtop instruments such as Fourier transform infrared spectrometers for sensor development as they are small and have high spectral power density. They also allow for the investigation of multiple analytes due to their broad tuneability and through the use of multivariate analysis. This article presents an in vitro investigation with two fiber-coupled measurement setups based on attenuated total reflection spectroscopy and direct transmission spectroscopy for sensing. A pulsed EC-QCL (1200-900 cm - 1 ) was used for measurements of glucose and albumin in aqueous solutions, with lactate and urea as interferents. This analyte composition was chosen as an example of a complex aqueous solution with relevance for biomedical sensors. Glucose concentrations were determined in both setup types with root-mean-square error of cross-validation (RMSECV) of less than 20 mg/dL using partial least-squares (PLS) regression. These results demonstrate accurate analyte measurements, and are promising for further development of fiber-coupled, miniaturised in vivo sensors based on mid-infrared spectroscopy.

WaterSpy: A High Sensitivity, Portable Photonic Device for Pervasive Water Quality Analysis.

In this paper, we present WaterSpy, a project developing an innovative, compact, cost-effective photonic device for pervasive water quality sensing, operating in the mid-IR spectral range. The approach combines the use of advanced Quantum Cascade Lasers (QCLs) employing the Vernier effect, used as light source, with novel, fibre-coupled, fast and sensitive Higher Operation Temperature (HOT) photodetectors, used as sensors. These will be complemented by optimised laser driving and detector electronics, laser modulation and signal conditioning technologies. The paper presents the WaterSpy concept, the requirements elicited, the preliminary architecture design of the device, the use cases in which it will be validated, while highlighting the innovative technologies that contribute to the advancement of the current state of the art.

Ppbv-Level Ethane Detection Using Quartz-Enhanced Photoacoustic Spectroscopy with a Continuous-Wave, Room Temperature Interband Cascade Laser.

A ppbv-level quartz-enhanced photoacoustic spectroscopy (QEPAS)-based ethane (C2H6) sensor was demonstrated by using a 3.3 µm continuous-wave (CW), distributed feedback (DFB) interband cascade laser (ICL). The ICL was employed for targeting a strong C2H6 absorption line located at 2996.88 cm-1 in its fundamental absorption band. Wavelength modulation spectroscopy (WMS) combined with the second harmonic (2f) detection technique was utilized to increase the signal-to-noise ratio (SNR) and simplify data acquisition and processing. Gas pressure and laser frequency modulation depth were optimized to be 100 Torr and 0.106 cm-1, respectively, for maximizing the 2f signal amplitude. Performance of the QEPAS sensor was evaluated using specially prepared C2H6 samples. A detection limit of 11 parts per billion in volume (ppbv) was obtained with a 1-s integration time based on an Allan-Werle variance analysis, and the detection precision can be further improved to ~1.5 ppbv by increasing the integration time up to 230 s.

Sensitive Spectroscopy of Acetone Using a Widely Tunable External-Cavity Quantum Cascade Laser.

We employed a single-mode, widely tunable (~300 cm−1) external-cavity quantum cascade laser operating around 8 µm for broadband direct absorption spectroscopy and wavelength modulation spectroscopy where a modulation frequency of 50 kHz was employed with high modulation amplitudes of up to 10 GHz. Using a compact multipass cell, we measured the entire molecular absorption band of acetone at ~7.4 µm with a spectral resolution of ~1 cm−1. In addition, to demonstrate the high modulation dynamic range of the laser, we performed direct absorption (DAS) and second harmonic wavelength modulation spectroscopy (WMS-2f) of the Q-branch peak of acetone molecular absorption band (HWHM ~10 GHz) near 1365 cm−1. With WMS-2f, a minimum detection limit of 15 ppbv in less than 10 s is achieved, which yields a noise equivalent absorption sensitivity of 1.9 × 10−8 cm−1 Hz−1/2.

Implementation of a quantum cascade laser-based gas sensor prototype for sub-ppmv H2S measurements in a petrochemical process gas stream.

The implementation of a sensitive and selective as well as industrial fit gas sensor prototype based on wavelength modulation spectroscopy with second harmonic detection (2f-WMS) employing an 8-µm continuous-wave distributed feedback quantum cascade laser (CW-DFB-QCL) for monitoring hydrogen sulfide (H2S) at sub-ppm levels is reported. Regarding the applicability for analytical and industrial process purposes aimed at petrochemical environments, a synthetic methane (CH4) matrix of up to 1000 ppmv together with a varying H2S content was chosen as the model environment for the laboratory-based performance evaluation performed at TU Wien. A noise-equivalent absorption sensitivity (NEAS) for H2S targeting the absorption line at 1247.2 cm-1 was found to be 8.419 × 10-10 cm-1 Hz-1/2, and a limit of detection (LOD) of 150 ppbv H2S could be achieved. The sensor prototype was then deployed for on-site measurements at the petrochemical research hydrogenation platform of the industrial partner OMV AG. In order to meet the company's on-site safety regulations, the H2S sensor platform was installed in an industry rack and equipped with the required safety infrastructure for protected operation in hazardous and explosive environments. The work reports the suitability of the sensor prototype for simultaneous monitoring of H2S and CH4 content in the process streams of a research hydrodesulfurization (HDS) unit. Concentration readings were obtained every 15 s and revealed process dynamics not observed previously.

Nanoscopic voltage distribution of operating cascade laser devices in cryogenic temperature.

A nanoscopic exploratory measurement technique to measure voltage distribution across an operating semiconductor device in cryogenic temperature has been developed and established. The cross-section surface of the terahertz (THz) quantum cascade laser (QCL) has been measured that resolves the voltage distribution at nanometer scales. The electric field dissemination across the active region of the device has been attained under the device's lasing conditions at cryogenic temperature of 77 K.

Tunable Microcavity-Stabilized Quantum Cascade Laser for Mid-IR High-Resolution Spectroscopy and Sensing.

The need for highly performing and stable methods for mid-IR molecular sensing and metrology pushes towards the development of more and more compact and robust systems. Among the innovative solutions aimed at answering the need for stable mid-IR references are crystalline microresonators, which have recently shown excellent capabilities for frequency stabilization and linewidth narrowing of quantum cascade lasers with compact setups. In this work, we report on the first system for mid-IR high-resolution spectroscopy based on a quantum cascade laser locked to a CaF2 microresonator. Electronic locking narrows the laser linewidth by one order of magnitude and guarantees good stability over long timescales, allowing, at the same time, an easy way for finely tuning the laser frequency over the molecular absorption line. Improvements in terms of resolution and frequency stability of the source are demonstrated by direct sub-Doppler recording of a molecular line.

II-VI Quantum Cascade emitters in the 6-8µm range.

We present the growth and characterization of ZnCdSe/ZnCdMgSe quantum cascade (QC) heterostructures grown by molecular beam epitaxy (MBE) and designed to operate at 6-8µm. These structures utilize the better-understood ZnCdMgSe with InP lattice matched compositions yielding a bandgap of 2.80 eV as compared to previous work which used ZnCdMgSe compositions with bandgaps at 3.00 eV. Grown structures posses good structural and optical properties evidenced in X-ray diffraction and photoluminescence studies. Fabricated mesa devices show temperature dependent I-V measurements with differential resistance of 3.6 Ω, and a turn on voltage of 11V consistent with design specifications. Electroluminescence was observed in these devices up to room temperature with emission centered at 7.1 µm and line widths of ∼16%(ΔE/E) at 80K. The results show that these are well-behaved electroluminescent structures. Addition of waveguide layers and further improvements in well barrier interfaces are being pursued in efforts to demonstrate lasing.

Impact of 3MeV Energy Proton Particles on Mid-IR QCLs.

This paper reports the results obtained for a distributed-feedback quantum cascade laser (DFB-QCL) exposed to different fluences of proton particles: 1014, 1015 and 1016 p/cm2. Dedicated laboratory setups were developed to assess the irradiation-induced changes in this device. Multiple parameters defining the QCL performances were investigated prior to and following each irradiation step: (i) voltage-driving current; (ii) emitted optical power-driving current; (iii) central emitting wavelength-driving current; (iv) emitted spectrum-driving current; (v) transversal mode structure-driving current, maintaining the system operating temperature at 20 °C. The QCL system presented, before irradiation, two emission peaks: a central emission peak and a side peak. After proton irradiation, the QCL presented a spectral shift, and the ratio between the two peaks also changed. Even though, after irradiation, the tunning spectral range was reduced, at the end of the tests, the system was still functional.

Real-Time Measure of the Lattice Temperature of a Semiconductor Heterostructure Laser via an On-Chip Integrated Graphene Thermometer.

The on-chip integration of two-dimensional nanomaterials, having exceptional optical, electrical, and thermal properties, with terahertz (THz) quantum cascade lasers (QCLs) has recently led to wide spectral tuning, nonlinear high-harmonic generation, and pulse generation. Here, we transfer a large area (1 × 1 cm2) multilayer graphene (MLG), to lithographically define a microthermometer, on the bottom contact of a single-plasmon THz QCL to monitor, in real-time, its local lattice temperature during operation. We exploit the temperature dependence of the MLG electrical resistance to measure the local heating of the QCL chip. The results are further validated through microprobe photoluminescence experiments, performed on the front-facet of the electrically driven QCL. We extract a heterostructure cross-plane conductivity of k⊥= 10.2 W/m·K, in agreement with previous theoretical and experimental reports. Our integrated system endows THz QCLs with a fast (∼30 ms) temperature sensor, providing a tool to reach full electrical and thermal control on laser operation. This can be exploited, inter alia, to stabilize the emission of THz frequency combs, with potential impact on quantum technologies and high-precision spectroscopy.

Near-Full Current Dynamic Range THz Quantum Cascade Laser Frequency Comb.

The present study proposes a terahertz quantum cascade laser frequency comb (THz QCL FC) with a semi-insulated surface plasma waveguide characterized by a low threshold current density, high power and a wide current dynamic range. The gain dispersion value and the nonlinear susceptibility were optimized based on the combination of a hybrid bound-to-continuum active region with a semi-insulated surface plasmon waveguide. Without any extra dispersion compensator, stable frequency comb operation within a current dynamic range of more than 97% of the total was revealed by the intermode beat note map. Additionally, a total comb spectral emission of about 300 GHz centered around 4.6 THz was achieved for a 3 mm long and 150 µm wide device. At 10 K, a maximum output power of 22 mW was obtained with an ultra-low threshold current density of 64.4 A·cm-2.

Accurately Measuring Molecular Rotational Spectra in Excited Vibrational Modes.

Although gas phase rotational spectroscopy is a mature field for which millions of rotational spectral lines have been measured in hundreds of molecules with sub-MHz accuracy, it remains a challenge to measure these rotational spectra in excited vibrational modes with the same accuracy. Recently, it was demonstrated that virtually any rotational transition in excited vibrational modes of most molecules may be made to lase when pumped by a continuously tunable quantum cascade laser (QCL). Here, we demonstrate how an infrared QCL may be used to enhance absorption strength or induce lasing of terahertz rotational transitions in highly excited vibrational modes in order to measure their frequencies more accurately. To illustrate the concepts, we used a tunable QCL to excite v3 R-branch transitions in N2O and either enhanced absorption or induced lasing on 20 v3 rotational transitions, whose frequencies between 299 and 772 GHz were then measured using either heterodyne or modulation spectroscopy. The spectra were fitted to obtain the rotational constants B3 and D3, which reproduce the measured spectra to within the experimental uncertainty of ± 5 kHz. We then show how this technique may be generalized by estimating the threshold power to make any rotational transition lase in any N2O vibrational mode.