Tunable External-cavity Quantum Cascade Lasers Research Articles

External-Cavity Quantum Cascade Laser-Based Gas Sensor for Sulfur Hexafluoride Detection

The external-cavity quantum cascade laser (ECQCL) is an ideal mid-infrared (MIR) spectral light source for determining large molecular-absorption spectral features with broad transition bands. For this paper, a gas sensor system was developed using a broadband tunable ECQCL and a direct absorption spectroscopy detection scheme with a short path absorption cell of 29.6 cm. For spectral signal detection, a cheap and miniaturized quartz crystal tuning fork- (QCTF) based light detector was used for laser signal detection. The characteristics of the QCTF detector were theoretically simulated and experimentally observed. To demonstrate this sensing technique, sulfur hexafluoride (SF6) was selected as the analyte, which can be used as an effective indicator to identify fault-types of gas-insulated electrical equipment. Preliminary results indicated that a good agreement was obtained between experimentally observed data and reference spectra according to the NIST database and previous publications, and the gas sensor system showed a good linear response to SF6 gas concentration. Finally, Allan–Werle deviation analysis indicated that detection limits of 1.89 ppm for SF6 were obtained with a 1 s integration time, which can be further improved to ~0.38 ppm by averaging up to 131 s.

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.

Use of a novel infrared wavelength-tunable laser Mueller-matrix polarimetric scatterometer to measure nanostructured optical materials.

Nanostructured optical materials, for example, metamaterials, have unique spectral, directional, and polarimetric properties. Samples designed and fabricated for infrared (IR) wavelengths have been characterized using broadband instruments to measure specular polarimetric transmittance or reflectance as in ellipsometry or integrated hemisphere transmittance or reflectance. We have developed a wavelength-tunable IR Mueller-matrix (Mm) polarimetric scatterometer which uses tunable external-cavity quantum-cascade lasers (EC-QCLs) to tune onto and off of the narrowband spectral resonances of nanostructured optical materials and performed full polarimeteric and directional evaluation to more fully characterize their behavior. Using a series of EC-QCLs, the instrument is tunable over 4.37-6.54 μm wavelengths in the mid-wave IR and 7.41-9.71 μm in the long-wave IR and makes measurements both at specular angles, acting as a Mm polarimeter, and at off-specular angles, acting as a Mm scatterometer. Example measurements of an IR thermal metamaterial are shown.

Intracavity photoacoustic sensing of water vapor with a continuously tunable external-cavity quantum-cascade laser operating near 5.5 μm.

A gas sensor integrating a pulsed external-cavity quantum-cascade laser and a photoacoustic (PA) cell placed inside the laser cavity is described. The laser design allows a continuously tunable and mode-hop-free operation with an estimated instrument-limited linewidth of 0.063 cm-1 in Littrow or Littman-Metcalf cavity configurations. Due to higher intracavity power levels, the PA signal for the cell located within the laser cavity is 80-320 times stronger than the signal for the same cell placed outside the cavity. The sensor shows a good capability to identify individual absorption lines of isotopic H2O16, H2O8, and H2O17 species within a narrow spectral interval from 1814 to 1821 cm-1 at natural isotope abundances.

Development of a mid-infrared nitrogen dioxide sensor based on Faraday rotation spectroscopy

A sensitive nitrogen dioxide (NO2) sensor system based on Faraday Rotation Spectroscopy (FRS) was developed. The advantages of FRS include high detection sensitivity, zero background and free from the influence of diamagnetic species, such as humidity and carbon dioxide. A widely tunable external cavity quantum cascade laser (EC-QCL) was used as the excitation source. The tunable EC-QCL operates mode-hop free between 1600cm−1 and 1650cm−1 and allows targeting the optimum 441<−440 Q-branch transition of NO2 at 1613.2cm−1 with an optical power of ∼135mW. A custom made 22.47cm long multipass gas cell (MPGC) was implemented in which the EC-QCL radiation was passed 45 times and provided an effective optical path length of 10.1m in order to design a compact sensor system with high detection sensitivity. An air core solenoid surrounding the MPGC was used for generating a magnetic field of 200G. Performance details of a FRS based sensor and its application for long time continuous NO2 measurements are reported. The long time stability of the sensor system was evaluated. A NO2 detection sensitivity based on an Allan deviation plot of ∼95ppt was obtained by averaging the associated data for 300s.

Low-threshold external-cavity quantum cascade laser around 7.2 μ m

Room-temperature continuous wave (CW) operation of a tunable external-cavity quantum cascade laser (EC-QCL) at center wavelength around 7.2 μm is presented. The EC-QCL was implemented in a Littrow configuration. The gain chip is based on a diagonal bound-to-continuum design with a high-reflection coating on the back facet. A two-layer antireflection (AR) coating consisting of Al2O3 and ZnSe was designed and deposited on the front facet of the chip to suppress the Fabry–Perot modes. With this AR coating, single-mode tuning range of 128 cm−1 was achieved, from 1346.7 to 1475.3 cm−1 (6.78 to 7.43 μm). High side-mode suppression ratio over 30 dB was achieved near the center gain region. A very low-threshold current density of 0.89 kA/cm2 and a high output power of 50 mW were obtained when the EC-QCL was operated in CW mode at 20°C.

External-Cavity Quantum Cascade Laser Spectroscopy for Mid-IR Transmission Measurements of Proteins in Aqueous Solution.

In this work, we report mid-IR transmission measurements of the protein amide I band in aqueous solution at large optical paths. A tunable external-cavity quantum cascade laser (EC-QCL) operated in pulsed mode at room temperature allowed one to apply a path length of up to 38 μm, which is four times larger than that applicable with conventional FT-IR spectrometers. To minimize temperature-induced variations caused by background absorption of the ν2-vibration of water (HOH-bending) overlapping with the amide I region, a highly stable temperature control unit with relative temperature stability within 0.005 °C was developed. An advanced data processing protocol was established to overcome fluctuations in the fine structure of the emission curve that are inherent to the employed EC-QCL due to its mechanical instabilities. To allow for wavenumber accuracy, a spectral calibration method has been elaborated to reference the acquired IR spectra to the absolute positions of the water vapor absorption bands. Employing this setup, characteristic spectral features of five well-studied proteins exhibiting different secondary structures could be measured at concentrations as low as 2.5 mg mL(-1). This concentration range could previously only be accessed by IR measurements in D2O. Mathematical evaluation of the spectral overlap and comparison of second derivative spectra confirm excellent agreement of the QCL transmission measurements with protein spectra acquired by FT-IR spectroscopy. This proves the potential of the applied setup to monitor secondary structure changes of proteins in aqueous solution at extended optical path lengths, which allow experiments in flow through configuration.

High resolution spectroscopy of silane with an external-cavity quantum cascade laser: Absolute line strengths of the ν3 fundamental band at [formula omitted

The introduction of room temperature continuous wave external-cavity quantum cascade lasers (EC-QCLs) with narrow linewidths has greatly facilitated high resolution spectroscopy over wide spectral ranges in the mid-infrared (MIR) region. Using the wide tuning range of an EC-QCL we have measured the absolute line strengths of many P-branch transitions of the stretching dyad of the ν3 fundamental band of 28SiH4 between 2096 and 2178cm−1. Furthermore, the high spectral resolution available has enabled us to resolve and measure representative examples of the tetrahedral splittings associated with each component of the P-branch. The positions of these components are in excellent agreement with spherical top data system (STDS) predictions and theoretical transitions from the TDS spectroscopic database for spherical top molecules. These are the first measurements of these line strengths of 28SiH4 and are an example of the applicability of high-powered, widely tunable EC-QCLs to high resolution spectroscopy.

Reagent-free monitoring of multiple clinically relevant parameters in human blood plasma using a mid-infrared quantum cascade laser based sensor system

We present a semi-automated point-of-care (POC) sensor approach for the simultaneous and reagent-free determination of clinically relevant parameters in blood plasma. The portable sensor system performed direct mid-infrared (MIR) transmission measurements of blood plasma samples using a broadly tunable external-cavity quantum cascade laser source with high spectral power density. This enabled the use of a flow cell with a long path length (165μm) which resulted in high signal-to-noise ratios and a rugged system, insensitive to clogging. Multivariate calibration models were built using well established Partial-Least-Squares (PLS) regression analysis. Selection of spectral pre-processing procedures was optimized by an automated evaluation algorithm. Several analytes, including glucose, lactate, triglycerides, cholesterol, total protein as well as albumin, were successfully quantified in routinely taken blood plasma samples from 67 critically ill patients. Although relying on a spectral range from 1030cm(-1) to 1230cm(-1), which is optimal for glucose and lactate but rather unusual for protein analysis, it was possible to selectively determine the albumin and total protein concentrations with sufficient accuracy for POC application.

Atmospheric vertical profiles of O3, N2O, CH4, CCl2F2, and H2O retrieved from external-cavity quantum-cascade laser heterodyne radiometer measurements

Atmospheric vertical profiles of ozone, nitrous oxide, methane, dichlorodifluoromethane, and water are retrieved from data collected with a widely tunable external-cavity quantum-cascade laser heterodyne radiometer (EC-QC-LHR) covering a spectral range between 1120 and 1238 cm(-1). The instrument was operated in solar occultation mode during a two-month measurement campaign at Rutherford Appleton Laboratory in Oxfordshire, UK, in winter 2010/2011, and ultrahigh-resolution (60 MHz or 0.002 cm(-1)) transmission spectra were recorded for multiple narrow spectral windows (~1 cm(-1) width) specific to each molecule. The ultrahigh spectral resolution of the EC-QC-LHR allows retrieving altitudinal profiles from transmission spectra that contain only few (1-3) significant absorption lines of a target molecule. Profiles are validated by comparing with European Centre for Medium-Range Weather Forecasts operational atmospheric profiles (ozone and water), with other data in the literature (nitrous oxide, methane, dichlorodifluoromethane), and with retrievals from a lower resolution (600 MHz or 0.02 cm(-1)) Fourier transform spectroscopy data that were also recorded during the measurement campaign.

Quantum-Cascade Laser-Based Vibrational Circular Dichroism

Vibrational circular dichroism (VCD) spectra were recorded with a tunable external-cavity quantum-cascade laser (QCL). In comparison with standard thermal light sources in the IR, QCLs provide orders of magnitude more power and are therefore promising for VCD studies in strongly absorbing solvents. The brightness of this novel light source is demonstrated with VCD and IR absorption measurements of a number of compounds, including proline in water.