Cavity-enhanced optical feedback-assisted photo-acoustic spectroscopy with a 10.4 μm external cavity quantum cascade laser

An ultra-sensitive photo-acoustic spectrometer using a 10.4 μm broadly tunable mid-IR external cavity quantum cascade laser (EC-QCL) coupled with optical feedback to an optical power buildup cavity with high reflectivity mirrors was developed and tested. A laser optical power buildup factor of 181 was achieved, which corresponds to an intra-cavity power of 9.6 W at a wavelength of 10.4 μm. With a photo-acoustic resonance cell placed inside the cavity this resulted in the noise-equivalent absorption coefficient of 1.9 × 10^?10 cm^?1 Hz^?1/2, and a normalized noise-equivalent absorption of 1.1 × 10^?11 cm^?1 W Hz^?1/2. A novel photo-acoustic signal normalization technique makes the photo-acoustic spectrometer’s response immune to changes and drifts in the EC-QCL excitation power, EC-QCL to cavity coupling efficiency and cavity mirrors aging and contamination. An automatic lock of the EC-QCL to the cavity and optical feedback phase optimization permitted long wavelength scans within the entire EC-QCL spectral tuning range.     

Mid-infrared fiber-coupled QCL-QEPAS sensor

An innovative spectroscopic system based on an external cavity quantum cascade laser (EC-QCL) coupled with a mid-infrared (mid-IR) fiber and quartz enhanced photoacoustic spectroscopy (QEPAS) is described. SF₆ has been selected as a target gas in demonstration of the system for trace gas sensing. Single mode laser delivery through the prongs of the quartz tuning fork has been obtained employing a hollow waveguide fiber with inner silver–silver iodine (Ag–AgI) coatings and internal core diameter of 300 μm. A detailed design and realization of the QCL fiber coupling and output collimator system allowed almost practically all (99.4 %) of the laser beam to be transmitted through the spectrophone module. The achieved sensitivity of the system is 50 parts per trillion in 1 s, corresponding to a record for QEPAS normalized noise-equivalent absorption of 2.7 × 10^?10 W cm^?1 Hz^?1/2.     

An Infrared Method,with Reduced Solvent Consumption,for the Determination of Chlorsulfuron in Pesticide Formulations

A simple method has been developed for the determination of Chlorsulfuron in pesticide formulations by Fourier Transform Infrared (FTIR). Samples were diluted with CHCl_3^? , and the FTIR spectra of the samples and standards were obtained at a nominal resolution of 4 cm^? 1 from 4000 to 900 cm^? 1 with the accumulation of 25 scans. Chlorsulfuron determination was based on the measurement of peak area values from 1373 to 1363 cm^? 1 which were corrected by use of a two points baseline defined from 1401 to 1302 cm^? 1. The limit of detection achieved, which was of the order of 6 µg g^? 1, was appropriate for the determination of Chlorsulfuron in commercially available formulations. FTIR results were statistically comparable with those found by High Performance Liquid Chromatography (HPLC). The procedure reduces organic solvent consumption per sample to less than 3 ml CHCl₃, reduces waste generation and increases the sample measurement frequency up to 60 h^? 1.     

Quartz-enhanced photoacoustic spectroscopy-based sensor system for sulfur dioxide detection using a CW DFB-QCL

Sulfur dioxide (SO₂) trace gas detection based on quartz-enhanced photoacoustic spectroscopy (QEPAS) using a continuous wave, distributed feedback quantum cascade laser operating at 7.24 μm was performed. Influence of water vapor addition on monitored QEPAS SO₂ signal was also investigated. A normalized noise equivalent absorption coefficient of NNEA (1σ) = 1.21 × 10^?8 cm^?1 W Hz^?1/2 was obtained for the ν ₃ SO₂ line centered at 1,380.93 cm^?1 when the gas sample was moisturized with 2.3 % H₂O. This corresponds to a minimum detection limit (1σ) of 63 parts per billion by volume for a 1 s lock-in time constant.     

Off-beam quartz-enhanced photoacoustic spectroscopy with LEDs

A photoacoustic ozone sensor based on quartz-enhanced photoacoustic spectroscopy is presented. Instead of a laser, a UV-LED at 285 nm is utilized as light source. Using an acoustical resonator in off-beam configuration, it is feasible to align the light of the LED through the resonator tube. The sensor is integrated in a miniaturized flow-through gas cell which allows fast gas exchange. The sensor performance and the influence of the speed of sound on the measurement signal are investigated. For the detection of ozone in the Hartley band, a detection limit of S = 1.27 ± 0.08 ppmv (1σ) and a noise equivalent absorption sensitivity of D = (3.02 × 10^?8 ± 1 × 10^?10) cm^?1W(Hz)^?1/2 have been achieved.     

A miniature prototype of a resonance photoacoustic cell for gas sensing

We present a miniature prototype of a resonance photoacoustic cell with a banana-shaped internal cavity with a volume of less than ～5 mm³. The cell design and the experimental setup used for testing operational characteristics of the prototype are described. The results of testing the prototype in the experiments on photoacoustic detection of radiation absorption by ammonia in a nitrogen flow by using a single-mode diode laser generating radiation near ～1.53 μm are presented. The amplitude-frequency characteristic of the photoacoustic response induced by absorption of radiation in the presence and absence of ammonia is analyzed. The experiment revealed that sensitivity of gas sensing is limited only by the microphone noise. The measured noise-limited minimal detectable absorption was found to be about 8.48 × 10^?8 cm^?1 W Hz^?1/2.     

Simultaneous detection of trace gases using multiplexed tunable diode lasers and a photoacoustic cell containing a cantilever microphone

We report what we believe to be a novel demonstration of simultaneous detection of multiple trace gases by near-IR tunable diode laser photoacoustic spectroscopy using a cell containing a cantilever microphone. Simultaneous detection of carbon monoxide (CO), ethyne (C₂H₂), methane (CH₄) and combined carbon monoxide/carbon dioxide (CO+CO₂) in nitrogen-based gas mixtures was achieved by modulation frequency division multiplexing the outputs of four near-IR tunable diode lasers. Normalized noise-equivalent absorption coefficients of 3.4×10^?9, 3.6×10^?9 and 1.4×10^?9 cm^?1?W?Hz^?1/2 were obtained for the simultaneous detection of CO, C₂H₂ and CH₄ at atmospheric pressure. These corresponded to noise-equivalent detection limits of 249.6 ppmv (CO), 1.5 ppmv (C₂H₂) and 293.7 ppmv (CH₄) respectively over a measurement period of 2.6 s at the relevant laser power. The performance of the system was not influenced by the number of lasers deployed, the main source of noise arising from ambient acoustic effects. The results confirm that small-volume photoacoustic cells can be used with low optical power tunable diode lasers for rapid simultaneous detection of trace gases with high sensitivity and specificity.     

A compact resonant Π-shaped photoacoustic cell with low window background for gas sensing

A resonant photoacoustic cell capable of detecting the traces of gases at an amplitude-modulation regime is represented. The cell is designed so as to minimize the window background for the cell operation at a selected acoustic resonance. A compact prototype cell (the volume of acoustic cavity of ~0.2 cm³, total cell weight of 3.5 g) adapted to the narrow diffraction-limited beam of near-infrared laser is produced and examined experimentally. The noise-associated measurement error and laser-initiated signals are studied as functions of modulation frequency. The background signal and useful response to light absorption by the gas are analyzed in measurements of absorption for ammonia traces in nitrogen flow with the help of a pigtailed DFB laser diode operated near a wavelength of 1.53 µm. The performance of absorption detection and gas-leak sensing for the prototype operated at the second longitudinal acoustic resonance (the resonance frequency of ~4.38 kHz, Q-factor of ~13.9) is estimated. The noise-equivalent absorption normalized to laser-beam power, and detection bandwidth is ~1.44 × 10^?9 cm^?1 W Hz^?1/2. The amplitude of the window-background signal is equivalent to an absorption coefficient of ~2.82 × 10^?7 cm^?1.     

Compact QEPAS sensor for trace methane and ammonia detection in impure hydrogen

A compact two-gas sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) was developed for trace methane and ammonia quantification in impure hydrogen. The sensor is equipped with a micro-resonator to confine the sound wave and enhance QEPAS signal. The normalized noise-equivalent absorption coefficients (1σ) of 2.45×10^?8 cm^?1?W/ $\sqrt{}$ Hz and 9.1×10^?9 cm^?1?W/ $\sqrt{}$ Hz for CH₄ detection at 200 Torr and NH₃ detection at 50 Torr were demonstrated with the QEPAS sensor configuration, respectively. The influence of water vapor on the CH₄ channel was also investigated.     

Vibrational Spectrometry Strategies for Quality Control of Procymidone in Pesticide Formulations

Abstract

Two vibrational spectrometry–based methodologies were developed for procymidone determination in wettable powdered pesticide formulations. The Fourier‐transform infrared (FTIR) procedure was based on the selective extraction of procymidone by chloroform and determination by peak area measurement between 1451 and 1441 cm^?1, using a baseline correction established between 1490 and 1410 cm^?1, and a precision of 0.4% and a limit of detection of 0.01% w/w procymidone for a sample mass of 25 mg were obtained. For FT‐Raman determination, the selected conditions were peak area measurement between 1005 and 995 cm^?1 Raman shift, with a baseline correction fixed between 1030 and 947 cm^?1, and a relative standard deviation of 1% and a limit of detection of 0.8% procymidone in the original sample were obtained. The sample frequency for FTIR determination was 30 hr^?1, lower than that for Raman with 40 hr^?1. FT‐Raman reduces to the minimum the reagent consumption and waste generation, also avoiding the sample handling and contact of the operator with the pesticide. It can be concluded that the proposed methods are appropriate for quality control in commercial pesticide formulations.     

Direct determination of glucose, lactate and triglycerides in blood serum by a tunable quantum cascade laser-based mid-IR sensor

This work reports on a compact sensor for fast and reagent-free point-of-care determination of glucose, lactate and triglycerides in blood serum based on a tunable (1030–1230 cm^?1) external-cavity quantum cascade laser (EC-QCL). For simple and robust operation a single beam set-up was designed and only thermoelectric cooling was used for the employed laser and detector. Full computer control of analysis including liquid handling and data analysis facilitated routine measurements. A high optical pathlength (>100 μm) is a prerequisite for robust measurements in clinical practice. Hence, the optimum optical pathlength for transmission measurements in aqueous solution was considered in theory and experiment. The experimentally determined maximum signal-to-noise ratio (SNR) was around 140 μm for the QCL blood sensor and around 50 μm for a standard FT-IR spectrometer employing a liquid nitrogen cooled mercury cadmium telluride (MCT) detector. A single absorption spectrum was used to calculate the analyte concentrations simultaneously by using a partial-least-squares (PLS) regression analysis. Glucose was determined in blood serum with a prediction error (RMSEP) of 6.9 mg/dl and triglycerides with an error of cross-validation (RMSECV) of 17.5 mg/dl in a set of 42 different patients. In spiked serum samples the lactate concentration could be determined with an RMSECV of 8.9 mg/dl.     

Acetylene detection based on diode laser QEPAS: combined wavelength and residual amplitude modulation

Quartz-enhanced photoacoustic spectroscopy (QEPAS) is demonstrated for acetylene detection at atmospheric pressure and room temperature with a fiber-coupled distributed feedback (DFB) diode laser operating at ~1.53 μm. An efficient approach for gas concentration calibration is demonstrated. The effect of residual amplitude modulation on the performance of wavelength modulated QEPAS is investigated theoretically and experimentally. With optimized spectrophone parameters and modulation depth, a minimum detectable limit (1σ) of ~2 part-per-million volume (ppmv) was achieved with an 8.44-mW diode laser, which corresponds to a normalized noise equivalent coefficient (1σ) of 6.16 × 10^?8 cm^?1 W/Hz^1/2.     

Grating-coupled external-cavity short-wavelength (λ ≈ 3.9 μm) InGaAs/InAlAs/AlAs quantum-cascade lasers

In this work, the tunability properties of short-wavelength (λ ~ 3.9 μm) quantum-cascade lasers (QCLs) were studied, which is a first in the world at such short wavelengths. The experimental setup of an external cavity (EC) QCL was arranged in a Littrow configuration. A tuning range over 75 cm^?1 has been achieved by using an uncoated 23 μm stripe-width QCL at room temperature. A single-mode operation could be obtained at 2527 and 2544 cm^?1 at different grating angles by using an anti-reflection (AR) coated 23 μm ridge. A 5 μm stripe-width QCL without an AR coating could be tuned over 160 cm^?1.     

Optical-feedback cavity-enhanced absorption spectroscopy with a quantum-cascade laser yields the lowest formaldehyde detection limit

We report on the first application of Optical Feedback-Cavity Enhanced Absorption Spectroscopy to formaldehyde trace gas analysis at mid-infrared wavelengths. A continuous-wave room-temperature, distributed-feedback quantum cascade laser emitting around 1,769 cm^?1 has been successfully coupled to an optical cavity with finesse 10,000 in an OF-CEAS spectrometer operating on the ν₂ fundamental absorption band of formaldehyde. This compact setup (easily transportable) is able to monitor H₂CO at ambient concentrations within few seconds, presently limited by the sample exchange rate. The minimum detectable absorption is 1.6 × 10^?9 cm^?1 for a single laser scan (100 ms, 100 data points), with a detectable H₂CO mixing ratio of 60 pptv at 10 Hz. The corresponding detection limit at 1 Hz is 5 × 10^?10 cm^?1, with a normalized figure of merit of 5 × 10^?11cm $^{-1}/\sqrt{\rm Hz}$ (100 data points recorded in each spectrum taken at 10 Hz rate). A preliminary Allan variance analysis shows white noise averaging down to a minimum detection limit of 5 pptv at an optimal integration time of 10 s, which is significantly better than previous results based on multi-pass or cavity-enhanced tunable QCL absorption spectroscopy.     

Diagnostic and characterization of the VCSEL diodes based on GaSb

Vertical-Cavity Surface-Emitting Laser (VCSEL) diodes are among the youngest members of the semiconductor laser diode family. The main aim of our work focuses on the measurement of the basic properties (the spectral range of the laser emission, temperature and current tunability) of experimental VCSEL diode lasers based on GaSb operating in the infrared region around 4250 cm^?1. A high-resolution FTIR Bruker IFS 120 HR spectrometer with a maximum resolution of 0.0035 cm^?1 was used in the emission setup for the laser diagnostic research. The absorption spectra of atmospheric pollutants like methane, carbon monoxide and ammonia have been measured using these VCSELs for the first time.     

A sensitive amperometric detection of dopamine agonist drug pramipexole at functionalized multi-walled carbon nanotubes (f-MWCNTs) modified electrode

The electrochemical detection of dopaminergic agonist drug pramipexole dihydrochloride monohydrate (PPX) has been investigated by cyclic voltammetric (CV) and amperometric i–t techniques at functionalized multi-walled carbon nanotubes-modified glassy carbon electrode. For the first time, a sensitive and rapid electrochemical method was developed for the determination of PPX. The surface morphological characteristics of the proposed electrode have been studied by using transmission electron microscopy (TEM); further, electrochemical impedance spectroscopy (EIS) and Fourier transform infrared spectroscopy (FTIR) have been employed. PPX shows an irreversible anodic peak, which may be ascribed to the oxidation of the –NH groups of PPX. The proposed method was showing good sensitivity of 0.993 μA μM^?1 cm^?2 with a linear range of 5 to 340 μM by amperometric i–t and CV technique shows a linear range of 12.5 to 313 μM with a sensitivity of 1.92 μA μM^?1 cm^?2. The recovery of PPX from blood serum samples was found 100.6 and 98.9 %, respectively. Furthermore, the proposed method has been demonstrated for the determination of PPX in commercially available pharmaceutical samples and good agreement of results obtained.     

Fourier Transform Mid-Infrared Photoacoustic Spectroscopy for Presymptomatic Detection of Powdery Mildew Infection in Rubus corchorifolius L.

A powdery mildew fungi-induced disease appearing on leaves of Rubus corchorifolius L. has been observed in China, which resulted in seriously influencing the yield and quality of the fruit, and a presymptomatic detection of powdery mildew infection is needed to guarantee the yield and quality through removing the fungi in an early stage. Depth-profiling Fourier transform mid-infrared photoacoustic spectroscopy was applied to characterize both the healthy leaves and powdery mildew-infected leaves of Rubus corchorifolius L. The profiled surface could be divided into out layer (depth of about 1.32 µm) and deep layer (depth of about 1.87 µm). There were numerous differences in the total spectral range (500–4000 cm^?1) between healthy leaves and infected leaves, especially the intensity of absorption bands of 2800–3000 cm^?1 (aliphatic C–H vibration) and 2250–2350 cm^?1 (CO₂) significantly decreased when the leaf was infected by powdery mildew. For the out layer the standard spectral variance between healthy leaf and infected leaf was 7.33 × 10², whereas it was 1.86 × 10⁴ for the deep layer; the standard spectral variance between out layer and deep layer for healthy leaf was 3.38 × 10³, whereas it was 1.84 × 10⁴ for infected leaf, which implied that both out layer and deep layer responded to powdery mildew infection. Combining spectral differences between healthy leaf and infected leaf and variances between out layer and deep layer, a presymptomatic detection of powdery mildew infection was successfully made, which provided an alternative option and noninvasive method for the fast diagnosis of powdery mildew infection on Rubus corchorifolius L.     

Detection of C2H2 and HCl using mid-infrared degenerate four-wave mixing with stable beam alignment: towards practical in situ sensing of trace molecular species

A stable and convenient optical system to realize the forward phase-matching geometry for degenerate four-wave mixing (DFWM) is demonstrated in the mid-infrared spectral region by measuring DFWM signals generated in acetylene (C₂H₂) and hydrogen chloride (HCl) molecules by probing the fundamental ro-vibrational transitions. IR laser pulses tunable from 2900 cm^?1 to 3350 cm^?1 with a 0.025 cm^?1 linewidth were obtained using a laser system composed of an injection seeded Nd:YAG laser, a dye laser, and a frequency mixing unit. At room temperature and atmospheric pressure, a detection limit of 35 ppm (～ 9.5×10¹⁴ molecules/cm³) for C₂H₂ was achieved in a gas flow of a C₂H₂/N₂ mixture by scanning the P(11) line of the (010(11)⁰)–(0000⁰0⁰) band. The detection limit of the HCl molecule was measured to be 25 ppm (～6.8×10¹⁴ molecules/cm³) in the same environment by probing the R(4) line. The dependences of signal intensities on molecular concentrations and laser pulse energies were demonstrated using C₂H₂ as the target species. The variations of the signal line shapes with changes in the buffer gas pressures and laser intensities were recorded and analyzed. The experimental setup demonstrated in this work facilitates the practical implementation of in situ, sensitive molecular species sensing with species-specific, spatial and temporal resolution in the spectral region of 2.7–3.3 μm (3000–3700 in cm^?1), where various molecular species important in combustion have absorption bands.     

Sensitive detection of acrolein and acrylonitrile with a pulsed quantum-cascade laser

We report on spectroscopic measurements of acrolein and acrylonitrile at atmospheric pressure using a pulsed distributed feedback quantum-cascade laser in combination with intra- and inter-pulse techniques and compare the results. The measurements were done in the frequency region around 957 cm^?1. In the inter-pulse technique, the laser is excited with short current pulses (5–10 ns), and the pulse amplitude is modulated with an external current ramp resulting in a ～2.3 cm^?1 frequency scan. In the intra-pulse technique, a linear frequency down-chirp during the pulse is used for sweeping across the absorption line. Long current pulses up to 500 ns were used for these measurements which resulted in a spectral window of ～2.2 cm^?1 during the down-chirp. These comparatively wide spectral windows facilitated the measurements of the relatively broad absorption lines (～1 cm^?1) of acrolein and acrylonitrile. The use of a room-temperature mercury-cadmium-telluride detector resulted in a completely cryogen-free spectrometer. We demonstrate ppb level detection limits within a data acquisition time of ～10 s with these methodologies.     

Determination of the low absorption coefficients of thick semi-conductor samples using rear side photoacoustic spectroscopy detection

Based on the Rosencwaig and Gersho theory, we have theoretically derived the photoacoustic signal in the gaz behind the unilluminated surface of thick samples and presented a simple analytical procedure for determining the low optical absorption spectra of these samples.The rear side photoacoustic spectroscopy (PAS) detection has been employed on thick samples of GaP (0,2-1mm) and optical absorption coefficients in the region between 15 to 200 cm^?1 were measured.Our results are discussed in comparison with those obtained by usual front side PAS detection and spectroscopic ellipsometry.