Quartz-Enhanced Photoacoustic Spectroscopy Assisted by Partial Least-Squares Regression for Multi-Gas Measurements.

We report on the use of quartz-enhanced photoacoustic spectroscopy (QEPAS) for multi-gas detection. Photoacoustic (PA) spectra of mixtures of water (H2O), ammonia (NH3), and methane (CH4) were measured in the mid-infrared (MIR) wavelength range using a mid-infrared (MIR) optical parametric oscillator (OPO) light source. Highly overlapping absorption spectra are a common challenge for gas spectroscopy. To mitigate this, we used a partial least-squares regression (PLS) method to estimate the mixing ratio and concentrations of the individual gasses. The concentration range explored in the analysis varies from a few parts per million (ppm) to thousands of ppm. Spectra obtained from HITRAN and experimental single-molecule reference spectra of each of the molecular species were acquired and used as training data sets. These spectra were used to generate simulated spectra of the gas mixtures (linear combinations of the reference spectra). Here, in this proof-of-concept experiment, we demonstrate that after an absolute calibration of the QEPAS cell, the PLS analyses could be used to determine concentrations of single molecular species with a relative accuracy within a few % for mixtures of H2O, NH3, and CH4 and with an absolute sensitivity of approximately 300 (±50) ppm/V, 50 (±5) ppm/V, and 5 (±2) ppm/V for water, ammonia, and methane, respectively. This demonstrates that QEPAS assisted by PLS is a powerful approach to estimate concentrations of individual gas components with considerable spectral overlap, which is a typical scenario for real-life adoptions and applications.

Isotopic gas analysis by means of mid-infrared photoacoustic spectroscopy targeting human exhaled air.

There is a great need for cost-efficient non-invasive medical diagnostic tools for analyzing humanly exhaled air. Compared to present day methods, photoacoustic spectroscopy (PAS) can provide a compact and portable (bedside), sensitive and inexpensive solution. We demonstrate a novel portable photoacoustic spectroscopic platform for isotopic measurements of methane (CH4). We identify and discriminate the 12CH4- and 13CH4 isotopologues and determine their mixing ratio. An Allan deviation analysis shows that the noise equivalent concentration for CH4 is 200 ppt (pmol/mol) at 100 s of integration time, corresponding to a normalized noise equivalent absorption coefficient of 5.1×10-9Wcm-1Hz-1/2, potentially making the PAS sensor a truly disruptive instrument for bedside monitoring using isotope tracers by providing real-time metabolism data to clinical personnel.

Calibration of Quartz-Enhanced Photoacoustic Sensors for Real-Life Adaptation.

We report on the use of quartz-enhanced photoacoustic spectroscopy for continuous carbon-dioxide measurements in humid air over a period of six days. The presence of water molecules alters the relaxation rate of the target molecules and thus the amplitude of the photoacoustic signal. Prior to the measurements, the photoacoustic sensor system was pre-calibrated using CO2 mole fractions in the range of 0-10-3 (0-1000 ppm) and at different relative humidities between 0% and 45%, while assuming a model hypothesis that allowed the photoacoustic signal to be perturbed linearly by H2O content. This calibration technique was compared against an alternative learning-based method, where sensor data from the first two days of the six-day period were used for self-calibration. A commercial non-dispersive infrared sensor was used as a CO2 reference sensor and provided the benchmark for the two calibration procedures. In our case, the self-calibrated method proved to be both more accurate and precise.

Intrinsic Spectral Resolution Limitations of QEPAS Sensors for Fast and Broad Wavelength Tuning.

Quartz-enhanced photoacoustic sensing is a promising method for low-concentration trace-gas monitoring due to the resonant signal enhancement provided by a high-Q quartz tuning fork. However, quartz-enhanced photoacoustic spectroscopy (QEPAS) is associated with a relatively slow acoustic decay, which results in a reduced spectral resolution and signal-to-noise ratio as the wavelength tuning rate is increased. In this work, we investigate the influence of wavelength scan rate on the spectral resolution and signal-to-noise ratio of QEPAS sensors. We demonstrate the acquisition of photoacoustic spectra from 3.1 µm to 3.6 µm using a tunable mid-infrared optical parametric oscillator. The spectra are attained using wavelength scan rates differing by more than two orders of magnitude (from 0.3 nm s-1 to 96 nm s-1). With this variation in scan rate, the spectral resolution is found to change from 2.5 cm-1 to 9 cm-1. The investigated gas samples are methane (in nitrogen) and a gas mixture consisting of methane, water, and ethanol. For the gas mixture, the reduced spectral resolution at fast scan rates significantly complicates the quantification of constituent gas concentrations.

Continuous-wave coherent Raman spectroscopy for improving the accuracy of Raman shifts.

Raman spectroscopy is an appealing technique that probes molecular vibrations in a wide variety of materials with virtually no sample preparation. However, accurate and reliable Raman measurements are still a challenge and require more robust and practical calibration methods. We demonstrate the implementation of a simple low-cost continuous-wave (cw) stimulated Raman spectroscopy scheme for accurate and high-resolution spectroscopy. We perform shot noise-limited cw stimulated Raman scattering as well as cw coherent anti-Stokes Raman scattering on polystyrene samples. Our method enables accurate determination of Raman shifts with an uncertainty below 0.1 cm-1. The setup is used for the characterization of reference materials required for the calibration of Raman spectrometers. Compared with existing standards, we provide an order of magnitude improvement of the uncertainty of Raman energy shifts in a polystyrene reference material.

Versatile photoacoustic spectrometer based on a mid-infrared pulsed optical parametric oscillator.

We demonstrate the usefulness of a nanosecond-pulsed single-mode mid-infrared (MIR) optical parametric oscillator (OPO) for photoacoustic (PA) spectroscopic measurements. The maximum wavelength ranges for the signal and idler are 1.4 µm to 1.7 µm and 2.8 µm to 4.6 µm, respectively, with a MIR output power of up to 500 mW, making the OPO useful for different spectroscopic PA trace-gas measurements targeting the major market opportunity of environmental monitoring and breath gas analysis. We perform spectroscopic measurements of methane (CH4), nitrogen dioxide (NO2), and ammonia (NH3) in the 2.8 µm to 3.7 µm wavelength region. The measurements were conducted with a constant flow rate of 300 mL/min, thus demonstrating the suitability of the gas sensor for real-time trace-gas measurements. The acquired spectra are compared with data from the HITRAN database, and good agreement is found, demonstrating a resolution bandwidth of 1.5 cm1. An Allan deviation analysis shows that the detection limit for methane at optimum integration time for the PA sensor is 8 ppbV (nmol/mol) at 105 s of integration time, corresponding to a normalized noise equivalent absorption coefficient of 2.9×10-7 W cm-1 Hz-1/2.

Simple and robust speckle detection method for fire and heat detection in harsh environments.

Standard laser-based fire detection systems are often based on measuring the variation of optical signal amplitude. However, mechanical noise interference and loss from dust and steam can obscure the detection signal, resulting in faulty results or the inability to detect a potential fire. The presented fire detection technology will allow the detection of fire in harsh and dusty areas, which are prone to fires, where current systems show limited performance or are unable to operate. It is not the amount of light or its wavelength that is used for detecting fire, but how the refractive index randomly fluctuates due to heat convection from the fire. In practical terms, this means that light obstruction from ambient dust particles will not be a problem as long as a small fraction of the light is detected and that fires without visible flames can still be detected. The standalone laser system consists of a Linux-based Red Pitaya system, a cheap 650 nm laser diode, and a positive-intrinsic-negative photo-detector. Laser light propagates through the monitored area and reflects off a retroreflector generating a speckle pattern. Every 3 s, time traces and frequency noise spectra are measured, and eight descriptors are deduced to identify a potential fire. Both laboratory and factory acceptance tests have been performed with success.

Off-axis quartz-enhanced photoacoustic spectroscopy using a pulsed nanosecond mid-infrared optical parametric oscillator: publisher's note.

This publisher's note corrects an affiliation error in Opt. Lett.41, 4118 (2016)OPLEDP0146-959210.1364/OL.41.004118.

Design and experimental verification of a photoacoustic flow sensor using computational fluid dynamics.

A photoacoustic (PA) sensor for fast and real-time gas sensing is demonstrated. The PA sensor is a stand-alone system controlled by a field-programmable gate array. The PA cell has been designed for flow noise immunity using computational fluid dynamics (CFD) analysis. The aim of the CFD analysis was to investigate and minimize the influence of the gas distribution and flow noise on the PA signal. PA measurements were conducted at different flow rates by exciting molecular C-H stretch vibrational bands of hexane (C6H14) and decane (C10H22) molecules in clean air at 2950 cm-1 (3.38 µm) with a custom-made mid-infrared interband cascade laser. We observe a (1σ, standard deviation) sensitivity of 0.4±0.1 ppb (nmol/mol) for hexane in clean air at flow rates up to 1.7 L/min, corresponding to a normalized noise equivalent absorption coefficient of 2.5×10-9 W cm-1 Hz-1/2, demonstrating high sensitivity and fast real-time gas analysis. An Allan deviation analysis for decane shows that the detection limit at optimum integration time is 0.25 ppbV (nmol/mol).

Compact and versatile laser system for polarization-sensitive stimulated Raman spectroscopy.

We demonstrate a compact and versatile laser system for stimulated Raman spectroscopy (SRS). The system is based on a tunable continuous wave (CW) probe laser combined with a home-built semi-monolithic nanosecond pulsed pump Nd:YVO4 laser at 1064 nm. The CW operation of the probe laser offers narrow linewidth, low noise and the advantage that temporal synchronization with the pump is not required. The laser system enables polarization-sensitive stimulated Raman spectroscopy (PS-SRS) with fast high resolution measurement of the depolarization ratio by simultaneous detection of Raman scattered light in orthogonal polarizations, thus providing information about the symmetry of the Raman-active vibrational modes. Measurements of the depolarization ratios of the carbon-hydrogen (CH) stretching modes in two different polymer samples in the spectral range of 2825-3025 cm-1 were performed. Raman spectra are obtained at a sweep rate of 20 nm/s (84 cm-1/s) with a resolution of 0.65 cm-1. A normalization method is introduced for the direct comparison of the simultaneously acquired orthogonal polarized Raman spectra.

Photo-acoustic sensor for detection of oil contamination in compressed air systems.

We demonstrate an online (in-situ) sensor for continuous detection of oil contamination in compressed air systems complying with the ISO-8573 standard. The sensor is based on the photo-acoustic (PA) effect. The online and real-time PA sensor system has the potential to benefit a wide range of users that require high purity compressed air. Among these are hospitals, pharmaceutical industries, electronics manufacturers, and clean room facilities. The sensor was tested for sensitivity, repeatability, robustness to molecular cross-interference, and stability of calibration. Explicit measurements of hexane (C6H14) and decane (C10H22) vapors via excitation of molecular C-H vibrations at approx. 2950 cm-1 (3.38 µm) were conducted with a custom made interband cascade laser (ICL). For the decane measurements a (1 σ) standard deviation (STD) of 0.3 ppb was demonstrated, which corresponds to a normalized noise equivalent absorption (NNEA) coefficient for the prototype PA sensor of 2.8×10-9 W cm-1 Hz1/2.

Off-axis quartz-enhanced photoacoustic spectroscopy using a pulsed nanosecond mid-infrared optical parametric oscillator.

A trace-gas sensor, based on quartz-enhanced photoacoustic spectroscopy (QEPAS), consisting of two acoustically coupled micro-resonators (mR) with an off-axis 20 kHz quartz tuning fork (QTF) is demonstrated. The complete acoustically coupled mR system is optimized based on finite-element simulations and is experimentally verified. The QEPAS sensor is pumped resonantly by a nanosecond pulsed single-mode mid-infrared optical parametric oscillator. The sensor is used for spectroscopic measurements on methane in the 3.1-3.5 µm wavelength region with a resolution bandwidth of 1 cm-1 and a detection limit of 0.8 ppm. An Allan deviation analysis shows that the detection limit at the optimum integration time for the QEPAS sensor is 32 ppbv at 190 s, and that the background noise is due solely to the thermal noise of the QTF.

Spatial characterization of nanotextured surfaces by visual color imaging.

We present a method using an ordinary color camera to characterize nanostructures from the visual color of the structures. The method provides a macroscale overview image from which micrometer-sized regions can be analyzed independently, hereby revealing long-range spatial variations of the structures. The method is tested on injection-molded polymer line gratings, and the height and filling factor are determined with confidence intervals similar to more advanced imaging scatterometry setups.

Differential high-resolution stimulated CW Raman spectroscopy of hydrogen in a hollow-core fiber.

We demonstrate sensitive high-resolution stimulated Raman measurements of hydrogen using a hollow-core photonic crystal fiber (HC-PCF). The Raman transition is pumped by a narrow linewidth (< 50 kHz) 1064 nm continuous-wave (CW) fiber laser. The probe light is produced by a homebuilt CW optical parametric oscillator (OPO), tunable from around 800 nm to 1300 nm (linewidth ∼ 5 MHz). These narrow linewidth lasers allow for an excellent spectral resolution of approximately 10(-4) cm(-1). The setup employs a differential measurement technique for noise rejection in the probe beam, which also eliminates background signals from the fiber. With the high sensitivity obtained, Raman signals were observed with only a few mW of optical power in both the pump and probe beams. This demonstration allows for high resolution Raman identification of molecules and quantification of Raman signal strengths.

A versatile integrating sphere based photoacoustic sensor for trace gas monitoring.

A compact versatile photoacoustic (PA) sensor for trace gas detection is reported. The sensor is based on an integrating sphere as the PA absorption cell with an organ pipe tube attached to increase the sensitivity of the PA sensor. The versatility and enhancement of the sensitivity of the PA signal is investigated by monitoring specific ro-vibrational lines of CO(2) in the 2 µm wavelength region and of NO(2) in the 405 nm region. The measured enhancement factor of the PA signal exceeds 1200, which is due to the acoustic resonance of the tube and the absorption enhancement of the integrating sphere relatively to a non-resonant single pass cell. It is observed that the background absorption signals are highly attenuated due to the thermal conduction and diffusion effects in the polytetrafluoroethylene cell walls. This demonstrates that careful choice of cell wall materials can be highly beneficial to the sensitivity of the PA sensor. These properties makes the sensor suitable for various practical sensor applications in the ultraviolet (UV) to the near infrared (NIR) wavelength region, including climate, environmental and industrial monitoring.

Fiber laser optical frequency standard at 1.54 µm.

A 32 mW fiber laser is stabilized to the (13)C(2)H(2) P(16) (ν1 + ν3) transition at 1542 nm using saturated absorption. The short-term shot-noise limited fractional frequency instability is 5.0 × 10(-13)(τ/s)-½ for averaging times τ up to about 100 s. The relative lock-point repeatability over 2½ month is 4.3 × 10(-13) corresponding to 83 Hz. The simple setup includes a 21 cm long gas cell, but it does not require an enhancement cavity or external modulators. The spectroscopic lineshape is analyzed with respect to optical power and acetylene pressure. Narrow linewidths of 300 kHz FWHM are observed with a signal to noise ratio of 35 dB in a 9 Hz bandwidth.

Microwave optical double resonance spectroscopy of ammonia in a hollow-core fiber.

We have demonstrated microwave optical double resonance spectroscopy of the nu(1) + nu(3) and nu(1) + 2nu(4) bands of ammonia in a hollow-core photonic bandgap fiber. Signal strength and lineshapes are analyzed. Spectroscopic assignments of previously assigned lines and previously proposed assignments have been confirmed and new assignments have been made. Several microwave transitions in the excited vibrational states have been measured for the first time.

Transmission properties of hollow-core photonic bandgap fibers in relation to molecular spectroscopy.

The transmission properties of five types of hollow-core photonic bandgap fibers (HC-PBFs) are characterized in the telecom wavelength range around 1.5 microm. The variations in optical transmission are measured as a function of laser frequency over a 2 GHz scan range as well as a function of time over several hours. The influence of these variations on spectroscopy of molecules in a HC-PBF is simulated.

High resolution spectroscopy of ammonia in a hollow-core fiber.

We have demonstrated frequency modulation saturation spectroscopy of the nu(1) +nu(3) band of ammonia in hollow-core photonic bandgap fibers (HC-PBFs). Previously blended lines have been resolved and the corresponding molecular transitions assigned. Cross-over resonances are observed between transitions that do not share a common level. We have measured the pressure dependence of the line shape and determined the collisional self-broadening coefficients for ammonia. The many absorption lines of ammonia in the 1.5 microm wavelength region are potential frequency references lines for optical communication as well as candidates for spectroscopic trace gas monitoring.

Saturated optical absorption by slow molecules in hollow-core photonic band-gap fibers.

We report on saturated absorption in a hollow-core photonic band-gap fiber filled with 12C2H2 molecules. We find that slow molecules provide a major contribution to the signal in the limit of low optical power and low pressure where the signal deviates significantly from the usual Lorentzian line shape. In particular, we observe a linewidth reduction of about 3 times as compared to the transit-time limited linewidth.