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.

Quantum frequency conversion of vacuum squeezed light to bright tunable blue squeezed light and higher-order spatial modes.

Quantum frequency conversion, the process of shifting the frequency of an optical quantum state while preserving quantum coherence, can be used to produce non-classical light at otherwise unapproachable wavelengths. We present experimental results based on highly efficient sum-frequency generation (SFG) between a vacuum squeezed state at 1064 nm and a tunable pump source at 850 nm ± 50 nm for the generation of bright squeezed light at 472 nm ± 4 nm, currently limited by the phase-matching of the used nonlinear crystal. We demonstrate that the SFG process conserves part of the quantum coherence as a 4.2(±0.2) dB 1064 nm vacuum squeezed state is converted to a 1.6(±0.2) dB tunable bright blue squeezed state. We furthermore demonstrate simultaneous frequency- and spatial-mode conversion of the 1064-nm vacuum squeezed state, and measure 1.1(±0.2) dB and 0.4(±0.2) dB of squeezing in the TEM01 and TEM02 modes, respectively. With further development, we foresee that the source may find use within fields such as sensing, metrology, spectroscopy, and imaging.

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.

Cavity-enhanced sum-frequency generation of blue light with near-unity conversion efficiency.

We report on double-resonant highly efficient sum-frequency generation in the blue range. The system consists of a 10-mm-long periodically poled KTP crystal placed in a double-resonant bow-tie cavity and pumped by a fiber laser at 1064.5 nm and a Ti:sapphire laser at 849.2 nm. An optical power of 375 mW at 472.4 nm in a TEM00 mode was generated with pump powers of 250 mW at 849.2 nm and 200 mW at 1064.5 nm coupled into the double-resonant ring resonator with 88% mode-matching. The resulting internal conversion efficiency of 95(±3)% of the photons mode-matched to the cavity constitutes, to the best of our knowledge, the highest overall achieved quantum conversion efficiency using continuous-wave pumping. Very high conversion efficiency is rendered possible due to very low intracavity loss on the level of 0.3% and high nonlinear conversion coefficient up to 0.045(0.015) W-1. Power stability measurements performed over one hour show a stability of 0.8%. The generated blue light can be tuned within 5 nm around the center wavelength of 472.4 nm, limited by the phase-matching of our nonlinear crystal. This can however be expanded to cover the entire blue spectrum (420 nm to 510 nm) by proper choice of nonlinear crystals and pump lasers. Our experimental results agree very well with analytical and numerical simulations taking into account cavity impedance matching and depletion of the pump fields.

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.

All-optical detection of acoustic pressure waves with applications in photoacoustic spectroscopy.

An all-optical detection method for the detection of acoustic pressure waves is demonstrated. The detection system is based on a stripped (bare) single-mode fiber. The fiber vibrates as a standard cantilever and the optical output from the fiber is imaged to a displacement-sensitive optical detector. The absence of a conventional microphone makes the demonstrated system less susceptible to the effects that a hazardous environment might have on the sensor. The sensor is also useful for measurements in high-temperature (above 200°C) environments where conventional microphones will not operate. The proof-of-concept of the all-optical detection method is demonstrated by detecting sound waves generated by the photoacoustic effect of NO2 excited by a 455 nm LED, where a detection sensitivity of approximately 50 ppm was achieved.

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.

Optics miniaturization strategy for demanding Raman spectroscopy applications.

Raman spectroscopy provides non-destructive, label-free quantitative studies of chemical compositions at the microscale as used on NASA's Perseverance rover on Mars. Such capabilities come at the cost of high requirements for instrumentation. Here we present a centimeter-scale miniaturization of a Raman spectrometer using cheap non-stabilized laser diodes, densely packed optics, and non-cooled small sensors. The performance is comparable with expensive bulky research-grade Raman systems. It has excellent sensitivity, low power consumption, perfect wavenumber, intensity calibration, and 7 cm-1 resolution within the 400-4000 cm-1 range using a built-in reference. High performance and versatility are demonstrated in use cases including quantification of methanol in beverages, in-vivo Raman measurements of human skin, fermentation monitoring, chemical Raman mapping at sub-micrometer resolution, quantitative SERS mapping of the anti-cancer drug methotrexate and in-vitro bacteria identification. We foresee that the miniaturization will allow realization of super-compact Raman spectrometers for integration in smartphones and medical devices, democratizing Raman technology.

Quantum-enhanced micromechanical displacement sensitivity.

We report on a hitherto unexplored application of squeezed light: for quantum-enhancement of mechanical transduction sensitivity in microcavity optomechanics. Using a toroidal silica microcavity, we experimentally demonstrate measurement of the transduced phase modulation signal in the frequency range 4-5.8 MHz with a sensitivity -0.72(±0.01) dB below the shot noise level. This is achieved for resonant probing in the highly undercoupled regime, by preparing the probe in a weak coherent state with phase squeezed vacuum states at sideband frequencies.

Gaussian error correction of quantum states in a correlated noisy channel.

Noise is the main obstacle for the realization of fault-tolerant quantum information processing and secure communication over long distances. In this work, we propose a communication protocol relying on simple linear optics that optimally protects quantum states from non-Markovian or correlated noise. We implement the protocol experimentally and demonstrate the near-ideal protection of coherent and entangled states in an extremely noisy channel. Since all real-life channels are exhibiting pronounced non-Markovian behavior, the proposed protocol will have immediate implications in improving the performance of various quantum information protocols.