As the world pivots away from hydrocarbon to hydrogen energy sources, new detection methodologies will be required to maintain safety. A critical factor in the safe use of hydrogen energy sources is access to low-cost, high-performance stand-off detection technology which can readily and autonomously detect hydrogen leaks. The tried-and-trusted path of absorption spectroscopy cannot be utilized with hydrogen due to the absence of optical absorption features for hydrogen. In addition to this, the difficulty in performing range-resolved absorption measurements, precludes the use of backscatter-absorption techniques for hydrogen detection. However, the significant Raman scattering cross-section for hydrogen can be exploited as a route to detection. This approach mandates the use of time-correlated single photon techniques and so confers significant advantage over absorption techniques: specifically, revealing the nature and position of the target substance. We therefore exploit hydrogen’s Raman-scattering cross-section, together with state-of-the-art UV excitation laser and single-photon detection technology to realize a practical handheld system permitting sub-percent level measurements within a 3m range with ~1second integration times. In this paper, we will outline the need for this detection methodology; the challenges associated with realizing practical systems based upon it; and demonstrate our recently developed hand-held hydrogen sensing device.
Rapid substance screening is a vital yet difficult task. Different materials are best analysed by different techniques, and therefore a single tool may not always be able to identify an unknown substance. This can be addressed by a multimodal approach, simultaneously combining several orthogonal techniques into a single tool. Here we demonstrate a proof-of-concept for a solution based on three complementing techniques - infrared spectroscopy, ultraviolet fluorescence spectroscopy and microscopic imaging – for rapid acquisition of a rich dataset well suited for biochemical samples classification, with dedicated signal processing extracting the descriptive features and identifying the nature of the material.
Here, we report on the development of a diode-pumped single-frequency transition-metal-doped crystalline lasers designed in a miniature Fabry-Perot-type resonator by utilizing a narrow-bandwidth volume Bragg grating output coupler. Namely, single-longitudinal-mode operation was achieved from Ti:sapphire and Alexandrite lasers with a maximum output power of 570 mW and 275 mW near 813 nm and 780 nm, respectively. The mode-hop-free laser frequency tunability of up to 30 GHz was achieved by the cavity temperature and length variation with the Ti:sapphire system. The laser linewidth was measured to be in the 180 kHz range when locked to an external reference cavity transmission peak.
A proof-of-concept of a scanning stand-off dual-comb spectrometer for explosives detection and identification at 3 m distance is demonstrated. Detection of two types of explosives: RDX and PETN on various surfaces was carried out in reflection-absorption and backscattering modes. A scanning area of 18 cm X 18 cm (400 pixels) was covered in ~2.5 sec. Identification method was based on Pearson’s correlation coefficients between the recorded reflection-absorption (backscatter reflection) spectra and transmission (reflection) FTIR of substances, with baseline subtraction using the asymmetric least square smoothing algorithm. Detection limits of the laboratory system of < 2 ug/cm2 were achieved.
The stand-off, range-resolved detection of hydrogen production rates is a valuable mechanism for the long-term condition monitoring of packages containing intermediate-level nuclear materials. To exploit this effect we have developed a long-range optical sensor system which uses Raman detection of hydrogen. Our need for operation over extended ranges (up to 100m) results in very low Raman signals. We therefore use time-correlated (with respect to the outgoing excitation laser pulse) and spectrally-resolved single-photon detection to ascertain molecular species, position and concentration as revealed by photon energy, arrival time and number, respectively.
The dual requirement for high spatial and substance specificity makes stand-off in-theatre biological detection of surface biological contaminants extremely challenging. We will describe a novel combined fluorescence multispectral imaging (MSI) and stand-off Raman approach which are united through their use of deep-UV (sub-250 nm excitation. This allows high-confidence location and classification of candidate contamination sites over the camera field of view, and subsequent resonance-Raman classification of these identified sites. Stand-off Raman is enabled through the use of a novel, extremely high-throughput Spatial Heterodyne spectrometer. The viability of this approach is confirmed through its use on application relevant biological simulant samples.
GaN laser diodes have the potential to be a key enabler for many quantum technologies, including quantum sensing, optical atomic clocks and ion-trap & neutral atom quantum computing, since the AlGaInN material system allows for laser diodes to be fabricated over a wide range of wavelengths from ultra-violet to visible, allowing the development of very high specification laser diode sources that are portable, robust and provide practical solutions that are otherwise unobtainable using more conventional laser sources.
We report our latest results on a range of AlGaInN diode-lasers targeted to meet optical atomic clock and quantum gravity sensor applications. This includes the [5s2S1/2-5p2P1/2] cooling transition in strontium+ ion optical clocks at 422 nm, the [5s21S0-5p1P1] cooling transition in neutral strontium clocks at 461 nm and the [5s2s1/2 – 6p2P3/2] transition in rubidium at 420 nm.
We report on an investigation addressing the challenge of the rapid detection of in-theatre surface chemical, biological and explosive (CBE) contaminants at a stand-off distance (<1m). The techniques we will describe are fundamentally underpinned by highly characteristic, molecule-specific Raman scattering. The implementation of Raman-at-range is problematic due to the extremely weak scattering cross-sections associated with this process, particularly when undertaken at the near-infrared wavelengths usually mandated by the need to suppress fluorescence. Excitation at shorter (near-UV) wavelengths can result in a two-order increase in scatter and this, combined with the extremely high throughput associated with Spatial Heterodyne Spectrometer (SHS) instrumentation, proves a viable route to Raman-at-range. We then implement time resolved spectral measurements on the ~100ps time scale to exploit the difference in generation timescale associated with Raman scatter and fluorescence generation; once so divorced the characteristics (both temporal and spectral) of the previously-troublesome fluorescent light can be embraced as an additional detection tool. We will show how SHS instrumentation, coupled with low-noise detector technology, can offer over four orders of magnitude improvement in spectral signal-to-noise level compared to conventional Czerny-Turner ‘slitted’ spectrometers using lower-cost linear CCD detectors. Finally, we show how a move to the deep-UV “Resonance-Raman” excitation region of sub- 250nm excitation leads both to enormous improvements in generated Raman signal, and spectral separation of the precious Raman from the troublesome fluorescence signal. We show the viability of this approach with biological spore simulant samples provided by DSTL.
We present a spectroscopic technique based upon optical phase-fluctuation spectroscopy for very high levels of sensitivity and specificity with application for detecting the presence of concealed explosives by detection in the vapor phase. The approach enables recent advances in deep-infrared QCL spectroscopic sources to be utilised without the need for cooled detectors and gives multi-pass Herriott-type cell performance from a highly compact form factor. The system has been evaluated in the mid-infrared using a continuous-wave optical parametric oscillator as a spectroscopic excitation source, and Ethane as a sample molecule for detection. With this setup we have demonstrated the specificity of the device by being able to resolve characteristic spectral lines of the molecule of interest against other contaminants in the sample with similar spectral response, and a noise-equivalent sensitivity of 15ppb. Sensitivity is currently limited by ambient mechanical noise and routes to minimize this are considered.
Here we report our recent achievements towards a compact, portable, handheld device for contactless real-time detection and identification of explosives and hazardous substances via reflectance spectroscopy in the 7.5 μm – 10 μm spectral region. The mid-IR spectroscopic measurement principle relies on selective illumination of the target using broadly tunable external cavity quantum cascade lasers (EC-QCLs). A resonant micro-opto-electro-mechanical systems (MOEMS) grating enables fast wavelength tuning in the external cavity, allowing the full spectral scan to be completed in <1 ms. The diffusely backscattered light’s intensity dependence on illumination wavelength provides spectroscopic information to identify threat compounds via our spectral database, containing a large number of materials relevant in a security context. We present a handheld portable, albeit tethered, device capable of real-time identification of hazardous substances at a range of 1 m. We will outline future improvements to increase the system’s usability, such as integrated computing power, automated focusing to that allow use over a range of detection distances and spatial scanning for background subtraction.
We report an optical molecular gas sensor exhibiting high levels of selectivity and sensitivity. The outstanding sensitivity demonstrated by our technology is rooted in a novel combination of photoacoustic spectroscopy (PAS) operated within the cavity of a continuous-wave, intra-cavity Optical Parametric Oscillator (OPO). We exploit the very high circulating field present within the resonant down-converted cavity as the excitation source of the photoacoustic effect, conferring orders-of-magnitude improvement in optical excitation power. Additionally, the wide selectivity of the system arises from the inherent broad tunability and narrow optical linewidth of an OPO. Here we report the use of this technology for the detection of ammonia (NH3) as a simulant target molecule. A 3-D printed miniature PAS cell with microelectromechanical systems based (MEMS) microphone is used for the gas detection. The resonance frequency of the cell was measured at 17.9 kHz with a Q-factor of 9. The down-converted signal wave resonating within its optical cavity was tuned to 6605.6cm-1 (corresponding to a strong local NH3 absorption line) through a combination of phase matching and intra-cavity etalon control. The laser was amplitude modulated at the resonance frequency of the PAS cell, producing an average optical excitation power of ~10W in the signal arm of the OPO, to induce the photoacoustic effect for only 4W of primary diode pump power. In this work we show detection limit at the level of single parts-per-billion (ppb). Additionally, we will discuss how this technology could be readily refined to potentially demonstrate a sensitivity of tens parts-per-quadrillion.
Laser absorption spectroscopy utilizes a tunable infrared source, providing the necessary selectivity, to detect the characteristic fingerprint spectral absorption of an abundant gas. In a simple embodiment such as single-pass absorption, sensitivity is limited as attenuation becomes minuscule for trace level concentrations; a problem exacerbated in the midinfrared region due to significant detector noise. Sensitivity can be improved by increasing interaction between the optical field and molecular ensemble with methods such as a multiple-pass Herriot cell or resonant cavity ring-down spectroscopy but these techniques have a substantial overhead in instrumentation. An alternative approach to this problem is Phase Fluctuation Optical Heterodyne (PFLOH) spectroscopy. Here, interferometric effects are used to detect the minute heating of the sample gas when incident laser light of the appropriate wavelength is absorbed. More specifically, by placing the absorption chamber within one arm of a Mach-Zehnder interferometer, heat-induced changes in the optical path length can be detected with great sensitivity through the resulting fringe modulation. A secondary benefit is that although excitation occurs in the infrared, its effects can be detected using visible lasers and silicon detectors, thereby obviating the need for cooled, infrared detectors. We will present our results used to detect ethane using absorption in the 3.33-3.37 μm region. The Mach-Zehnder interferometer used a Helium Neon laser for the probe laser, and a broadly tunable Optical Parametric Oscillator (OPO) for spectroscopic excitation. We have demonstrated detection levels at parts per billion with further sensitivity possible by implementing several identified improvements.
We report on mid-IR spectroscopic measurements performed with rapidly tunable external cavity quantum cascade lasers (EC-QCLs). Fast wavelength tuning in the external cavity is realized by a microoptoelectromechanical systems (MOEMS) grating oscillating at a resonance frequency of about 1 kHz with a deflection amplitude of up to 10 deg. The entire spectral range of the broadband QCL can therefore be covered in just 500 μs, paving the way for real-time spectroscopy in the mid-IR region. In addition to its use in spectroscopic measurements conducted in backscattering and transmission geometry, the MOEMS-based laser source is characterized regarding pulse intensity noise, wavelength reproducibility, and spectral resolution.
Optical clocks have demonstrated an improvement in temporal accuracy of several orders of magnitude over existing time standards based on caesium. Such systems hold great promise in many industrial sectors including financial time stamping, GPS-free navigation and network synchronisation. Atom interferometry has proven to be a reliable method of precision gravity sensing and finds application in geological studies, including earthquake warning systems and oil exploration. Such systems require a number of sophisticated lasers in a compact and reliable format for use outside of a laboratory environment, suitable for commercialisation and user transportation. Of particular interest, is emerging AlGaInN laser diode technology that has the potential to provide practical solutions for next generation optical clock technology.
The most desirable configuration for detection of toxic chemicals utilises the maximum distance between detector and
hazard. This approach minimises the contamination of equipment or personnel. Where the target chemical is an involatile liquid, indirect detection of the liquid contamination is made difficult by inherently low vapour pressure. In this instance, direct detection of the chemical hazard is the best approach. Recent technology developments have allowed spectroscopic systems to provide multiple options for the stand-off detection of involatile chemical warfare agents (CWAs). Two different stand-off spectroscopic systems, based upon IR absorption and Raman spectroscopic techniques are described here. The Negative Contrast Imager (NCI) is based upon an optical parametric oscillator (OPO) source comprising a Q-switched intracavity MgO:PPLN crystal. This crystal has a fanned grating design and wavelength tuning is achieved by translating the PPLN crystal within the 1064 nm pump beam. This approach enables the production of shortwave and midwave IR radiation (1.5 – 1.8 μm and 2.6 – 3.8 μm, respectively), which is scanned across the scene of interest. Target materials that have an absorption feature commensurate with the wavelength of incoming radiation reduce the intensity of returned signal, resulting in dark pixels in the acquired image. This method enables location and classification of the target material. Stand-off Raman spectroscopy allows target chemicals to be identified at range through comparison of the acquired signature relative to a spectral database. In this work, we used a Raman system based upon a 1047 nm Nd:YLF laser source and a proprietary InGaAsP camera system. Utilisation of a longer excitation wavelength than most conventional stand-off detection systems (e.g. 532 or 785 nm) enables reduction of fluorescence from both the surface and the deposited chemicals, thereby revealing the Raman spectrum. NCI and Raman spectroscopy are able to detect CWAs on surfaces at distances of 2 – 10 metres and have potential to detect over longer ranges. We report the successful identification of at least 60 μl of nitrogen mustard at a distance of a 2 m and 10 m using NCI and Raman spectroscopy.
The ability to remotely locate and classify potential liquid hazards is desirable in a variety of civilian and military
applications. Candidate technologies to satisfy these requirements include the fusion of imaging and optical
spectroscopy. Hence, a novel system based on IR Negative Contrast Imaging (NCI) is presented. The NCI system is
based on an OPO comprising a periodically-poled LiNbO3 (PPLN) crystal of fanned grating design that operates in both
the shortwave and midwave IR spectral regions (1.5 - 1.9 μm and 2.4 - 3.8 μm, respectively). Wavelength tuning is
achieved by translating the PPLN crystal within the 1064 nm pump beam. System size and complexity are minimised by
the use of InGaAs and Zn doped MCT single element detectors and the intracavity OPO design. Images are composed by
raster scanning the monochromatic beam over the scene of interest; the reflection and/or absorption of the incident
radiation by target chemicals and their surrounding environment provide a method for spatial location of the hazard. The
NCI has been employed to detect liquid chemicals on a variety of surfaces; initial results of laboratory investigations are
presented here.
The in situ identification and spatial location of gases, discrete liquid droplets and residues on surfaces is a technically
challenging problem. Active Infrared (IR) hyperspectral imaging is a powerful technique that combines real-time
imaging and optical spectroscopy for "standoff" detection of suspected chemical substances, including chemical warfare
agents, toxic industrial chemicals, explosives and narcotics. An active IR hyperspectral imaging system requires a
coherent, broadly tunable IR light source of high spectral purity, in order to detect a broad range of target substances. In
this paper we outline a compact and power-efficient IR illumination source with high stability, efficiency, tuning range
and spectral purity based upon an optical parametric oscillator (OPO). The fusion of established OPO technology with
novel diode-pumped laser technology and electro-mechanical scanning has enabled a broadly applicable imaging system.
This system is capable of hyperspectral imaging at both Near-IR (1.3 - 1.9 μm) and Mid-IR (2.3 - 4.6 μm) wavelengths
simultaneously with a line width of < 3 cm-1. System size and complexity are minimised by using a dual InGaAs/InSb
single element detector, and images are acquired by raster scanning the coaxial signal and idler beams simultaneously, at
ranges up to 20 m. Reflection, absorption and scatter of incident radiation by chemical targets and their surroundings
provide a method for spatial location, and characteristic spectra obtained from each sample can be used to identify targets
uniquely. To date, we have recognized liquids in sample sizes as small 20 μl-and gases with sensitivity as high as
10ppm.m-at detection standoff distances > 10 m.
The in situ location and identification of discrete liquid droplets on surfaces is a technically challenging problem.
Successful solutions often combine real time imaging and optical spectroscopic techniques. To this end, we present
results of initial experiments using a dual-band mid- and shortwave IR (1.3 - 4.5 μm) imaging device to differentiate
between a selection of mineral and synthetic oils. The illumination source is an optical parametric oscillator comprising a
periodically-poled LiNbO3 crystal internally pumped by a Nd:YVO4 laser, which is pumped by a 3 W diode laser. The
source can produce output powers of ca. 0.3 and 0.1 W in the signal and idler fields, respectively. System size and
complexity are minimised by use of an MCT single element detector and images are acquired by raster scanning of the
target. The reflection, absorption and/or scatter of the incident radiation by the liquids and their surroundings provide a
method for spatial location, whereas the characteristic spectra obtained from each sample can be used to uniquely
identify the deposited substance. Both static and video images can be obtained at a range of < 10 metres by this
apparatus.
We describe a compact mid-infrared active spectroscopic imaging system for the rapid, stand-off detection of gas /
chemical agents. Based upon the back-scatter absorption gas imaging (BAGI) technique, the system utilises a
miniaturised, extremely efficient all solid state intracavity optical parametric oscillator (OPO) as the imaging
illumination source. The OPO produces up to 250mW of tunable radiation in the signal and idler fields over the range 1.3-4.5μm, for a diode pump power of only 3W. Due to the nature of the nonlinear crystal employed within the OPO, the
system can be tuned across its spectral range in ~1 second. We obviate the very high cost and complexity of a cooled
MCT or InSb video array by raster-scanning the collimated illumination beam over the area of interest and
reconstructing the image by sampling the back-scattered radiation with a single element MCT photo-detector at each
pixel point. This approach also improves the ultimate signal to noise ratio. Video-like frame rates of 10 f.p.s. have been
demonstrated via this technique. The range limit of the instrument is currently <10 meters which is limited by the
detector we currently employ. We demonstrate how the system has been used to detect, in real time, leaks of multi-species
hydrocarbon gases.
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