Absorption Path Length Research Articles

Fabrication of Low-Cost Miniaturized Gas Cells via SLA 3D-Printing for UV-Based Gas Sensors.

The use of 3D-printing technology for producing optical devices (i.e., mirrors and waveguides) remains challenging, especially in the UV spectral regime. Gas sensors based on absorbance measurements in the UV region are suitable for determining numerous volatile species in a variety of samples and analytical scenarios. The performance of absorbance-based gas sensors is dependent on the ability of the gas cell to propagate radiation across the absorption path length and facilitate interaction between photons and analytes. In this technical note, we present a 3D-printed substrate-integrated hollow waveguide (iHWG) to be used as a miniaturized and ultralightweight gas cell used in UV gas-sensing schemes. The substrates were fabricated via UV stereolithography and polished, and the light-guiding channel was coated with aluminum for UV reflectivity. This procedure resulted in a surface roughness of 11.2 nm for the reflective coating, yielding a radiation attenuation of 2.25 W/cm2. The 3D-printed iHWG was coupled to a UV light source and a portable USB-connected spectrometer. The sensing device was applied for the quantification of isoprene and acetone, serving as a proof-of-concept study. Detection limits of 0.22 and 0.03% in air were obtained for acetone and isoprene, respectively, with a nearly instantaneous sensor response. The development of portable, low-cost, and ultralightweight UV optical sensors enables their use in a wide range of scenarios ranging from environmental monitoring to clinical/medical applications.

Coherent field sensing of nitrogen dioxide.

We introduce a portable dual-comb spectrometer operating in the visible spectral region for atmospheric monitoring of NO2, a pollution gas of major importance. Dual-comb spectroscopy, combining key advantages of fast, broadband and accurate measurements, has been established in the infrared as a method for the investigation of atmospheric gases with kilometer-scale absorption path lengths. With the presented dual-comb spectrometer centered at 517 nm, we make use of the strong absorption cross section of NO2 in this spectral region. In combination with a multi-pass approach through the atmosphere, we achieve an interaction path length of almost a kilometer while achieving both advanced spatial resolution (90 m) and a detection sensitivity of 5 ppb. The demonstrated temporal resolution of one minute outperforms the standard chemiluminescence-based NO2 detector that is commercially available and used in this experiment, by a factor of three.

Towards a Miniaturized Photoacoustic Sensor for Transcutaneous CO2 Monitoring.

A photoacoustic sensor system (PAS) intended for carbon dioxide (CO2) blood gas detection is presented. The development focuses on a photoacoustic (PA) sensor based on the so-called two-chamber principle, i.e., comprising a measuring cell and a detection chamber. The aim is the reliable continuous monitoring of transcutaneous CO2 values, which is very important, for example, in intensive care unit patient monitoring. An infrared light-emitting diode (LED) with an emission peak wavelength at 4.3 µm was used as a light source. A micro-electro-mechanical system (MEMS) microphone and the target gas CO2 are inside a hermetically sealed detection chamber for selective target gas detection. Based on conducted simulations and measurement results in a laboratory setup, a miniaturized PA CO2 sensor with an absorption path length of 2.0 mm and a diameter of 3.0 mm was developed for the investigation of cross-sensitivities, detection limit, and signal stability and was compared to a commercial infrared CO2 sensor with a similar measurement range. The achieved detection limit of the presented PA CO2 sensor during laboratory tests is 1 vol. % CO2. Compared to the commercial sensor, our PA sensor showed less influences of humidity and oxygen on the detected signal and a faster response and recovery time. Finally, the developed sensor system was fixed to the skin of a test person, and an arterialization time of 181 min could be determined.

Quantum cascade laser absorption sensor for in-situ, real-time and sensitive measurement of high-temperature SO2 and SO3

Quantum cascade laser absorption sensor for in-situ, real-time and sensitive measurement of high-temperature SO2 and SO3

Triple-range adjustable plane-concave multipass gas cell for high-precision trace gas detection based on TDLAS

Triple-range adjustable plane-concave multipass gas cell for high-precision trace gas detection based on TDLAS

High sensitivity miniaturized multi-pass absorption enhanced differential Helmholtz photoacoustic gas sensor

High sensitivity miniaturized multi-pass absorption enhanced differential Helmholtz photoacoustic gas sensor

Quantitative analysis method of laser-induced breakdown spectroscopy based on temperature iterative correction of self-absorption effect

Laser-induced breakdown spectroscopy (LIBS) is an ideal real-time on-line method of detecting minor elements in alloys. However, in the case of laser-produced high-density plasma, the self-absorption is usually an undesired effect because it not only reduces the true line intensity, leading the line intensity to become nonlinear with the increase of emitting species content, but also affects the characterization parameters of the plasma, and finally affects the accuracy of quantitative analysis. Since the plasma electron temperature <inline-formula><tex-math id="Z-20240228161235">\begin{document}$(T)$\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231541_Z-20240228161235.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231541_Z-20240228161235.png"/></alternatives></inline-formula>, radiation particle number density and absorption path length (<i>Nl</i> ) determine the degree of self-absorption and affect the corrected spectral line intensity, a new self-absorption correction method is proposed based on temperature iteration. The initial <i>T</i> is obtained by using this method through spectral line intensity, and the self-absorption coefficient SA is calculated based on the initial <i>Nl</i> parameter to correct the spectral line intensity. Then a new <i>T</i> is obtained from the new spectral line intensity and the new SA is calculated to further correct the spectral line intensity. Through continuous calculation and correction of these two parameters, self-absorption correction is finally achieved. The experimental results of alloy steel samples show that the linearity of Boltzmann plot is increased from 0.867 without self-absorption correction to 0.974 with self-absorption correction, and the linear correlation coefficient <i>R</i><sup>2</sup> of the single variable calibration curve for Mn element increases from 0.971 to 0.997. The relative error of elemental content measurement is improved from 4.32% without self-absorption correction to 1.23% with self-absorption correction. Compared with the commonly applied self-absorption correction methods, this method has obvious advantages of simpler programming, higher computation efficiency, and its independence of the availability or accuracy of Stark broadening coefficients. Moreover, this method can directly obtain the radiation particle number density and absorption path length, which is beneficial to the diagnosis and quantitative analysis of plasma.

Double-channel sensors for high precision measurement of methane based on a dual-path Herriott cell.

A double-channel methane (CH4) sensor was developed using a dual-pass multipass cell (DP-MPC) and a novel method that combines averaging dual-channel concentration signals with optimized detector gain configuration. This DP-MPC features two input/output coupling holes, resulting in absorption path lengths of approximately 95.8 m and 35.8 m, respectively. By optimizing the photodetector gain configuration and averaging the dual-channel concentration signals, the detection performance of the sensor was further enhanced. Allan deviation analysis indicated that after optimizing the detector gain, the measurement precision after dual-channel averaging reaches 21 ppb with an integration time of 1 s at a concentration of 2 ppm CH4, which is approximately 1.4 times higher than the measurement precision of the long-path channel (31 ppb) and short-path channel (30 ppb). The time required to achieve a measurement precision of 21 ppb is 2.4 s for the long-path channel and 2.1 s for the short-path channel. The response speed of the dual-channel averaging is approximately 2 times that of any single channel. Meanwhile, the sensor demonstrated its stability and reliability through continuous outdoor atmospheric CH4 measurements.

A new instrumentation for simultaneous terahertz and mid-infrared spectroscopy in corrosive gaseous mixtures.

The correct interpretation of infrared (IR) observations of planetary atmospheres requires an accurate knowledge of temperature and partial and global pressures. Precise laboratory measurements of absorption intensities and line profiles, in the 200-350K temperature range, are, therefore, critical. However, for gases only existing in complex chemical equilibria, such as nitrous or hypobromous acids, it is not possible to rely on absolute pressure measurements to measure absolute integrated optical absorption cross sections or IR line intensities. To overcome this difficulty, a novel dual-beam terahertz (THz)/mid-IR experimental setup has been developed, relying on the simultaneous use of two instruments. The setup involves a newly constructed temperature-controlled (200-350K) cross-shaped absorption cell made of inert materials. The cell is traversed by the mid-IR beam from a high-resolution Fourier transform spectrometer using along a White-cell optical configuration providing absorption path lengths from 2.8 to 42m and by a THz radiation beam (82.5GHz to 1.1THz), probing simultaneously the same gaseous sample. The THz channel records pure rotational lines of molecules for which the dipole moment was previously measured with high precision using Stark spectroscopy. This allows for a determination of the partial pressure in the gaseous mixture and enables absolute line intensities to be retrieved for the mid-IR range. This new instrument opens a new possibility for the retrieval of spectroscopic parameters for unstable molecules of atmospheric interest. The design and performance of the equipment are presented and illustrated by an example of simultaneous THz and mid-IR measurement on nitrous acid (HONO) equilibrium.

Water vapor absorption spectroscopy and validation tests of databases in the far-infrared (50–720 cm−1). Part 2: H217O and HD17O

Water vapor absorption spectroscopy and validation tests of databases in the far-infrared (50–720 cm−1). Part 2: H217O and HD17O

A white cell based broadband transient UV-vis absorption spectroscopy with pulsed laser photolysis reactors for chemical kinetics under variable temperatures and pressures

UV-vis spectroscopy is widely used for kinetic studies in physical chemistry, as species’ absolute cross-sections are usually less sensitive to experimental conditions (i.e., temperature and pressure). Here, we present the design and characterization of a multipass UV-vis absorption spectroscopy white cell coupled to a pulsed-laser photolysis flow reactor. The glass reactor was designed to facilitate studies of gas phase chemical reactions over a range of conditions (239–293 K and 10–550 Torr). Purged windows mitigate contamination from chemical precursors and photolysis products. We report the measured impact of this purging on temperature uniformity and the absorption length and present some supporting flow calculations. The combined optical setup is unique and enables the photolysis laser to be coaligned with a well-defined absorption pathlength probe beam. This alignment leverages the use of one long-pass filter to increase the spectrum flatness and increase the light intensity vs other systems that use two dichroic mirrors. The probe beam is analyzed with a dual exit spectrograph, customized to split the light between an intensified CCD and photomultiplier tube, enabling simultaneous spectrum and single wavelength detection. This multipass system yields a pathlength of ∼450 cm and minimum observable concentrations of ∼3.7 × 1011 molecule cm−3 (assuming cross-sections ∼1.2 × 10−17 cm2). The temperature profile across the reaction region is ±2 K, defined by the worst-case temperature of 239 K, validated by measurements of the N2O4 equilibrium constant. Finally, the system is implemented to study the simplest Criegee intermediate, demonstrating the instrument performance and advantages of simultaneous spectrum and temporal profile measurements.

Highly sensitive portable laser absorption spectroscopy formaldehyde sensor using compact spherical mirror multi-pass cell

Highly sensitive portable laser absorption spectroscopy formaldehyde sensor using compact spherical mirror multi-pass cell

Detections of 21 cm absorption with a blind FAST survey atz≤ 0.09

We present the early science results from a blind search of the extragalactic H I21 cm absorption lines atz ≤ 0.09 with the drift-scan observation of the Five-hundred-meter Aperture Spherical radio Telescope (FAST). We carried out the search using the data collected over 643.8 h by the ongoing Commensal Radio Astronomy FasT Survey (CRAFTS), which spans a sky area of 3155 deg2(∼81% of CRAFTS sky coverage up to January 2022) and covers 44827 radio sources with a flux density greater than 12 mJy. Due to the radio frequency interference (RFI), only the relatively clean data in the frequency range of 1.3–1.45 GHz are used in the present work. Under the assumption ofTs/cf = 100 K, the total completeness-corrected comoving absorption path length spanned by our data and sensitive to Damped LymanαAbsorbers (DLAs;NH I⩾ 2 × 1020cm−2) is ΔXinv = 8.33 × 103(Δzinv = 7.81 × 103) for intervening absorption. For associated absorption, the corresponding value is ΔXasc = 1.28 × 101(Δzasc = 1.19 × 101). At each time point of the drift scan, a matched-filtering approach is used to search H Iabsorbers. Combining the information of observation mode and the distribution of the beams that detect the same candidates, spurious absorbers are successfully excluded. Three known H Iabsorbers (UGC 00613, 3C 293, and 4C +27.14) and two new H Iabsorbers (towards the direction of NVSS J231240–052547 and NVSS J053118+315412) are detected blindly. We fitted the H Iprofiles with multi-component Gaussian functions and calculated the redshift (0.063, 0.066), width, flux density, optical depth, and H Icolumn densities for each absorption. Our results demonstrate the power of FAST in blindly searching H Iabsorbers. For absorption towards NVSS J231240–052547, the optical counterparts are faint and currently lack existing spectra. The most likely interpretation is that a radio-loud active galactic nucleus (AGN) is faint in the optical as the background source, with a faint optical absorber in between. NVSS J053118+315412 exhibits an associated absorption with a complex profile, which may suggest unsettled gas structures or gas accretion onto the supermassive black hole (SMBH). The expanding collection of blind radio detections in the ongoing CRAFTS survey offers a valuable opportunity to study AGNs, associated interstellar medium (ISM) interaction, and intervening absorbers optically without overwhelming quasi-stellar object (QSO) background light.

Inverted metamorphic photovoltaics for space applications utilizing a distributed Bragg reflector compatible with epitaxial lift-off

MicroLink Devices manufactures triple-junction inverted metamorphic solar cells on GaAs wafers with a selectively etched release layer in an epitaxial lift-off (ELO) process to create ultra-thin foils of semiconductor with a metal backing. To improve radiation tolerance, each absorber layer is thinned and doping levels are reduced. The bottom subcell employs a mirror structure to maintain current, while the middle subcell requires a distributed Bragg reflector (DBR) to increase the absorption path length and maintain current. MicroLink utilizes a non-conventional In x (Al y Ga1−y )1−x P/GaAs DBR that is compatible with ELO. The DBR has a bandwidth of ∼110 nm and a peak reflectance in air near 95%. Average cell efficiencies of 28% (1-Sun AM0) are achieved with a power retention of 84% after 1E15 cm−2 electron dosing (1 MeV energy). Large-area cells and coupons underwent internal thermal stress testing and showed no degradation. Clear pathways to achieve >29% efficient cells with >85% power retention are discussed.

Multi-pass Differential Photoacoustic Sensor for Real-Time Measurement of SF6Decomposition Component H2S at the ppb Level

We designed and implemented a photoacoustic (PA) sensor for H2S detection in SF6 background gas based on a multi-pass differential photoacoustic cell (MDPC) and a near-infrared distributed feedback (DFB) laser. In the MDPC apparatus, two resonators with identical geometric parameters were vertically and symmetrically embedded. The differential processing algorithm of two phase-reversed signals realized the effective enhancement of the PA signal and suppressed the flow noise in the dynamic sampling process. In addition, the λ/4 buffer chamber in the MDPC was utilized as a muffler to further reduce the flow noise and realize the dynamic detection of H2S. The collimated excitation light was reflected 30 times in a multi-pass structure constituted of two gold-plated concave mirrors, and an absorption path length of 4.92 m was achieved. Due to the high gas density of SF6, the relationship between the signal-to-noise ratio (SNR) and the gas flow was different between SF6 and N2 background gases. The maximum flow rate of the characteristic gas components detected in the SF6 background is 150 standard cubic centimeters per minute (SCCM), which is lower than 350 SCCM in N2. The linearity property was analyzed, and the results show that the sensitivity of the sensor to H2S in the SF6 background was 27.3 μV/ppm. With the structure, parameters, temperature, gas flow, and natural frequency of the MDPC been optimized, a minimum detection limit (MDL) of 11 ppb was reached with an averaging time of 1000 s, which furnished an effective preventive implement for the safe operation of gas insulation equipment.

Broadband cavity enhanced UV-VIS absorption spectroscopy for picolitre liquid samples†

Absorption spectroscopy is a widely used analytical technique due to its label-free nature, however its application to small liquid samples is hampered by the associated short absorption pathlengths, which limit sensitivity. A novel concept for the development of an ultrasensitive broadband absorption spectrometer optimised for thin liquid films is presented here. To enhance sensitivity of the absorbance measurements an optical cavity is implemented on a fibre-based absorption spectrometer (CEASpec). Light is circulated multiple times through the sample of interest to increase sensitivity. The bandwidth of the instrument is chosen by the choice of the dielectric mirrors forming the optical cavity spectra and, in this implementation, has been set to be 200 nm wide (250–450 nm). The sensing volume of the spectroscope is prescribed by the choice of optical fibres employed to deliver light to the sample, and in this implementation fibres of 400 μm in diameter were employed, giving a sensing volume of 630 picolitres for a thin film of 5 μm in thickness. Amphotericin B, a broad light absorber in the 280–450 nm region of the spectrum, was used here to prove the capabilities of the proposed cavity enhanced absorption spectroscope. Cavity enhancement factors, the equivalent pathlength increase over classical absorption spectroscopy, in the range of 200× have been achieved across a broad wavelength range.

Monolithically integrated mid-infrared sensor with a millimeter-scale sensing range.

On-chip sensors based on quantum cascade laser technology are attracting broad attention because of their extreme compactness and abundant absorption fingerprints in the mid-infrared wavelength range. Recent continuous wave operation microcavity quantum cascade lasers are well suited for high-density optoelectronic integration because their volumes are small and thresholds are low. In this experimental work, we demonstrate a monolithically integrated sensor comprising a notched elliptical resonator as transmitter, a quantum cascade detector as receiver, and a surface plasmon structure as light-sensing waveguide. The sensor structure is designed to exploit the highly unidirectional lasing properties of the notched elliptical resonator to increase the optical absorption path length. Combined with the evanescent nature of the dielectric loaded surface plasmon polariton waveguides, the structure also ensures a strong light-matter interactions. The sensing transmission distance obtained is approximately 1.16 mm, which is about one order of magnitude improvement over the traditional Fabry-Perot waveguide. This sensor opens new opportunities for long-range and high-sensitivity on-chip gas sensing and spectroscopy.

Intracavity absorption spectroscopy of HCl isotopes, H2O, CH4, C2H4, and C2H6 in the 3.1-3.4 µm spectral range using a Cr:CdSe laser.

We demonstrate the first application of a Cr:CdSe laser for highly-sensitive multicomponent intracavity absorption spectroscopy around λ = 3.1-3.4 µm. A detection scheme based on an integrated recording of multiple (∼70) individual Cr:CdSe laser pulses after a single pump-pulse excitation is reported. The sensitivity of our system corresponds to an effective absorption path length of Leff ≈ 850 m. Exemplary measurements of atmospheric H2O and CH4, and additionally introduced gas-phase HCl, C2H4, or C2H6 are presented. The achieved noise-equivalent detection limits are in the ppb range. Possibilities for further sensitivity enhancement by up to a factor of 104 are discussed.

Water vapor absorption spectroscopy and validation tests of databases in the far-infrared (50–720 cm-1). Part 1: Natural water

Water vapor absorption spectroscopy and validation tests of databases in the far-infrared (50–720 cm-1). Part 1: Natural water

Terahertz-Wave Absorption Gas Sensing for Dimethyl Sulfoxide

Gas sensing for dimethyl sulfoxide (DMSO) based on rotational absorption spectroscopy is demonstrated in the 220–330 GHz frequency range using a robust electronic THz-wave spectrometer. DMSO is a flammable liquid commonly used as a solvent in the food and pharmaceutical industries, materials synthesis, and manufacturing. DMSO is a hazard to human health and the work environment; hence, remote gas sensing for DMSO environmental and process monitoring is desired. Absorption measurements were carried out for pure DMSO at 297 K and 0.4 Torr (53 Pa). DMSO was shown to have a unique rotational fingerprint with a series of repeating absorption bands. The frequencies of transitions observed in the present study were found to be in good agreement with spectral simulations carried out based on rotational parameters derived in prior work. Newly, intensities of the rotational absorption lines were experimentally observed and reported for DMSO in this study. Measured intensities for major absorption lines were found in very good agreement with relative line intensities estimated by quantum mechanical calculations. The sensor developed here exhibited a detection limit of 1.3 × 1015–2.6 × 1015 DMSO molecules/cm3 per meter of absorption path length, with the potential for greater sensitivity with signal-to-noise improvements. The study illustrates the potential of all electronic THz-wave systems for miniaturized remote gas sensors.