Mid-infrared Absorption Research Articles

Reversible symmetry-breaking of BIC graphene plasmons for tunable mid-infrared absorption

Reversible symmetry-breaking of BIC graphene plasmons for tunable mid-infrared absorption

Intraband Exciton Dynamics of n-Doped Silver Selenide Quantum Dots.

AgxSe (x > 2) colloidal quantum dots (CQDs) have recently emerged as a promising environmentally friendly material contender for mid- and long-wave infrared optoelectronics, leveraging their intraband transition (1Se-1Pe). However, multicarrier interactions in CQDs, particularly Auger recombination, have profound implications on the optoelectronic properties of the materials and their potential in device applications. Understanding the intraband excited-state dynamics in n-doped AgxSe is therefore essential for the assessment and successful implementation of this material platform in devices. We, herein, investigate the carrier dynamics of AgxSe in both solution and thin-film states using a femtosecond mid-infrared transient absorption spectrometer. Our observations reveal that the multicarrier Auger process depends on the degree of doping in AgxSe CQDs and accelerates when the Fermi energy (EF) level approaches the 1Pe state. The calculated intraband Auger coefficients (CA) are measured to be on the order of ∼10-28 cm6 s-1, significantly larger compared to analogous n-doped HgS/Se CQDs.

Optimized waveguides for mid-infrared lab-on-chip systems: A rigorous design approach

Mid-infrared absorption spectroscopy is a well-established technique for non-destructive quantitative molecular analysis. Waveguide-integrated sensors provide a particularly compact solution operating with reduced sample volumes while exhibiting exquisite molecular selectivity, sensitivity, and ultra-low limits of detection. Recent advances in mid-infrared technologies along with the integration of on-chip sources, detectors and microfluidics, have brought mid-infrared lab-on-chip systems closer to reality. A variety of material platforms has been proposed for the implementation of such systems. However, the lack of a consistent waveguide design approach renders a fair comparison between different alternatives – and a deliberate material selection – challenging, limiting the development of optimized on-chip spectroscopic devices. In the present study, a systematic waveguide design approach has been developed, facilitating evanescent field absorption-based sensing, in particular for aqueous analytes. Our strategy enables a rigorous comparison of several state-of-the-art thin-film waveguides using parametric expressions to predict the achievable limits of detection of the sensing system, while indicating optimum waveguide dimensions and absorption pathlengths, pivotal for the development of next-generation mid-infrared lab-on-chip devices.

(Invited) Influence of Y6 Aggregation on Energetics and Charge Generation in High Performance OPV Blends

We investigated the origin of the high ratio of open circuit voltage to charge transfer state energy (eVOC/ECT) of OPV polymer blends consisting of the electron donating polymer PM6 and the non-fullerene electron acceptor Y6. PM6-Y6 and related donor-acceptor OPV blends exhibit remarkable optoelectronic properties and record power conversion efficiencies in part because of their unusually high eVOC/ECT ratios, which is believed to be related to the small energetic offset of the HOMO levels of PM6 and Y6. In this study, we varied the amount of Y6 in PM6 blends as a means to control the aggregation of Y6 molecules. We examined the corresponding influence that Y6 aggregation has on the energetic offsets and the charge generation efficiency of the materials by probing the appearance of polaron absorption signals in the mid-infrared using time-resolved infrared spectroscopy. Furthermore, we examined the optical absorption and emission spectra of the PM6-Y6 blends over the range of compositions to correlate the efficiency of charge generation with the signatures of Y6 aggregation in the optical spectra. We observed an abrupt transition around 30 mass% Y6 content at which polarons were efficiently generated by charge separation from PM6 to Y6. Comparison to composition dependent GIWAXS studies of PM6-Y6 blends revealed the formation of Y6 aggregates around the same 30 mass% threshold. These observations demonstrate that aggregation of Y6 molecules is required for charge separation to occur from PM6 to Y6 as measured through the mid-infrared absorption of polarons in the TRIR spectra. Although charges were efficiently generated in blends with only 30 mass% Y6 content, OPV device studies revealed that 50-60 mass% Y6 was needed to reach optimized short-circuit current and OPV device efficiency because these measurements convolve charge generation with charge transport. These findings clarify the optoelectronic properties of the novel class of Y6 acceptors and emphasize the importance of molecular aggregation for tuning the energetics of high performance systems that minimize energy offsets for maximum OPV power conversion efficiencies.

Nitric Oxide and Temperature Measurement Using Laser Absorption Spectroscopy in Arc-Heater Plenum

A mid-infrared tunable diode laser absorption spectroscopy (TDLAS) sensor to measure rovibrational temperature and nitric oxide (NO) mole fraction in the arc-heater plenum was developed and employed in the Arc Heated Combustion Tunnel-II (ACT-II) facility at the University of Illinois at Urbana-Champaign. From this study, TDLAS-inferred temperatures were found to differ from the conventional method to estimate temperature by over 13%. Chemical equilibrium simulations were performed at the TDLAS-inferred temperatures to understand how chemical relaxation timescales compare with plenum residence times. Results from this study show NO levels higher than equilibrium concentrations, with relaxation timescales that exceed plenum residence times. With insufficient time to reach equilibrium, elevated NO levels are expected to remain in the test gas and persist into the scramjet model.

On the Interpretation of Mid-infrared Absorption Lines of Gas-phase H2O as Observed by JWST/MIRI

Rovibrational absorption lines of H2O in the 5–8 μm wavelength range selectively probe gas against the mid-infrared continuum-emitting background of the inner regions of young stellar objects and active galactic nuclei and deliver important information about these warm, dust-obscured environments. JWST/Mid-Infrared Instrument (MIRI) detects these lines in many lines of sight at a moderate spectral resolving power of R ∼ 3500 (full width at half-maximum of 85 km s−1). Based on our analysis of high-resolution SOFIA/EXES observations, we find that the interpretation of JWST/MIRI absorption spectra can be severely hampered by the blending of individual transitions and the lost information on the intrinsic line width or the partial coverage of the background continuum source. In this paper, we point out problems such as degeneracy that arise in deriving physical properties from an insufficiently resolved spectrum. This can lead to differences in the column density by 2 orders of magnitude. We emphasize the importance of weighting optically thin and weak lines in spectral analyses and provide recipes for breaking down the coupled parameters. We also provide an online tool to generate the H2O absorption line spectra that can be compared to observations.

Thermotunable mid-infrared metamaterial absorption material based on combined hollow cylindrical VO2 structure

We have designed a metamaterial absorption material based on the VO2 phase transition effect. The aim is to realize thermally tunable broadband absorption in the mid-infrared band. The metamaterial absorption material is a three-layer structure. From top to bottom, the combined hollow cylindrical VO2 resonant layer, the SiO2 dielectric layer and the Ti substrate. In this work, we perform numerical simulations using the three-dimensional time-domain finite element difference method. The simulation shows that the absorption material's average absorption intensity is adjustable by temperature between 0.09 and 0.95. At a temperature of 342 K, the absorption material has an absorption bandwidth of 17.3 μm (6.43 μm to 23.73 μm) with an absorption rate above 90%. And the average absorption in this band range is 94.95%. And this band covers the wavelength of the atmospheric transparency window (8 μm∼14 μm), which suggests that our absorption material has great application prospects. In this work, we first analyze the electromagnetic field at the absorption material's resonant wavelength and explain the absorption material's absorption mechanism. Then, we investigated the absorption effect of the absorption material under the VO2 structure with different temperatures. And we explain temperature's effect on the absorption material's absorption effect by analyzing the electric field's change on the absorption material's surface at different temperatures for the same wavelength. The effect of the absorption material structural parameters on the absorption material absorption performance to determine the optimal structural parameters was then investigated. Finally, we investigate the absorption curves of the absorption material under different columnar VO2 layers and demonstrate the innovative and unique nature of the designed absorption material. The absorption material we designed has a simple structure and is easy to configure. And the absorption material has high average absorption rate and a wide absorption bandwidth. We therefore believe that the metamaterial absorption material has great application prospects in optoelectronic detection, infrared imaging and infrared stealth.

Mid-infrared Doppler-free saturation absorption spectroscopy of the Q branch of CH4ν3 = 1 band using a rapid-scanning continuous-wave optical parametric oscillator.

We have developed a mid-infrared Doppler-free saturation absorption spectroscopy apparatus that employs a commercial continuous-wave optical parametric oscillator (CW OPO), complemented by a home-built automation and wavelength scanning system. Here, we report a comprehensive spectral scan of the Q branch transitions of the ν3 = 1 band of methane (CH4) with an average linewidth (FWHM) of 4.5 MHz. The absolute frequency calibration was achieved using previously reported transition frequencies determined using optical frequency combs, while a Fabry-Perot etalon was used for the relative frequency calibration. We report 15 transitions with improved accuracies of 1.13 MHz (3.76 × 10-5 cm-1).

Real-time monitoring of CH4 and N2O emissions from livestock using mid-infrared external cavity quantum cascade laser absorption spectroscopy

The largest share of greenhouse gas (GHG) emissions related to livestock originates from methane (CH4) and nitrous oxide (N2O) which have a far higher influence on global warming, it is therefore necessary to accurately monitor CH4 and N2O emissions to provide theoretical and practical basis for further estimating and regulating GHG emissions from livestock and improving livestock production performance. For the purpose of sensing CH4 and N2O emissions during livestock living process in real time, an optical sensor based on continuous-wave (CW) external cavity quantum cascade laser (EC-QCL) operating at room temperature was developed. CH4 and N2O absorption lines, located around 8 μm, of the ν4 and ν1 fundamental vibrational bands, respectively, were chosen for direct absorption spectroscopy, which allows for sensitive, selective and simultaneous measurement of CH4 and N2O concentrations. Use of a Herriot multi-pass cell with an effective path-length of 100 m, 1σ (SNR = 1) limits of detection of 26.8 ppbv, 20.3 ppbv and 0.01 % for CH4, N2O and H2O vapor were achieved, respectively. Field measurement of CH4 and N2O emissions from horses has been carried out in a stable over two weeks at the Vernaelde farm in Couderkerque Branche city, France. Concentrations of CH4 and N2O up to 10 times and 1.5 times higher than their levels in the local ambient air (∼ 2.12 ppmv and ∼ 427 ppbv) were observed, respectively.

Experimental temperature- and pressure-dependent absorbance cross sections and a pseudo-line-list model for methyl formate near [formula omitted]

We first present quantitative, broadband absorbance cross sections of the C=O stretch fundamental rovibrational band of methyl formate in the 1670–1850 cm−1 range at temperatures of 300, 600, 800, and 1000 K and pressures of 1–2 atm. The title molecular spectra were additionally studied across the pressure range of 1 to 35 atm at room temperature. Elevated temperature measurements were taken in argon bath gas behind the reflected shock wave of a shock tube by a rapid-tuning, broad-scan external cavity quantum cascade laser. The room temperature cross section of methyl formate was collected to validate our method and agreed well with previous room-temperature measurements by Sharpe et al. Then, to extend the utility of the collected data across intermediate temperatures, a pseudo-line-list (PLL) absorbance model was generated through a simultaneous fit of line-by-line intensities and lower-state energies to the measured cross sections. This PLL model was able to replicate the measurements within 3% across most of the spectral range and within 8% around the extremely sharp Q-branch feature present at room temperature. Cross-validation was then performed by re-fitting the PLL excluding the 800 K data set and demonstrated that the PLL approach is effective in interpolating between measured absorption cross sections at discrete temperatures. Finally, the additional room-temperature measurements from 1 to 35 atm were collected in a high-pressure static cell in nitrogen bath gas. These measurements revealed a notable Q-branch cross section pressure dependence while the P- and R-branch wings remained largely pressure independent across this wide pressure range. The collected methyl formate cross sections comprise the latest addition to the Stanford ShockGas-IR database for mid-infrared polyatomic absorption cross sections at elevated temperatures.

Background-free mid-infrared absorption spectroscopy using sub-cycle pulses

We have demonstrated highly sensitive single-shot based background-free mid-infrared (MIR) absorption spectroscopy using sub-cycle MIR pulses generated through filamentation. The MIR pulse transmitted through a sample was upconverted with a fast rising and long tailing gate pulse through four-wave difference frequency generation in a silicon membrane. By recording the upconverted spectrum of the free induction decay alone, we successfully measured the absorption spectrum as a positive signal in the wavenumber range from 500 to 4500 cm−1, which covers both the fingerprint and functional group regions. We obtained an absorption spectrum of ∼50 mM of aqueous glucose, which is not detectable with a standard Fourier transform infrared spectrometer.

Methodology for the quantification of the absorption potential of greenhouse - and pollutant gases by climbing plants used in façade greening; a case study on ivy (Hedera helix)

How much do specific climbing plants contribute to the cleansing or absorption of harmful greenhouse and pollutant gases; often regarded as the main environmental threat in cities due to their adverse effects on human health? One of the main hurdles in the quantification of such ecosystem services is associated with the difficulty to obtain and design systems that provide detailed information on the interaction between various gases and the plant in question. To tackle these questions, two highly precise and accurate instruments, namely a mid-infrared laser absorption spectrometer (TDL) and a cavity-ring-down spectrometer (CRDS) were used to monitor the fate of gases when exposed to façade climbing plants like ivy. In a laboratory setting, a relaxation type of experiment was used consisting of a reaction chamber equipped with plant species and continuously flushed by synthetic air. This setup was used to determine the timescales of decay after short injections of the above-mentioned gases. After these injections, all gases followed simple exponential decay curves. N2O, a non-reactive (inert) tropospheric gas, was used as a reference to which all other gases were compared and thereby quantified. This paper focuses on the detailed description of methods and processes to analyse the gas-absorptive behaviour of plants when exposed to gaseous pollutants. For demonstration purposes, quantified absorption features of nitrogen oxide (NO2) are presented for ivy of the variety Hedera helix “Plattensee”. Results of this method of quantification showed that - as compared to N2O (control), - NO2 had a reduced residence time (time scale) of 100 s, while N2O resulted in a 600 s residence time (indicating no interference with the plant). This is equivalent to a 0.3 cm/s deposition velocity/ absorption rate of NO2 under light conditions.

Behavioral and physiological responses of Girardia tigrina exposed to polyethylene microplastics.

Microplastic particles appear in great abundance and variety in freshwater ecosystems across the globe, spanning lakes and rivers, with increasingly frequent exposure of aquatic organisms. Studies on the mechanisms of any effects of plastic particles are still scarce, particularly in relation to the regenerative capacity of biota, for which there is no established model organism; however, planaria have shown sensitivity for assessing these risks to the aquatic environment. Thus, the present study aimed to investigate the behavioral and regeneration responses of the freshwater planaria Girardia tigrina exposed to polyethylene (PE) microplastics (MPs) incorporated into their food source. The greatest effect was observed on planarian regeneration, which was manifested at 10μg/mg liver. Planaria reproduction and fertility were affected at 50μg/mg liver; however, planaria locomotion was not affected at the concentrations evaluated. Mid-infrared absorption spectroscopy (FT-IR) was used to identify the constituent polymers, and ingestion of the polyethylene microplastic by the planaria was confirmed by infrared spectroscopy. The results highlight the potential adverse effects of exposure to polyethylene microplastic and show that the reproductive behavior and regeneration of a freshwater organism can be indicators of toxicity resulting from environmental pollution.

Fourier-transform infrared spectroscopy with undetected photons from high-gain spontaneous parametric down-conversion

Fourier-transform infrared spectroscopy (FTIR) is an indispensable analytical method that allows label-free identification of substances via fundamental molecular vibrations. However, traditional FTIR spectrometers require mid-infrared (MIR) elements, including low-efficiency MIR photodetectors. SU(1,1) interferometry has previously enabled FTIR with undetected MIR photons via spontaneous parametric down-conversion in the low-parametric-gain regime, where the number of photons per mode is much less than one and sensitive photodetectors are needed. In this work, we develop a high-parametric-gain SU(1,1) interferometer for MIR-range FTIR with undetected photons. Using our method, we demonstrate three major advantages: a high photon number at the interferometer output, a considerably lower photon number at the sample, and improved interference contrast. In addition, we broaden the spectral range of the interferometer by aperiodic poling in the gain medium. Exploiting the broadband SU(1,1) interferometer, we measure and evaluate the MIR absorption spectra of polymers in the 3-μm region.

Modifications of astrophysical ices induced by cosmic rays

Aims. Astrophysical ices on dust grain mantles in the interstellar medium (ISM) and dense circumstellar envelopes (CSEs) are continuously exposed to galactic cosmic rays (GCRs). In a laboratory setting, we studied the physical and chemical modifications of ice layers induced by energetic heavy ions as GCR analogues. The ice layers used have a molecular composition similar to that of icy grain mantles. Methods. Mixtures of H2O:CO:CH3OH molecules (percentages 73:24:3, 68:30:3, and 58:38:3) were condensed on a substrate at 15 K and irradiated with 40 MeV 58Ni11+ ion beams. Irradiation-induced modifications were followed using the mid-infrared absorption spectroscopy technique. Results. We observed the evolution of infrared bands of CO2, HCO, HCOOH, CH4, H2CO,H2O2, and more complex synthesised molecules. From the molecular column densities, cross-sections and sputtering yields were determined and compared to published results of water and carbon monoxide. Analysis of the chemical modifications reveals that the precursors are easily destroyed when they are in a molecular mixture, while others are desorbed. Conclusions. The main radiolitic modifications induced by GCR irradiations are molecular decomposition and sputtering. Extrapolation to astrophysical radiation conditions shows a strong dependence on the intensity of the GCR distributions at low energies, which allows the analysis of the ice evolution at timescales comparable to those of the ISM and CSE.

A novel multi-model estimation of phosphorus in coal and its ash using FTIR spectroscopy

The level of phosphorus must be carefully monitored for proper and effective utilization of coal and coal ash. The phosphorus content needs to be assessed to optimize combustion efficiency and maintenance costs of power plants, ensure quality, and minimize the environmental impact of coal and coal ash. The detection of low levels of phosphorus in coal and coal ash is a significant challenge due to its complex chemical composition and low concentration levels. Effective monitoring requires accurate and sensitive equipment for the detection of phosphorus in coal and coal ash. X-ray fluorescence (XRF) is a commonly used analytical technique for the determination of phosphorus content in coal and coal ash samples but proves challenging due to their comparatively weak fluorescence intensity. Fourier Transform Infrared spectroscopy (FTIR) emerges as a promising alternative that is simple, rapid, and cost-effective. However, research in this area has been limited. Until now, only a limited number of research studies have outlined the estimation of major elements in coal, predominantly relying on FTIR spectroscopy. In this article, we explore the potential of FTIR spectroscopy combined with machine learning models (piecewise linear regression—PLR, partial least square regression—PLSR, random forest—RF, and support vector regression—SVR) for quantifying the phosphorus content in coal and coal ash. For model development, the methodology employs the mid-infrared absorption peak intensity levels of phosphorus-specific functional groups and anionic groups of phosphate minerals at various working concentration ranges of coal and coal ash. This paper proposes a multi-model estimation (using PLR, PLSR, and RF) approach based on FTIR spectral data to detect and rapidly estimate low levels of phosphorus in coal and its ash (R2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^2$$\\end{document} of 0.836, RMSE of 0.735 ppm, RMSE (%) of 34.801, MBE of − 0.077 ppm, MBE (%) of 5.499, and MAE of 0.528 ppm in coal samples and R2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^2$$\\end{document} of 0.803, RMSE of 0.676 ppm, RMSE (%) of 38.050, MBE of − 0.118 ppm, MBE (%) of 4.501, and MAE of 0.474 ppm in coal ash samples). Our findings suggest that FTIR combined with the multi-model approach combining PLR, PLSR, and RF regression models is a reliable tool for rapid and near-real-time measurement of phosphorus in coal and coal ash and can be suitably modified to model phosphorus content in other natural samples such as soil, shale, etc.

Oxygen intercalation in 2D layered PtSe2 for tunable bandgap infrared photoelectric materials

Infrared materials play a pivotal role in driving societal advancement across various domains. Bilayer PtSe2 with bandgap of 0.2 eV is an ideal material for infrared applications. However, the inherent limitation of the untunable bandgap in bilayer PtSe2 restricts its utility, particularly in the context of state-of-the-art two-color infrared detectors. Therefore, by introduction of quantum confinement effect, PtSe2[O]y superlattice was constructed via intercalating O atoms into interlayer space of PtSe2, and kinetic stability was confirmed by ab initio molecular dynamics. Considering van der Waals interactions of interlayer, PtSe2[O]y superlattice can be exfoliated into few-layer PtSe2[O]y. By employing density functional theory, optical and electrical properties of PtSe2[O]y superlattice and few-layer PtSe2[O]y were calculated. Tunable bandgaps were achieved by manipulating the O composition y, ranging from 0 eV to 0.21 eV (covering wavelengths > 5.9 μm) for the PtSe2[O]y superlattice and from 1.12 eV to 0.15 eV (covering wavelengths from 1.1 μm to 8.3 μm) for monolayer PtSe2[O]y. Considering the continuously tunable bandgap covering from near-infrared to mid-infrared absorption spectrum, PtSe2[O]y could be a promising candidate with a wide-application in the field of infrared photoelectric materials.

Mid-infrared gas absorption spectroscopy using a silicon germanium waveguide based chirped supercontinuum

We report the simulations of coherent supercontinuum generation from 2.63 to 8.04 μm in a silicon germanium photonic waveguide. The influence of input quantum noise pulses on coherence of the generated spectra was investigated. A high value of first order degree of coherence (i.e. 0.98) on supercontinuum spectra was predicted numerically. Our mid-infrared simulated coherent chirped supercontinuum source was then used as the input light source in absorption spectroscopy of carbon dioxide and methane gases. The simulated absorbance spectra for these greenhouse gases have high molecular contrast, thanks to the intense, chirped supercontinuum used.

Tunable mid-infrared broadband absorption in the atmospheric window of wavelength in 3–5 μm using VO2 phase transition in a three-layer metamaterial

Tunable metasurfaces have garnered considerable attention for their remarkable ability to manipulate electromagnetic waves within carefully designed nanostructures. Achieving resonant absorption requires precise control over the geometry and size of micro-nano structures. This study introduces a highly versatile metasurface platform that leverages the unique phase transition properties of vanadium dioxide (VO2) for controlled absorption. Our design features a planar layered structure with a 0.1 μm thick VO2 top layer, enabling tunability in both thermal and intensity aspects. We demonstrate significant tuning of broadband light absorption across the mid-infrared spectrum, with absorption rates ranging from approximately 30 %–98 % in the critical atmospheric infrared window of 3–5 μm. This range is crucial for infrared sensing, imaging, and communication applications. Notably, the absorption rate increases as the temperature decreases, indicating a positive shift in dynamics, for which we provide a physical explanation. Numerical simulations highlight the ability to control absorption bandwidth by adjusting the thickness and temperature of VO2 layer. These adaptable broadband absorbers hold significant promise for a diverse range of applications, including absorption filters, thermal emitters, thermos photovoltaics, and thermal imaging. Furthermore, the introduced thermally switchable, spectrally selective metamaterials can find applications in dynamic infrared camouflage and active radiative thermal management, opening new horizons in the realm of metamaterial-based technologies.

A systematic mid-infrared spectroscopic study of thermally processed H2S ices

The positive identification of the molecular components of interstellar icy grain mantles is critically reliant upon the availability of laboratory-generated mid-infrared absorption spectra which can be compared against data acquired by ground- and space-borne telescopes. However, one molecule which remains thus far undetected in interstellar ices is H2S, despite its important roles in astrochemical and geophysical processes. Such a lack of a detection is surprising, particularly in light of its relative abundance in cometary ices which are believed to be the most pristine remnants of pre-solar interstellar ices available for study. In this paper, we present the results of an extensive and quantitative mid-infrared spectroscopic characterisation of H2S ices deposited at 20, 40, and 70 K and thermally processed to sublimation in an ultrahigh-vacuum system. We anticipate our results to be useful in confirming the detection of interstellar H2S ice using high-resolution and high-sensitivity instruments such as the James Webb Space Telescope, as well as in the identification of solid H2S in icy environments in the outer Solar System, such as comets and moons.