Terahertz Absorption Spectroscopy Research Articles

Universality in the Structure and Dynamics of Water under Lipidic Mesophase Soft Nanoconfinement.

Water under soft nanoconfinement features physical and chemical properties fundamentally different from bulk water; yet, the multitude and specificity of confining systems and geometries mask any of its potentially universal traits. Here, we advance in this quest by resorting to lipidic mesophases as an ideal nanoconfinement system, allowing inspecting the behavior of water under systematic changes in the topological and geometrical properties of the confining medium, without altering the chemical nature of the interfaces. By combining Terahertz absorption spectroscopy experiments and molecular dynamics simulations, we unveil the presence of universal laws governing the physics of nanoconfined water, recapitulating the data collected at varying levels of hydration and nanoconfinement topologies. This geometry-independent universality is evidenced by the existence of master curves characterizing both the structure and dynamics of simulated water as a function of the distance from the lipid-water interface. Based on our theoretical findings, we predict a parameter-free law describing the amount of interfacial water against the structural dimension of the system (i.e., the lattice parameter), which captures both the experimental and numerical results within the same curve, without any fitting. Our results offer insight into the fundamental physics of water under soft nanoconfinement and provide a practical tool for accurately estimating the amount of nonbulk water based on structural experimental data.

Performance of a High-Speed Pyroelectric Receiver as Cryogen-Free Detector for Terahertz Absorption Spectroscopy Measurements

The application of terahertz (THz) radiation in scientific research as well as in applied and commercial technology has expanded rapidly in recent years. One example is the progress in high-resolution THz spectroscopy based on quantum cascade lasers, which has enabled new observations in astronomy, atmospheric research, and plasma diagnostics. However, the lack of easy-to-use and miniaturised detectors has hampered the development of compact THz spectroscopy systems out of the laboratory environment. In this paper, we introduce a new high-speed pyroelectric receiver as a cryogen-free detector for THz absorption spectroscopy. Its performance is characterised by absorption spectroscopy measurements on a reference gas cell (RGC) with ammonia using a tunable THz quantum cascade laser at approximately 4.75 THz as the light source. It is shown that the receiver can record spectra up to 281 Hz without any artefacts to the observed spectral absorption profile, and the results reproduce the known pressure of ammonia in the RGC. This demonstrates that the pyroelectric receiver can be reliably used as an alternative to helium-cooled bolometers for absorption spectroscopy measurements in the THz range, with its main advantages being the high bandwidth, compactness, relatively low cost, and room-temperature operation. Its simplicity and high sensitivity make this receiver a key component for compact THz spectroscopy systems.

Quantitative, multi-species gas sensing using broadband terahertz time-domain spectroscopy

The broadband terahertz wave, with its correspondence to the fingerprint spectra of gas molecules and relatively high transmittance through smoke, aerosol, and combustion environments, bears great potential for gas detection and combustion diagnostics. While access to rotational spectral fingerprints in the terahertz region provides opportunities for species-selective diagnostics with minimized background and cross interference, few studies have been devoted to direct, quantitative, and simultaneous analysis of multiple components exploiting the terahertz region. In this work, we achieve quantitative measurements of CO, NH3 and H2O gas concentrations at standard temperatures and pressures over a bandwidth of 1 THz, using direct absorption spectrum from femtosecond-laser-based terahertz time-domain spectroscopy. Spectral fitting of the fully resolved rotational lines yields good precision and accuracy with validation against calibrated mixtures. The estimated detection limits of the multi-species sensing system are 250 ppm m, 7 ppm m and 4 ppm m for CO, NH3 and H2O, respectively. The demonstration of quantitative, multi-species gas sensing indicates the feasibility and practical value of using broadband terahertz absorption spectroscopy for real-time, quantitative analysis and speciation of multicomponent gases in complicated practical environments such as combustion and multi-phase flows.

Validation of THz absorption spectroscopy by a comparison with ps-TALIF measurements of atomic oxygen densities

Terahertz (THz) absorption spectroscopy has recently been developed as a diagnostic technique for measuring absolute ground-state atomic oxygen densities in plasmas. To demonstrate the validity of this approach, we present in this Letter a benchmark against a more established method. Atomic oxygen densities were measured with THz absorption spectroscopy and compared to those obtained from picosecond (ps) two-photon absorption laser induced fluorescence (TALIF) measurements on the same capacitively coupled radio frequency oxygen discharge. Similar changes in the atomic oxygen density were observed with both diagnostics when varying the applied power (20–100 W) and the gas pressure (0.7–1.3 mbar). Quantitatively, the results are in good agreement as well, especially when considering the total margin of error of the two diagnostics. For example, for a gas pressure of 1.3 mbar and an applied power of 30 W, atomic oxygen densities measured with THz absorption spectroscopy and TALIF were (7.0 ± 1.7)×1014 cm−3 and (5.3 ± 3.2)×1014 cm−3, respectively. This shows that THz absorption spectroscopy is an accurate technique that can be reliably used for real-world applications to determine atomic oxygen densities in plasmas.

Terahertz Absorption Spectroscopy in Bicrystal Josephson Junctions Formed from Mutually Tilted c-Axes YBa2Cu3O7−x Films

Spectral analysis of terahertz (THz) and sub-THz emission from quantum cascade lasers has been recently demonstrated using conventional YBa2Cu3O7−x bicrystal Josephson junctions made from c-axes thin films. Josephson frequencies of alternative bicrystal junctions made from YBa2Cu3O7−x films with mutually tilted c-axes extend further into the THz range. However, these THz oscillations can weaken due to new absorption channels in the junction environment. Here, using Josephson admittance spectroscopy, THz losses in YBa2Cu3O7−x bicrystal junctions with mutually tilted c-axes are studied. Absorption maximizes at a reproducible set of THz frequencies close to those of collective modes in bulk YBa2Cu3O7−x recovered by Fourier spectroscopy. Annealing junctions in atomic oxygen reduces the losses at frequencies of 2.7 and 3.6 THz, while the losses increase at frequencies of 2.3 and 4.6 THz. Thus, as a THz spectrum analyzer, YBa2Cu3O7−x bicrystal junctions require post-fabrication correction of the oxygen content. In addition, the fine structure of the absorption spectrum appears at frequencies near 4.6 THz. Significant absorption near 2.3 THz may be due to effects associated with the second Josephson harmonic or second-order nonlinearity of the susceptibility in YBa2Cu3O7−x. This work paves the way towards probing collective modes in high-Tc materials in situ using the Josephson oscillations.

Amino-acid classification based on terahertz absorption spectroscopy with Gaussian process and maximum likelihood

The rotational and vibrational energy levels of numerous biomolecules lie in the terahertz (THz) band, which makes THz spectroscopy a viable option for biosensing and monitoring the chemical processes such as the formation of hydrogen bonds. However, classifying the fingerprint THz spectra of various molecules has constantly challenged real-world applications. Here, a machine learning model based on a discrete Gaussian process and maximum likelihood estimation (DGPML) for classifying an ensemble of 20 amino acids is proposed. The model demonstrates a prediction accuracy of 99.5% in the presence of scattering noise and various experimental conditions and is able to distinguish spectra without significant absorption peaks. Compared to the conventional Gaussian process classifier, which generally exhibits less time and space complexity than neural-network models, DGPML requires 99% less training time and achieves 1530 times faster processing speed with around 0.29 million parameters. Regarding the DGPML, a database that encloses the THz absorption spectrum and its covariance matrix, which describes the deviation of the absorption spectrum under various experimental conditions, is designed. Due to the compact size and high efficiency of the proposed model, it has the potential to power the THz chemical sensor in the future.

Highly boosted trace-amount terahertz vibrational absorption spectroscopy based on defect one-dimensional photonic crystal.

Although terahertz (THz) spectroscopy demonstrates great application prospects in the fields of fingerprint sensing and detection, traditional sensing schemes face unavoidable limitations in the analysis of trace-amount samples. In this Letter, a novel, to the best of our knowledge, absorption spectroscopy enhancement strategy based on a defect one-dimensional photonic crystal (1D-PC) structure is proposed to achieve strong wideband terahertz wave-matter interactions for trace-amount samples. Based on the Fabry-Pérot resonance effect, the local electric field in a thin-film sample can be boosted by changing the length of the photonic crystal defect cavity, so that the wideband signal of the sample fingerprint can be greatly enhanced. This method exhibits a great absorption enhancement factor, of about 55 times, in a wide terahertz frequency range, facilitating the identification of different samples, such as thin α-lactose films. The investigation reported in this Letter provides a new research idea for enhancing the wide terahertz absorption spectroscopy of trace samples.

Terahertz absorption spectroscopy for measuring atomic oxygen densities in plasmas

This paper describes the first implementation of terahertz (THz) quantum cascade lasers for high-resolution absorption spectroscopy on plasmas. Absolute densities of ground state atomic oxygen were directly obtained by using the fine structure transition at approximately 4.75 THz. Measurements were performed on a low-pressure capacitively coupled radio frequency oxygen discharge. The detection limit in this arrangement was found to be cm−3, while the measurement accuracy was within 5%, as demonstrated by reference measurements of a well-defined ammonia transition. The results show that the presented method is well suited to measure atomic oxygen densities, and it closes the THz gap for quantitative atomic density measurements in harsh environments such as plasmas.

Highly Altered State of Proton Transport in Acid Pools in Charged Reverse Micelles.

Transport mechanisms of solvated protons of 1 M HCl acid pools, confined within reverse micelles (RMs) containing the negatively charged surfactant sodium bis(2-ethylhexyl) sulfosuccinate (NaAOT) or the positively charged cetyltrimethylammonium bromide (CTABr), are analyzed with reactive force field simulations to interpret dynamical signatures from TeraHertz absorption and dielectric relaxation spectroscopy. We find that the forward proton hopping events for NaAOT are further suppressed compared to a nonionic RM, while the Grotthuss mechanism ceases altogether for CTABr. We attribute the sluggish proton dynamics for both charged RMs as due to headgroup and counterion charges that expel hydronium and chloride ions from the interface and into the bulk interior, thereby increasing the pH of the acid pools relative to the nonionic RM. For charged NaAOT and CTABr RMs, the localization of hydronium near a counterion or conjugate base reduces the Eigen and Zundel configurations that enable forward hopping. Thus, localized oscillatory hopping dominates, an effect that is most extreme for CTABr in which the proton residence time increases dramatically such that even oscillatory hopping is slow.

Boosting the terahertz absorption spectroscopy based on the stretchable metasurface.

Terahertz (THz) absorption spectroscopy is widely used for molecular label-free fingerprinting detection, but it is not capable of efficiently analyzing trace-amount sample materials. For improving the efficiency of terahertz absorptance spectroscopy detection, we propose a sensing strategy by treating the geometry sweeping spoof surface plasmon polariton (SSP) of the stretchable metasurface. For the first time, the geometry sweeping can be realized by dynamically stretching the polydimethylsiloxane (PDMS) flexible substrate, leading to the resonant frequency variation of the unit cell. This design provides a significant absorption enhancement factor about 270 times for a 0.1 μm lactose film in a broad terahertz band, enabling the unambiguous identification of different trace-amount samples. The designed method exhibits a novel solution for the enhancement of broad-band terahertz absorption spectroscopy and great application potential in the field of detecting trace-amount samples.

Enhancement of wide-band trace terahertz absorption spectroscopy based on microstructures: a review.

Research on the interaction between nanoscale materials and light holds significant scientific significance for the development of fields such as optoelectronic conversion and biosensing. The study of micro- and nano-optics has produced numerous outstanding research achievements by utilizing the dielectric optical coupling mechanism and plasmon effects to enhance the interaction between light and matter. These findings have demonstrated tremendous potential for applications in the field of molecular fingerprint sensing. This review focuses on a retrospective analysis of recent research studies in the enhancement of wide-band trace terahertz absorption spectroscopy. The physical mechanisms of using waveguide structures, dielectric metasurfaces/meta-gratings, and spoof surface plasmon polaritons (SSPs) to improve the interaction between light and trace-amount matters are introduced. The new approaches and methods for enhancing broad-band terahertz absorption spectroscopy of trace samples using microstructure designs are discussed. Additionally, we elucidate the scientific ideas and exploratory achievements in enhancing terahertz fingerprint spectroscopy detection. Finally, we provide an outlook on the research and development direction and potential practical applications of absorption spectroscopy enhancement detection.

Dissociation and Recombination Processes in Lactose Monohydrate Detected by THz Time-Domain Spectroscopy

The terahertz (THz) region has much appeal for differentiating between hydrate systems and for physically characterizing pharmaceutical drug materials. The present study employs THz absorption spectroscopy to investigate the effect of heating on dehydration and hydration in α-lactose monohydrate. Distinctive THz absorption spectra were observed following various heating durations. The THz absorption spectra for α-lactose monohydrate and anhydrous α-lactose exhibit clear differences. Pure α-lactose monohydrate displays clear absorption peaks at 0.53, 1.05, 1.11, 1.33, and 1.56 THz. The complete dehydration of α-lactose monohydrate takes only 15 mins at 145°C (418 K). Moreover, the THz refractive index of α-lactose monohydrate decreases during dehydration. The dehydration of α-lactose monohydrate was also studied using Beer–Lambert law to compare THz absorption spectra as functions of the heating time. The absorption coefficient spectra recorded at 0.53 and 1.35 THz for α-lactose monohydrate after different dehydration times vary linearly with the remaining water content.

A novel aging characterization method for silicone rubber based on terahertz absorption spectroscopy

To address the challenge of the lack of aging characterization methods for outdoor silicone rubber-based insulation materials in power engineering applications, this paper proposes a novel high precision non-destructive characterization method for aging of organic materials based on the vibration characteristics of silicone rubber materials in the terahertz frequency band. In order to analyze and verify the method proposed in this paper, the sources of vibration peaks in the THz band absorption spectrum of aged silicone rubber are discussed by accelerating test, microscopic characterization, and molecular simulation. Finally, the characteristic peak frequency and quantitative calculation method of aged silicone rubber are obtained. Compared to other aging assays, this method overcomes the limitations of the existing THz assay which requires testing in a nitrogen atmosphere, and has the advantage of not damaging the sample.

Quantitative analysis of textile delusterant based on terahertz spectral and data fusion strategies

Titanium dioxide is a delusterant and an important component in the manufacturing of polyester fiber. For the need of fast, accurate and nondestructive detection of matting agents in textiles, a quantitative analysis method based on terahertz absorption spectroscopy and derivative spectroscopy, combined with chemometrics and data fusion strategy is proposed. This experiment was used two spectra for fusion. The terahertz absorption spectra were obtained in the band of 0.2–1.9 THz by optical parameter extraction. The derivative spectrum was derived from the first-order derivative of the absorption spectrum. Partial least squares (PLS) and data fusion were used to construct a prediction model for titanium dioxide concentration in polyester fiber. Low-level data fusion was the direct combination of two spectral data; The successive projections algorithm (SPA) and Monte Carlo uninformative variable elimination (MCUVE) were employed by mid-level data fusion for feature selection, after which the feature variables were fused; multiple linear regression was used for fusion by high-level data fusion. The prediction accuracy of the high-level data fusion model is higher than that of other models, which the correlation coefficient of cross-validation (Rcv) and correlation coefficient of prediction (Rp) are 0.9229 and 0.9227. The mean relative error (MRE) is 0.2654. The results show that terahertz spectroscopy combined with chemometric methods and high-level data fusion strategies can achieve rapid, accurate and non-destructive detection of titanium dioxide in polyester fiber, which can lay the theoretical foundation for terahertz spectroscopy detection methods for textile additives.

Highly enhanced trace amount terahertz fingerprint spectroscopy by multiplexing surface spoof plasmon metasurfaces in a single layer

Terahertz (THz) absorption spectroscopy has a large potential for molecular label-free fingerprinting. But it should overcome barriers to effectively measure the spectra of trace-amount analysis in a real application. The popular solution is enhancing the broadband spectral signals by localizing electromagnetic fields in dielectric metagrating or metasurfaces. In this paper, we numerically demonstrate a sensing scheme based on the geometry multiplexing of metal metasurfaces in one layer steel sheet with a series of spoof surface plasmon (SSP) sharp resonances. The SSP resonances are excited by normal THz incidents. The meta device is easy to manufacture and measure. The linked resonances peaks build an enhanced absorption spectrum. The envelope curve shows a substantial absorption enhancement factor of about 104 times for the 0.1μm lactose film sample in 0.46∼0.60 THz. The proposed method offers a flexible way for the wide terahertz spectra enhancement in trace-amount chemical, organic, or biomedical materials detection.

Quantitative analysis of composition and temperature of semiconductor processing plasmas via terahertz spectroscopy

The application of terahertz (THz) absorption spectroscopy was developed for chemical characterization in inductively coupled plasmas. Plasma processing is a complex and important tool of the semiconductor manufacturing industry, which makes use of several diagnostic methods for precise process control. Electronically based THz spectroscopy is a technique with favorable attributes for the characterization of plasmas and process control in semiconductor reactors. These attributes include (1) plasmas are transparent and noise-free for THz transmission/detection, (2) concentration and temperatures of molecules can be calculated from first principles without adjustable variables, and (3) the technique has very high resolution and has absolute specificity. However, rotational spectroscopy requires that the molecule have a permanent dipole moment, precluding direct observation of atomic and symmetric species such as fluorine or CF4. In this work, an electronically based 500–750 GHz absorption spectrometer and a method to accurately and simultaneously determine number densities and temperatures were developed. Density and temperature measurements of molecular species in Ar/CF4/CHF3 and N2/CF4/CHF3 plasmas as a function of flow ratio, power, and pressure will be discussed. In addition, a quantitative survey of spectroscopically measurable molecules and radicals was conducted for plasma mixtures using varying quantities of CF4, CHF3, N2, and O2 feedstock gases.

Enhanced trace-amount terahertz vibrational absorption spectroscopy using surface spoof polarization in metasurface structures.

Terahertz (THz) absorption spectroscopy is a powerful tool for molecular label-free fingerprinting, but it faces a formidable hurdle in enhancing the broadband spectral signals in trace-amount analysis. In this paper, we propose a sensing method based on the geometry scanning of metal metasurfaces with spoof surface polarization sharp resonances by numerical simulation. This scheme shows a significant absorption enhancement factor of about 200 times in an ultra-wide terahertz band to enable the explicit identification of various analytes, such as a trace-amount thin lactose film samples. The proposed method provides a new, to the best of our knowledge, choice for the enhancement of wide terahertz absorption spectra, and paves the way for the detection of trace-amount chemical, organic, or biomedical materials in the terahertz regime.

Enhanced on-chip terahertz vibrational absorption spectroscopy using evanescent fields in silicon waveguide structures

In this study, we demonstrate on-chip terahertz absorption spectroscopy using dielectric waveguide structures. The structures' evanescent fields interact with the sample material surrounding the waveguide, enabling the absorption signature of the material to be captured. The ability of fabricated terahertz dielectric waveguide structures, based on the newly developed silicon-BCB-quartz platform, to capture the fingerprint of α-lactose powder (as an example material) at 532 GHz is examined. Enhancement of the spectroscopy sensitivity through techniques such as tapering the waveguide, confining the field in a slot dielectric waveguide, and increasing the interaction length using a spiral-shaped waveguide are investigated experimentally. The proposed on-chip spectroscopy structures outperform conventional and state-of-the-art approaches in terms of sensitivity and compactness.

An isolated water droplet in the aqueous solution of a supramolecular tetrahedral cage

Water under nanoconfinement at ambient conditions has exhibited low-dimensional ice formation and liquid-solid phase transitions, but with structural and dynamical signatures that map onto known regions of water's phase diagram. Using terahertz (THz) absorption spectroscopy and ab initio molecular dynamics, we have investigated the ambient water confined in a supramolecular tetrahedral assembly, and determined that a dynamically distinct network of 9 ± 1 water molecules is present within the nanocavity of the host. The low-frequency absorption spectrum and theoretical analysis of the water in the Ga4L612- host demonstrate that the structure and dynamics of the encapsulated droplet is distinct from any known phase of water. A further inference is that the release of the highly unusual encapsulated water droplet creates a strong thermodynamic driver for the high-affinity binding of guests in aqueous solution for the Ga4L612- supramolecular construct.

Detection of gene mutation responsible for Huntington's disease by terahertz attenuated total reflection microfluidic spectroscopy.

Terahertz absorption spectroscopy based on attenuated total reflection (ATR) from a microfluidic sample cell was designed and implemented to detect gene mutations leading to Huntington's disease (HD). The self-developed compact ATR microfluidic system was employed to detect two groups of base-repeated DNA molecules combined with a terahertz time-domain spectrometer in a marker-free manner. The first group featured different repetition patterns of oligonucleotide fragments, and the second group included the HD gene. For the oligonucleotides of different repetition patterns, there were significant differences among the three oligonucleotides with three repeats of the double bases, which could be unambiguously classified and identified; For the HD gene, it was found that the magnitude of the terahertz absorption coefficients of the four oligonucleotide solutions was, in ascending order, CAG-4 < CAG-16 < CAG-32 < CAG-40 (the numbers are the repeat times of the CAG base segment, with 40 repeats belonging to the HD gene), when the concentration of oligonucleotide was 1 mg/mL. Principal component analysis result indicated that the spectral differences of the four oligonucleotide solutions with different CAG repeat times were statistically significant and clearly distinguishable. These results demonstrate the potential of terahertz spectroscopy as a noninvasive, unmarked, fast and low-cost assay for gene diagnosis and clinical disease detection.