Emergence of threefold symmetric helical photocurrents in epitaxial low twinned Bi2Se3.

We present evidence of a strong circular photon drag effect (PDE) in topological insulators (TIs) through the observation of helicity-dependent topological photocurrents with threefold rotational symmetry using THz spectroscopy in epitaxially-grown Bi2Se3 with reduced crystallographic twinning. We establish how twinned domains introduce competing nonlinear optical (NLO) responses inherent to the crystal structure that obscure geometry-sensitive optical processes through the introduction of a spurious mirror symmetry. Minimizing the twinning defect reveals strong NLO response currents whose magnitude and direction depend on the alignment of the excitation to the crystal axes and follow the threefold rotational symmetry of the crystal. Notably, photocurrents arising from helical light reverse direction for left/right circular polarizations and maintain a strong azimuthal dependence-a result uniquely attributable to the circular PDE, where the photon momentum acts as an applied in-plane field stationary in the laboratory frame. Our results demonstrate new levels of control over the magnitude and direction of photocurrents in TIs and that the study of single-domain films is crucial to reveal hidden phenomena that couple topological order and crystal symmetries.

The birth and evolution of solvated electrons in the water.

The photo-induced radiolysis of water is an elementary reaction in biology and chemistry, forming solvated electrons, OH radicals, and hydronium cations on fast time scales. Here, we use an optical-pump terahertz-probe spectroscopy setup to trigger the photoionization of water molecules with optical laser pulses at ~400 nm and then time-resolve the transient solvent response with broadband terahertz (THz) fields with a ~90 fs time resolution. We observe three distinct spectral responses. The first is a positive broadband mode that can be attributed to an initial diffuse, delocalized electron with a radius of (22 ± 1) Å, which is short lived (<200 fs) because the absorption is blue-shifting outside of the THz range. The second emerging spectroscopic signature with a lifetime of about 150 ps is attributed to an intermolecular mode associated with a mass rearrangement of solvent molecules due to charge separation of radicals and hydronium cations. After 0.2 ps, we observe a long-lasting THz signature with depleted intensity at 110 cm-1 that is well reproduced by ab initio molecular dynamics. We interpret this negative band at 110 cm-1 as the solvent cage characterized by a weakening of the hydrogen bond network in the first and second hydration shells of the cavity occupied by the localized electron.

Anisotropic Electron-Phonon Interactions in 2D Lead-Halide Perovskites.

Two-dimensional (2D) hybrid organic-inorganic metal halide perovskites offer enhanced stability for perovskite-based applications. Their crystal structure's soft and ionic nature gives rise to strong interaction between charge carriers and ionic rearrangements. Here, we investigate the interaction of photogenerated electrons and ionic polarizations in single-crystal 2D perovskite butylammonium lead iodide (BAPI), varying the inorganic lamellae thickness in the 2D single crystals. We determine the directionality of the transition dipole moments (TDMs) of the relevant phonon modes (in the 0.3-3 THz range) by the angle- and polarization-dependent THz transmission measurements. We find a clear anisotropy of the in-plane photoconductivity, with a ∼10% reduction along the axis parallel with the transition dipole moment of the most strongly coupled phonon. Detailed calculations, based on Feynman polaron theory, indicate that the anisotropy originates from directional electron-phonon interactions.

Tuning the Inter-Nanoplatelet Distance and Coupling Strength by Thermally Induced Ligand Decomposition.

CdSe nanoplatelets (NPLs) are promising 2D semiconductors for optoelectronic applications, in which efficient charge transport properties are desirable. It is reported that thermal annealing constitutes an effective strategy to control the optical absorption and electrical properties of CdSe NPLs by tuning the inter-NPL distance. Combining optical absorption, transmission electron microscopy, and thermogravimetric analysis, it is revealed that the thermal decomposition of ligands (e.g., cadmium myristate) governs the inter-NPL distance and thus the inter-NPL electronic coupling strength. Employing ultrafast terahertz spectroscopy, it is shown that this enhanced electronic coupling increases both the free carrier generation efficiency and the short-range mobility in NPL solids. The results show a straightforward method of controlling the interfacial electronic coupling strength for developing functional optoelectronic devices through thermal treatments.

Studying Local Electrostatics by Terahertz Spectroscopy Using Amines as a Probe.

In a previous study[1] we could show that a large amplitude mode of the zwitterion glycine can serve as a sensitive probe for protonation and allows to deduce local pKa values. Here we show that the underlying concept is more general: We present the results of a pH dependent measurement of Terahertz-FTIR (THz-FTIR) spectra of solvated amines, i. e. Diethylamine (DEA), Triethylamine (TEA), and Diisopropylamine (DiPA). We show that amines serve as a sensitive, label free probe for local protonation. Protonation of the amines yield intensity changes which can be quantified by precise THz spectroscopy (30 cm-1 -450 cm-1 ). A detailed analysis allows us to correlate the titration spectra of solvated amines in the THz range with pKa values. This demonstrates the potential of THz spectroscopy to probe the charge state of biomolecules in water in a label free manner.

Where do the Fluorine Atoms Go in Inorganic-Oxide Fluorinations? A Fluorooxoborate Illustration under Terahertz Light.

The substitution of fluorine atoms for oxygen atoms/hydroxyl groups has emerged as a promising strategy to enhance the physical and chemical properties of oxides/hydroxides in fluorine chemistry. However, distinguishing fluorine from oxygen/hydroxyl in the reaction products poses a significant challenge in existing characterization methods. In this study, we illustrate that terahertz (THz) spectroscopy provides a powerful tool for addressing this challenge. To this end, we investigated two fluorination reactions of boric acid, utilizing MHF2 (M=Na, C(NH2)3) as fluorine reagents. Through an interplay between THz spectroscopy and solid-state density functional theory, we have conclusively demonstrated that fluorine atoms exclusively bind with the sp3-boron but not with the sp2-boron in the reaction products of Na[B(OH)3][B3O3F2(OH)2] (NaBOFH) and [C(NH2)3]2B3O3F4OH (GBF2). Based on this evidence, we have proposed a reaction pathway for the fluorinations under investigation, a process previously hindered due to structural ambiguity. This work represents a step forward in gaining a deeper understanding of the precise structures and reaction mechanisms involved in the fluorination of oxides/hydroxides, illuminated by the insights provided by THz spectroscopy.

Density-Dependence of Surface Transport in Tellurium-Enriched Nanograined Bulk Bi2 Te3.

Three-dimensional topological insulators (3D TI) exhibit conventional parabolic bulk bands and protected Dirac surface states. A thorough investigation of the different transport channels provided by the bulk and surface carriers using macroscopic samples may provide a path toward accessing superior surface transport properties. Bi2 Te3 materials make promising 3D TI models; however, due to their complicated defect chemistry, these materials have a high number of charge carriers in the bulk that dominate the transport, even as nanograined structures. To partially control the bulk charge carrier density, herein the synthesis of Te-enriched Bi2 Te3 nanoparticles is reported. The resulting nanoparticles are compacted into nanograined pellets of varying porosity to tailor the surface-to-volume ratio, thereby emphasizing the surface transport channels. The nanograined pellets are characterized by a combination of resistivity, Hall- and magneto-conductance measurements together with (THz) time-domain reflectivity measurements. Using the Hikami-Larkin-Nagaoka (HLN) model, a characteristic coherence length of ≈200 nm is reported that is considerably larger than the diameter of the nanograins. The different contributions from the bulk and surface carriers are disentangled by THz spectroscopy, thus emphasizing the dominant role of the surface carriers. The results strongly suggest that the surface transport carriers have overcome the hindrance imposed by nanoparticle boundaries.

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.

Enhanced Terahertz Fingerprint Sensing Mechanism Study of Tiny Molecules Based on Tunable Spoof Surface Plasmon Polaritons on Composite Periodic Groove Structures.

Highly sensitive detection of enhanced terahertz (THz) fingerprint absorption spectrum of trace-amount tiny molecules is essential for biosensing. THz surface plasmon resonance (SPR) sensors based on Otto prism-coupled attenuated total reflection (OPC-ATR) configuration have been recognized as a promising technology in biomedical detection applications. However, THz-SPR sensors based on the traditional OPC-ATR configuration have long been associated with low sensitivity, poor tunability, low refractive index resolution, large sample consumption, and lack of fingerprint analysis. Here, we propose an enhanced tunable high-sensitivity and trace-amount THz-SPR biosensor based on a composite periodic groove structure (CPGS). The elaborate geometric design of the spoof surface plasmon polaritons (SSPPs) metasurface increases the number of electromagnetic hot spots on the surface of the CPGS, improves the near-field enhancement effect of SSPPs, and enhances the interaction between THz wave and the sample. The results show that the sensitivity (S), figure of merit (FOM) and Q-factor (Q) can be increased to 6.55 THz/RIU, 4234.06 1/RIU and 629.28, respectively, when the refractive index range of the sample to measure is between 1 and 1.05 with the resolution 1.54×10-5 RIU. Moreover, by making use of the high structural tunability of CPGS, the best sensitivity (SPR frequency shift) can be obtained when the resonant frequency of the metamaterial approaches the biological molecule oscillation. These advantages make CPGS a strong candidate for the high-sensitivity detection of trace-amount biochemical samples.

Impact of nuclear quantum effects on the structural inhomogeneity of liquid water.

The 2D Raman-terahertz (THz) response of liquid water is studied in dependence of temperature and isotope substitution ([Formula: see text]O, [Formula: see text]O, and [Formula: see text]O). In either case, a very short-lived (i.e., between 75 and 95 fs) echo is observed that reports on the inhomogeneity of the low-frequency intermolecular modes and hence, on the heterogeneity of the hydrogen bond networks of water. The echo lifetime slows down by about 20% when cooling the liquid from room temperature to the freezing point. Furthermore, the echo lifetime of [Formula: see text]O is [Formula: see text] slower than that of [Formula: see text]O, and both can be mapped on each other by introducing an effective temperature shift of [Formula: see text] K. In contrast, the temperature-dependent echo lifetimes of [Formula: see text]O and [Formula: see text]O are the same within error. [Formula: see text]O and [Formula: see text]O have identical masses, yet [Formula: see text]O is much closer to [Formula: see text]O in terms of nuclear quantum effects. It is, therefore, concluded that the echo is a measure of the structural inhomogeneity of liquid water induced by nuclear quantum effects.

A General Neural Network Model for Complex Refractive Index Extraction of Low-Loss Materials in the Transmission-Mode THz-TDS.

The complex refractive index for low-loss materials is conventionally extracted by either approximate analytical formula or numerical iterative algorithm (such as Nelder-Mead and Newton-Raphson) based on the transmission-mode terahertz time domain spectroscopy (THz-TDS). A novel 4-layer neural network model is proposed to obtain optical parameters of low-loss materials with high accuracy in a wide range of parameters (frequency and thickness). Three materials (TPX, z-cut crystal quartz and 6H SiC) with different dispersions and thicknesses are used to validate the robustness of the general model. Without problems of proper initial values and non-convergence, the neural network method shows even smaller errors than the iterative algorithm. Once trained and tested, the proposed method owns both high accuracy and wide generality, which will find application in the multi-class object detection and high-precision characterization of THz materials.

Low-Frequency Vibrational Spectroscopy Characteristic of Pharmaceutical Carbamazepine Co-Crystals with Nicotinamide and Saccharin.

The pharmaceutical co-crystal has attracted increasing interest due to the improvement of physicochemical properties of active pharmaceutical ingredients. The characterization of pharmaceutical co-crystal is an integral part of the pharmaceutical field. In this paper, the low-frequency vibrational properties for carbamazepine co-crystals with nicotinamide and saccharin (CBZ-NIC and CBZ-SAC) have been characterized by combining the THz spectroscopy with low-wavenumber Raman spectroscopy. The experiment results show that, compared with the individual constituents, CBZ-NIC and CBZ-SAC co-crystals not only have different characteristic absorption peaks in the 0.3-2.5 THz region, but also have significant low-wavenumber Raman characteristic peaks in 0-100 cm-1. Density functional theory was performed to simulate the terahertz and low-wavenumber Raman spectra of the two co-crystals, where the calculation agreed well with the measured vibrational peak positions. The vibrational modes of CBZ-NIC and CBZ-SAC co-crystals were assigned through comparing theoretical results with the experimental spectra. Meanwhile, the low-frequency infrared and/or Raman active of characteristic peaks for such co-crystals were discussed. The results indicate the combination of THz spectroscopy and low-wavenumber Raman spectroscopy can provide more comprehensive low-frequency vibrational information for pharmaceutical co-crystals, such as collective vibration and skeleton vibration, which could play an important role in pharmaceutical science.

Epithelial Sodium Channel Inhibition by Amiloride Addressed with THz Spectroscopy and Molecular Modeling.

THz spectroscopy is important for the study of ion channels because it directly addresses the low frequency collective motions relevant for their function. Here we used THz spectroscopy to investigate the inhibition of the epithelial sodium channel (ENaC) by its specific blocker, amiloride. Experiments were performed on A6 cells' suspensions, which are cells overexpressing ENaC derived from Xenopus laevis kidney. THz spectra were investigated with or without amiloride. When ENaC was inhibited by amiloride, a substantial increase in THz absorption was noticed. Molecular modeling methods were used to explain the observed spectroscopic differences. THz spectra were simulated using the structural models of ENaC and ENaC-amiloride complexes built here. The agreement between the experiment and the simulations allowed us to validate the structural models and to describe the amiloride dynamics inside the channel pore. The amiloride binding site validated using THz spectroscopy agrees with previous mutagenesis studies. Altogether, our results show that THz spectroscopy can be successfully used to discriminate between native and inhibited ENaC channels and to characterize the dynamics of channels in the presence of their specific antagonist.

A Nanographene-Based Two-Dimensional Covalent Organic Framework as a Stable and Efficient Photocatalyst.

Synthesis of covalent organic frameworks (COFs) with desirable organic units furnishes advanced materials with unique functionalities. As an emerging class of two-dimensional (2D) COFs, sp2 -carbon-conjugated COFs provide a facile platform to build highly stable and crystalline porous polymers. Herein, a 2D olefin-linked COF was prepared by employing nanographene, namely, dibenzo[hi,st]ovalene (DBOV), as a building block. The DBOV-COF exhibits unique ABC-stacked lattices, enhanced stability, and charge-carrier mobility of ≈0.6 cm2 V-1 s-1 inferred from ultrafast terahertz photoconductivity measurements. The ABC-stacking structure was revealed by the high-resolution transmission electron microscopy and powder X-ray diffraction. DBOV-COF demonstrated remarkable photocatalytic activity in hydroxylation, which was attributed to the exposure of narrow-energy-gap DBOV cores in the COF pores, in conjunction with efficient charge transport following light absorption.

Spectroscopic Fingerprints of Cavity Formation and Solute Insertion as a Measure of Hydration Entropic Loss and Enthalpic Gain.

Hydration free energies are dictated by a subtle balance of hydrophobic and hydrophilic interactions. We present here a spectroscopic approach, which gives direct access to the two main contributions: Using THz-spectroscopy to probe the frequency range of the intermolecular stretch (150-200 cm-1 ) and the hindered rotations (450-600 cm-1 ), the local contributions due to cavity formation and hydrophilic interactions can be traced back. We show that via THz calorimetry these fingerprints can be correlated 1 : 1 with the group specific solvation entropy and enthalpy. This allows to deduce separately the hydrophobic (i.e. cavity formation) and hydrophilic contributions to thermodynamics, as shown for hydrated alcohols as a case study. Accompanying molecular dynamics simulations quantitatively support our experimental results. In the future our approach will allow to dissect hydration contributions in inhomogeneous mixtures and under non-equilibrium conditions.

Interface-Dominated Topological Transport in Nanograined Bulk Bi2 Te3.

3D topological insulators (TI) host surface carriers with extremely high mobility. However, their transport properties are typically dominated by bulk carriers that outnumber the surface carriers by orders of magnitude. A strategy is herein presented to overcome the problem of bulk carrier domination by using 3D TI nanoparticles, which are compacted by hot pressing to macroscopic nanograined bulk samples. Bi2 Te3 nanoparticles well known for their excellent thermoelectric and 3D TI properties serve as the model system. As key enabler for this approach, a specific synthesis is applied that creates nanoparticles with a low level of impurities and surface contamination. The compacted nanograined bulk contains a high number of interfaces and grain boundaries. Here it is shown that these samples exhibit metallic-like electrical transport properties and a distinct weak antilocalization. A downward trend in the electrical resistivity at temperatures below 5 K is attributed to an increase in the coherence length by applying the Hikami-Larkin-Nagaoka model. THz time-domain spectroscopy reveals a dominance of the surface transport at low frequencies with a mobility of above 103 cm2 V-1 s-1 even at room temperature. These findings clearly demonstrate that nanograined bulk Bi2 Te3 features surface carrier properties that are of importance for technical applications.

Terahertz spectroscopy technology as an innovative technique for food: Current state-of-the-Art research advances.

With the dramatic development of source and detector components, terahertz (THz) spectroscopy technology has recently shown a renaissance in various fields such as medical, material, biosensing and pharmaceutical industry. As a rapid and noninvasive technology, it has been extensively exploited to evaluate food quality and ensure food safety. In this review, the principles and processes of THz spectroscopy are first discussed. The current state-of-the-art applications of THz and imaging technologies focused on foodstuffs are then discussed. The advantages and challenges are also covered. This review offers detailed information for recent efforts dedicated to THz for monitoring the quality and safety of various food commodities and the feasibility of its widespread application. THz technology, as an emerging and unique method, is potentially applied for detecting food processing and maintaining quality and safety.

Experimental Observation of Strong Exciton Effects in Graphene Nanoribbons.

Graphene nanoribbons (GNRs) with atomically precise width and edge structures are a promising class of nanomaterials for optoelectronics, thanks to their semiconducting nature and high mobility of charge carriers. Understanding the fundamental static optical properties and ultrafast dynamics of charge carrier generation in GNRs is essential for optoelectronic applications. Combining THz spectroscopy and theoretical calculations, we report a strong exciton effect with binding energy up to ∼700 meV in liquid-phase-dispersed GNRs with a width of 1.7 nm and an optical band gap of ∼1.6 eV, illustrating the intrinsically strong Coulomb interactions between photogenerated electrons and holes. By tracking the exciton dynamics, we reveal an ultrafast formation of excitons in GNRs with a long lifetime over 100 ps. Our results not only reveal fundamental aspects of excitons in GNRs (strong binding energy and ultrafast exciton formation etc.) but also highlight promising properties of GNRs for optoelectronic devices.

Nucleation and Growth Bottleneck in the Conductivity Recovery Dynamics of Nickelate Ultrathin Films.

We investigate THz conductivity dynamics in NdNiO3 and EuNiO3 ultrathin films (15 unit cells, u.c., ∼5.7 nm thick) following a photoinduced thermal quench into the metallic state and reveal a clear contrast between first- and second-order dynamics. While in EuNiO3 the conductivity recovers exponentially, in NdNiO3 the recovery is nonexponential and slower than a simple thermal model. Crucially, it is consistent with first-order dynamics and well-described by a 2d Avrami model, with supercooling leading to metastable phase coexistence on the nano- to mesoscopic scale. This novel observation is a fundamentally dynamic manifestation of the first-order character of the insulator-to-metal transition, which the nanoscale thickness of our films and their fast cooling rate enable us to detect. The large transients seen in our films are promising for fast electronic (and magnetic) switching applications.

Proton Traffic Jam: Effect of Nanoconfinement and Acid Concentration on Proton Hopping Mechanism.

The properties of the water network in concentrated HCl acid pools in nanometer-sized reverse nonionic micelles were probed with TeraHertz absorption, dielectric relaxation spectroscopy, and reactive force field simulations capable of describing proton hopping mechanisms. We identify that only at a critical micelle size of W0 =9 do solvated proton complexes form in the water pool, accompanied by a change in mechanism from Grotthuss forward shuttling to one that favors local oscillatory hopping. This is due to a preference for H+ and Cl- ions to adsorb to the micelle interface, together with an acid concentration effect that causes a "traffic jam" in which the short-circuiting of the hydrogen-bonding motif of the hydronium ion decreases the forward hopping rate throughout the water interior even as the micelle size increases. These findings have implications for atmospheric chemistry, biochemical and biophysical environments, and energy materials, as transport of protons vital to these processes can be suppressed due to confinement, aggregation, and/or concentration.