Index of Refraction and Absorption Coefficient Spectra of Paratellurite in the Terahertz Region

Index of refraction and absorption coefficient spectra of pure paratellurite (α-TeO₂) crystal as a potential material for terahertz (THz) applications were determined in the 0.25–2 THz frequency range at room temperature by THz time domain spectroscopy (THz-TDS). The investigation was performed with beam polarization both parallel (extraordinary polarization) and perpendicular (ordinary polarization) to the optical axis [001] of the crystal. Similarly to the visible spectral range, positive birefringence was observed in the THz range as well. It was shown that the values of the refractive index for extraordinary polarization are higher and show significantly larger dispersion than for the ordinary one. The absorption coefficient values are also larger for extraordinary polarization. The measured values were fitted by theoretical curves derived from the complex dielectric function containing independent terms of Lorentz oscillators due to phonon-polariton resonances. The results are compared with earlier publications, and the observed significant discrepancies are discussed.     

A Comprehensive Study of Albumin Solutions in the Extended Terahertz Frequency Range

Sensitivity of the THz frequency range to the solutions of biomolecules originates from the decrease of absorption and dispersion of water in its bound state. Correct measurement and interpretation of the THz spectra of water-containing samples is still a challenging task because the reliable relaxation model for such spectra is not well established. The transmission and the attenuated total internal reflection geometries data were combined for precise analysis of the spectra of the aqueous solutions of bovine serum albumin within the range 0.05–3.2 THz. We compare the concentration dependencies of the dielectric function at “low,” “middle,” and “high” frequency and do not confirm an anomalous increase in absorption for concentrations below 17 mg/mL published by other teams.     

The measurement of the dielectric and optical properties of nano thin films by THz differential time-domain spectroscopy

As feature sizes of circuits and devices approach 100 nm and chip frequencies climb into the upper GHz to THz range, it becomes increasingly important to have a convenient method of characterizing properties of thin dielectric films in the GHz to THz frequency range. THz time-domain spectroscopy provides a non-contact, non-destructive and highly sensitive optical tool to characterize the dielectric and optical properties of micron to nanometer scaled thin films at GHz and THz frequencies. The measurement of the dielectric and the optical properties of nanometer scaled dielectric films is performed using the THz differential time-domain spectroscopy. The real and imaginary parts of the complex dielectric constants and the optical constants of a variety of nano thin films are measured at GHz and THz frequencies.     

Experimental and Theoretical Study on Terahertz Absorption Characteristics and Spectral De-noising of Three Plant Growth Regulators

Accurate identification of terahertz (THz) absorption peaks of biological macromolecules is of great significance in practical applications. In this work, the experimental and theoretical fundamentals of detecting three plant growth regulators (PGRs), including 6-Benzylaminopurine (6-BA), paclobutrazol (PBZ), and maleic hydrazide (MH) were investigated by using THz time-domain spectroscopy (THz-TDS). THz absorption coefficient and refractive index in frequencies of 0.06–4 THz were obtained. The wavelet threshold de-noising (WTD) method was used to remove spectral noise and improve the signal-to-noise ratio (SNR). The density functional theory (DFT) was applied to the molecular characterization and theoretical calculation of PGRs. Experimental results showed that the three PGRs had unique characteristic absorption peaks. Based on the sym4 wavelet function and four-layer wavelet decomposition, the de-noising performance of hard threshold WTD was better than that of soft threshold WTD. The spectra processed by hard threshold de-noising achieved higher peak SNR (6-BA: 40.22, PBZ: 37.73, MH: 34.83) and lower root mean square error (6-BA: 0.41, PBZ:0.40, MH:0.54). In addition, the characteristic absorption and anomalous dispersion of 6-BA were found at 2.08 and 3.00 THz, those of PBZ were shown at 0.71, 1.30, 1.88, and 2.67 THz, and those of MH were shown at 2.34 THz. The absorption peaks in THz spectra processed by hard threshold WTD were demonstrated to be in good agreement with the simulation results of DFT. These results show the effectiveness of WTD in THz spectral de-noising and the feasibility of using THz-TDS to detect PGRs.     

Tuning of Terahertz Resonances of Pyridyl Benzamide Derivatives by Electronegative Atom Substitution

N-(pyridin-2-yl) benzamide (Ph2AP)-based organic molecules with prominent terahertz (THz) signatures (less than 5 THz) have been synthesized. The THz resonances are tuned by substituting the most electronegative atom, fluorine, at ortho (2F-Ph2AP), meta (3F-Ph2AP), and para (4F-Ph2AP) positions in a Ph2AP molecule. Substitution of fluorine helps in varying the charge distribution of the atoms forming hydrogen bond and hence strength of the hydrogen bond is varied which helps in tuning the THz resonances. The tuning of lower THz resonances of 2F-Ph2AP, 3F-Ph2AP, and 4F-Ph2AP has been explained in terms of compliance constant (relaxed force constant). Four-molecule cluster simulations have been carried out using Gaussian09 software to calculate the compliance constant of the hydrogen bonds. Crystal structure simulations of the above molecules using CRYSTAL14 software have been carried out to understand the origin of THz resonances. It has been observed that THz resonances are shifted to higher frequencies with stronger hydrogen bonds. The study shows that 3F-Ph2AP and 4F-Ph2AP have higher hydrogen bond strength and hence the THz resonances originating due to stretching of intermolecular hydrogen bonds have been shifted to higher frequencies compared to 2F-Ph2AP. The methodology presented here will help in designing novel organic molecules by substituting various electronegative atoms in order to achieve prominent THz resonances.     

Characterization and Classification of Coals and Rocks Using Terahertz Time-Domain Spectroscopy

Being the key unaddressed problem in unmanned mining condition, a new method for the coal-rock interface recognition was proposed in the study. Firstly, terahertz time-domain spectroscopy (THz-TDS) was employed to measure 10 kinds of coals/rocks which were common in China. Secondly, the physical properties of coals/rocks such as absorption coefficient spectra, refractive index, and dielectric properties in THz band were studied. The different responses in THz range caused by diverse components in coals/rocks were discussed, and the dielectric property of coals/rocks in THz band was well fitted by the Lorentz model. Finally, by the means of principal component analysis (PCA), support vector machine (SVM), and THz spectral data, the recognition rate of coals/rocks reaches to 100 % and the recognition rate of different bituminous coals reaches to 97.5 %. The experimental results show that the proposed method is fast, stable, and accurate for the detection of coal-rock interface and could be a promising tool for the classification of different bituminous coals.     

Comparative Study of Hydration Kinetics of Cement and Tricalcium Silicate Using Terahertz Spectroscopy and Density Functional Theory Simulations

Cement hydration is a process involving simultaneous reactions of cement constituents, primarily tricalcium silicate (C3S) and dicalcium silicate (C2S), with the formation of key hydration products, calcium silicate hydrate (C–S–H) and calcium hydroxide (Ca(OH)₂). Compared to the conventionally explored mid-infrared spectroscopy which is bond specific, terahertz (THz) spectroscopy is highly sensitive to crystalline arrangements and resonances in THz frequency range are primarily due to bulk vibrational modes. Hence, THz spectroscopy can be an effective complimentary tool to study the hydration process as C3S gets converted to different polymorphs of C–S–H. To understand the origin and variation of THz resonances of C3S, C–S–H polymorphs and Ca(OH)₂, vibrational modes of C3S, tobemorite 9, tobermorite 14, jennite, and portlandite have been calculated using density functional theory simulations. The origin of the main resonances has been studied using vibrational density of states. Simulations show, for C3S, the resonance around 520 cm^?1 appears due to combined effect of symmetric and asymmetric vibrations in SiO₄ tetrahedra, the resonance around 450 cm^?1 appears due to the combined effect of symmetric and asymmetric SiO₄ tetrahedra, and CaO vibrations and the resonance around 318 cm^?1 is primarily due to CaO vibrations. THz spectroscopy has been performed to track and understand the contribution of C3S in cement hydration. By combining the simulation and experiments, this work clearly explains the reduction of 520 cm^?1 resonance, the constant intensity of 450 cm^?1 resonance and frequency shift of the main resonances as C3S is transformed into various polymorphs of C–S–H during hydration.     

由散射系数反演电磁参量的一种改进算法

传输/反射法中存在的多值性问题多年来颇受关注。本文考察了两套由散射系数反演电磁参量的公式,表明在满足折射率虚部不小于零、阻抗实部大于零和折射率正切角取值范围受阻抗正切角限制关系三条件时,两套公式均可确定阻抗和折射率虚部,并给出数量有限的、可能的折射率实部。在此基础上,利用相邻频率点电磁参量的连续性,可分别求出数个差异显著的电磁响应谱。依据对材料电磁性能的初步认识,不难选出合适的介电常数和磁导率。最后,通过实例检验了上述方法的有效性。     

Plasmonic Crystals: A Platform to Catalog Resonances from Ultraviolet to Near‐Infrared Wavelengths in a Plasmonic Library

Surface plasmons are responsible for a variety of phenomena, including nanoscale optical focusing, negative refraction, and surface‐enhanced Raman scattering. Their characteristic evanescent electromagnetic fields offer opportunities for sub‐diffraction imaging, optical cloaking, and label‐free molecular sensing. The selection of materials for such applications, however, has been traditionally limited to the noble metals Au and Ag because there has been no side‐by‐side comparison of other materials. This feature article describes recent progress on manipulating surface plasmons from ultraviolet to near‐infrared wavelengths using plasmonic crystals made from 2D nanopyramidal arrays. A library of plasmon resonances is constructed in the form of dispersion diagrams for a series of unconventional and new composite plasmonic materials. These resonances are tuned by controlling both intrinsic factors (unit cell shape, materials type) and extrinsic factors (excitation conditions, dielectric environment). Finally, plasmonic crystals with reduced lattice symmetries are fabricated as another means to tailor resonances for broadband coupling.     

Modes and Pseudomodes in Dielectric Waveguides (Correspondence)

It is shown that a medium whose dielectric constant has a square-law distribution with complex coefficients possesses guided mode solutions even under the extreme condition that both the real and the imaginary part of the index of refraction have their lowest value at the axis of the waveguide. However, the resulting modes are unstable (pseudomodes). Stable guided modes exist if the imaginary part of the refractive index has its highest value on axis.     

Terahertz Multivariate Spectral Analysis and Molecular Dynamics Simulations of Three Pyrethroid Pesticides

The terahertz (THz) multivariate spectral characteristics and the molecular dynamics of three pyrethroid pesticides, including deltamethrin, fenvalerate, and beta-cypermethrin, were studied in this paper. THz spectra of the pesticides were measured in frequency range of 0.06–3.5 THz by using THz time-domain spectroscopy (THz-TDS). To improve the THz spectral quality, the wavelet threshold de-noising (WTD) method was used to remove spectral noise and the spectral baseline correction (SBC) method was used to remove baseline drift. Specific absorption peaks were observed in the processed THz spectra of the three pesticides. Deltamethrin showed three peaks at 0.90, 1.49, and 2.32 THz. Fenvalerate had five peaks at 1.13, 1.43, 1.61, 1.98, and 2.58 THz. Beta cypermethrin had four peaks at 1.27, 1.84, 2.12, and 2.92 THz. The density functional theory (DFT) was used to characterize the molecular dynamics and formation mechanism of the absorption peaks. Results showed that there was a good matching effect between the THz experimental spectra and the DFT quantum calculation spectra. Based on the characterized fingerprint absorption peaks, the linear addition model was used to simulate the THz spectra of mixed pesticides. The simulated spectra of multicomponent pesticides were demonstrated to be in good agreement with those obtained by THz-TDS. By analyzing the absorption peaks of THz spectra, the composition and concentration of multicomponent pesticides could be determined. The proposed strategy presented an analytical methodology for studying the THz spectral characteristics of pesticides. In addition, this work provided experimental and theoretical basis for the detection potential of pesticides in agricultural products based on THz technology.     

Terahertz Time-Domain Spectroscopy for In Situ Monitoring of Ceramic Nuclear Waste Forms

The use of terahertz time-domain spectroscopy (THz-TDS) is presented as a non-contact method for in situ monitoring of ceramic waste forms. Single-phase materials of zirconolite (CaZrTi₂O₇), pyrochlore (Nd₂Ti₂O₇), and hollandite (BaCs_0.3Cr_2.3Ti_5.7O₁₆ and BaCs_0.3CrFeAl_0.3Ti_5.7O₁₆) were characterized. The refractive index and dielectric properties in THz frequencies demonstrate the ability to distinguish between these materials. Differences in processing methods show distinct changes in both the THz-TDS spectra and optical and dielectric properties of these ceramic phases. The temperature dependence of the refractive index and relative permittivity of pyrochlore and zirconolite materials in the range of 25–200 °C is found to follow an exponential increasing trend. This can also be used to monitor the temperature of the ceramic waste forms on storage over extended geological time scales.     

Terahertz Reflection Spectroscopy of Aqueous NaCl and LiCl Solutions

We present spectroscopic measurements of the full dielectric function of aqueous solutions of sodium chloride and lithium chloride at concentrations approaching their solubility limits at room temperature. We find that the dielectric properties of the two salts are rather different at THz frequencies. Whereas both the real and imaginary part of the permittivity of NaCl increases with concentration, we see that the imaginary part of the permittivity of LiCl (related to the absorption) decreases with increasing salt concentration. We relate these changes to the behavior of slow and fast Debye relaxation processes in the solutions.     

Sharp Absorption Peaks in THz Spectra Valuable for Crystal Quality Evaluation of Middle Molecular Weight Pharmaceuticals

Middle molecular weight (MMW) pharmaceuticals (MW 400~4000) are attracting attention for their possible use in new medications. Sharp absorption peaks were observed in MMW pharmaceuticals at low temperatures by measuring with a high-resolution terahertz (THz) spectrometer. As examples, high-resolution THz spectra for amoxicillin trihydrate, atorvastatin calcium trihydrate, probucol, and α,β,γ,δ-tetrakis(1-methylpyridinium-4-yl)porphyrin p-toluenesulfonate (TMPyP) were obtained at 10 K. Typically observed as peaks with full width at half-height (FWHM) values as low as 5.639 GHz at 0.96492 THz in amoxicillin trihydrate and 8.857 GHz at 1.07974 THz for probucol, many sharp peaks of MMW pharmaceuticals could be observed. Such narrow absorption peaks enable evaluation of the crystal quality of MMW pharmaceuticals and afford sensitive detection of impurities.     

Terahertz Radiation Shaping Based on Third-Order Dispersion and Self-Phase Modulation in Standard Single-Mode Optical Fiber

Third-order dispersion and self-phase modulation in standard single-mode fibers are employed in a fiber-based THz time domain spectroscopy system for radiation shaping. Ultra-short optical pulses are converted into trains of pulses, thus shaping the THz radiation emitted by photoconductive antennas operating at telecom wavelengths. The proposed architecture allows narrowband and wideband THz emission as well as tunability of the central frequency. Since the shaping takes place in standard optical fiber the architecture could be potentially implemented without requiring any additional device. Experiments showing the principle of operation have been performed demonstrating tunability of the central frequency between 350 and 800 GHz and bandwidth from 150 GHz to the full bandwidth of the system.     

Resonant Terahertz InSb Waveguide Device for Sensing Polymers

We have demonstrated the possibility of employing a device, designed to operate at terahertz (THz) frequencies, for sensing materials. The device consists of a waveguide section with a pair of stubs located at the middle and oriented transversely to the waveguide axis. The two stubs function as a resonator and, hence, the device would behave as a filter in the THz domain. The device was fabricated by laser micromachining of InSb pellets and was characterized by THz time-domain transmission spectroscopy. For a waveguide width of 740 μm and stub length of 990 μm, a transmission minimum is seen to occur at 0.265 THz. We investigated the capability of the device to sense polystyrene, dissolved in toluene, loaded into the stubs. The consequent change in the refractive index in the stubs alters the transmitted signal intensity. Our results show that, a change in concentration of polystyrene even by 1 mol/L, leads to measurable change in the transmission coefficient close to the resonant frequency of the device. Thus, our device operating at THz frequencies shows promising potential as chemical and bio sensors.     

Temperature-Dependent Refractive Index of Quartz at Terahertz Frequencies

Characterisation of materials often requires the use of a substrate to support the sample being investigated. For optical characterisation at terahertz frequencies, quartz is commonly used owing to its high transmission and low absorption at these frequencies. Knowledge of the complex refractive index of quartz is required for analysis of time-domain terahertz spectroscopy and optical pump terahertz probe spectroscopy for samples on a quartz substrate. Here, we present the refractive index and extinction coefficient for α-quartz between 0.5 THz and 5.5 THz (17–183 cm^??1) taken at 10, 40, 80, 120, 160, 200 and 300 K. Quartz shows excellent transmission and is thus an ideal optical substrate over the THz band, apart from the region 3.9 ± 0.1 THz owing to a spectral feature originating from the lowest energy optical phonon modes. We also present the experimentally measured polariton dispersion of α-quartz over this frequency range.     

3D-Printed Broadband Dielectric Tube Terahertz Waveguide with Anti-Reflection Structure

We demonstrate broadband, low loss, and close-to-zero dispersion guidance of terahertz (THz) radiation in a dielectric tube with an anti-reflection structure (AR-tube waveguide) in the frequency range from 0.2 to 1.0 THz. The anti-reflection structure (ARS) consists of close-packed cones in a hexagonal lattice arranged on the outer surface of the tube cladding. The feature size of the ARS is in the order of the wavelength between 0.2 and 1.0 THz. The waveguides are fabricated with the versatile and cost efficient 3D-printing method. Terahertz time-domain spectroscopy (THz-TDS) measurements as well as 3D finite-difference time-domain simulations (FDTD) are performed to extensively characterize the AR-tube waveguides. Spectrograms, attenuation spectra, effective phase refractive indices, and the group-velocity dispersion parameters β ₂ of the AR-tube waveguides are presented. Both the experimental and numerical results confirm the extended bandwidth and smaller group-velocity dispersion of the AR-tube waveguide compared to a low loss plain dielectric tube THz waveguide. The AR-tube waveguide prototypes show an attenuation spectrum close to the theoretical limit given by the infinite cladding tube waveguide.     

氧化镁单晶在太赫兹波段的介电特性

利用太赫兹时域光谱系统,在0.5~9.5 THz范围内对氧化镁单晶基片的介电特性进行了研究,并获得折射率、吸收系数以及复介电函数信息。实验数据表明,在低频（ 2 THz）范围内,氧化镁单晶透过性较好,折射率在3.12~3.15之间。折射率和吸收系数均随频率增加而增大,且在3.16 THz和8.11 THz两处存在明显的吸收峰。通过经典的赝简谐振动理论很好地拟合了实验结果,分析了晶体中的横向光学声子振动模式,为氧化镁单晶在宽带太赫兹波段的应用提供了有益参考。     

超电大复杂目标太赫兹散射特性建模微波方法延拓研究

微波方法到太赫兹散射特性建模的延拓面临两个关键的科学问题研究,其一是材料响应特性延拓,包括金属属性向合金属性过渡导致Drude模型无法准确描述,以及介质材料在太赫兹频段的响应模型研究;其二是表面随机粗糙结构、以及复杂细微精细结构在太赫兹频段下的散射行为建模方法的延拓研究。微波频段下可视同为光滑的金属表面在太赫兹频段可能呈现出表面微粗糙特性。此外,针对含介质涂覆或全介质表面太赫兹散射特性的建模,需要结合随机边界散射理论,建立多层描述模型,以涵盖其中的面散射和体散射现象。该文首先采用积分方程方法描述和分析了金属粗糙表面的太赫兹散射规律,与实测数据吻合较好。其次,对于含涂覆或介质材料的目标表面,除表面粗糙的影响外,材料内部的微小粒子成分(如碳粉、石墨、金属粉等)的电尺寸与太赫兹波长相比拟,实验显示其体散射贡献不可忽视。该文尝试用矢量辐射传输理论与积分方程方法结合的多层模型来描述含介质材料表面的散射特性,很好地解释了实测规律。最后,该文提出基于“半确定性”描述的射线追踪高频算法,实现了复杂目标表面相干和非相干散射特性的一体化快速建模,为超电大复杂目标太赫兹散射特性的建模分析提供有效手段。