Isotopic analysis based on terahertz spectrum

As a new promising detection technology in the terahertz research field,the terahertz time-domain spec-troscopy(THz-TDS)has very broad application potential in many fields because its advantage on the characteristic spectrum,wide spectrum and non-destructive analysis of interested substances.In this paper,the terahertz absorption spectra of gases mixed with 12 CO and 13 CO in the spec-trum range of 0.5–2.5 THz are measured by terahertz time-domain spectroscopy for the first time.Several isotopo-logues can be clearly distinguished based on the difference in their rotational energies and the consequent terahertz spectrum.The experimental results show that 12 CO and 13 CO have obvious characteristic absorption peaks in the spectrum range of 0.5–2.5 THz due to the difference in rotational energy,and the rotational constant B can be calculated according to the experimental values to distin-guish the two gaseous isotopologues.The frequency posi-tions of the characteristic absorption peak measured by this experiment and the rotation constant B calculated accord-ing to the experimental values are compared with those previous theoretical calculations and experimental results,and they are in good agreement.This result lays a foun-dation for developing more sophisticated terahertz instru-ments to the detection of different isotopologues.

Research on Detection of Food additives Based on Terahertz Spectroscopy and Analytic Hierarchy Process

Terahertz time-domain spectroscopy is a kind of far-infrared spectroscopy technology,and its spectrum reflects the internal properties of substances with rich physical and chemical information,so the use of terahertz waves can be used to qualitatively identify food additives containing nitrogen elements.Analytic hierarchy process(AHP)was originally used to solve evaluation-type problems,and this paper introduces it into the field of terahertz spectral qualitative analysis,proposes a terahertz time-domain spectral qualitative identification method combined with analytic hierarchy process,and verifies the feasibility of the method by taking four common food additives(xylitol,L-alanine,sorbic acid,and benzoic acid)and two illegal additives(melamine,and Sudan Red No.I)as the objects of study.Firstly,the collected terahertz time-domain spectral data were pre-processed and transformed into a data set consisting of peaks,peak positions,peak numbers and overall trends;then,the data were divided into comparison and test sets,and a qualitative additive identification model incorporating analytic hierarchy process was constructed and parameter optimisation was performed.The results showed that the qualitative identification accuracies of additives based on single factors,i.e.,overall trend,peak value,peak position,and peak number,were 80.23%,70.93%,67.44%,and 40.70%,respectively,whereas the identification accuracy of the analytic hierarchy process qualitative identification method based on multi-factors could be improved to 92.44%.In addition,the fuzzy characterisation of the absorption spectrum data was binarised in the data pre-processing stage and used as the base data for the overall trend,and the recognition accuracy was improved to 94.19%by combining the fuzzy characterisation method of such data with the hierarchical analysis qualitative recognition model.The results show that it is feasible to use terahertz technology to identify different varieties of additives,and this paper constructs a hierarchical analytical qualitative model with better effect,which provides a new means for food additives detection,and the method is simple in steps,with a small demand for samples,which is suitable for the rapid detection of small samples.

Investigation of copper sulfate pentahydrate dehydration by terahertz time-domain spectroscopy

Copper sulfate pentahydrate is investigated by terahertz time-domain spectroscopy. It is shown that the terahertz absorption coefficients are correlated with the particle size of the samples, as well as the heating rates of the ambient temperature. Furthermore, the water molecules of copper sulfate pentahydrate can be quantitatively characterized due to the high sensitivity of the terahertz wave to water molecules. Based on such results, the status of water incorporated in mineral opal is also characterized using terahertz time-domain spectroscopy. It indicates that terahertz technology can be considered as an efficient method to detect the dehydration of minerals.

Broadband terahertz time-domain spectroscopy and fast FMCW imaging: Principle and applications

We report a broadband terahertz time-domain spectroscopy(THz-TDS)which enables twenty vibrational modes of adenosine nucleoside to be resolved in a wide frequency range of 1-20 THz.The observed spectroscopic features of adenosine are in good agreement with the published spectra obtained using Fourier transform infrared spectroscopy(FTIR)and Raman spectroscopy.This much extended bandwidth leads to enhanced material characterization capability as it provides spectroscopic information on both intra-and inter-molecular vibrations.In addition,we also report a low-cost frequency modulation continuous wave(FMCW)imaging system which has a fast measurement speed of 40000 waveforms per second.Cross-sectional imaging capability through cardboard has also been demonstrated using its excellent penetration capability at a frequency range of 76-81 GHz.We anticipate that the integration of these two complementary imaging technologies would be highly desirable for many real-world applications because it provides both spectroscopic discrimination and penetration capabilities in a single instrument.

Terahertz spectrum clustering of traditional Chinese medicine based on first derivative characteristics

In order to deal with the unclear absorption peak caused by the absorption peak overlap of traditional Chinese medicine(TCM)and other mixtures,a method of three unsupervised clustering algorithms as K-means,K-medoids and Fuzzy C-means(FCM)combined with the first derivative characteristics of terahertz absorption spectrum,is proposed to perform the terahertz spectra clustering of Sanchi and other three kinds of TCM compared with their easily-confused products(ECPs).These three unsupervised clustering methods complement the scope of the supervised learning classification method.The first derivative of the spectrum could amplify the difference in the absorption coefficient with different substances,so that the obvious absorption peak can be revealed.Experiments shows that these three clustering algorithms can achieve good results by combining the origin absorption coefficient with its first-order derivative as the characteristic data,and among which K-means does the best with the accuracy of95.32%.Compared with pure absorption coefficient data clustering,the accuracy in this study has been significantly improved,especially for the non-absorption-peak TCM classification.And the accuracy of K-means algorithm is improved by5.38%.Besides,clustering algorithms in this study have strong anti-interference ability to the error data.

Absorption Spectrum Studies on the RDX Crystals with Different Granularity in Terahertz Frequency Range

The absorption spectrum of the cyclotrime-thylenetrinitramine （RDX） with four different particle sizes are measured in the frequency range from 0.1THz to 2.5THz by using the terahertz time-domain spectroscopy （THz-TDS）, and the characteristic absorption peaks are acquired. All the samples are measured in a loose condition, which is very close to the real using environment of the RDX. The results show that the four kinds of samples have similar absorption peaks around the frequency of 0.82THz, 1.05 THz, 1.30THz, 1.46THz, 1.65THz, and 1.95THz. The sample with a large particle size obtains more peaks than the small one, while the peaks obtained from the sample with a small size are more protrudent. The reasons for these differences can be the refraction, scattering, and attenuation of the terahertz wave when it passes through the crystal samples. The theoretical terahertz spectrum of RDX was simulated by using density functional calculations, in which, the Becke ＆amp; Perdew-Wang＇s functional is used in a double numerical plus polarization method （BP/DNP）. Good agreements between the experimental and computed results show that the three peaks located in the frequency of 1.30THz, 1.48THz, and 1.96THz are caused respectively by the twisting of three-nitrogen heterocyclic, the symmetrical oscillations of the double nitro groups, and the oscillations of a single nitro group.

Far-infrared conductivity of CuS nanoparticles measured by terahertz time-domain spectroscopy

This paper reports that terahertz time-domain spectroscopy is used to measure the optical properties of CuS nanoparticles in composite samples. The complex conductivity of pure CuS nanoparticles is extracted by applying the Bruggeman effective medium theory. The experimental data are consistent with the Drude-Smith model of conductivity in the range of 0.2 1.5 THz. The results demonstrate that carriers become localized with a backscattering behaviour in small-size nanostructures. In addition, the time constant for the carrier scattering is obtained and is only 64.3 fs due to increased electron interaction with interfaces and grain boundaries.

Two-Dimensional Terahertz Time-Domain Spectroscopy and Its Applications

In this work, we review the developing progress of two-dimensional terahertz time-domain spectroscopy（THz-TDS） and its diverse applications, including analyzing the polarization of THz radiation from a laser-induced plasma source and studying the corresponding physical mechanism, and characterizing the optical properties of crystals, etc.

Terahertz Time-Domain Spectroscopy and Its Applications

The terahertz time-domain spectroscopy （THz-TDS） system and the related technology and the applications in Capital Normal University are presented. The most often used THz-TDS system as a spectroscopic measurement setup in our lab is introduced in detail, including the THz radiation source, the THz detection method and its measurement, and the control system. THz spectra of various materials is summarized and discussed. These materials include but not limited to two kinds of typical matter-the illegal drugs and explosives. The biological macro-molecules, cosmetics and fine chemical materials, edible pigments and food additives, homocysteic acid and related compounds, heavy ions in soil, Chinese medicines, tobacco and crops, oil and chemical products, carbon nanotubes, superconductors, and various semiconductors and their heterojunctions, are presented. THz emissions from the InAs and InN semiconductors surface are compared. THz spectral investigation of metallic mesh structures is summarized. Finally, an outlook of THz spectroscopic applications is given.

Low-Frequency Vibrations of Indole Derivatives by Terahertz Time-Domain Spectroscopy

Several indole derivatives with different ＇3-＇ substituents have been investigated by terahertz （THz） time-domain spectroscopy. The low-frequency absorption spectra and refractive indices were obtained in the range of 0.2 THz to 2.5 THz （7 cm-1 to 83 cm-1）. These derivatives with different substituents present distinct features, which suggests that THz spectroscopy is sensitive to different structures and components of these chemicals. The density functional theory was employed to calculate the low-frequency vibrational properties of indole-3-carboxylic acid and indole-3-propionic acid based on their crystal structures, and the intermolecular interactions were involved. Meanwhile, the temperature dependence of the spectra agreed with the calculated results. The quantitative analysis of a ternary mixture was studied by taking the THz fingerprints into account, and the results demonstrate THz spectroscopy has great potential for the practical applications in biochemistry and pharmaceutics.

The transmission enhancement of a THz pulse through an Ag/Ag_2 O layer detected by terahertz time-domain spectroscopy

This paper reports a new way to detect the enhanced transmission of a THz electromagnetic wave through an Ag/Ag2O layer by THz-TDS （time-domain spectroscopy）. As the THz beam illuminates the sub-wavelength Ag particles gained by Ag2O thermal decomposition, the evanescent wave is generated. The evanescent wave is coupled by a 500μm-GaAs substrate, which attaches behind the Ag/Ag2O layer, and then it transmits to the far field to be detected. The experimental results indicate that the transmitting amplitude is enhanced, as well as the frequent shifting and spectra broadening.

Terahertz Spectroscopic Characterization and Thickness Evaluation of Internal Delamination Defects in GFRP Composites

The use of terahertz time-domain spectroscopy(THz-TDS)for the nondestructive testing and evaluation(NDT&E)of materials and structural systems has attracted significant attention over the past two decades due to its superior spatial resolution and capabilities of detecting and characterizing defects and structural damage in non-conducting materials.In this study,the THz-TDS system is used to detect,localize and evaluate hidden multi-delamination defects(i.e.,a three-level multi-delamination system)in multilayered GFRP composite laminates.To obtain accurate results,a wavelet shrinkage de-noising algorithm is used to remove the noise from the measured time-of-flight(TOF)signals.The thickness and location of each delamination defect in the z-direction(i.e.,through-the-thickness direction)are calculated from the de-noised TOF signals considering the interaction between the pulsed THz waves and the different interfaces in the GFRP composite laminates.A comparison between the actual and the measured thickness values of the delamination defects before and after the wavelet shrinkage denoising process indicates that the latter provides better results with less than 3.712%relative error,while the relative error of the non-de-noised signals reaches 16.388%.Also,the power and absorbance levels of the THz waves at every interface with different refractive indices in the GFRP composite laminates are evaluated based on analytical and experimental approaches.The present study provides an adequate theoretical analysis that could help NDT&E specialists to estimate the maximum thickness of GFRP composite materials and/or structures with different interfaces that can be evaluated by the THz-TDS.Also,the accuracy of the obtained results highlights the capabilities of the THz-TDS for the NDT&E of multilayered GFRP composite laminates.

Temperature and Pressure Effects on Terahertz Time-Domain Spectroscopy of Crystalline Methedrine by Molecular Dynamics Simulation

In this study, the terahertz time-domain spectroscopy (THz-TDS) of crystalline methedrine, which is one of the illegal drugs, is performed using molecular dynamics simulation by the Fourier transform of time derivative auto-correlation functions of the dipole moment. In order to accurately detect the drugs from samples, it is necessary to build a complete database for terahertz spectra under different external conditions from theoretical calculation, which are hardly obtained from the experiments directly. Our results show remarkable consistency with the available experimental data in the frequency range of 10 - 100 cm-1 indicating that the presented method has significant capability to simulate terahertz spectra at various conditions. We investigated the effects of temperature and pressure on THz-TDS by simulating the system at temperature range between 78.4 K and 400 K at pressures up to 100 atm. Results show the spectral features of THz-TDS both in intensity and profile are highly sensitive to the variation of temperature and with a lower magnitude to the variation of pressure. The vanishing, rebuilding and shifting of spectral peaks are due to the complex mechanisms such as the anharmonicity, shifting in the vibration energy levels, formation and destruction of hydrogen-binding and the deformation of the potential energy surface during the environment changing. This improved our understanding for complicated THz-TDS of crystalline methedrine and would be useful for assignment of the practical measurements.

Integrated system of traditional THz time-domain spectroscopy and asynchronous optical sampling

Terahertz time-domain spectroscopy(THz-TDS)system,as a new means of spectral analysis and detection,plays an increasingly pivotal role in basic scientific research.However,owing to the long scanning time of the traditional THz-TDS system and the complex control of the asynchronous optical scanning(ASOPS)system,which requires frequent calibration,we combine traditional THz-TDS and ASOPS systems to form a composite system and propose an all-fiber trigger signal generation method based on the time overlapping interference signal generated by the collinear motion of two laser pulses.Finally,the time-domain and frequency-domain spectra are obtained by using two independent systems in the integrated systems.It is found that the full width at half maximum(FWHM)of the time-domain spectra and the spectral width of the frequency-domain spectra are almost the same,but the sampling speed of the ASOPS system is significantly faster than that of the traditional THz-TDS system,which conduces to the study of the transient characteristics of substances.

基于太赫兹时域光谱系统的双折射率晶体非接触式表征方法

晶体的各向异性探测技术正逐渐向非接触和非破坏性方法发展。太赫兹辐射由于其对许多介电材料的大穿透深度和非电离特性,在各向异性材料的双折射研究中具有广阔的前景。石英、蓝宝石、液晶以及含有亚波长结构的超材料等都表现出太赫兹双折射,作为偏振功能器件中的常用材料,其参数测量对于太赫兹器件研发具有重要意义。材料双折射率的提取往往依赖光轴方向和晶体厚度等先验参数。材料的光轴方向表征其各向异性的优先方向,对于已知光轴取向的晶体,可以根据经验选择合适的琼斯向量,而在实际应用中,只要选择探测太赫兹波的线偏振方向、光轴、探测轴。可以很容易地测量出寻常光和非常光,并直接从时域信号中计算出各自的折射率。对于光轴方向未知的材料,需要旋转样品以不同的方位角进行测量。双折射率的提取依赖于材料厚度的确定,通过游标卡尺或千分尺所得测量值与真实值存在较大差异,容易在样品表面造成划痕。无论是旋转样品还是厚度测量,人为操作都会为双折射率表征引入不确定性。基于透射式太赫兹时域光谱系统(THz-TDS)开发了一种双折射晶体光轴方向和晶片厚度的非接触式测量方法,不依赖于晶体先验参数,即可获取晶体完整的折射率。通过控制样品旋转配合光学延迟线动作实现光轴自动定位,利用传递函数迭代逼近算法提取晶体厚度和完整的折射率。为验证该方法,选择了在太赫兹波段具有双折射特性的(10-10)取向蓝宝石晶体进行测量,准确地提取了晶体在0.3~1.5 THz频率范围的平均寻常光折射率3.39±0.02,非常光折射率3.08±0.02,双折射率-0.31±0.02,并绘制了吸收谱。结果证明,所建立的测量方法避免了人工操作引起的样品损坏和定位误差,提高了双折射晶体太赫兹频段材料参数的测量速度、稳定性和精确度,对偏振敏感太赫兹测量技术及其应用具有重要意义。

太赫兹生物医学应用研究现状

近年来,太赫兹(Terahertz,THz)技术在生物医学领域的应用研究发展迅速。科技工作者利用THz技术在生物分子、细胞、组织及生物个体等层面取得了一系列的重要研究成果,为生物医学研究和诊疗提供了新视角和手段。作者从THz光谱检测、成像及生物效应三个方面总结了THz技术在生物医学领域的研究现状,分析了THz技术在生物医学应用中所面临的挑战,并对未来的发展方向进行了展望。

Different Types of Bone Fractures Observed by Terahertz Time-Domain Spectroscopy

Microcracks are common in compact bone,but their continued propagation can lead to macroscopic fractures.These microcracks cannot be visualized radiographically,necessitating alternative noninvasive methods to identify excessive microcracking and prevent fractures.In this study,terahertz time-domain spectroscopy(THz-TDS)was used to examine bone interiors near cracks resulting from loading in bovine tibia samples.Various loading configurations,such as impact,quasi-static loading,and fatigue loading,known to induce different types of micro-scale damage,were applied.The values of refractive index and absorption coefficient of the bone samples were then determined from the THz-TDS spectra acquired before loading and after fracture.The study revealed that different loading configurations led to varying terahertz optical coefficients associated with various types of bone fractures.Specifically,the refractive index notably increased under fatigue loading but remained relatively stable during quasi-static bending.The absorption coefficient of bone decreased only under fatigue loading.Furthermore,samples were subjected to axial and radial impacts without sustaining damage.Results indicated that in the undamaged state,the change in refractive index was smaller compared to after impact failure,while the change in absorption coefficient remained consistent after failure.Under radial impact loading,changes in refractive index and absorption coefficient were significantly more pronounced than under axial loading.Prior to loading,the measured value of refractive index was 2.72±0.11,and the absorption coefficient was 6.33±0.09 mm^(−1)at 0.5 THz.

太赫兹频段高速移动场景参考信号方案研究

针对太赫兹频段高速移动场景,提出了一种参考信号方案——增强型离散傅里叶变换扩展正交频分复用(E DFT-s-OFDM)DMRS:将具有循环前缀(CP)和循环后缀(CS)的参考信号序列分割为首部和尾部参考信号序列,然后分别嵌入每个OFDM符号的尾部和首部。这种方案的优点在于,前一个OFDM符号的尾部和后一个OFDM符号的首部构成一个完整的参考信号序列,从而允许接收端在每个OFDM符号间隔内都能进行信道估计,提高了信道估计的精度和实时性。此外,相邻OFDM符号的首部和尾部参考信号序列相同,从而省去了每个OFDM符号的传统循环前缀(CP),提高了频谱效率。仿真结果表明,在太赫兹频段高速移动场景下,与5G NR DFT-s-OFDM波形的DMRS方案相比,该方案的信道估计更精确,通信系统的频谱效率更高。

基于太赫兹频谱的绝缘油中微量甲醇无损检测新方法

甲醇是油纸绝缘中纤维素老化的特有标志物,目前采用的顶空气相色谱/质谱测试方法过程繁琐,无法实现无损快速检测。现有的拉曼光谱和红外光谱也难以实现低浓度甲醇(mg·L^(-1)级)的感知。利用太赫兹检测技术对极性物质的敏感性,提出了一种实现绝缘油中微量甲醇的无损检测新方法。通过采用克拉玛依25#矿物绝缘油和色谱级别的甲醇配制浓度为99、59.4、19.8、9.9、4.95、2.48、1.24、0.62、0.31和0.15 mg·L^(-1)的含甲醇的绝缘油混合溶液。检测含微量甲醇的绝缘油在太赫兹频段的吸收光谱,发现在1.7 THz左右存在特征峰,其与油中甲醇浓度有较好的定量相关关系,初步在实验室中实现了0.15 mg·L^(-1)的绝缘油中微量甲醇的测量。基于量子化学计算分析揭示了甲醇与绝缘油之间复杂的分子间力使油与甲醇分子协同振动,是太赫兹频段特征峰的机理。甲醇和绝缘油之间复杂的分子间作用力,使得两种分子在太赫兹频段产生协同振动。同时,随着甲醇浓度的增加,甲醇分子间会形成氢键,更易缔合,减少了甲醇分子与绝缘油分子缔合的比例,从而1.7 THz左右的特征峰增长速度变缓。因此,吸收峰的强度与甲醇浓度存在非线性关系。含微量甲醇的老化绝缘油的太赫兹频谱在1.7 THz左右同样出现了吸收峰,在同一甲醇浓度时,吸收峰的强度随着老化天数的增加而增加,增幅与老化程度存在非线性关系,这可能与不同时期的绝缘油裂解的产物含量有关。聚合物和绝缘油对太赫兹波的低吸收性,有机会实现变压器上绝缘油中低浓度甲醇的快速原位检测。未来将通过进一步增大光程、绝缘油老化产物与甲醇的协同振动机理分析以及自适应大数据信号提取算法来提高测试下限,并排除老化因素的影响,实现全周期绝缘油中甲醇含量的准确无损测量。

基于可拉伸反射基底介质超光栅的太赫兹增强吸收谱

提出了一种利用纳米银浆作为反射层的可拉伸介质超光栅的亚波长增强结构,在指纹谱检测时可以有效提升待测物周围的局域场而实现超宽带太赫兹吸收谱信号增强。当太赫兹波以一定角度照射到可拉伸弹性衬底介质超光栅上表面时,对衬底进行一系列拉伸,不同的拉伸因子激发出一系列导模共振,对应的介质超光栅响应曲线上的谐振峰频率覆盖0.46~0.61 THz。选择0.2~1.0μmα-乳糖薄膜作为待测微量分析物时,各拉伸因子对应的谐振峰幅度随待测物的吸收谱大幅度改变,其包络线组成的吸收谱峰值比没有介质超光栅周期结构时,最多增强111倍。该基于金属基底的可拉伸微结构为微量分析物的太赫兹高灵敏度检测提供了一种新的有效方法。