Guest Editorial TTA Special Section on Applications of Terahertz Time Domain Spectroscopy

Terahertz （THz） radiation, whose frequency ranges from 0.1 THz to 10.0 THz, has rich science, but limited technology. It has long been considered the last remaining scientific gap in the electromagnetic spectrum. Far from being fully exploited, it offers great opportunities in science, innovation, new technology, and potential applications. THz science and technology enables fundamental research directly impact our lives, from industrial quality control,

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.

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.

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.

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.

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.

Terahertz Time-Domain Spectroscopy method for optical parameter extraction of plastic materials

A method for extracting optical parameters of plastics materials based on terahertz time domain spectroscopy is presented. The transmission-type Terahertz Time-Domain Spectroscopy(THz TDS) system is adopted to detect the refractive index and extinction coefficient on different plastic materials. Then the corresponding spectral information is obtained by Fourier transform of the terahertz time domain waveform of the sampling points, including the corresponding amplitude and phase information of the waveform. The optical parameter extraction model is built. By using the simplex optimization method, the curves of the refractive index and extinction coefficient for the plastic material are obtained. The experimental samples are made of different plastic parallel plate materials. The experimental results show that the optimization of optical parameters can improve their extraction accuracy, and the error of refractive index is ±0.005. Extraction technology with the simplex optimization method of optical parameter based on THz TDS can help to extract the optical parameters of engineering plastics. It is of great significance for the research of terahertz nondestructive testing.

Terahertz time-domain spectroscopy and micro-cavity components for probing samples: a review

We give a brief review of the developments in terahertz time-domain spectroscopy(THz-TDS) systems and microcavity components for probing samples in the University of Shanghai for Science and Technology. The broadband terahertz(THz) radiation sources based on GaAs m-i-n diodes have been investigated by applying high electric fields. Then, the free space THz-TDS and fiber-coupled THz-TDS systems produced in our lab and their applications in drug/cancer detection are introduced in detail. To further improve the signal-to-noise ratio(SNR) and enhance sensitivity, we introduce three general micro-cavity approaches to achieve tiny-volume sample detection, summarizing our previous results about their characteristics, performance, and potential applications.

Investigation of solid-state reaction by terahertz time-domain spectroscopy

Terahertz time-domain spectroscopy(THz-TDS)was utilized to investigate the solid-state reaction between L(+)-Tartaric acid and sodium hydrogen carbonate.Solid sodium hydrogen L(+)-tartrate monohydrate was synthesized efficiently by mechanical grinding,which is particularly sustainable and environmentally benign.Distinct THz absorptions were observed for pure reactants and the proposed product.The reaction process could be clearly visualized by THz spectral patterns of the reaction mixtures at different grinding time.The observed results were further confirmed by synchrotron radiation X-ray powder diffraction(SRXRPD)and Fourier transform infrared (FT-IR)spectroscopy.The study demonstrates that THz-TDS is an effective novel tool to monitor solid-state reactions in pharmaceutical industry.

Spectroscopy Studies on Stream Sediments in the Terahertz Range

In order to study stream sediments in the terahertz range, we have measured six reference stream sediment samples by terahertz time-domain spectroscopy (THz-TDS). We obtained the absorption coefficients and refractive indexes. By analyzing the spectra, we got different drops in amplitude and delays in time. The absorption and refractive properties of samples changed with its components and types. In addition, we also found there was a nearly linear relationship between the absorption coefficient and the frequency. We calculated the slope value (K) of each sample by linear fitting, and find the K was corresponding to the contents of the samples. The results showed THz-TDS was an effective method to the analysis of stream sediments.

Terahertz radiation of a butterfly-shaped photoconductive antenna(invited)

The terahertz(THz) far-field radiation properties of a butterfly-shaped photoconductive antenna(PCA) were experimentally studied using a home-built THz time-domain spectroscopy(THz-TDS) setup.To distinguish the contribution of in-gap photocurrent and antenna structure to far-field radiation,polarization-dependent THz field was measured and quantified as the illuminating laser beam moved along the bias field within the gap region of electrodes. The result suggests that, although the far-field THz radiation originates from the in-gap photocurrent, the antenna structure of butterfly-shaped PCA dominates the overall THz radiation. In addition, to explore the impact of photoconductive material,radiation properties of butterfly-shaped PCAs fabricated on both low-temperature-grown GaAs(LT-GaAs) and semi-insulating GaAs(Si-GaAs) were characterized and compared. Consistent with previous experiments, it is observed that while Si-GaAs-based PCA can emit higher THz field than LT-GaAs-based PCA at low laser power, it would saturate more severely as laser power increased and eventually be surpassed by LT-GaAs-based PCA. Beyond that, it is found the severe saturation effect of Si-GaAs was due to the longer carrier lifetime and higher carrier mobility, which was confirmed by the numerical simulation.

Research on terahertz time-domain spectroscopy methodology of liquid samples

Terahertz(THz) time-domain spectroscopy(TDS) has been applied to investigate liquid's optical property in recent years.However,comprehensive discussion of how to compute liquids' complex refractive indices and absorption rates are seldom reported.So,in this work,we try to find a way to compute liquids' optical property accurately and conveniently.

Detecting NO3- concentration in nitrate solutions using terahertz time-domain spectroscopy

In this paper, we employed terahertz time domain spectroscopy （THz-TDS） to investigate the nitrate 0 concentration in four types of nitrate solution （sodium nitrate, aluminum nitrate, calcium nitrate and magnesium nitrate）. Their absorption coefficient and refractive index were calculated in 0.2-2.5THz, and a logarithmic relationship was observed between NO3 concentrations and selected optical parameters regardless of the kinds of nitrate solution. Partial least square （PLS） model was built between THz-TDS and NO3 concentration. The correlation coefficient of PLS model was calculated. The results make the quantitative analysis of NO3 concentration possible by THz-TDS and indicate the bright future in practical application.

Identifying PM2.5 samples collected in different environment by using terahertz time-domain spectroscopy

Particulate matter with the diameter of less than 2.5 μm （PM2.5） is the most important causation of air pollution. In this study, PM2.5 samples were collected in three different environment including ordinary atmo- spheric environment, lampblack environment and the environment with an air conditioning exhaust fan, and analyzed by using terahertz time-domain spectroscopy （THz-TDS）. The linear regression analysis and the principal component analysis （PCA） are used to identify PM2.5 samples collected in different environment. The results indicate that combining THz-TDS with statistical methods can serve as a contactless and efficient approach to identify air pollutants in different environment.

Quantitative determination of n-heptane and n-octane using terahertz time-domain spectroscopy with chemometrics methods

This paper introduces the terahertz time- domain spectroscopy （THz-TDS） used for the quantitative detection of n-heptane volume ratios in 41 n-heptane and n-octane mixtures with the concentration range of 0-100% at the intervals of 2.5%. Among 41 samples, 33 were used for calibration and the remaining 8 tbr validation. Models of chemometrics methods, including partial least squares （PLS） and back propagation-artificial neural network （BP-ANN）, were built between the THz- TDS and the n-heptane percentage. To evaluate the quality of the built models, we calculated the correlation coefficient （R） and root-mean-square errors （RMSE） of calibration and validation models. R and RMSE of two methods were close to 1 and 0 within acceptable levels, respectively, demonstrating that the combination of THz- TDS and chemometrics methods is a potential and promising tool for further quantitative detection of n- alkanes.

Optical response of tunable terahertz plasmon in a grating-gated graphene transistor

Tunable terahertz plasmon in a graphene-based device with a grating serving as a top gate is studied. Transmission spectra exhibit a distinct peak in the terahertz region when the terahertz electric field is perpendicular to the grating fingers.Our results show that the extinction in the transmission of single-layer graphene shields beyond 80%. Electronic results further show that the graphene plasmon can be weakly adjusted by tuning the gate voltage. Theoretical calculation also implies that the plasmon frequency of graphene can fall into the terahertz region of 1–2 THz by improving the sustaining ability and capacitance of the top gate.

Electrical and optical properties of MWNTs/HDPE composites in Terahertz region

Optical and electrical properties of composites,prepared by filling of high density polyethylene(HDPE) with two kinds of multi-walled carbon nanotubes(MWNTs) differing in diameters,were explored by terahertz time-domain spectroscopy(THz-TDS) in the frequency range from 0.2 to 1.6 THz.It is found that composite with larger-diameter MWNTs possesses larger absorption coefficient and conductivity at the same concentration.The real part of the ac conductivity of the composites follows a power law dependence on frequency.And the power index is around 0.75 regardless of the MWNT concentration and diameter.The experimental data were analyzed with Cole-Cole equation under the assumption that the conductive clusters dispersed in the polymer matrix behave like dipoles and contribute mainly to the dielectric loss.It is found that both of the composites have similar values of relaxation time and distribution parameter.With increase of the MWNTs concentration,the relaxation time increases and tends to saturate at 0.7 ps after passing through the percolation threshold.

Characterization of cocrystals formed by grinding amino acids through terahertz time-domain spectroscopy

In this paper,we used terahertz time-domain spectroscopy(THz-TDS)over a range of 0.3–2.5 THz to investigate the formation of solid-state cocrystals of amino acids,formed by grinding mixtures of two different kinds of amino acids.For comparison,we prepared dual-layer samples,combined by pressing two single-component pellets together without grinding.In the ground-mixture samples,some extra absorption peaks appeared,different from the characteristic peaks of the pure components,but these peaks did not appear in the dual-layer samples.Thus,these extra absorption peaks in the THz range are unique features of cocrystals.From our results,we believe that THz-TDS is a promising technique to characterize cocrystals.

Terahertz time-domain spectroscopic investigation on quinones

Well resolved far-infrared spectra of 1,4-benzoquinone, 1,4-naphthoquinone, and 9, 10-anthraquinonme in polycrystalline form have been measured with terahertz time domain spectroscopy at room tem- perature. The characterizations of power absorption and index of refraction in the frequency range 0.3 -2.0 THz are presented. Theoretical calculation is applied to assist the analysis and assignment of individual THz absorption spectra of the p-quinones with semiempirical AM1, Hartree-Fock (HF), and density functional theory (DFT) method. Observed THz responses are assigned to the translational and torsional vibrations of p-quinone dimer held together by weak hydrogen bonds.

THz time domain monostatic radar cross section measurement of metallic plates and dihedrons

THz Radar Cross Section(RCS)measurement setup based on THz Time Domain Spectroscopy(TDS)is built to provide large scaled targets test ability in recent years.As calibrations,the metal plates and dihedrons are used in our experiments.The measurements are performed in a monostatic terahertz time-domain setup.The author proposed time domain and frequency domain calibration methods for angular RCS of calibrations,comparing the measurements with the theory to verify the ability of the time domain measurement setup.