Time-domain Transmission Spectroscopy Research Articles

Terahertz time-domain transmission spectroscopy of water and hydrogel thin films: Extraction of optical parameters and application to agarose gel characterization

Terahertz time-domain spectroscopy (THz-TDS) is an emerging optical technique that has potential applications in the characterization of (bio)materials. However, the complicated extraction of optical parameters from multi-layered and optically thin samples is a barrier towards its acceptance by applied scientists. Therefore, the aim of this work is to provide a straightforward approach for the extraction of the THz absorption coefficient and index of refraction profiles of aqueous thin films in a window-sample-window configuration, which is ubiquitous in many laboratories (i.e., sample in a cuvette). A numerical approach-based methodology that accounts for multiple layers, Fabry–Pérot effect, and sample thickness is elaborated which involves an optical interference model based on a tri-layer structure and a simple thickness estimation technique. This method was validated on water samples where a good agreement was found with the THz optical parameters of water reported in the literature, while the use of a commercial software resulted in erroneous optical parameters estimates when used without due regard to its limitations. A case study was then performed to demonstrate the ability of the proposed method to characterize agarose hydrogels with varying degree of sulfation. It was demonstrated that THz-TDS can provide insight into the hydration state of the agarose hydrogels, including the relative number of the hydrogen bonds between the hydroxyl moieties of water and the polysaccharide network which is perturbed by the presence of sulfate. The trend in the index of refraction profiles suggested microstructural differences between the agarose hydrogels, which were confirmed by visualizing the agarose network morphology using cryo-SEM imaging.

Observation of magnetoconductivity with terahertz probes for ferromagnetic Fe films

Ultrafast characterization of spin-dependent transport behavior in ferromagnetic systems without contact probes has been of strong demand, recently. We have experimentally investigated spin-dependent complex conductivity for ferromagnetic Fe films of various thickness by means of terahertz time-domain transmission spectroscopy. Comparison of the transmitted terahertz wave amplitude and the spin-dependent conductivity reveals that the magnetization state of films effectively determines the complex conductivity. Non-invasive observation of spin-dependent conductivity by contact-free terahertz probe method is proven to be promising in further investigating spintronic materials, particularly on an ultrafast timescale.

Wideband dielectric properties of silicon and glass substrates for terahertz integrated circuits and microsystems

This paper presents a comprehensive study of the optical and electrical dielectric material properties of six commonly-used silicon and glass substrates at terahertz (THz) frequencies, including refractive index, absorption coefficient, dielectric constant and loss factor. The material characterization techniques used in this paper feature THz time-domain transmission and reflection spectroscopy with the measurement frequencies from 0.5 THz up to a maximum of 6.5 THz. Of the six selected dielectric and semiconductor substrates, two are silicon wafers with resistivities ranging from 0.001 to 0.02 Ω-cm. From the measurement results, loss tangents of the selected silicon wafers range from 0.680 to 5.455 and the dielectric constants are from 1.079 to 17.735. The four other wafers are all glass-based substrates: D263 glass, Borofloat 33 glass, fused silica and Sapphire. From the measurements, it is found that the THz dielectric properties vary considerably between the substrate samples e.g. dielectric constants range from 1.925 to 3.207 while loss tangents are from 0.042 × 10−3 to 0.127. Most of the selected silicon and glass-based substrates are quite useful for many THz applications, e.g., THz integrated circuits (THz ICs), THz microsystem technologies (THz MSTs) and THz system-on-a-chip (THz SoC) and system-on-substrate (SiP).

Intrinsic Charge Dynamics in High-T_{c} AFeAs(O,F) Superconductors.

We report the first determination of the in-plane complex optical conductivity of 1111 high-T_{c} superconducting iron oxypnictide single crystals PrFeAs(O,F) and thin films SmFeAs(O,F) by means of conventional and microfocused infrared spectroscopy, ellipsometry, and time-domain THz transmission spectroscopy. A strong itinerant contribution is found to exhibit a dramatic difference in coherence between the crystal and the film. Using extensive temperature-dependent measurements of THz transmission, we identify a previously undetected 2.5-meV collective mode in the optical conductivity of SmFeAs(O,F), which is strongly suppressed at T_{c} and experiences an anomalous T-linear softening and narrowing below T^{*}≈110 K≫T_{c}. The suppression of the infrared absorption in the superconducting state reveals a large optical superconducting gap with a similar gap ratio 2Δ/k_{B}T_{c}≈7 in both materials, indicating strong pairing.

Simultaneous measurement of doping concentration and carrier lifetime in silicon using terahertz time-domain transmission

In this work, we present a measurement approach enabling the simultaneous determination of sheet resistance and carrier lifetime in semiconductor samples. It is based on a classic Terahertz (THz) time-domain transmission spectroscopy scheme extended by quasi-steady state optical excitation. The carrier lifetime is determined by contactless THz probing of the increase in sheet conductance associated with quasi-steady-state excitation. Combining a successive etch-back of the surface with repeated THz measurements yields a depth profile of the doping concentration and the carrier lifetime, which is important for the optimization of the emitter of solar cells, for instance. The viability of our approach is demonstrated by investigating a phosphorous doped emitter of a silicon solar cell with the THz approach and comparing the results with electrochemical capacitance voltage measurements.

Calculation and Study of Graphene Conductivity Based on Terahertz Spectroscopy

Based on terahertz time-domain spectroscopy system and two-dimensional scanning control system, terahertz transmission and reflection intensity mapping images on a graphene film are obtained, respectively. Then, graphene conductivity mapping images in the frequency range 0.5 to 2.5 THz are acquired according to the calculation formula. The conductivity of graphene at some typical regions is fitted by Drude-Smith formula to quantitatively compare the transmission and reflection measurements. The results show that terahertz reflection spectroscopy has a higher signal-to-noise ratio with less interference of impurities on the back of substrates. The effect of a red laser excitation on the graphene conductivity by terahertz time-domain transmission spectroscopy is also studied. The results show that the graphene conductivity in the excitation region is enhanced while that in the adjacent area is weakened which indicates carriers transport in graphene under laser excitation. This paper can make great contribution to the study on graphene electrical and optical properties in the terahertz regime and help design graphene terahertz devices.

Precisely THz spectroscopy measurement of a three-layer structure using THz-TDS waveform rebuilding technology

We extracted optical material parameter of a middle sample layer in a three-layer structure from THz time-domain transmission spectroscopy by waveform rebuilding technology. The sample waveform is rebuilt by a reference signal in air and the transfer function of three-layer structure with liquid as a sample. Material parameters were calculated by minimizing the difference between the measured sample waveform and a rebuilt one in time domain. The method has wide application in the investigation of liquids in a known-thickness cuvette with high absorption in THz range.

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.

Dielectric constants of bulk ferroelectric PZT measured by terahertz time-domain spectroscopy

The complex permittivity of bulk ceramic ferroelectric of nominal composition PbZr0.4Ti0.6O3 was measured in the range 0.2–2 THz using transmission time-domain spectroscopy. The results indicate strong absorption and dispersion in this frequency range as often seen in highly disordered and polar materials. The results are compared to equivalent thin film data in the literature, and significant differences in the real and imaginary permittivity suggest that substrate clamping and degree of polarisation of the ferroelectric thin film materials affect dielectric properties even at these high frequencies.

Far infrared and Raman response in tetragonal PZT ceramic films

PbZr0.38Ti0.62O3 and PbZr0.36Ti0.64O3 thick films deposited by screen printing on (0001) single crystal sapphire substrates and prepared at two different sintering temperatures, were studied by Fourier-transform infrared reflectivity, time-domain THz transmission spectroscopy and micro-Raman spectroscopy. The dielectric response is discussed using the Lichtenecker model to account for the porosity of the films and to obtain the dense bulk dielectric functions. Results are compared with bulk tetragonal PZT 42/58 ceramics. The dynamic response in the films is dominated by an overdamped lead-based vibration in the THz range, as known in PZT, but its evaluated dielectric contribution is affected by the porosity and roughness of the surface.

Application of terahertz time-domain spectroscopy combined with chemometrics to quantitative analysis of imidacloprid in rice samples

Terahertz time-domain spectroscopy (THz-TDS) has been utilized as an effective tool for quantitative analysis of imidacloprid in rice powder samples. Unlike previous studies, our method for sample preparation was mixing imidacloprid with rice powder instead of polyethylene. Then, terahertz time domain transmission spectra of these mixed samples were measured and the absorption coefficient spectra of the samples with frequency range extending from 0.3 to 1.7THz were obtained. Asymmetric least square (AsLS) method was utilized to correct the slope baselines that are presented in THz absorption coefficient spectra and improve signal-to-noise ratio of THz spectra. Chemometrics methods, including partial least squares (PLS), support vector regression (SVR), interval partial least squares (iPLS), and backward interval partial least squares (biPLS), were used for quantitative model building and prediction. To achieve a reliable and unbiased estimation, bootstrapped Latin partition was chosen as an approach for statistical cross-validation. Results showed that the mean value of root mean square error of prediction (RMSEP) for PLS (0.5%) is smaller than SVR (0.7%), these two methods were based on the whole absorption coefficient spectra. In addition, PLS performed a better performance with a lower RMSEP (0.3%) based on the THz absorption coefficient spectra after AsLS baseline correction. Alternatively, two methods for variable selection, namely iPLS and biPLS, yielded models with improved predictions. Comparing with conventional PLS and SVR, the mean values of RMSEP were 0.4% (iPLS) and 0.3% (biPLS) by selecting the informative frequency ranges. The results demonstrated that an accurate quantitative analysis of imidacloprid in rice powder samples could be achieved by terahertz time-domain transmission spectroscopy combined with chemometrics. Furthermore, these results demonstrate that THz time-domain spectroscopy can be used for quantitative determinations of other pesticides in other agricultural products.

Precise Determination of Thicknesses of Multilayer Polyethylene Composite Materials by Terahertz Time-Domain Spectroscopy

The multilayer structure of an ultra-high molecular weight polyethylene (UHMWPE) composite material was investigated in the terahertz (THz) spectral range by means of time-domain spectroscopy (TDS) technique. Such structures consist of many alternating layers of fibers, each being perpendicular to the other and each having a thickness of about 50 μm. Refractive indices of two composite samples and of a sample composed of four single layers (plies) having the same fiber orientation were determined for two orthogonal orientations of the electric field in a transmission TDS system. The birefringence of a single layer was measured, and the origin of this phenomenon is discussed. Using the TDS system in reflection, the formation of many pulses shifted in time was observed originating from reflections from interfaces of successive layers caused by the periodic modulation of the refractive index along the propagation of the THz radiation. This phenomenon is theoretically described and simulated by means of a transfer matrix method (TMM). A time-domain fitting procedure was used to determine thicknesses of all layers of the composite material. The reconstructed waveform based on the optimized thicknesses shows very good agreement with the measured waveform, with typical differences between measurements and simulations between 3 and 7 μm (depending on the sample). As a result, we were able to determine the thicknesses of all layers of two multilayer (~200 plies) structures by means of the reflection TDS technology with high accuracy.

Origin of potential errors in the quantitative determination of terahertz optical properties in time-domain terahertz spectroscopy

We demonstrate theoretically and experimentally how changes of a terahertz (THz) beam induced by the sample affect the accuracy of the determination of THz dielectric properties in THz time-domain transmission spectroscopy (TDTS). We apply a Gaussian beam and the ABCD matrix formalism to describe the propagation of the THz beam in a focused beam setup. The insertion of the sample induces a focus displacement which is absent in the reference measurement without a sample. We show how the focus displacement can be corrected. The THz optical properties after focus displacement correction reported in this Letter are in quantitative agreement with those obtained using collimated beam THz–TDTS in previous work.

Effect of pore conformation on dielectric anisotropy of oven-dry wood evaluated using terahertz time-domain spectroscopy and eigenvalue problems for two-dimensional photonic crystals

To clarify the effect of pore conformation on the dielectric anisotropy of wood, the relative permittivity along the longitudinal and tangential axes of flat-sawn oven-dry specimens of 12 different wood species was measured using terahertz time-domain transmission spectroscopy and compared with the values calculated using the eigenvalue problem for two-dimensional photonic crystals. The measured dielectric anisotropy, which is the ratio of the relative permittivity along longitudinal axis to that along the tangential axis, was well explained by the calculated value. It was concluded that the ratio of tangential to radial widths of wood pores affects the relative permittivity along the tangential axis, and that the dielectric anisotropy decreased with an increase in the ratio. This discussion can also be applied to the relative permittivity in frequencies below 0.15 THz. These findings show promise as a new method for evaluating the porous structure of wood.

Terahertz time-domain spectroscopy of absorbing materials

In this paper, we study the noise-limited precision on the complex refractive index value of materials in the terahertz frequency range as determined by terahertz time-domain spectroscopy. As absorbing samples are almost opaque, transmission measurements are not suitable to determine the refractive index and reflection indices have to be employed instead, but at the expense of precision. We give rules to select the most adapted technique, i.e. in transmission or in reflection, for any given sample of arbitrary transparence Full Text: PDF References M. van Exter and D. Grischkowsky, "Optical and electronic properties of doped silicon from 0.1 to 2 THz", Appl. Phys. Lett. 56, 1694 (1990); CrossRef Sensing with Terahertz Radiation, ed. D. Mittleman, Springer Series in Optical Sciences Vol. 85, Berlin (2003). DirectLink For example: http://www.menlosystems.com; , http://www.rainbowphotonics.com; , http://www.teraview.com; , http://www.ekspla.com; , http://www.picometrix.com; , http://www.zomega-terahertz.com; . T. Dorney, R. Baraniuk, and D. Mittleman, "Material parameter estimation with terahertz time-domain spectroscopy", J. Opt. Soc. Am. A 18, 1562 (2001); CrossRef I. Pupeza, R. Wilk, and M. Koch, "Highly accurate optical material parameter determination with THz time-domain spectroscopy", Opt. Exp. 15, Issue 7, 4335 (2007). CrossRef L. Thrane, R. H. Jacobsen, P. U. Jepsen, and S. R. Keiding, "THz reflection spectroscopy of liquid water", Chem. Phys. Lett. 240, 330 (1995); CrossRef S. C. Howells and L. A. Schlie, "Transient terahertz reflection spectroscopy of undoped InSb from 0.1 to 1.1 THz", Appl. Phys. Lett. 69, 550 (1996). CrossRef P. Uhd Jepsen and B. M. Fischer, "Dynamic range in terahertz time-domain transmission and reflection spectroscopy", Optics Letters 30, 29 (2005). CrossRef L. Duvillaret, F. Garet, J.-L. Coutaz, "Influence of noise on the characterization of materials by terahertz time-domain spectroscopy", J. Opt. Soc. Amer. B17, 452 (2000). CrossRef

Three-dimensional terahertz computed tomography of human bones

Three-dimensional terahertz computed tomography has been used to investigate dried human bones such as a lumbar vertebra, a coxal bone, and a skull, with a direct comparison with standard radiography. In spite of lower spatial resolution compared with x-ray, terahertz imaging clearly discerns a compact bone from a spongy one, with strong terahertz absorption as shown by additional terahertz time-domain transmission spectroscopy.

Optical conductivity of superconductingRb2Fe4Se5single crystals

We report the complex dielectric function of high-quality nearly-stoichiometric Rb2Fe4Se5 (RFS) single crystals with Tc=32 K determined by wide-band spectroscopic ellipsometry and time-domain transmission spectroscopy in the spectral range 1 meV<=$\hbar$\omega<=6.5 eV at temperatures 4 K<=T<=300 K. This compound simultaneously displays a superconducting and a semiconducting optical response. It reveals a direct band-gap of 0.45 eV determined by a set of spin-controlled interband transitions. Below 100 K we observe in the lowest THz spectral range a clear metallic response characterized by the negative dielectric permittivity \epsilon 1 and bare (unscreened) \omega pl=100 meV. At the superconducting transition this metallic response exhibits a signature of a superconducting gap below 8 meV. Our findings suggest a coexistence of superconductivity and magnetism in this compound as two separate phases.

Effect of solvent on carrier transport in poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) studied by terahertz and infrared-ultraviolet spectroscopy

The effect of solvent such as ethylene glycol (EG) on the carrier transport in poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS) was studied by the combination of terahertz (THz) time-domain transmission spectroscopy (0.1–3 THz) and broadband reflectance spectroscopy (4–800 THz). While the broadband reflectance showed a plasma edge in the near-infrared, the frequency dependence of the THz conductivity of PEDOT/PSS indicated weakly localized carrier behavior. The simultaneous fitting of both spectra by the localization-modified Drude model allowed us to conclude that the significant increase in conductivity with the addition of EG is due to improved carrier mobility in the PEDOT/PSS.

Improved TL-RLC model for terahertz circular split-ring resonators

Three geometries of split-ring resonators (SRRs) including circular geometry and two elliptical geometries were fabricated by modern photolithography process. The samples were measured by terahertz time-domain transmission spectroscopy. These spectra clearly revealed the lower-frequency LC resonances and the higher-frequency dipole resonances; meanwhile, the coupling effect between the LC and dipole resonance had played an important role in the overall response. Comparing the results shows that the LC resonance, dipole resonance, and the coupling effect can be designed. A simple transmission-line (TL) RLC circuit model was used to help us understand this coupling behavior and the extent of its effects. But the simple model has some disadvantage. For better matching TL-RLC model results with measured data, an improved model was introduced for the circular and y-direction stretched elliptical geometry SRRs. Other resonances and modes existing at higher frequencies except the typical LC and dipole resonances were revealed by the improved model.

Measurement of Refractive Index for High Reflectance Materials with Terahertz Time Domain Reflection Spectroscopy

A method to measure the refractive index for high reflectance materials in the terahertz range with terahertz time domain reflection spectroscopy is proposed. In this method, the THz waveforms reflected by a silicon wafer and high reflectance sample are measured respectively. The refractive index of the silicon wafer, measured with the THz time domain transmission spectroscopy, is used as a reference in the THz time domain reflective spectroscopy. Therefore, the complex refractive index of the sample can be obtained by resorting to the known reflective index of the silicon and the Fresnel law. To improve the accuracy of the phase shift, the Kramers–Kronig transform is adopted. This method is also verified by the index of the silicon in THz reflection spectroscopy. The bulk metal plates have been taken as the sample, and the experimentally obtained metallic refractive indexes are compared with the simple Drude model.