Fourier-transform THz spectroscopy based on electric-field interferometry using THz-PMT.

We demonstrate a high dynamic range (DR) Fourier-transform-based terahertz (THz) spectrometer by combining a THz photomultiplier tube (PMT) with a metasurface and a conventional Michelson interferometer. Because the THz-PMT response depends on the incident electric-field strength following the Fowler-Nordheim equation, we can directly obtain an electric field interferogram without any synchronized optical probe pulse in contrast to conventional THz-time-domain-spectroscopy (THz-TDS). The DR of the corresponding power spectrum using the proposed method was 4.6 × 105 without the use of a lock-in amplifier. The complex refractive index of a quartz glass plate obtained using the proposed method was in good agreement with the results of conventional THz-TDS.

Mapping nanoscale carrier confinement in polycrystalline graphene by terahertz spectroscopy.

Terahertz time-domain spectroscopy (THz-TDS) can be used to map spatial variations in electrical properties such as sheet conductivity, carrier density, and carrier mobility in graphene. Here, we consider wafer-scale graphene grown on germanium by chemical vapor deposition with non-uniformities and small domains due to reconstructions of the substrate during growth. The THz conductivity spectrum matches the predictions of the phenomenological Drude-Smith model for conductors with non-isotropic scattering caused by backscattering from boundaries and line defects. We compare the charge carrier mean free path determined by THz-TDS with the average defect distance assessed by Raman spectroscopy, and the grain boundary dimensions as determined by transmission electron microscopy. The results indicate that even small angle orientation variations below 5° within graphene grains influence the scattering behavior, consistent with significant backscattering contributions from grain boundaries.

Bottom-Up-Etching-Mediated Synthesis of Large-Scale Pure Monolayer Graphene on Cyclic-Polishing-Annealed Cu(111).

Synthesis of large-scale single-crystalline graphene monolayers without multilayers involves the fabrication of proper single-crystalline substrates and the ubiquitous formation of multilayered graphene islands during chemical vapor deposition. Here, a method of cyclic electrochemical polishing combined with thermal annealing, which allows the conversion of commercial polycrystalline Cu foils to single-crystal Cu(111) with an almost 100% yield, is presented. A global "bottom-up-etching" method that is capable of fabricating large-area pure single-crystalline graphene monolayers without multilayers through selectively etching bottom multilayered graphene underneath large area as-grown graphene monolayer on Cu(111) surface is demonstrated. Terahertz time-domain spectroscopy (THz-TDS) measurement of the pure monolayer graphene film shows a high average sheet conductivity of 2.8 mS and mean carrier mobility of 6903 cm2 V-1 s-1 over a large area. Density functional theory (DFT) calculations show that the selective etching is induced by the much easier diffusion of hydrogen atoms than hydrocarbon radicals across the edges of the top graphene layer, and the simulated selective etching processes based on phase field modeling are well consistent with experimental observations. This work provides new ways toward the production of single-crystal Cu(111) and the synthesis of pure monolayer graphene with high electronic quality.

Reference-free THz-TDS conductivity analysis of thin conducting films.

We present a reference-free method to determine electrical parameters of thin conducting films by steady state transmission-mode terahertz time-domain spectroscopy (THz-TDS). We demonstrate that the frequency-dependent AC conductivity of graphene can be acquired by comparing the directly transmitted THz pulse with a transient internal reflection within the substrate which avoids the need for a standard reference scan. The DC sheet conductivity, scattering time, carrier density, mobility, and Fermi velocity of graphene are retrieved subsequently by fitting the AC conductivity with the Drude model. This reference-free method was investigated with two complementary THz setups: one commercial fibre-coupled THz spectrometer with fast scanning rate (0.2-1.5 THz) and one air-plasma based ultra-broadband THz spectrometer for greatly extended frequency range (2-10 THz). Certain propagation correction terms for more accurate retrieval of electrical parameters are discussed.

Wafer-scale graphene quality assessment using micro four-point probe mapping.

Micro four-point probes (M4PP) provide rapid and automated lithography-free transport properties of planar surfaces including two-dimensional materials. We perform sheet conductance wafer maps of graphene directly grown on a 100 mm diameter SiC wafer using a multiplexed seven-point probe with minor additional measurement time compared to a four-point probe. Comparing the results of three subprobes we find that compared to a single-probe result, our measurement yield increases from 72%-84% to 97%. The additional data allows for correlation analysis between adjacent subprobes, that must measure the same values in case the sample is uniform on the scale of the electrode pitch. We observe that the relative difference in measured sheet conductance between two adjacent subprobes increase in the transition between large and low conductance regions. We mapped sheet conductance of graphene as it changed over several weeks. Terahertz time-domain spectroscopy conductivity maps both before and after M4PP mapping showed no significant change due to M4PP measurement, with both methods showing the same qualitative changes over time.

Conductivity mapping of graphene on polymeric films by terahertz time-domain spectroscopy.

Fast inline characterization of the electrical properties of graphene on polymeric substrates is an essential requirement for quality control in industrial graphene production. Here we show that it is possible to measure the sheet conductivity of graphene on polymer films by terahertz time-domain spectroscopy (THz-TDS) when all internally reflected echoes in the substrate are taken into consideration. The conductivity measured by THz-TDS is comparable to values obtained from four point probe measurements. THz-TDS maps of 25x30 cm2 area graphene films were recorded and the DC conductivity and carrier scattering time were extracted from the measurements. Additionally, the THz-TDS conductivity maps highlight tears and holes in the graphene film, which are not easily visible by optical inspection.

Terahertz wafer-scale mobility mapping of graphene on insulating substrates without a gate.

We demonstrate wafer-scale, non-contact mapping of essential carrier transport parameters, carrier mobility (µdrift), carrier density (Ns), DC sheet conductance (σdc), and carrier scattering time (τsc) in CVD graphene, using spatially resolved terahertz time-domain conductance spectroscopy. σdc and τsc are directly extracted from Drude model fits to terahertz conductance spectra obtained in each pixel of 10 × 10 cm2 maps with a 400 µm step size. σdc- and τsc-maps are translated into µdrift and Ns maps through Boltzmann transport theory for graphene charge carriers and these parameters are directly compared to van der Pauw device measurements on the same wafer. The technique is compatible with all substrate materials that exhibit a reasonably low absorption coefficient for terahertz radiation. This includes many materials used for transferring CVD graphene in production facilities as well as in envisioned products, such as polymer films, glass substrates, cloth, or paper substrates.

Graphene mobility mapping.

Carrier mobility and chemical doping level are essential figures of merit for graphene, and large-scale characterization of these properties and their uniformity is a prerequisite for commercialization of graphene for electronics and electrodes. However, existing mapping techniques cannot directly assess these vital parameters in a non-destructive way. By deconvoluting carrier mobility and density from non-contact terahertz spectroscopic measurements of conductance in graphene samples with terahertz-transparent backgates, we are able to present maps of the spatial variation of both quantities over large areas. The demonstrated non-contact approach provides a drastically more efficient alternative to measurements in contacted devices, with potential for aggressive scaling towards wafers/minute. The observed linear relation between conductance and carrier density in chemical vapour deposition graphene indicates dominance by charged scatterers. Unexpectedly, significant variations in mobility rather than doping are the cause of large conductance inhomogeneities, highlighting the importance of statistical approaches when assessing large-area graphene transport properties.

Electrically continuous graphene from single crystal copper verified by terahertz conductance spectroscopy and micro four-point probe.

The electrical performance of graphene synthesized by chemical vapor deposition and transferred to insulating surfaces may be compromised by extended defects, including for instance grain boundaries, cracks, wrinkles, and tears. In this study, we experimentally investigate and compare the nano- and microscale electrical continuity of single layer graphene grown on centimeter-sized single crystal copper with that of previously studied graphene films, grown on commercially available copper foil, after transfer to SiO2 surfaces. The electrical continuity of the graphene films is analyzed using two noninvasive conductance characterization methods: ultrabroadband terahertz time-domain spectroscopy and micro four-point probe, which probe the electrical properties of the graphene film on different length scales, 100 nm and 10 µm, respectively. Ultrabroadband terahertz time-domain spectroscopy allows for measurement of the complex conductance response in the frequency range 1-15 terahertz, covering the entire intraband conductance spectrum, and reveals that the conductance response for the graphene grown on single crystalline copper intimately follows the Drude model for a barrier-free conductor. In contrast, the graphene grown on commercial copper foil shows a distinctly non-Drude conductance spectrum that is better described by the Drude-Smith model, which incorporates the effect of preferential carrier backscattering associated with extended, electronic barriers with a typical separation on the order of 100 nm. Micro four-point probe resistance values measured on graphene grown on single crystalline copper in two different voltage-current configurations show close agreement with the expected distributions for a continuous 2D conductor, in contrast with previous observations on graphene grown on commercial copper foil. The terahertz and micro four-point probe conductance values of the graphene grown on single crystalline copper shows a close to unity correlation, in contrast with those of the graphene grown on commercial copper foil, which we explain by the absence of extended defects on the microscale in CVD graphene grown on single crystalline copper. The presented results demonstrate that the graphene grown on single crystal copper is electrically continuous on the nanoscopic, microscopic, as well as intermediate length scales.

Graphene conductance uniformity mapping.

We demonstrate a combination of micro four-point probe (M4PP) and non-contact terahertz time-domain spectroscopy (THz-TDS) measurements for centimeter scale quantitative mapping of the sheet conductance of large area chemical vapor deposited graphene films. Dual configuration M4PP measurements, demonstrated on graphene for the first time, provide valuable statistical insight into the influence of microscale defects on the conductance, while THz-TDS has potential as a fast, non-contact metrology method for mapping of the spatially averaged nanoscopic conductance on wafer-scale graphene with scan times of less than a minute for a 4-in. wafer. The combination of M4PP and THz-TDS conductance measurements, supported by micro Raman spectroscopy and optical imaging, reveals that the film is electrically continuous on the nanoscopic scale with microscopic defects likely originating from the transfer process, dominating the microscale conductance of the investigated graphene film.

Modeling terahertz heating effects on water.

We apply Kirchhoff's heat equation to model the influence of a CW terahertz beam on a sample of water, which is assumed to be static. We develop a generalized model, which easily can be applied to other liquids and solids by changing the material constants. If the terahertz light source is focused down to a spot with a diameter of 0.5 mm, we find that the steady-state temperature increase per milliwatt of transmitted power is 1.8?C/mW. A quantum cascade laser can produce a CW beam in the order of several milliwatts and this motivates the need to estimate the effect of beam power on the sample temperature. For THz time domain systems, we indicate how to use our model as a worst-case approximation based on the beam average power. It turns out that THz pulses created from photoconductive antennas give a negligible increase in temperature. As biotissue contains a high water content, this leads to a discussion of worst-case predictions for THz heating of the human body in order to motivate future detailed study. An open source Matlab implementation of our model is freely available for use at www.eleceng.adelaide.edu.au/thz.

Characterization of aqueous alcohol solutions in bottles with THz reflection spectroscopy.

We demonstrate a method based on self-referenced THz time-domain spectroscopy for inspection of aqueous liquids, and in particular alcohol solutions, inside closed containers. We demonstrate that it is possible to determine the alcohol content of an aqueous solution, and that liquids can be classified as either harmless or inflammable. The method operates in reflection mode with the result that liquids opaque to THz radiation can be characterized with little influence of the bottle shape. The method works with plastic bottles as well as glass bottles, with absorption of THz radiation by the plastic or the glass being the limiting factor. The reflection mode allows for automatic control of the validity of the measurement. The method will be useful in liquid scanning systems at security checkpoints.