Terahertz Cross-Correlation Spectroscopy and Imaging of Large-Area Graphene.

We demonstrate the use of a novel, integrated THz system to obtain time-domain signals for spectroscopy in the 0.1-1.4 THz range. The system employs THz generation in a photomixing antenna excited by a broadband amplified spontaneous emission (ASE) light source and THz detection with a photoconductive antenna by coherent cross-correlation sampling. We benchmark the performance of our system against a state-of-the-art femtosecond-based THz time-domain spectroscopy system in terms of mapping and imaging of the sheet conductivity of large-area graphene grown by chemical vapor deposition (CVD) and transferred to a PET polymer substrate. We propose to integrate the algorithm for the extraction of the sheet conductivity with the data acquisition, thereby enabling true in-line monitoring capability of the system for integration in graphene production facilities.

Non-Linear Conductivity Response of Graphene on Thin-Film PET Characterized by Transmission and Reflection Air-Plasma THz-TDS.

We demonstrate that the conductivity of graphene on thin-film polymer substrates can be accurately determined by reflection-mode air-plasma-based THz time-domain spectroscopy (THz-TDS). The phase uncertainty issue associated with reflection measurements is discussed, and our implementation is validated by convincing agreement with graphene electrical properties extracted from more conventional transmission-mode measurements. Both the reflection and transmission THz-TDS measurements reveal strong non-linear and instantaneous conductivity depletion across an ultra-broad bandwidth (1-9 THz) under relatively high incident THz electrical field strengths (up to 1050 kV/cm).

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.

Selective area oxidation of copper derived from chemical vapor deposited graphene microstructure.

The barrier properties of graphene coating are highly correlated with its microstructure which is then determined by the chemical vapor deposition (CVD) growth history on metals. We demonstrate here an unrevealed selective area oxidation of copper under graphene, which is derived from the implicit-etching-controlled CVD growth mode of graphene. By charactering and analyzing the selective area patterns of Cu oxidation, an etched pattern trace with nano/microvoids during graphene growth has been proposed to account for this. Based on such selective oxidation of Cu, distributed galvanic corrosion will be triggered and proceed locally at the interface of graphene-Cu system to coalescence together under a continuous corrosion environment, eventually presenting a homogeneous oxidation of Cu and gradual decoupling of graphene-Cu system. This discovery will assist our understanding of the barrier properties of two-dimensional materials and can be extended to other applications related to quality monitoring of grown materials and defects-based chemical modifications.

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.

Wafer-Scale Synthesis of Graphene on Sapphire: Toward Fab-Compatible Graphene.

The adoption of graphene in electronics, optoelectronics, and photonics is hindered by the difficulty in obtaining high-quality material on technologically relevant substrates, over wafer-scale sizes, and with metal contamination levels compatible with industrial requirements. To date, the direct growth of graphene on insulating substrates has proved to be challenging, usually requiring metal-catalysts or yielding defective graphene. In this work, a metal-free approach implemented in commercially available reactors to obtain high-quality monolayer graphene on c-plane sapphire substrates via chemical vapor deposition is demonstrated. Low energy electron diffraction, low energy electron microscopy, and scanning tunneling microscopy measurements identify the Al-rich reconstruction 31 × 31 R ± 9 ° of sapphire to be crucial for obtaining epitaxial graphene. Raman spectroscopy and electrical transport measurements reveal high-quality graphene with mobilities consistently above 2000 cm2 V-1 s-1 . The process is scaled up to 4 and 6 in. wafers sizes and metal contamination levels are retrieved to be within the limits for back-end-of-line integration. The growth process introduced here establishes a method for the synthesis of wafer-scale graphene films on a technologically viable basis.

A Graphene-Edge Ferroelectric Molecular Switch.

We show that polar molecules (water, ammonia, and nitrogen dioxide) adsorbed solely at the exposed edges of an encapsulated graphene sheet exhibit ferroelectricity, collectively orienting and switching reproducibly between two available states in response to an external electric field. This ferroelectric molecular switching introduces drastic modifications to the graphene bulk conductivity and produces a large and ambipolar charge bistability in micrometer-size graphene devices. This system comprises an experimental realization of envisioned memory capacitive ("memcapacitive") devices whose capacitance is a function of their charging history, here conceived via confined and correlated polar molecules at the one-dimensional edge of a two-dimensional crystal.

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.

Quality assessment of terahertz time-domain spectroscopy transmission and reflection modes for graphene conductivity mapping.

We present a comparative study of electrical measurements of graphene using terahertz time-domain spectroscopy in transmission and reflection mode, and compare the measured sheet conductivity values to electrical van der Pauw measurements made independently in three different laboratories. Overall median conductivity variations of up to 15% were observed between laboratories, which are attributed mainly to the well-known temperature and humidity dependence of non-encapsulated graphene devices. We conclude that terahertz time-domain spectroscopy performed in either reflection mode or transmission modes are indeed very accurate methods for mapping electrical conductivity of graphene, and that both methods are interchangeable within measurement uncertainties. The conductivity obtained via terahertz time-domain spectroscopy were consistently in agreement with electrical van der Pauw measurements, while offering the additional advantages associated with contactless mapping, such as high throughput, no lithography requirement, and with the spatial mapping directly revealing the presence of any inhomogeneities or isolating defects. The confirmation of the accuracy of reflection-mode removes the requirement of a specialized THz-transparent substrate to accurately measure the conductivity.

Robust mapping of electrical properties of graphene from terahertz time-domain spectroscopy with timing jitter correction.

We demonstrate a method for reliably determining the electrical properties of graphene including the carrier scattering time and carrier drift mobility from terahertz time- domain spectroscopy measurements (THz-TDS). By comparing transients originating from directly transmitted pulses and the echoes from internal reflections in a substrate, we are able to extract electrical properties irrespective of random time delays between pulses emitted in a THz-TDS setup. If such time delays are not accounted for they can significantly influence the extracted properties of the material. The technique is useful for a robust determination of electrical properties from THz-TDS measurements and is compatible with substrate materials where transients from internal reflections are well-separated in time.

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.

Transfer of Direct and Moiré Patterns by Reactive Ion Etching Through Ex Situ Fabricated Nanoporous Polymer Masks.

We present a conceptually simple approach to nanolithographic patterning utilizing ex situ fabricated nanoporous masks from block copolymers. The fabricated block copolymer (BC) masks show predictable morphology based on the correlation between BC composition and bulk properties, independent of substrates' surface properties. The masks are prepared by microtoming of prealigned nanoporous polymer monoliths of hexagonal morphology at controlled angles; they appear as 30-60 nm thick films of typical dimensions 100 µm × 200 µm. Masks cut perpendicular to the cylindrical axis show monocrystalline hexagonal packing of 10 nm pores with a principal period of 20 nm. We demonstrate the transfer of the hexagonal pattern onto silicon by means of reactive ion etching through the masks. In addition, patterns of elliptic and slit-like holes on silicon are obtained by utilizing masks cut at 45° relative to the cylinder axis. Finally, we demonstrate the first transfer of moiré patterns from block copolymer masks to substrate. The nanoporous masks prepared ex situ show outstanding long-range order and can be applied directly onto any flat substrate, eliminating the need for topographic and chemical surface modification, which are essential prerequisites for the conventional procedure of block copolymer directed self-assembly. The demonstrated elliptic and moiré pattern transfers prove that the proposed ex situ procedure allows us to realize nanolithographic patterns that are difficult to realize by the conventional approach alone.

Plasmon-phonon coupling in large-area graphene dot and antidot arrays fabricated by nanosphere lithography.

Nanostructured graphene on SiO2 substrates paves the way for enhanced light-matter interactions and explorations of strong plasmon-phonon hybridization in the mid-infrared regime. Unprecedented large-area graphene nanodot and antidot optical arrays are fabricated by nanosphere lithography, with structural control down to the sub-100 nm regime. The interaction between graphene plasmon modes and the substrate phonons is experimentally demonstrated, and structural control is used to map out the hybridization of plasmons and phonons, showing coupling energies of the order 20 meV. Our findings are further supported by theoretical calculations and numerical simulations.

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.

Directed self-assembled crystalline oligomer domains on graphene and graphite.

We observe the formation of thin films of fibre-like aggregates from the prototypical organic semiconductor molecule para-hexaphenylene (p-6P) on graphite thin flakes and on monolayer graphene. Using atomic force microscopy, scanning electron microscopy, x-ray diffraction, polarized fluorescence microscopy, and bireflectance microscopy, the molecular orientations on the surface are deduced and correlated to both the morphology as well as to the high-symmetry directions of the graphitic surface: the molecules align with their long axis at ±11° with respect to a high-symmetry direction. The results show that the graphene surface can be used as a growth substrate to direct the self-assembly of organic molecular thin films and nanofibres, both with and without lithographical processing.

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.

Ultra-high aspect ratio replaceable AFM tips using deformation-suppressed focused ion beam milling.

Fabrication of ultra-high aspect ratio exchangeable and customizable tips for atomic force microscopy (AFM) using lateral focused ion beam (FIB) milling is presented. While on-axis FIB milling does allow high aspect ratio (HAR) AFM tips to be defined, lateral milling gives far better flexibility in terms of defining the shape and size of the tip. Due to beam-induced deformation, it has so far not been possible to define HAR structures using lateral FIB milling. In this work we obtain aspect ratios of up to 45, with tip diameters down to 9 nm, by a deformation-suppressing writing strategy. Several FIB milling strategies for obtaining sharper tips are discussed. Finally, assembly of the HAR tips on a custom-designed probe as well as the first AFM scanning is shown.

In situ TEM creation and electrical characterization of nanowire devices.

We demonstrate the observation and measurement of simple nanoscale devices over their complete lifecycle from creation to failure within a transmission electron microscope. Devices were formed by growing Si nanowires, using the vapor-liquid-solid method, to form bridges between Si cantilevers. We characterize the formation of the contact between the nanowire and the cantilever, showing that the nature of the connection depends on the flow of heat and electrical current during and after the moment of contact. We measure the electrical properties and high current failure characteristics of the resulting bridge devices in situ and relate these to the structure. We also describe processes to modify the contact and the nanowire surface after device formation. The technique we describe allows the direct analysis of the processes taking place during device formation and use, correlating specific nanoscale structural and electrical parameters on an individual device basis.

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.