José M. Caridad

The hot pick-up technique for batch assembly of van der Waals heterostructures

The assembly of individual two-dimensional materials into van der Waals heterostructures enables the construction of layered three-dimensional materials with desirable electronic and optical properties. A core problem in the fabrication of these structures is the formation of clean interfaces between the individual two-dimensional materials which would affect device performance. We present here a technique for the rapid batch fabrication of van der Waals heterostructures, demonstrated by the controlled production of 22 mono-, bi- and trilayer graphene stacks encapsulated in hexagonal boron nitride with close to 100% yield. For the monolayer devices, we found semiclassical mean-free paths up to 0.9 μm, with the narrowest samples showing clear indications of the transport being affected by boundary scattering. The presented method readily lends itself to fabrication of van der Waals heterostructures in both ambient and controlled atmospheres, while the ability to assemble pre-patterned layers paves the way for complex three-dimensional architectures.

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.

Graphene transport properties upon exposure to PMMA processing and heat treatments

The evolution of grapheneʼs electrical transport properties due to processing with the polymer polymethyl methacrylate (PMMA) and heat are examined in this study. The use of stencil (shadow mask) lithography enables fabrication of graphene devices without the usage of polymers, chemicals or heat, allowing us to measure the evolution of the electrical transport properties during individual processing steps from the initial as-exfoliated to the PMMA-processed graphene. Heating generally promotes the conformation of graphene to SiO2 and is found to play a major role for the electrical properties of graphene while PMMA residues are found to be surprisingly benign. In accordance with this picture, graphene devices with initially high carrier mobility tend to suffer a decrease in carrier mobility, while in contrast an improvement is observed for low carrier mobility devices. We explain this by noting that flakes conforming poorly to the substrate will have a higher carrier mobility which will however be reduced as heat treatment enhance the conformation. We finally show the electrical properties of graphene to be reversible upon heat treatments in air up to 200 °C.

Controllable growth of metallic nano-helices at room temperature conditions

We report on a method to produce multiple-pitch, regularly shaped, aligned, and freestanding metallic nano-helices at room temperature. This method overcomes the limitations of the standard glancing angle deposition approach through a heat-management technique devoid of active substrate cooling and is even applicable for metals with low melting point, that is, high surface adatom diffusion. The structural quality and optical activity response of these metal nano-helices are comparable to state of the art helices produced by employing substrates cooled down to cryogenic temperatures.

An electrical analogy to Mie scattering

Mie scattering is an optical phenomenon that appears when electromagnetic waves, in particular light, are elastically scattered at a spherical or cylindrical object. A transfer of this phenomenon onto electron states in ballistic graphene has been proposed theoretically, assuming a well-defined incident wave scattered by a perfectly cylindrical nanometer scaled potential, but experimental fingerprints are lacking. We present an experimental demonstration of an electrical analogue to Mie scattering by using graphene as a conductor, and circular potentials arranged in a square two-dimensional array. The tabletop experiment is carried out under seemingly unfavourable conditions of diffusive transport at room-temperature. Nonetheless, when a canted arrangement of the array with respect to the incident current is chosen, cascaded Mie scattering results robustly in a transverse voltage. Its response on electrostatic gating and variation of potentials convincingly underscores Mie scattering as underlying mechanism. The findings presented here encourage the design of functional electronic metamaterials.

A two-dimensional Dirac fermion microscope

The electron microscope has been a powerful, highly versatile workhorse in the fields of material and surface science, micro and nanotechnology, biology and geology, for nearly 80 years. The advent of two-dimensional materials opens new possibilities for realizing an analogy to electron microscopy in the solid state. Here we provide a perspective view on how a two-dimensional (2D) Dirac fermion-based microscope can be realistically implemented and operated, using graphene as a vacuum chamber for ballistic electrons. We use semiclassical simulations to propose concrete architectures and design rules of 2D electron guns, deflectors, tunable lenses and various detectors. The simulations show how simple objects can be imaged with well-controlled and collimated in-plane beams consisting of relativistic charge carriers. Finally, we discuss the potential of such microscopes for investigating edges, terminations and defects, as well as interfaces, including external nanoscale structures such as adsorbed molecules, nanoparticles or quantum dots.

Hot-Volumes as Uniform and Reproducible SERS-Detection Enhancers in Weakly-Coupled Metallic Nanohelices

Reproducible and enhanced optical detection of molecules in low concentrations demands simultaneously intense and homogeneous electric fields acting as robust signal amplifiers. To generate such sophisticated optical near-fields, different plasmonic nanostructures were investigated in recent years. These, however, exhibit either high enhancement factor (EF) or spatial homogeneity but not both. Small interparticle gaps or sharp nanostructures show enormous EFs but no near-field homogeneity. Meanwhile, approaches using rounded and separated monomers create uniform near-fields with moderate EFs. Here, guided by numerical simulations, we show how arrays of weakly-coupled Ag nanohelices achieve both homogeneous and strong near-field enhancements, reaching even the limit forreproducible detection of individual molecules. The unique near-field distribution of a single nanohelix consists of broad hot-spots, merging with those from neighbouring nanohelices in specific array configurations and generating a wide and uniform detection zone (“hot-volume”). We experimentally assessed these nanostructures via surface-enhanced Raman spectroscopy, obtaining a corresponding EF of ~107 and a relative standard deviation <10%. These values demonstrate arrays of nanohelices as state-of-the-art substrates for reproducible optical detection as well as compelling nanostructures for related fields such as near-field imaging.

Quality assessment of graphene: Continuity, uniformity, and accuracy of mobility measurements

With the increasing availability of large-area graphene, the ability to rapidly and accurately assess the quality of the electrical properties has become critically important. For practical applications, spatial variability in carrier density and carrier mobility must be controlled and minimized. We present a simple framework for assessing the quality and homogeneity of large-area graphene devices. The field effect in both exfoliated graphene devices encapsulated in hexagonal boron nitride and chemical vapor-deposited (CVD) devices was measured in dual current–voltage configurations and used to derive a single, gate-dependent effective shape factor, β, for each device. β is a sensitive indicator of spatial homogeneity that can be obtained from samples of arbitrary shape. All 50 devices investigated in this study show a variation (up to tenfold) in β as a function of the gate bias. Finite element simulations suggest that spatial doping inhomogeneity, rather than mobility inhomogeneity, is the primary cause of the gate dependence of β, and that measurable variations of β can be caused by doping variations as small as 1010 cm−2. Our results suggest that local variations in the position of the Dirac point alter the current flow and thus the effective sample shape as a function of the gate bias. We also found that such variations lead to systematic errors in carrier mobility calculations, which can be revealed by inspecting the corresponding β factor.

High quality sub-10 nm graphene nanoribbons by on-chip PS-b-PDMS block copolymer lithography

A block copolymer self-assembly holds great promise as a rapid, cheap and scalable approach to nanolithography. We present a straightforward method for fabrication of sub-10 nm line patterns from a lamellar polystyrene-b-polydimethylsiloxane (SD) block copolymer with a total average molecular weight of 10.5 kg mol−1. Thin SD films directly spin cast onto silicon substrates and on graphene, form regular line patterns of sub-10 nm pitch on the substrates after a few minutes of annealing at 45 °C in the presence of toluene vapour. Perfect pattern alignment was achieved by confining the films inside the trenches of graphoepitaxial substrates. The SD template was furthermore used as a lithographic mask to fabricate high-quality sub-10 nm graphene nanoribbons. This was realized by one step oxygen plasma treatment, which accomplishes three tasks: hardening the PDMS block by oxidation, and etching both the PS block and the graphene under PS. Raman analysis supports the formation of graphene nanoribbons with an average distance between defects corresponding to the oxidized PDMS pitch, with no sign of defects generated in the ribbon channel. This suggests a high degree of protection of the nanoribbons by the hard oxidized PDMS mask formed in situ during oxygen plasma etching.

Conductance quantization suppression in the quantum Hall regime

Conductance quantization is the quintessential feature of electronic transport in non-interacting mesoscopic systems. This phenomenon is observed in quasi one-dimensional conductors at zero magnetic field B, and the formation of edge states at finite magnetic fields results in wider conductance plateaus within the quantum Hall regime. Electrostatic interactions can change this picture qualitatively. At finite B, screening mechanisms in narrow, gated ballistic conductors are predicted to give rise to an increase in conductance and a suppression of quantization due to the appearance of additional conduction channels. Despite being a universal effect, this regime has proven experimentally elusive because of difficulties in realizing one-dimensional systems with sufficiently hard-walled, disorder-free confinement. Here, we experimentally demonstrate the suppression of conductance quantization within the quantum Hall regime for graphene nanoconstrictions with low edge roughness. Our findings may have profound impact on fundamental studies of quantum transport in finite-size, two-dimensional crystals with low disorder.Conductance quantization is the hallmark of non-interacting confined systems. The authors show that the quantization in graphene nanoconstrictions with low edge disorder is suppressed in the quantum Hall regime. This is explained by the addition of new conductance channels due to electrostatic screening.