Andrew J. Pollard

Multifunctional Nanoprobes for Nanoscale Chemical Imaging and Localized Chemical Delivery at Surfaces and Interfaces

Double take: Double-barrel carbon nanoprobes with integrated distance control for simultaneous nanoscale electrochemical and ion conductance microscopy can be fabricated with a wide range of probe sizes in less than two minutes. The nanoprobes allow simultaneous noncontact topographical (left image) and electrochemical imaging (right) of living neurons, as well as localized K+ delivery and simultaneous neurotransmitter detection.

Nucleation control for large, single crystalline domains of monolayer hexagonal boron nitride via Si-doped Fe catalysts.

The scalable chemical vapor deposition of monolayer hexagonal boron nitride (h-BN) single crystals, with lateral dimensions of ∼0.3 mm, and of continuous h-BN monolayer films with large domain sizes (>25 μm) is demonstrated via an admixture of Si to Fe catalyst films. A simple thin-film Fe/SiO2/Si catalyst system is used to show that controlled Si diffusion into the Fe catalyst allows exclusive nucleation of monolayer h-BN with very low nucleation densities upon exposure to undiluted borazine. Our systematic in situ and ex situ characterization of this catalyst system establishes a basis for further rational catalyst design for compound 2D materials.

Understanding and Controlling Cu-Catalyzed Graphene Nucleation: The Role of Impurities, Roughness, and Oxygen Scavenging

The mechanism by which Cu catalyst pretreatments control graphene nucleation density in scalable chemical vapor deposition (CVD) is systematically explored. The intrinsic and extrinsic carbon contamination in the Cu foil is identified by time-of-flight secondary ion mass spectrometry as a major factor influencing graphene nucleation and growth. By selectively oxidizing the backside of the Cu foil prior to graphene growth, a drastic reduction of the graphene nucleation density by 6 orders of magnitude can be obtained. This approach decouples surface roughness effects and at the same time allows us to trace the scavenging effect of oxygen on deleterious carbon impurities as it permeates through the Cu bulk. Parallels to well-known processes in Cu metallurgy are discussed. We also put into context the relative effectiveness and underlying mechanisms of the most widely used Cu pretreatments, including wet etching and electropolishing, allowing a rationalization of current literature and determination of the relevant parameter space for graphene growth. Taking into account the wider CVD growth parameter space, guidelines are discussed for high-throughput manufacturing of “electronic-quality” monolayer graphene films with domain size exceeding 1 mm, suitable for emerging industrial applications, such as electronics and photonics.

High-resolution electrochemical and topographical imaging using batch-fabricated cantilever probes.

New cantilever probes for combined scanning electrochemical microscopy-atomic force microscopy (SECM-AFM) have been batch-fabricated, and their application to high resolution electrochemical-topographical imaging has been demonstrated. The conical probes yield outstanding quality Faradaic current maps alongside subnm level topographical information as exemplified by the electrochemical imaging of exfoliated graphene and graphite samples. Current mapping reveals significant heterogeneities in the electroactivity of these carbon surfaces that do not directly correlate to topographical features, suggesting the presence of adsorbed chemical contaminants or intrinsic impurities.

Quantitative characterization of defect size in graphene using Raman spectroscopy

The quantitative determination of the lattice disorder present in graphene layers will be crucial if this 2-D material is to be commercialized. Raman spectroscopy has been shown to be a powerful technique for characterizing the density of these defects in graphene layers. Here, we study the evolution of Raman spectra with defect size, for vacancy defects created via ion bombardment. Raman spectroscopy was used to analyze the variation in the D-peak and G-peak intensity ratio for single-layer graphene, whilst the equivalent defects in highly ordered pyrolytic graphite were characterized using scanning tunneling microscopy to determine their lateral dimensions. Vacancy defects of larger lateral sizes were shown to have an associated coalescence of defects at a larger inter-defect distance, through changes in the intensity ratio of the D- and G-peaks, as well as the D-peak width. This is in agreement with a phenomenological model previously determined for calculating the defect density in graphene layers, and experimentally reveals the effect of graphene defect size for Raman spectroscopy measurements. Importantly, these results show how the graphene defect size must be obtained separately to allow the quantification of the graphene defect density using Raman spectroscopy. The measurement of single-layer graphene with several different defect sizes has also enabled an accurate determination of the phase-breaking length of graphene of 2.4 ± 0.6 nm.

In Situ Graphene Growth Dynamics on Polycrystalline Catalyst Foils

The dynamics of graphene growth on polycrystalline Pt foils during chemical vapor deposition (CVD) are investigated using in situ scanning electron microscopy and complementary structural characterization of the catalyst with electron backscatter diffraction. A general growth model is outlined that considers precursor dissociation, mass transport, and attachment to the edge of a growing domain. We thereby analyze graphene growth dynamics at different length scales and reveal that the rate-limiting step varies throughout the process and across different regions of the catalyst surface, including different facets of an individual graphene domain. The facets that define the domain shapes lie normal to slow growth directions, which are determined by the interfacial mobility when attachment to domain edges is rate-limiting, as well as anisotropy in surface diffusion as diffusion becomes rate-limiting. Our observations and analysis thus reveal that the structure of CVD graphene films is intimately linked to that of the underlying polycrystalline catalyst, with both interfacial mobility and diffusional anisotropy depending on the presence of step edges and grain boundaries. The growth model developed serves as a general framework for understanding and optimizing the growth of 2D materials on polycrystalline catalysts.

Probing individual point defects in graphene via near-field Raman scattering

The Raman scattering D-peak in graphene is spatially localised in close proximity to defects. Here, we demonstrate the capability of tip-enhanced Raman spectroscopy (TERS) to probe individual point defects, even for a graphene layer with an extremely low defect density. This is of practical interest for future graphene electronic devices. The measured TERS spectra enable a direct determination of the average inter-defect distance within the graphene sheet. Analysis of the TERS enhancement factor of the graphene Raman peaks highlights the preferential enhancement and symmetry-dependent selectivity of the D-peak intensity caused by zero-dimensional Raman scatterers.

Covalent Carbene Functionalization of Graphene: Toward Chemical Band-Gap Manipulation.

In this work, we employ dibromocarbene (DBC) radicals to covalently functionalize solution exfoliated graphene via the formation of dibromocyclopropyl adducts. This is achieved using a basic aqueous/organic biphasic reaction mixture to decompose the DBC precursor, bromoform, in conjunction with a phase-transfer catalyst to facilitate ylide formation and carbene migration to graphene substrates. DBC-functionalized graphene (DBC-graphene) was characterized using a range of spectroscopic and analytical techniques to confirm the covalent nature of functionalization. Modified optical and electronic properties of DBC-graphene were investigated using UV-vis spectroscopy, analysis of electrical I-V transport properties, and noncontact terahertz time-domain spectroscopy. The implications of carbene functionalization of graphene are considered in the context of scalable radical functionalization methodologies for bulk-scale graphene processing and controlled band-gap manipulation of graphene.

Effects of temperature and ammonia flow rate on the chemical vapour deposition growth of nitrogen-doped graphene

We doped graphene in situ during synthesis from methane and ammonia on copper in a low-pressure chemical vapour deposition system, and investigated the effect of the synthesis temperature and ammonia concentration on the growth. Raman and X-ray photoelectron spectroscopy was used to investigate the quality and nitrogen content of the graphene and demonstrated that decreasing the synthesis temperature and increasing the ammonia flow rate results in an increase in the concentration of nitrogen dopants up to ca. 2.1% overall. However, concurrent scanning electron microscopy studies demonstrate that decreasing both the growth temperature from 1000 to 900 °C and increasing the N/C precursor ratio from 1/50 to 1/10 significantly decreased the growth rate by a factor of six overall. Using scanning tunnelling microscopy we show that the nitrogen was incorporated mainly in substitutional configuration, while current imaging tunnelling spectroscopy showed that the effect of the nitrogen on the density of states was visible only over a few atom distances.

Investigations of the effect of SiC growth face on graphene thickness uniformity and electronic properties

A study of the growth of graphene on the silicon-face (0001) and the carbon-face (000−1) of SiC is presented. The morphology and layer thickness is investigated using atomic force microscopy and scanning Kelvin probe microscopy and demonstrates the more wrinkled and less uniform thickness of the graphene growth on the C-face compared to the Si-face which shows uniform monolayer growth with some bilayer areas. Raman spectroscopy confirms the predominantly monolayer nature of the Si-face graphene and the inhomogeneous nature of the C-face graphene growth. Raman studies on the C-face show overlapping peaks as observed for spectra of Bernal-stacked graphene but we argue that the graphene is turbostratic with nanoscale differences in substrate effects leading to shifting of the Raman modes. Further samples show uniform scanning Kelvin probe maps of the carbon face along with very low bilayer coverage on the Si-face. Epitaxially grown graphene on the Si-face of SiC is reported to have a high carrier concentration and low mobility, however, van Der Pauw measurements demonstrate the low sheet resistance and relatively low carrier concentration of the graphene on the Si-face, in agreement with microwave measurements (Hao et al 2013 Appl. Phys. Lett. 103 123103) and scanning Kelvin probe maps which demonstrate the uniformity of the graphene.