Towards a general growth model for graphene CVD on transition metal catalysts.

The chemical vapour deposition (CVD) of graphene on three polycrystalline transition metal catalysts, Co, Ni and Cu, is systematically compared and a first-order growth model is proposed which can serve as a reference to optimize graphene growth on any elemental or alloy catalyst system. Simple thermodynamic considerations of carbon solubility are insufficient to capture even basic growth behaviour on these most commonly used catalyst materials, and it is shown that kinetic aspects such as carbon permeation have to be taken into account. Key CVD process parameters are discussed in this context and the results are anticipated to be highly useful for the design of future strategies for integrated graphene manufacture.We wish to thank Dr. M.-B. Martin for careful reading of the manuscript. A.C.V. acknowledges the Conacyt Cambridge Scholarship and Roberto Rocca Fellowship. R.S.W. acknowledges a Research Fellowship from St. John’s College, Cambridge and a Marie Skłodowska-Curie Individual Fellowship (Global) under grant ARTIST (no. 656870) from the European Union’s Horizon 2020 research and innovation programme. S.C. acknowledges funding from EPSRC (Doctoral training award). S.H. acknowledges funding from ERC grant InsituNANO (No. 279342) and EPSRC under grant GRAPHTED (Ref. EP/K016636/1).This is the final version of the article. It first appeared from the Royal Society of Chemistry via http://dx.doi.org/10.1039/C5NR06873

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.This research was supported by the ERC under grant InsituNANO (279342), the EPSRC under grant GRAPHTED (EP/K016636/1), and the Innovation R&D programme of the National Measurement System of the U.K. Department of Business, Innovation and Skills (project number 118616)

Dirac-Point Shift by Carrier Injection Barrier in Graphene Field-Effect Transistor Operation at Room Temperature.

A positive shift in the Dirac point in graphene field-effect transistors was observed with Hall-effect measurements coupled with Kelvin-probe measurements at room temperature. This shift can be explained by the asymmetrical behavior of the contact resistance by virtue of the electron injection barrier at the source contact. As an outcome, an intrinsic resistance is given to allow a retrieval of an intrinsic carrier mobility found to be decreased with increasing gate bias, suggesting the dominance of short-range scattering in a single-layer graphene field-effect transistor. These results analytically correlate the field-effect parameters with intrinsic graphene properties

Contactless graphene conductivity mapping on a wide range of substrates with terahertz time-domain reflection spectroscopy.

We demonstrate how terahertz time-domain spectroscopy (THz-TDS) operating in reflection geometry can be used for quantitative conductivity mapping of large area chemical vapour deposited graphene films on sapphire, silicon dioxide/silicon and germanium. We validate the technique against measurements performed with previously established conventional transmission based THz-TDS and are able to resolve conductivity changes in response to induced back-gate voltages. Compared to the transmission geometry, measurement in reflection mode requires careful alignment and complex analysis, but circumvents the need of a terahertz transparent substrate, potentially enabling fast, contactless, in-line characterisation of graphene films on non-insulating substrates such as germanium.H.L. and J.A.Z. acknowledge financial support from the EPSRC (Grant No. EP/L019922/1). P.B.W. acknowledges EPSRC Cambridge NanoDTC EP/G037221/1. R.D., H.E.B. and D. R. acknowledge financial support from the EPSRC (Grant No. EP/J017671/1, Coherent Terahertz Systems). S.H. acknowledges funding from the EPSRC (Grant No. EP/K016636/1, GRAPHTED)

Parameter Space of Atomic Layer Deposition of Ultrathin Oxides on Graphene.

Atomic layer deposition (ALD) of ultrathin aluminum oxide (AlO$_x$) films was systematically studied on supported chemical vapor deposition (CVD) graphene. We show that by extending the precursor residence time, using either a multiple-pulse sequence or a soaking period, ultrathin continuous AlO$_x$ films can be achieved directly on graphene using standard H$_2$O and trimethylaluminum (TMA) precursors even at a high deposition temperature of 200 °C, without the use of surfactants or other additional graphene surface modifications. To obtain conformal nucleation, a precursor residence time of >2s is needed, which is not prohibitively long but sufficient to account for the slow adsorption kinetics of the graphene surface. In contrast, a shorter residence time results in heterogeneous nucleation that is preferential to defect/selective sites on the graphene. These findings demonstrate that careful control of the ALD parameter space is imperative in governing the nucleation behavior of AlO$_x$ on CVD graphene. We consider our results to have model system character for rational two-dimensional (2D)/non-2D material process integration, relevant also to the interfacing and device integration of the many other emerging 2D materials.We acknowledge funding from the EPSRC (Grant EP/ K016636/1, GRAPHTED) and ERC (Grant 279342, InsituNANO). J.A.A.-W. acknowledges a Research Fellowship from Churchill College, Cambridge, U.K

Crystal Orientation Dependent Oxidation Modes at the Buried Graphene-Cu Interface.

We combine spatially resolved scanning photoelectron spectroscopy with confocal Raman and optical microscopy to reveal how the oxidation of the buried graphene-Cu interface relates to the Cu crystallographic orientation. We analyze over 100 different graphene covered Cu (high and low index) orientations exposed to air for 2 years. Four general oxidation modes are observed that can be mapped as regions onto the polar plot of Cu surface orientations. These modes are (1) complete, (2) irregular, (3) inhibited, and (4) enhanced wrinkle interface oxidation. We present a comprehensive characterization of these modes, consider the underlying mechanisms, compare air and water mediated oxidation, and discuss this in the context of the diverse prior literature in this area. This understanding incorporates effects from across the wide parameter space of 2D material interface engineering, relevant to key challenges in their emerging applications, ranging from scalable transfer to electronic contacts, encapsulation, and corrosion protection

Parameter Space of Atomic Layer Deposition of Ultrathin Oxides on Graphene.

Atomic layer deposition (ALD) of ultrathin aluminum oxide (AlOx) films was systematically studied on supported chemical vapor deposition (CVD) graphene. We show that by extending the precursor residence time, using either a multiple-pulse sequence or a soaking period, ultrathin continuous AlOx films can be achieved directly on graphene using standard H2O and trimethylaluminum (TMA) precursors even at a high deposition temperature of 200 °C, without the use of surfactants or other additional graphene surface modifications. To obtain conformal nucleation, a precursor residence time of >2s is needed, which is not prohibitively long but sufficient to account for the slow adsorption kinetics of the graphene surface. In contrast, a shorter residence time results in heterogeneous nucleation that is preferential to defect/selective sites on the graphene. These findings demonstrate that careful control of the ALD parameter space is imperative in governing the nucleation behavior of AlOx on CVD graphene. We consider our results to have model system character for rational two-dimensional (2D)/non-2D material process integration, relevant also to the interfacing and device integration of the many other emerging 2D materials.We acknowledge funding from the EPSRC (Grant EP/ K016636/1, GRAPHTED) and ERC (Grant 279342, InsituNANO). J.A.A.-W. acknowledges a Research Fellowship from Churchill College, Cambridge, U.K

Metamaterial/graphene active terahertz modulators

Within the last years there has been a tremendous thrust into research and technology in the THz spectral region (broadly defined as 0.1-10 THz) mainly driven by the unique potential where this radiation finds applications in, such as imaging, spectroscopy and communication. In all these fields a fast, integrated and versatile platform for modulating light is required. Metamaterial/graphene devices fulfill all these requirements as their subwavelength nature lends itself naturally to strong light-matter interaction, and therefore highly efficient and miniaturized devices. Graphene's unique properties, e.g. the large carrier concentration modulation, provide a large degree of compatibility with several architectures which can be exploited in a range of modulation or detection schemes. Finally, metamaterial/graphene devices realize a fast, versatile platform, which can be easily scaled to other frequencies, and adapted into amplitude, frequency, polarization and phase modulators, as well as integrated detectors, for the next generation of wireless-communication

Controlling Catalyst Bulk Reservoir Effects for Monolayer Hexagonal Boron Nitride CVD.

Highly controlled Fe-catalyzed growth of monolayer hexagonal boron nitride (h-BN) films is demonstrated by the dissolution of nitrogen into the catalyst bulk via NH3 exposure prior to the actual growth step. This "pre-filling" of the catalyst bulk reservoir allows us to control and limit the uptake of B and N species during borazine exposure and thereby to control the incubation time and h-BN growth kinetics while also limiting the contribution of uncontrolled precipitation-driven h-BN growth during cooling. Using in situ X-ray diffraction and in situ X-ray photoelectron spectroscopy combined with systematic growth calibrations, we develop an understanding and framework for engineering the catalyst bulk reservoir to optimize the growth process, which is also relevant to other 2D materials and their heterostructures.S.C. and R.W. acknowledge funding from EPSRC (Doctoral training award). R.S.W. acknowledges a Research Fellowship from St. John’s College, Cambridge and a EU Marie Skłodowska-Curie Individual Fellowship (Global) under grant ARTIST (no. 656870) from the European Union’s Horizon 2020 research and innovation programme. B.C.B. acknowledges funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 656214 - 2DInterFOX. B.C.B and J.C.M. acknowledge support from the Austrian Science Fund (FWF): P25721-N20 and the Austrian Research Promotion Agency (FFG): 848152 - GraphenMoFET. A.C.-V. acknowledges the Conacyt Cambridge Scholarship and Roberto Rocca Fellowship. S.H. acknowledges funding from ERC grant InsituNANO (no. 279342). We acknowledge the European Synchrotron Radiation Facility (ESRF) for provision of synchrotron radiation facilities at the BM20/ROBL beamline. We acknowledge the Helmholtz-Zentrum-Berlin Electron storage ring BESSY II for provision of synchrotron radiation at the ISISS beamline. We thank the ESRF and BESSY staff for continued support of our experiments and valuable discussion.This is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/acs.nanolett.5b0458

Active frequency modulation of metamaterial/graphene optoelectronic device using coupled resonators

We present the continuous frequency modulation of a metamaterial resonance using selective damping of coupled plasmonic resonators with electrostatically gated graphene. A resonance frequency tuning range >150 GHz is achieved at 1.5 THz making this device suitable for use as an optoelectronic, tunable frequency modulator for THz frequencies