Kinetic control of catalytic CVD for high-quality graphene at low temperatures.

Low-temperature (∼600 °C), scalable chemical vapor deposition of high-quality, uniform monolayer graphene is demonstrated with a mapped Raman 2D/G ratio of >3.2, D/G ratio ≤0.08, and carrier mobilities of ≥3000 cm(2) V(-1) s(-1) on SiO(2) support. A kinetic growth model for graphene CVD based on flux balances is established, which is well supported by a systematic study of Ni-based polycrystalline catalysts. A finite carbon solubility of the catalyst is thereby a key advantage, as it allows the catalyst bulk to act as a mediating carbon sink while optimized graphene growth occurs by only locally saturating the catalyst surface with carbon. This also enables a route to the controlled formation of Bernal stacked bi- and few-layered graphene. The model is relevant to all catalyst materials and can readily serve as a general process rationale for optimized graphene CVD.Acknowledgment. R.S.W. acknowledges funding from EPSRC (Doctoral Training Award). S.H. acknowledges funding from ERC grant InsituNANO (no. 279342). This research was partially supported by the EU FP7 Work Programme under grant GRAFOL (project reference 285275).This is the accepted manuscript. The final version is available from ACS at http://pubs.acs.org/doi/abs/10.1021/nn303674g

Free-standing graphene membranes on glass nanopores for ionic current measurements

A method is established to reliably suspend graphene monolayers across glass nanopores as a simple, low cost platform to study ionic transport through graphene membranes. We systematically show that the graphene seals glass nanopore openings with areas ranging from 180 nm2 to 20 μm2, allowing detailed measurements of ionic current and transport through graphene. In combination with in situ Raman spectroscopy, we characterise the defects formed in ozone treated graphene, confirming an increase in ionic current flow with defect density. This highlights the potential of our method for studying single molecule sensing and filtration.The authors would like to thank S. Purushothaman and K. Göpfrich for careful reading of the manuscript and V. Thacker for useful discussions. This work was supported by the EPSRC Cambridge NanoDTC, EP/G037221/1, and EPSRC grant GRAPHTED, EP/K016636/1. R.S.W. acknowledges a Research Fellowship from St. John's College, Cambridge. N.A.W.B. acknowledges an EPSRC doctoral prize award.This is the accepted manuscript. Copyright 2015 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The final version is available in Applied Physics Letters 106, 023119 (2015); doi: 10.1063/1.490623

Measuring the proton selectivity of graphene membranes

By systematically studying the proton selectivity of free-standing graphene membranes in aqueous solutions we demonstrate that protons are transported by passing through defects. We study the current-voltage characteristics of single-layer graphene grown by chemical vapour deposition (CVD) when a concentration gradient of HCl exists across it. Our measurements can unambiguously determine that H+ ions are responsible for the selective part of the ionic current. By comparing the observed reversal potentials with positive and negative controls we demonstrate that the as-grown graphene is only weakly selective for protons. We use atomic layer deposition to block most of the defects in our CVD graphene. Our results show that a reduction in defect size decreases the ionic current but increases proton selectivity.This is the author accepted manuscript. The final version is available from AIP via http://dx.doi.org/10.1063/1.493633

Substrate-assisted nucleation of ultra-thin dielectric layers on graphene by atomic layer deposition

We report on a large improvement in the wetting of Al2O3 thin films grown by un-seeded atomic layer deposition on monolayer graphene, without creating point defects. This enhanced wetting is achieved by greatly increasing the nucleation density through the use of polar traps induced on the graphene surface by an underlying metallic substrate. The resulting Al2O3/graphene stack is then transferred to SiO2 by standard methods.P.R.K. acknowledges funding from Cambridge Commonwealth Trust. R.S.W. acknowledges funding from EPSRC (Doctoral training award). S.H. acknowledges funding from ERC Grant InsituNANO (No. 279342) and EPSRC (Grant No. EP/ H047565/1).This is the accepted manuscript. The final version is available from AIP from http://scitation.aip.org/content/aip/journal/apl/100/17/10.1063/1.4707376

The parameter space of graphene chemical vapor deposition on polycrystalline Cu

A systematic study on the parameter space of graphene CVD on polycrystalline Cu foils is presented, aiming at a more fundamental process rationale in particular regarding the choice of carbon precursor and mitigation of Cu sublimation. CH4 as precursor requires H2 dilution and temperatures ≥1000°C to keep the Cu surface reduced and yield a high quality, complete monolayer graphene coverage. The H2 atmosphere etches as-grown graphene, hence maintaining a balanced CH4/H2 ratio is critical. Such balance is more easily achieved at low pressure conditions, at which however Cu sublimation reaches deleterious levels. In contrast, C6H6 as precursor requires no reactive diluent and consistently gives similar graphene quality at 100-150°C lower temperatures. The lower process temperature and more robust processing conditions allow the problem of Cu sublimation to be effectively addressed. Graphene formation is not inherently self-limited to a monolayer for any of the precursors. Rather, the higher the supplied carbon chemical potential the higher the likelihood of film inhomogeneity and primary and secondary multilayer graphene nucleation. For the latter, domain boundaries of the inherently polycrystalline CVD graphene offer pathways for a continued carbon supply to the catalyst. Graphene formation is significantly affected by the Cu crystallography, i.e. the evolution of microstructure and texture of the catalyst template form an integral part of the CVD process.S.H. acknowledges funding from ERC grant InsituNANO (n°279342) and from EPSRC (Grant Nr. EP/H047565/1). P.R.K. acknowledges funding from the Cambridge Commonwealth Trust and C.D. acknowledges funding from Royal Society.This is the accepted manuscript. The final version is available from ACS at http://pubs.acs.org/doi/abs/10.1021/jp303597m

Effects of polymethylmethacrylate-transfer residues on the growth of organic semiconductor molecules on chemical vapor deposited graphene

Scalably grown and transferred graphene is a highly promising material for organic electronic applications, but controlled interfacing of graphene thereby remains a key challenge. Here, we study the growth characteristics of the important organic semiconductor molecule para-hexaphenyl (6P) on chemical vapor deposited graphene that has been transferred with polymethylmethacrylate (PMMA) onto oxidized Si wafer supports. A particular focus is on the influence of PMMA residual contamination, which we systematically reduce by H2 annealing prior to 6P deposition. We find that 6P grows in a flat-lying needle-type morphology, surprisingly independent of the level of PMMA residue and of graphene defects. Wrinkles in the graphene typically act as preferential nucleation centers. Residual PMMA does however limit the length of the resulting 6P needles by restricting molecular diffusion/attachment. We discuss the implications for organic device fabrication, with particular regard to contamination and defect tolerance.B.C.B acknowledges a College Research Fellowship from Hughes Hall, Cambridge. P.R.K. acknowledges the Lindemann Trust Fellowship. A.M. and G.R. acknowledge support by the Serbian MPNTR through Projects OI 171005 and III 45018. R.S.W. acknowledges a research fellowship from St. John’s College, Cambridge. S.H. acknowledges funding from EPSRC (GRAPHTED, Grant No. EP/K016636/1). We want to thank Dr. Sarah M. Skoff (Vienna University of Technology, Austria) for fruitful discussions.This is the author accepted manuscript. The final published version is available via AIP at http://scitation.aip.org/content/aip/journal/apl/106/10/10.1063/1.4913948

Stability of graphene doping with MoO<inf>3</inf>and I<inf>2</inf>

We dope graphene by evaporation of MoO_3 or by solution-deposition of I_2 and assess the doping stability for its use as transparent electrodes. Electrical measurements show that both dopants increase the graphene sheet conductivity and find that MoO_3-doped graphene is significantly more stable during thermal cycling. Raman spectroscopy finds that neither dopant creates defects in the graphene lattice. In-situ photoemission determines the minimum necessary thickness of MoO_3 for full graphene doping.This is the author's accepted manuscript. Copyright (2014) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Applied Physics Letters (volume 105) and may be found at http://scitation.aip.org/content/aip/journal/apl/105/10/10.1063/1.489502

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