Time Evolution of the Wettability of Supported Graphene under Ambient Air Exposure.

The wettability of graphene is both fundamental and crucial for interfacing in most applications, but a detailed understanding of its time evolution remains elusive. Here we systematically investigate the wettability of metal-supported, chemical vapor deposited graphene films as a function of ambient air exposure time using water and various other test liquids with widely different surface tensions. The wettability of graphene is not constant, but varies with substrate interactions and air exposure time. The substrate interactions affect the initial graphene wettability, where, for instance, water contact angles of ∼85 and ∼61° were measured for Ni and Cu supported graphene, respectively, after just minutes of air exposure. Analysis of the surface free energy components indicates that the substrate interactions strongly influence the Lewis acid-base component of supported graphene, which is considerably weaker for Ni supported graphene than for Cu supported graphene, suggesting that the classical van der Waals interaction theory alone is insufficient to describe the wettability of graphene. For prolonged air exposure, the effect of physisorption of airborne contaminants becomes increasingly dominant, resulting in an increase of water contact angle that follows a universal linear-logarithmic relationship with exposure time, until saturating at a maximum value of 92-98°. The adsorbed contaminants render all supported graphene samples increasingly nonpolar, although their total surface free energy decreases only by 10-16% to about 37-41 mJ/m2. Our finding shows that failure to account for the air exposure time may lead to widely different wettability values and contradicting arguments about the wetting transparency of graphene.We acknowledge funding from EPSRC (Grant No. EP/K016636/1, GRAPHTED) and ERC (Grant No. 279342, InsituNANO). P.R. Kidambi acknowledges the Lindemann Trust Fellowship. R.S. Weatherup acknowledges a Research Fellowship from St. John’s College, Cambridge and a EU Marie Skłodowska-Curie Individual Fellowship under grant ARTIST (no. 656870) from the European Union’s Horizon 2020 research and innovation programme.This is the final version of the article. It first appeared from the American Chemical Society via https://doi.org/10.1021/acs.jpcc.5b1049

Graphene-passivated nickel as an efficient hole-injecting electrode for large area organic semiconductor devices

Efficient injection of charge from metal electrodes into semiconductors is of paramount importance to obtain high performance optoelectronic devices. The quality of the interface between the electrode and the semiconductor must, therefore, be carefully controlled. The case of organic semiconductors presents specific problems: ambient deposition techniques, such as solution processing, restrict the choice of electrodes to those not prone to oxidation, limiting potential applications. Additionally, damage to the semiconductor in sputter coating or high temperature thermal evaporation poses an obstacle to the use of many device-relevant metals as top electrodes in vertical metal–semiconductor–metal structures, making it preferable to use them as bottom electrodes. Here, we propose a possible solution to these problems by implementing graphene-passivated nickel as an air stable bottom electrode in vertical devices comprising organic semiconductors. We use these passivated layers as hole-injecting bottom electrodes, and we show that efficient charge injection can be achieved into standard organic semiconducting polymers, owing to an oxide free nickel/graphene/polymer interface. Crucially, we fabricate our electrodes with low roughness, which, in turn, allows us to produce large area devices (of the order of millimeter squares) without electrical shorts occurring. Our results make these graphene-passivated ferromagnetic electrodes a promising approach for large area organic optoelectronic and spintronic devices.We acknowledge funding from EPSRC (EP/P005152/1, EP/M005143/1). R.M. and K.N. acknowledges funding from the EPSRC Cambridge NanoDTC (Grant No. EP/G037221/1). J.A.-W. acknowledges the support of his Research Fellowship from the Royal Commission for the Exhibition of 1851, and Royal Society Dorothy Hodgkin Research Fellowship. R. S. W. acknowledges support from a CAMS-UK fellowship

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

CVD-Enabled Graphene Manufacture and Technology.

Integrated manufacturing is arguably the most challenging task in the development of technology based on graphene and other 2D materials, particularly with regard to the industrial demand for “electronic-grade” large-area films. In order to control the structure and properties of these materials at the monolayer level, their nucleation, growth and interfacing needs to be understood to a level of unprecedented detail compared to existing thin film or bulk materials. Chemical vapor deposition (CVD) has emerged as the most versatile and promising technique to develop graphene and 2D material films into industrial device materials and this Perspective outlines recent progress, trends, and emerging CVD processing pathways. A key focus is the emerging understanding of the underlying growth mechanisms, in particular on the role of the required catalytic growth substrate, which brings together the latest progress in the fields of heterogeneous catalysis and classic crystal/thin-film growth.Funding from the ERC (Grant No. 279342, InSituNANO) and EPSRC (Grant No. EP/K016636/1, GRAPHTED) is acknowledged. R.S.W. acknowledges a research fellowship from St. John’s College, Cambridge.This is the final version of the article. It first appeared from ACS via http://dx.doi.org/10.1021/acs.jpclett.5b0105

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

The influence of intercalated oxygen on the properties of graphene on polycrystalline Cu under various environmental conditions.

Intercalation of oxygen at the interface of graphene grown by chemical vapour deposition and its polycrystalline copper catalyst can have a strong impact on the electronic, chemical and structural properties of both the graphene and the Cu. This can affect the oxidation resistance of the metal as well as subsequent graphene transfer. Here, we show, using near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), X-ray absorption near edge spectroscopy (XANES), energy dispersive X-ray spectroscopy (EDX) and (environmental) scanning electron microscopy (ESEM) that both the oxygen intercalation and de-intercalation are kinetically driven and can be clearly distinguished from carbon etching. The obtained results reveal that a charge transfer between as grown graphene and Cu can be annulled by intercalating oxygen creating quasi-free-standing graphene. This effect is found to be reversible on vacuum annealing proceeding via graphene grain boundaries and defects within the graphene but not without loss of graphene by oxidative etching for repeated (de-)intercalation cycles.P.R.K. acknowledges the Lindemann Trust Fellowship. R.S.W. acknowledges a Research Fellowship from St. John’s College, Cambridge. S.H. acknowledges funding from ERC grant InsituNANO (No. 279342) and EPSRC under grant GRAPHTED (Ref. EP/K016636/1). R.B. and A.K.-G. acknowledge funding from EU project GRAFOL, grant 285275.This is the final published version. It first appeared at http://pubs.rsc.org/en/Content/ArticleLanding/2014/CP/c4cp04025b#!divAbstract

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.St. John’s College, Cambridge (Research Fellowship), European Union’s Horizon 2020 research and innovation programme (Marie Skłodowska-Curie Individual Fellowship (Global) under Grant ID: ARTIST (no. 656870)), National Science Foundation (graduate research fellowship (DGE-1324585)), European Research Council (Grant ID: InsituNANO (no. 279342)), EUFP7 Work Programme (Grant ID: GRAFOL (project reference 285275)) , Engineering and Physical Sciences Research Council (Grant ID: GRAPHTED (project reference EP/K016636/1)), Strategic Capability programme of the National Measurement System of the U.K. Department of Business, Innovation, and Skills (project no. 119376

Protecting nickel with graphene spin-filtering membranes: A single layer is enough

We report on the demonstration of ferromagnetic spin injectors for spintronics which are protected against oxidation through passivation by a single layer of graphene. The graphene monolayer is directly grown by catalytic chemical vapor deposition on pre-patterned nickel electrodes. X-ray photoelectron spectroscopy reveals that even with its monoatomic thickness, monolayer graphene still efficiently protects spin sources against oxidation in ambient air. The resulting single layer passivated electrodes are integrated into spin valves and demonstrated to act as spin polarizers. Strikingly, the atom-thick graphene layer is shown to be sufficient to induce a characteristic spin filtering effect evidenced through the sign reversal of the measured magnetoresistance.We acknowledge the Helmholtz-Zentrum-Berlin Electron storage ring BESSY II for provision of synchrotron radiation at the ISISS beamline and we thank the BESSY staff for continuous support of our experiments. R.S.W. acknowledges a Research Fellowship from St. John’s College, Cambridge. S.H. acknowledges funding from ERC grant InsituNANO (No. 279342) and EPSRC grant GRAPHTED (EP/K016636/1). P.S. acknowledges the Institut Universitaire de France for a junior fellowship. This research was partially supported by the EU FP7 Work Programme under Grant GRAFOL (No. 285275) and Graphene Flagship (No. 604391).This is the final published version. It first appeared at http://scitation.aip.org/content/aip/journal/apl/107/1/10.1063/1.4923401

In situ observations of the atomistic mechanisms of Ni catalyzed low temperature graphene growth.

The key atomistic mechanisms of graphene formation on Ni for technologically relevant hydrocarbon exposures below 600 °C are directly revealed via complementary in situ scanning tunneling microscopy and X-ray photoelectron spectroscopy. For clean Ni(111) below 500 °C, two different surface carbide (Ni2C) conversion mechanisms are dominant which both yield epitaxial graphene, whereas above 500 °C, graphene predominantly grows directly on Ni(111) via replacement mechanisms leading to embedded epitaxial and/or rotated graphene domains. Upon cooling, additional carbon structures form exclusively underneath rotated graphene domains. The dominant graphene growth mechanism also critically depends on the near-surface carbon concentration and hence is intimately linked to the full history of the catalyst and all possible sources of contamination. The detailed XPS fingerprinting of these processes allows a direct link to high pressure XPS measurements of a wide range of growth conditions, including polycrystalline Ni catalysts and recipes commonly used in industrial reactors for graphene and carbon nanotube CVD. This enables an unambiguous and consistent interpretation of prior literature and an assessment of how the quality/structure of as-grown carbon nanostructures relates to the growth modes.L.L.P. acknowledges funding from Area di Ricerca Scientifica e Tecnologica of Trieste and from MIUR through Progetto Strategico NFFA. C.A. acknowledges support from CNR through the ESF FANAS project NOMCIS. C.A. and C.C. acknowledge financial support from MIUR (PRIN 2010-2011 nº 2010N3T9M4). S.B. acknowledges funding from ICTP TRIL program. S.H. acknowledges funding from ERC grant InsituNANO (n°279342). R.S.W. acknowledges funding from EPSRC (Doctoral training award), and the Nano Science & Technology Doctoral Training Centre Cambridge (NanoDTC). The help of C. Dri and F. Esch (design) and P. Bertoch and F. Salvador (manufacturing) in the realization of the high temperature STM sample holder is gratefully acknowledged. We acknowledge the Helmholtz-Zentrum-Berlin Electron storage ring BESSY II for provision of synchrotron radiation at the ISISS beamline and we thank the BESSY staff for continuous support of our experiments.This is the accepted manuscript. The final version is available from ACS at http://pubs.acs.org/doi/abs/10.1021/nn402927q