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

Hybrid graphene nematic liquid crystal light scattering device.

A hybrid graphene nematic liquid crystal (LC) light scattering device is presented. This device exploits the inherent poly-crystallinity of chemical vapour deposited (CVD) graphene films to induce directional anchoring and formation of LC multi-domains. This thereby enables efficient light scattering without the need for crossed polarisers or separate alignment layers/additives. The hybrid LC device exhibits switching thresholds at very low electric fields (< 1 V μm(-1)) and repeatable, hysteresis free characteristics. This exploitation of LC alignment effects on CVD graphene films enables a new generation of highly efficient nematic LC scattering displays as well as many other possible applications.Funding from the EPSRC (Grant No. EP/K016636/1, GRAPHTED) is acknowledged. P.R.K. acknowledges funding from Cambridge Commonwealth Trust (CCT) and the Lindemann Trust Fellowship. A.A.K would like to thank the Higher Education of Pakistan (HEC) and the CCT for financial support. A.C.V. acknowledges funding from the Cambridge Conacyt Scholarship and the Roberto Rocca Fellowship. A.K. would like to thank the Luys Educational Foundation and Hovnanian Foundation for scholarships.This is the author accepted manuscript. The final version is available from the Royal Society of Chemistry via http://dx.doi.org/10.1039/c5nr04094

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.S.C. acknowledges funding from EPSRC (Doctoral training award). R.S.W. acknowledges a Research Fellowship from St. John ’ s College. B.C.B acknowledges a Research Fellowship at Hughes Hall. A.C.-V. acknowledges the Conacyt Cambridge Scholarship and Roberto Rocca Fellowship. S.H. acknowledges funding from ERC grant InsituNANO (No. 279342). B.B., S.J.S., K.M., and A.J.P. would like to acknowledge the National Measurement O ffi ce (NMO) for funding through the Innovation, Research and Development (IRD) programme (Project No. 115948). We acknowledge the European Synchrotron Radiation Fac ility (ESRF) for provision of synchrotron radiation, and we thank the sta ff for assistance in using beamline BM20/ROBL. We would also like to acknowl- edge Prof. Bonnie J. Tyler for discussions related to the manuscript.This is the final published article. It first appeared at http://pubs.acs.org/doi/abs/10.1021/nl5046632

Nitrogen controlled iron catalyst phase during carbon nanotube growth

Close control over the active catalyst phase and hence carbon nanotube structure remains challenging in catalytic chemical vapor deposition since multiple competing active catalyst phases typically co-exist under realistic synthesis conditions. Here, using in-situ X-ray diffractometry we show that the phase of supported iron catalyst particles can be reliably controlled via the addition of NH3 during nanotube synthesis. Unlike to polydisperse catalyst phase mixtures during H2 diluted nanotube growth, nitrogen addition controllably leads to phase-pure γ-Fe during pre-treatment and to phase-pure Fe3C during growth. We rationalize these findings in the context of ternary Fe-C-N phase diagram calculations and thus highlight the use of pretreatment- and add-gases as a key parameter towards controlled carbon nanotube growth.This is the author accepted manuscript. The final version is available from AIP via http://dx.doi.org/10.1063/1.489795

Engineering high charge transfer n-doping of graphene electrodes and its application to organic electronics.

Using thermally evaporated cesium carbonate (Cs2CO3) in an organic matrix, we present a novel strategy for efficient n-doping of monolayer graphene and a ∼90% reduction in its sheet resistance to ∼250 Ohm sq(-1). Photoemission spectroscopy confirms the presence of a large interface dipole of ∼0.9 eV between graphene and the Cs2CO3/organic matrix. This leads to a strong charge transfer based doping of graphene with a Fermi level shift of ∼1.0 eV. Using this approach we demonstrate efficient, standard industrial manufacturing process compatible graphene-based inverted organic light emitting diodes on glass and flexible substrates with efficiencies comparable to those of state-of-the-art ITO based devices.Funding via EU FP7 programme Grafol (Grant No. 285275) and EPSRC programme GRAPHTED (Grant No. EP/K016636/1) is acknowledged. P.R.K. acknowledges the Lindemann Trust Fellowship. J.A.A.-W. acknowledges a Research Fellowship from Churchill College, Cambridge. A.C.V. acknowledges the Conacyt Cambridge Scholarship and Roberto Rocca Fellowship.This is the author accepted manuscript. The final version is available from the Royal Society of Chemistry via http://dx.doi.org/10.1039/C5NR03246

Interdependency of subsurface carbon distribution and graphene-catalyst interaction.

The dynamics of the graphene-catalyst interaction during chemical vapor deposition are investigated using in situ, time- and depth-resolved X-ray photoelectron spectroscopy, and complementary grand canonical Monte Carlo simulations coupled to a tight-binding model. We thereby reveal the interdependency of the distribution of carbon close to the catalyst surface and the strength of the graphene-catalyst interaction. The strong interaction of epitaxial graphene with Ni(111) causes a depletion of dissolved carbon close to the catalyst surface, which prevents additional layer formation leading to a self-limiting graphene growth behavior for low exposure pressures (10(-6)-10(-3) mbar). A further hydrocarbon pressure increase (to ∼10(-1) mbar) leads to weakening of the graphene-Ni(111) interaction accompanied by additional graphene layer formation, mediated by an increased concentration of near-surface dissolved carbon. We show that growth of more weakly adhered, rotated graphene on Ni(111) is linked to an initially higher level of near-surface carbon compared to the case of epitaxial graphene growth. The key implications of these results for graphene growth control and their relevance to carbon nanotube growth are highlighted in the context of existing literature.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). 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 research was partially supported by the EU FP7 Work Programme under grant Graphene Flagship (No. 604391). PRK acknowledges funding the Cambridge Commonwealth Trust. H.A. and C.B. acknowledge J.-Y. Raty and B. Legrand for fruitful discussions.This is the final published version. It's also available from ACS at http://pubs.acs.org/doi/abs/10.1021/ja505454v

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

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