Stable, efficient p-type doping of graphene by nitric acid

We systematically dope monolayer graphene with different concentrations of nitric acid over a range of temperatures, and analyze the variation of sheet resistance under vacuum annealing up to 300 °C.</p

Efficient Transfer Doping of Carbon Nanotube Forests by MoO3.

We dope nanotube forests using evaporated MoO3 and observe the forest resistivity to decrease by 2 orders of magnitude, reaching values as low as ∼5 × 10(-5) Ωcm, thus approaching that of copper. Using in situ photoemission spectroscopy, we determine the minimum necessary MoO3 thickness to dope a forest and study the underlying doping mechanism. Homogenous coating and tube compaction emerge as key factors for decreasing the forest resistivity. When all nanotubes are fully coated with MoO3 and packed, conduction channels are created both inside the nanotubes and on the outside oxide layer. This is supported by density functional theory calculations, which show a shift of the Fermi energy of the nanotubes and the conversion of the oxide into a layer of metallic character. MoO3 doping removes the need for chirality control during nanotube growth and represents a step forward toward the use of forests in next-generation electronics and in power cables or conductive polymers.The authors acknowledge financial support from European project Grafol.This is the accepted manuscript. The final version is available at http://pubs.acs.org/doi/full/10.1021/acsnano.5b04644

From Growth Surface to Device Interface: Preserving Metallic Fe under Monolayer Hexagonal Boron Nitride

We investigate the interfacial chemistry between Fe catalyst foils and monolayer hexagonal boron nitride (h-BN) following chemical vapour deposition and during subsequent atmospheric exposure, using scanning electron microscopy, X-ray photoemission spectroscopy, and scanning photoelectron microscopy. We show that regions of the Fe surface covered by h-BN remain in a reduced state during exposure to moist air for ~40 hours at room temperature. This protection is attributed to the strong interfacial interaction between h-BN and Fe, which prevents the rapid intercalation of oxidizing species. Local Fe oxidation is observed on bare Fe regions and close to defects in the h-BN film (e.g. domain boundaries, wrinkles, and edges), which over the longer-term provide pathways for slow bulk oxidation of the Fe. We further confirm that the interface between h-BN and reduced Fe can be recovered by vacuum annealing at ~600 °C, although this is accompanied by the creation of defects within the h-BN film. We discuss the importance of these findings in the context of integrated manufacturing and transfer-free device integration of h-BN, particularly for technologically important applications where h-BN has potential as a tunnel barrier such as magnetic tunnel junctions.S.C. and L.D. acknowledge EPSRC Doctoral Training Awards. H.S. acknowledges a research fellowship from the Japanese Society for the Promotion of Science (JSPS). S.H. acknowledges funding from ERC grant InsituNANO (no. 279342). This research was partially supported by the EUFP7 Work Programme under grant GRAFOL (project reference 285275) and EPSRC under grant GRAPHTED (project reference EP/ ACS Applied Materials & Interfaces Research Article K016636/1). 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

The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron–carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes.S.H. acknowledges funding from ERC grant InsituNANO (No. 279342). We acknowledge the European Synchrotron Radiation Facility (ESRF) for provision of synchrotron radiation facilities. We acknowledge the use of facilities within the LeRoy Eyring Center for Solid State Science at Arizona State University. C.T.W. and C.S.E. acknowledge funding from the EC project Technotubes. A.D.G. acknowledges funding from the Marshall Aid Commemoration Commission and the National Science Foundation. R.S.W. acknowledges funding from EPSRC (Doctoral training award) and B.C.B. acknowledges a Research Fellowship at Hughes Hall, Cambridge.This is the accepted manuscript. The final version is available from ACS at http://pubs.acs.org/doi/abs/10.1021/cm301402g

Influence of packing density and surface roughness of vertically-aligned carbon nanotubes on adhesive properties of gecko-inspired mimetics.

We have systematically studied the macroscopic adhesive properties of vertically aligned nanotube arrays with various packing density and roughness. Using a tensile setup in shear and normal adhesion, we find that there exists a maximum packing density for nanotube arrays to have adhesive properties. Too highly packed tubes do not offer intertube space for tube bending and side-wall contact to surfaces, thus exhibiting no adhesive properties. Likewise, we also show that the surface roughness of the arrays strongly influences the adhesion properties and the reusability of the tubes. Increasing the surface roughness of the array strengthens the adhesion in the normal direction, but weakens it in the shear direction. Altogether, these results allow progress toward mimicking the gecko's vertical mobility.The authors acknowledge funding from the EC project Technotubes.This is the accepted manuscript. The final version is available at http://pubs.acs.org/doi/abs/10.1021/am507822b

Stability of graphene doping with MoO₃ and I₂

This is the author's accepted manuscript. \ud 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.\ud The following article appeared in Applied Physics Letters (volume 105) and may be found at http://scitation.aip.org/content/aip/journal/apl/105/10/10.1063/1.4895025We 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

Effect of Catalyst Pretreatment on Chirality-Selective Growth of Single-Walled Carbon Nanotubes

We show that catalyst pretreatment conditions can have a profound effect on the chiral distribution in single-walled carbon nanotube chemical vapor deposition. Using a SiO₂-supported cobalt model catalyst and pretreatment in NH₃, we obtain a comparably narrowed chiral distribution with a downshifted tube diameter range, independent of the hydrocarbon source. Our findings demonstrate that the state of the catalyst at the point of carbon nanotube nucleation is of fundamental importance for chiral control, thus identifying the pretreatment atmosphere as a key parameter for control of diameter and chirality distributions

Metal-Organic Framework ZIF‑8 Films As Low‑κ Dielectrics in Microelectronics

ZIF-8 films were deposited on silicon wafers and characterized to assess their potential as future insulators (low-κ dielectrics) in microelectronics. Scanning electron microscopy and gas adsorption monitored by spectroscopic ellipsometry confirmed the good coalescence of the crystals, the absence of intergranular voids, and the hydrophobicity of the pores. Mechanical properties were assessed by nanoindentation and tape tests, confirming sufficient rigidity for chip manufacturing processes (elastic modulus >3 GPa) and the good adhesion to the support. The dielectric constant was measured by impedance analysis at different frequencies and temperatures, indicating that κ was only 2.33 (±0.05) at 100 kHz, a result of low polarizability and density in the films. Intensity voltage curves showed that the leakage current was only 10^–8 A cm² at 1 MV cm^–1, and the breakdown voltage was above 2 MV cm^–1. In conclusion, metal-organic framework ZIF-8 films were experimentally found to be promising candidates as low-κ dielectrics in microelectronic chip devices. This opens a new direction for research into the application of metal-organic frameworks