The oxidation of Ge covered with graphene that is either grown on or transferred to the surface is investigated by X-ray photoelectron spectroscopy, Raman spectroscopy, and transmission electron microscopy. Graphene properly grown by chemical vapor deposition on Ge(100), (111), or (110) effectively inhibits room-temperature oxidation of the surface. When graphene is transferred to the Ge surface, oxidation is reduced relative to that on uncovered Ge but has the same power law dependence. We conclude that access to the graphene/Ge interface must occur via defects in the graphene. The excellent passivation provided by graphene grown on Ge should enhance applications of Ge in the electronic-device industry.

We compare the ultrafast dynamics of singlet fission and charge generation in pentacene films grown on glass and graphene. Pentacene grown on graphene is interesting because it forms large crystals with the long axis of the molecules "lying-down" (parallel to the surface). At low excitation fluence, spectra for pentacene on graphene contain triplet absorptions at 507 and 545 nm and no bleaching at 630 nm, which we show is due to the orientation of the pentacene molecules. We perform the first transient absorption anisotropy measurements on pentacene, observing negative anisotropy of the 507 and 545 nm peaks, consistent with triplet absorption. A broad feature at 853 nm, observed on both glass and graphene, is isotropic, suggesting hole absorption. At high fluence, there are additional features, whose kinetics and anisotropies are not explained by heating, that we assign to charge generation; we propose a polaron pair absorption at 614 nm. The lifetimes are shorter at high fluence for both pentacene on glass and graphene, indicative of triplet-triplet annihilation that likely enhances charge generation. The anisotropy decays more slowly for pentacene on graphene than on glass, in keeping with the smaller domain size observed via atomic force microscopy. Coherent acoustic phonons are observed for pentacene on graphene, which is a consequence of more homogeneous domains. Measuring the ultrafast dynamics of pentacene as a function of molecular orientation, fluence, and polarization provides new insight to previous spectral assignments.

Crystal orientation in organic thin films is one of the key parameters that determine absorption cross-section, interfacial energetics and excitonic states, and free charge properties. In this work, monolayer graphene is used to direct the crystal orientation of selected planar organic molecules. Lying-down orientation with π-stacking normal to the surface is achieved with graphene templating. The absorption spectra of the graphene-templated films are correlated to molecular orientation. The same set of absorption features with or without graphene suggests that no vibronic states are forbidden or newly introduced. However, the light absorption with graphene templating is enhanced due to the altered relative orientation between the transition dipole moment of the constituent molecules and the electric field of incident light. The energy level of the highest occupied molecular orbital (HOMO) of graphene templated p-type films is observed at a deeper-lying value (relative to vacuum) compared to untemplated diindenoperylene films grown on indium tin oxide. In contrast, the HOMO energy levels of graphene templated n-type films are observed at higher-lying energy levels (relative to vacuum) compared to the respective untemplated films due to surface dipoles. Such a change can potentially increase the theoretical V oc expected for photovoltaic devices incorporating these templated films.

The chemical vapor deposition of monolayer graphene on metal foils and thin films typically yields graphene that appears to be continuous and complete but that actually contains a high density of pinhole defects. These pinhole defects can be present at densities greater than 1 mu m(-2) and are problematic for many applications, ranging from the implementation of graphene in electronics to its use as a diffusion barrier. Here, we characterize pinhole defects in graphene films that are grown on Cu foils and epitaxial Cu thin films using CH4 as the precursor. On Cu foils, a relationship between surface roughness and the pinhole defect density is observed. A reduction in pinholes by a factor of similar to 40 is realized by decreasing the foil surface roughness via increasing the annealing temperature and duration. The pinhole density is further reduced by a factor of similar to 200 by using smoother epitaxial Cu thin films and additionally by extending the growth duration past the point of visual completion, as characterized by scanning electron microscopy. This study is expected to serve as a foundation for developing high quality substrates for graphene synthesis and realizing pinhole-free graphene. (C) 2015 Elsevier Ltd. All rights reserved.

A different mechanism was found for Cu transport through multi-transferred single-layer graphene serving as diffusion barriers on the basis of time-dependent dielectric breakdown tests. Vertical and lateral transport of Cu dominates at different stress electric field regimes. The classic E-model was modified to project quantitatively the effectiveness of the graphene Cu diffusion barrier at low electric field based on high-field accelerated stress data. The results are compared to industry-standard Cu diffusion barrier material TaN. 3.5 Å single-layer graphene shows the mean time-to-fail comparable to 4 nm TaN, while two-time and three-time transferred single-layer graphene stacks give 2× and 3× improvements, respectively, compared to single-layer graphene at a 0.5 MV/cm electric field. The influences of graphene grain boundaries on Cu vertical transport through the graphene layers are explored, revealing that large-grain (10-15 μm) single-layer graphene gives a 2 orders of magnitude longer lifetime than small-grain (2-3 μm) graphene. As a result, it is more effective to further enhance graphene barrier reliability by improving single-layer graphene quality through increasing grain sizes or using single-crystalline graphene than just by increasing thickness through multi-transfer. These results may also be applied for graphene as barriers for other metals.

The advantages of graphene diffusion barrier are studied and benchmarked to the industry-standard barrier material TaN for the first time. Even when the wire width is scaled to 10 nm, the effective resistivity of the Cu interconnect is maintained near the intrinsic value of Cu using a 3 Å single layer graphene (SLG) barrier. In the time dependent dielectric breakdown (TDDB) test, 4 nm multi-layer graphene (MLG) gives 6.5X shorter mean time to fail (MTTF) than 4 nm TaN. However, when the barrier thickness is reduced, 3 Å single-layer graphene (SLG) gives 3.3X longer MTTF than 2 nm TaN, showing that SLG has better scaling potential. The influences of SLG grain size and various transfer methods are presented for further improving the SLG barrier performance.

Graphene can be transformed from a semimetal into a semiconductor if it is confined into nanoribbons narrower than 10 nm with controlled crystallographic orientation and well-defined armchair edges. However, the scalable synthesis of nanoribbons with this precision directly on insulating or semiconducting substrates has not been possible. Here we demonstrate the synthesis of graphene nanoribbons on Ge(001) via chemical vapour deposition. The nanoribbons are self-aligning 3° from the Ge〈110〉 directions, are self-defining with predominantly smooth armchair edges, and have tunable width to <10 nm and aspect ratio to >70. In order to realize highly anisotropic ribbons, it is critical to operate in a regime in which the growth rate in the width direction is especially slow, <5 nm h −1 . This directional and anisotropic growth enables nanoribbon fabrication directly on conventional semiconductor wafer platforms and, therefore, promises to allow the integration of nanoribbons into future hybrid integrated circuits.

We report on the organization and dynamics of bacteria (Proteus mirabilis) dispersed within lyotropic liquid crystal (LC) films confined by pairs of surfaces that induce homeotropic (perpendicular) or hybrid (homeotropic and parallel orientations at each surface) anchoring of the LC. By using motile vegetative bacteria (3 µm in length) and homeotropically aligned LC films with thicknesses that exceed the length of the rod-shaped cells, a key finding reported in this paper is that elastic torques generated by the LC are sufficiently large to overcome wall-induced hydrodynamic torques acting on the cells, thus leading to LC-guided bacterial motion near surfaces that orient LCs. This result extends to bacteria within LC films with hybrid anchoring, and leads to the observation that asymmetric strain within a hybrid aligned LC rectifies motions of motile cells. In contrast, when the LC film thickness is sufficiently small that confinement prevents alignment of the bacteria cells along a homeotropically aligned LC director (achieved using swarm cells of length 10-60 µm), the bacterial cells propel in directions orthogonal to the director, generating transient distortions in the LC that have striking "comet-like" optical signatures. In this limit, for hybrid LC films, we find LC elastic stresses deform the bodies of swarm cells into bent configurations that follow the LC director, thus unmasking a coupling between bacterial shape and LC strain. Overall, these results provide new insight into the influence of surface-oriented LCs on dynamical bacterial behaviors and hint at novel ways to manipulate bacteria using confined LC phases that are not possible in isotropic solutions.

Environmental effects on the oxidative stability of graphene atomic membranes on SiO2 are studied and quantified using in situ spatially and temporally-resolved imaging Raman spectroscopy, electron microscopy, and charge-transport measurements.

Graphene is considered a next-generation electrode for indium tin oxide (ITO)-free organic photovoltaic devices (OPVs). However, to date, limited numbers of OPVs containing surface-modified graphene electrodes perform as well as ITO-based counterparts, and no devices containing a bare graphene electrode have been reported to yield satisfactory rectification characteristics. In this report, we provide experimental data to learn why. Time-resolved surface photoresponse measurements on templated pentacene-on-graphene films directly reveal that p-doped monolayer graphene efficiently extracts electrons, not holes, from photoexcited pentacene. Accordingly, a graphene/pentacene/MoO3 heterojunction displays a large surface photoresponse and, by inference, efficient dissociation of photogenerated excitons, with graphene serving as an electron extraction layer and MoO3 as a hole extraction layer. In contrast, a graphene/pentacene/C60 heterojunction yields a comparatively insignificant surface photoresponse because both graphene and C60 act as competing electron extraction layers. The data presented herein provide experimental insight for future endeavors involving bare graphene as an electrode for organic photovoltaic devices and strongly suggest that p-doped graphene is best considered a cathode for OPVs.

Highly transparent and conductive monolayer graphene was used as a template to tune the crystal orientation of pentacene from generic standing-up (001) to lying-down (022) in neat films. Spatially resolved Kelvin probe force microscopy (KPFM) was used to reveal the energy levels of pentacene thin films grown on substrates with and without the template graphene layer, as well as the energy level alignment in various pentacene-containing organicorganic heterojunctions. A correlation between crystal domain orientation and the work function was directly observed using KPFM. Up to 0.36 eV shifts in work function were observed in neat pentacene films over large areas (>0.5 in.(2)) upon orientation transition, likely due to the transition from Fermi level pinning (standing-up pentacene on ITO) to vacuum level alignment (lying-down pentacene on grapheneITO). Morphology-induced energy level shifts versus interfacial electronic equilibration effects were disentangled using atomic force microscopy, KPFM, X-ray diffraction, and Raman data for neat pentacene films and pentacene containing heterojunctions on monolayer graphene. The data detailed herein provide a fundamental picture of the major interfacial effects active in optoelectronic devices containing a bare graphene electrode.

The rational synthesis of graphene nanoribbons that are semiconducting with sub-10 nm width, controlled crystallographic orientation, and well-defined edges on non-metallic substrates has been a significant challenge. The growth of nanoribbons on metal substrates precludes their direct use in semiconducting electronics due to the conducting substrate, and the direct synthesis of nanoribbons in solution is complicated by challenges of their post-synthetic assembly. In this talk, we demonstrate the scalable synthesis of graphene nanoribbons from the bottom-up via chemical vapor deposition (CVD) on Ge(001). Low energy electron diffraction (LEED) and scanning tunneling microscopy (STM) show that the ribbons are self-orienting ±2.9° from the Ge[110] directions and are self-defining. The nanoribbons have predominately smooth armchair edges that give rise to electron interference patterns that are indicative of the high quality of the edges. By tuning the precursor flux, growth time, and growth temperature, the ribbon anisotropy and growth kinetics can be tailored to yield ribbons with controlled width < 10 nm and aspect ratio > 60. Compared to previous reports of the growth of low aspect ratio crystals of graphene on Ge, we find that in order to realize high aspect ratio nanoribbons, it is critical to operate in a regime in which the growth rate is especially slow, on the order of 5 nm/h for growth in the width direction. Scanning tunneling spectroscopy shows that the ribbons have electronic structures that are consistent with semiconductors with bandgaps that are > 500 meV and that vary inversely with width. This work is important because unlike continuous two-dimensional graphene, which is semimetallic, one-dimensional graphene nanoribbons can be semiconducting, allowing for the substantial modulation of their conductance and enabling their application in semiconductor logic, optoelectronics, photonics, and sensors. Moreover, the direct synthesis of ultranarrow and smooth graphene nanoribbons on Ge demonstrated here provides a scalable, high throughput pathway for integrating semiconducting graphene directly on conventional large-area semiconductor wafer platforms that are compatible with planar processing.

Field-effect transistors (FETs) that are stretchable up to 50% without appreciable degradation in performance are demonstrated. The FETs are based on buckled thin films of polyfluorene-wrapped semiconducting single-walled carbon nanotubes (CNTs) as the channel, a flexible ion gel as the dielectric, and buckled metal films as electrodes. The buckling of the CNT film enables the high degree of stretchability while the flexible nature of the ion gel allows it to maintain a high quality interface with the CNTs during stretching. An excellent on/off ratio of >10(4), a field-effect mobility of 10 cm(2) · V(-1) · s(-1), and a low operating voltage of <2 V are achieved over repeated mechanical cycling, with further strain accommodation possible. Deformable FETs are expected to facilitate new technologies like stretchable displays, conformal devices, and electronic skins.

Using a novel two-step fabrication scheme, we create highly semiconducting-enriched single-walled carbon nanotube (sSWNT) bulk heterojunctions (BHJs) by first creating highly porous interconnected sSWNT aerogels (sSWNT-AEROs), followed by back-filling the pores with [6,6]-phenyl-C(71)-butyric acid methyl ester (PC(71)BM). We demonstrate sSWNT-AERO structures with density as low as 2.5 mg cm(-3), porosity as high as 99.8%, and diameter of sSWNT fibers ≤ 10 nm. Upon spin coating with PC(71)BM, the resulting sSWNT-AERO-PC(71)BM nanocomposites exhibit highly quenched sSWNT photoluminescence, which is attributed to the large interfacial area between the sSWNT and PC(71)BM phases, and an appropriate sSWNT fiber diameter that matches the inter-sSWNT exciton migration length. Employing the sSWNT-AERO-PC(71)BM BHJ structure, we report optimized solar cells with a power conversion efficiency of 1.7%, which is exceptional among polymer-like solar cells in which sSWNTs are designed to replace either the polymer or fullerene component. A fairly balanced photocurrent is achieved with 36% peak external quantum efficiency (EQE) in the visible and 19% peak EQE in the near-infrared where sSWNTs serve as electron donors and photoabsorbers. Our results prove the effectiveness of this new method in controlling the sSWNT morphology in BHJ structures, suggesting a promising route towards highly efficient sSWNT photoabsorbing solar cells.

We evaluate the performance of exceptionally electronic-type sorted, semiconducting, aligned single-walled carbon nanotubes (s-SWCNTs) in field effect transistors (FETs). High on-conductance and high on/off conductance modulation are simultaneously achieved at channel lengths which are both shorter and longer than individual s-SWCNTs. The s-SWCNTs are isolated from heterogeneous mixtures using a polyfluorene-derivative as a selective agent and aligned on substrates via dose-controlled, floating evaporative self-assembly at densities of ∼50 s-SWCNTs μm−1. At a channel length of 9 μm the s-SWCNTs percolate to span the FET channel, and the on/off ratio and charge transport mobility are 2.2 × 107 and 46 cm2 V−1 s−1, respectively. At a channel length of 400 nm, a large fraction of the s-SWCNTs directly span the channel, and the on-conductance per width is 61 μS μm−1 and the on/off ratio is 4 × 105. These results are considerably better than previous solution-processed FETs, which have suffered from poor on/off ratio due to spurious metallic nanotubes that bridge the channel. 4071 individual and small bundles of s-SWCNTs are tested in 400 nm channel length FETs, and all show semiconducting behavior, demonstrating the high fidelity of polyfluorenes as selective agents and the promise of assembling s-SWCNTs from solution to create high performance semiconductor electronic devices.

It is shown that the performance of graphene diffusion barriers can be enhanced by stacking multiple layers of graphene and increasing grain size. The focus is on large-area barriers of graphene grown by chemical vapor deposition (CVD) in the context of passivating an underlying Cu substrate from oxidation in air at 200 degrees C and use imaging Raman spectroscopy as a tool to temporally and spatially map the barrier performance and to guide barrier design. At 200 degrees C in air, Cu oxidation proceeds in multiple regimes: fi rst slowly via transport through atomic-scale grain boundary defects inherent to CVD-graphene and then more rapidly as the graphene itself degrades and new defects are formed. In the initial regime, the graphene passivates better than previously reported. Whereas oxidation through single sheets primarily occurs through grain boundaries, oxidation through multiple sheets is spatially confi ned to their intersection. Performance further increases with grainsize. The degradation of the graphene itself at 200 degrees C ultimately limits high temperature but suggests superior low temperature barrier performance. This study is expected to improve the understanding of mass transport through CVD-graphene materials and lead to improved large area graphene materials for barrier applications.

Charge and energy transport in organic semiconductors is highly anisotropic and dependent on crystalline ordering. Here, we demonstrate a novel approach for ordering crystalline organic semiconductors, with orientations optimized for optoelectronics applications, by using a single monolayer of graphene as a molecular template. We show, in particular, that large-area graphene can be integrated on metals and oxides to modify their surface energies and used to template copper phthalocyanine (CuPc), a prototypical organic semiconductor. On unmodified substrates, thermally evaporated films of CuPc are small-grained, and the molecules are in the "standing-up" (100) orientation. On graphene modified substrates, CuPc is templated in favorable "lying-down" (112̅) and (012̅) orientations with drastically larger crystal sizes. This results in an 86% increase in the absorption coefficient at 700 nm and should furthermore result in enhanced energy and charge transport. The use of highly conductive and transparent (>95%) graphene membranes as templates is expected to be a foundation for developing future planar and nanostructured organic light-emitting diodes and organic photovoltaics with improved performance.