Strain Modulation of Graphene by Nanoscale Substrate Curvatures: A Molecular View.

Spatially nonuniform strain is important for engineering the pseudomagnetic field and band structure of graphene. Despite the wide interest in strain engineering, there is still a lack of control on device-compatible strain patterns due to the limited understanding of the structure-strain relationship. Here, we study the effect of substrate corrugation and curvature on the strain profiles of graphene via combined experimental and theoretical studies of a model system: graphene on closely packed SiO2 nanospheres with different diameters (20-200 nm). Experimentally, via quantitative Raman analysis, we observe partial adhesion and wrinkle features and find that smaller nanospheres induce larger tensile strain in graphene; theoretically, molecular dynamics simulations confirm the same microscopic structure and size dependence of strain and reveal that a larger strain is caused by a stronger, inhomogeneous interaction force between smaller nanospheres and graphene. This molecular-level understanding of the strain mechanism is important for strain engineering of graphene and other two-dimensional materials.

Solution-Synthesized Chevron Graphene Nanoribbons Exfoliated onto H:Si(100).

There has been tremendous progress in designing and synthesizing graphene nanoribbons (GNRs). The ability to control the width, edge structure, and dopant level with atomic precision has created a large class of accessible electronic landscapes for use in logic applications. One of the major limitations preventing the realization of GNR devices is the difficulty of transferring GNRs onto nonmetallic substrates. In this work, we developed a new approach for clean deposition of solution-synthesized atomically precise chevron GNRs onto H:Si(100) under ultrahigh vacuum. A clean transfer allowed ultrahigh-vacuum scanning tunneling microscopy (STM) to provide high-resolution imaging and spectroscopy and reveal details of the electronic structure of chevron nanoribbons that have not been previously reported. We also demonstrate STM nanomanipulation of GNRs, characterization of multilayer GNR cross-junctions, and STM nanolithography for local depassivation of H:Si(100), which allowed us to probe GNR-Si interactions and revealed a semiconducting-to-metallic transition. The results of STM measurements were shown to be in good agreement with first-principles computational modeling.

Imaging Excited Orbitals of Quantum Dots: Experiment and Electronic Structure Theory.

Electronically excited orbitals play a fundamental role in chemical reactivity and spectroscopy. In nanostructures, orbital shape is diagnostic of defects that control blinking, surface carrier dynamics, and other important optoelectronic properties. We capture nanometer resolution images of electronically excited PbS quantum dots (QDs) by single molecule absorption scanning tunneling microscopy (SMA-STM). Dots with a bandgap of ∼1 eV are deposited on a transparent gold surface and optically excited with red or green light to produce hot carriers. The STM tip-enhanced laser light produces a large excited-state population, and the Stark effect allows transitions to be tuned into resonance by changing the sample voltage. Scanning the QDs under laser excitation, we were able to image electronic excitation to different angular momentum states depending on sample bias. The shapes differ from idealized S- or P-like orbitals due to imperfections of the QDs. Excitation of adjacent QD pairs reveals orbital alignment, evidence for electronic coupling between dots. Electronic structure modeling of a small PbS QD, when scaled for size, reveals Stark tuning and variation in the transition moment of different parity states, supporting the simple one-electron experimental interpretation in the hot carrier limit. The calculations highlight the sensitivity of orbital density to applied field, laser wavelength, and structural fluctuations of the QD.

Annealing free, clean graphene transfer using alternative polymer scaffolds.

We examine the transfer of graphene grown by chemical vapor deposition (CVD) with polymer scaffolds of poly(methyl methacrylate) (PMMA), poly(lactic acid) (PLA), poly(phthalaldehyde) (PPA), and poly(bisphenol A carbonate) (PC). We find that optimally reactive PC scaffolds provide the cleanest graphene transfers without any annealing, after extensive comparison with optical microscopy, x-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy. Comparatively, films transferred with PLA, PPA, PMMA/PC, and PMMA have a two-fold higher roughness and a five-fold higher chemical doping. Using PC scaffolds, we demonstrate the clean transfer of CVD multilayer graphene, fluorinated graphene, and hexagonal boron nitride. Our annealing free, PC transfers enable the use of atomically-clean nanomaterials in biomolecule encapsulation and flexible electronic applications.

In(x)Ga(1-x)As nanowire growth on graphene: van der Waals epitaxy induced phase segregation.

The growth of high-density arrays of vertically oriented, single crystalline InAs NWs on graphene surfaces are realized through the van der Waals (vdW) epitaxy mechanism by metalorganic chemical vapor deposition (MOCVD). However, the growth of InGaAs NWs on graphene results in spontaneous phase separation starting from the beginning of growth, yielding a well-defined InAs-In(x)Ga(1-x)As (0.2 < x < 1) core-shell structure. The core-shell structure then terminates abruptly after about 2 µm in height, and axial growth of uniform composition In(x)Ga(1-x)As takes place without a change in the NW diameter. The In(x)Ga(1-x)As shell composition changes as a function of indium flow, but the core and shell thicknesses and the onset of nonsegregated In(x)Ga(1-x)As axial segment are independent of indium composition. In contrast, no InGaAs phase segregation has been observed when growing on MoS2, another two-dimensional (2D) layered material, or via the Au-assisted vapor-liquid-solid (VLS) mechanism on graphene. This spontaneous phase segregation phenomenon is elucidated as a special case of van der Waals epitaxy on 2D sheets. Considering the near lattice matched registry between InAs and graphene, InGaAs is forced to self-organize into InAs core and InGaAs shell segments since the lack of dangling bonds on graphene does not allow strain sharing through elastic deformation between InGaAs and graphene.

Nanosoldering carbon nanotube junctions by local chemical vapor deposition for improved device performance.

The performance of carbon nanotube network (CNN) devices is usually limited by the high resistance of individual nanotube junctions (NJs). We present a novel method to reduce this resistance through a nanoscale chemical vapor deposition (CVD) process. By passing current through the devices in the presence of a gaseous CVD precursor, localized nanoscale Joule heating induced at the NJs stimulates the selective and self-limiting deposition of metallic nanosolder. The effectiveness of this nanosoldering process depends on the work function of the deposited metal (here Pd or HfB2), and it can improve the on/off current ratio of a CNN device by nearly an order of magnitude. This nanosoldering technique could also be applied to other device types where nanoscale resistance components limit overall device performance.

Hybrid Edge Results in Narrowed Band Gap: Bottom-up Liquid-Phase Synthesis of Bent N = 6/8 Armchair Graphene Nanoribbons.

Scalable fabrication of graphene nanoribbons with narrow band gaps has been a nontrivial challenge. Here, we have developed a simple approach to access narrow band gaps using hybrid edge structures. Bottom-up liquid-phase synthesis of bent N = 6/8 armchair graphene nanoribbons (AGNRs) has been achieved in high efficiency through copolymerization between an o-terphenyl monomer and a naphthalene-based monomer, followed by Scholl oxidation. An unexpected 1,2-aryl migration has been discovered, which is responsible for introducing kinked structures into the GNR backbones. The N = 6/8 AGNRs have been fully characterized to support the proposed structure and show a narrow band gap and a relatively high electrical conductivity. In addition, their application in efficient gas sensing has also been demonstrated.

Scanning tunneling microscopy study and nanomanipulation of graphene-coated water on mica.

We study interfacial water trapped between a sheet of graphene and a muscovite (mica) surface using Raman spectroscopy and ultrahigh vacuum scanning tunneling microscopy (UHV-STM) at room temperature. We are able to image the graphene-water interface with atomic resolution, revealing a layered network of water trapped underneath the graphene. We identify water layer numbers with a carbon nanotube height reference. Under normal scanning conditions, the water structures remain stable. However, at greater electron energies, we are able to locally manipulate the water using the STM tip.

Sub-5 nm Contacts and Induced p-n Junction Formation in Individual Atomically Precise Graphene Nanoribbons.

This paper demonstrates the fabrication of nanometer-scale metal contacts on individual graphene nanoribbons (GNRs) and the use of these contacts to control the electronic character of the GNRs. We demonstrate the use of a low-voltage direct-write STM-based process to pattern sub-5 nm metallic hafnium diboride (HfB2) contacts directly on top of single GNRs in an ultrahigh-vacuum scanning tunneling microscope (UHV-STM), with all the fabrication performed on a technologically relevant semiconductor silicon substrate. Scanning tunneling spectroscopy (STS) data not only verify the expected metallic and semiconducting character of the contacts and GNR, respectively, but also show induced band bending and p-n junction formation in the GNR due to the metal-GNR work function difference. Contact engineering with different work function metals obviates the need to create GNRs with different characteristics by complex chemical doping. This is a demonstration of the successful fabrication of precise metal contacts and local p-n junction formation on single GNRs.

Effects of polycrystalline cu substrate on graphene growth by chemical vapor deposition.

Chemical vapor deposition of graphene on Cu often employs polycrystalline Cu substrates with diverse facets, grain boundaries (GBs), annealing twins, and rough sites. Using scanning electron microscopy (SEM), electron-backscatter diffraction (EBSD), and Raman spectroscopy on graphene and Cu, we find that Cu substrate crystallography affects graphene growth more than facet roughness. We determine that (111) containing facets produce pristine monolayer graphene with higher growth rate than (100) containing facets, especially Cu(100). The number of graphene defects and nucleation sites appears Cu facet invariant at growth temperatures above 900 °C. Engineering Cu to have (111) surfaces will cause monolayer, uniform graphene growth.

Printable Aligned Single-Walled Carbon Nanotube Film with Outstanding Thermal Conductivity and Electromagnetic Interference Shielding Performance.

Ultrathin, lightweight, and flexible aligned single-walled carbon nanotube (SWCNT) films are fabricated by a facile, environmentally friendly, and scalable printing methodology. The aligned pattern and outstanding intrinsic properties render "metal-like" thermal conductivity of the SWCNT films, as well as excellent mechanical strength, flexibility, and hydrophobicity. Further, the aligned cellular microstructure promotes the electromagnetic interference (EMI) shielding ability of the SWCNTs, leading to excellent shielding effectiveness (SE) of ~ 39 to 90 dB despite a density of only ~ 0.6 g cm-3 at thicknesses of merely 1.5-24 µm, respectively. An ultrahigh thickness-specific SE of 25 693 dB mm-1 and an unprecedented normalized specific SE of 428 222 dB cm2 g-1 are accomplished by the freestanding SWCNT films, significantly surpassing previously reported shielding materials. In addition to an EMI SE greater than 54 dB in an ultra-broadband frequency range of around 400 GHz, the films demonstrate excellent EMI shielding stability and reliability when subjected to mechanical deformation, chemical (acid/alkali/organic solvent) corrosion, and high-/low-temperature environments. The novel printed SWCNT films offer significant potential for practical applications in the aerospace, defense, precision components, and smart wearable electronics industries.

Separation-dependent electronic transparency of monolayer graphene membranes on III-V semiconductor substrates.

Ultrahigh vacuum scanning tunneling microscopy and first-principles calculations have been carried out to study monolayer graphene nanomembranes deposited in situ onto UHV-cleaved GaAs(110) and InAs(110) surfaces. A bias-dependent semitransparency effect is observed in which the substrate atomic structure is clearly visible through the graphene monolayer. Statistical data analysis and density functional theory calculations suggest that this semitransparency phenomenon is due to the scanning tunneling microscope tip pushing the graphene membrane away from its equilibrium location and closer to the substrate surface, causing their electronic states to intermix.

The influence of edge structure on the electronic properties of graphene quantum dots and nanoribbons.

Graphene shows promise as a future material for nanoelectronics owing to its compatibility with industry-standard lithographic processing, electron mobilities up to 150 times greater than Si and a thermal conductivity twice that of diamond. The electronic structure of graphene nanoribbons (GNRs) and quantum dots (GQDs) has been predicted to depend sensitively on the crystallographic orientation of their edges; however, the influence of edge structure has not been verified experimentally. Here, we use tunnelling spectroscopy to show that the electronic structure of GNRs and GQDs with 2-20 nm lateral dimensions varies on the basis of the graphene edge lattice symmetry. Predominantly zigzag-edge GQDs with 7-8 nm average dimensions are metallic owing to the presence of zigzag edge states. GNRs with a higher fraction of zigzag edges exhibit a smaller energy gap than a predominantly armchair-edge ribbon of similar width, and the magnitudes of the measured GNR energy gaps agree with recent theoretical calculations.

Enhanced Electrical and Mechanical Properties of Chemically Cross-Linked Carbon-Nanotube-Based Fibers and Their Application in High-Performance Supercapacitors.

The electrical conductivity and mechanical strength of fibers constructed from single-walled carbon nanotubes (CNTs) are usually limited by the weak interactions between individual CNTs. In this work, we report a significant enhancement of both of these properties through chemical cross-linking of individual CNTs. The CNT fibers are made by wet-spinning a CNT solution that contains 1,3,5-tris(2'-bromophenyl)benzene (2TBB) molecules as the cross-linking agent, and the cross-linking is subsequently driven by Joule heating. Cross-linking with 2TBB increases the conductivity of the CNT fibers by a factor of ∼100 and increases the tensile strength on average by 47%; in contrast, the tensile strength of CNT fibers fabricated without 2TBB decreases after the same Joule heating process. Symmetrical supercapacitors made from the 2TBB-treated CNT fibers exhibit a remarkably high volumetric energy density of ∼4.5 mWh cm-3 and a power density of ∼1.3 W cm-3.

Imaging of Carbon Nanotube Electronic States Polarized by the Field of an Excited Quantum Dot.

Efficient heat dissipation and large gate capacitance have made carbon nanotube field-effect transistors (CNT FETs) devices of interest for over 20 years. The mechanism of CNT FETs involves localization of the electronic structure due to a transverse electric field, yet little is known about the localization effect, nor has the electronic polarization been visualized directly. Here, we co-deposit PbS quantum dots (QDs) with CNTs and optically excite the QD so its excited-state dipolar field biases the local environment of a CNT. Using single-molecule absorption scanning tunneling microscopy, we show that the electronic states of the CNT become transversely localized. By nudging QDs to different distances from the CNT, the magnitude of the localization can be controlled. Different bias voltages probe the degree of localization in different CNT excited states. A simple tight-binding model for the CNT in an electrostatic field provides a semiquantitative model for the observed behavior.

STM Imaging of Localized Surface Plasmons on Individual Gold Nanoislands.

An optically modulated scanning tunneling microscopy technique developed for measurement of single-molecule optical absorption is used here to image the light absorption by individual Au nanoislands and Au nanostructures. The technique is shown to spatially map, with nanometer resolution, localized surface plasmons (LSPs) excited within the nanoislands. Electrodynamic simulations demonstrate the correspondence of the measured images to plasmonic near-field intensity maps. The optical STM imaging technique captures the wavelength, polarization, and geometry dependence of the LSP resonances and their corresponding near-fields. Thus, we introduce a tool for real-space, nanometer-scale visualization of optical energy absorption, transport, and dissipation in complex plasmonic nanostructures.

Lateral manipulation of single-walled carbon nanotubes on H-passivated Si(100) surfaces with an ultrahigh-vacuum scanning tunneling microscope.

Ultrahigh-vacuum (UHV) scanning tunneling microscopy (STM) can be used for the manipulation of individual atoms and molecules into complex arrangements for sensitive electrical and structural characterization. However, the systematic UHV STM manipulation of single-walled carbon nanotubes (SWNTs), high-aspect-ratio molecular wires derived from graphene that exist in both semiconducting and metallic forms, has yet to be reported. In this work, we demonstrate the room-temperature lateral manipulation of approximately 1-nm-diameter SWNTs on UHV-prepared, hydrogen-passivated Si(100) surfaces. We show the reproducible actuation of SWNTs having lengths as small as 13 nm, along with the partial division of a two-tube bundle. Moreover, UHV STM desorption of H at the SWNT/Si interface is introduced as a means of locally strengthening the interaction between the tube and the surface. The UHV STM manipulation scheme described here is potentially extensible to the orientational control of SWNTs interfaced with atomically clean semiconducting surfaces, such as InAs(110), GaAs(110), and unpassivated Si(100), for which first-principles calculations based on density functional theory have been reported recently in the literature.

Imaging and Manipulating Energy Transfer Among Quantum Dots at Individual Dot Resolution.

Many processes of interest in quantum dots involve charge or energy transfer from one dot to another. Energy transfer in films of quantum dots as well as between linked quantum dots has been demonstrated by luminescence shift, and the ultrafast time-dependence of energy transfer processes has been resolved. Bandgap variation among dots (energy disorder) and dot separation are known to play an important role in how energy diffuses. Thus, it would be very useful if energy transfer could be visualized directly on a dot-by-dot basis among small clusters or within films of quantum dots. To that effect, we report single molecule optical absorption detected by scanning tunneling microscopy (SMA-STM) to image energy pooling from donor into acceptor dots on a dot-by-dot basis. We show that we can manipulate groups of quantum dots by pruning away the dominant acceptor dot, and switching the energy transfer path to a different acceptor dot. Our experimental data agrees well with a simple Monte Carlo lattice model of energy transfer, similar to models in the literature, in which excitation energy is transferred preferentially from dots with a larger bandgap to dots with a smaller bandgap.

Interfacial Self-Assembly of Atomically Precise Graphene Nanoribbons into Uniform Thin Films for Electronics Applications.

Because of their intriguing electronic and optical properties, atomically precise graphene nanoribbons (GNRs) are considered to be promising materials for electronics and photovoltaics. However, significant aggregation and low solubility of GNRs in conventional solvents result in their poor processability for materials characterization and device studies. In this paper, we demonstrate a new fabrication approach for large-scale uniform thin films of nonfunctionalized atomically precise chevron-type GNRs. The method is based on (1) the exceptional solubility of graphitic materials in chlorosulfonic acid and (2) the original interfacial self-assembly approach by which uniform films that are single-GNR (∼2 nm) thick can be routinely prepared. These films can be transferred to various substrates including Si/SiO2 and used for the streamlined fabrication of arrays of GNR-based devices. The described self-assembly approach should be applicable to other types of solution-synthesized atomically precise GNRs as well as large polyaromatic hydrocarbon (PAH) molecules and therefore should facilitate and streamline their device characterization.