Superb resolution and contrast of transmission electron microscopy images of unstained biological samples on graphene-coated grids.

BACKGROUND: In standard transmission electron microscopy (TEM), biological samples are supported on carbon films of nanometer thickness. Due to the similar electron scattering of protein samples and graphite supports, high quality images with structural details are obtained primarily by staining with heavy metals. METHODS: Single-layered graphene is used to support the protein self-assemblies of different molecular weights for qualitative and quantitative characterizations. RESULTS: We show unprecedented high resolution and contrast images of unstained samples on graphene on a low-end TEM. We show for the first time that the resolution and contrast of TEM images of unstained biological samples with high packing density in their native states supported on graphene can be comparable or superior to uranyl acetate-stained TEM images. CONCLUSION: Our results demonstrate a novel technique for TEM structural characterization to circumvent the potential artifacts caused by staining agents without sacrificing image resolution or contrast, and eliminate the need for toxic metals. Moreover, this technique better preserves sample integrity for quantitative characterization by dark-field imaging with reduced beam damage. GENERAL SIGNIFICANCE: This technique can be an effective alternative for bright-field qualitative characterization of biological samples with high packing density and those not amenable to the standard negative staining technique, in addition to providing high quality dark-field unstained images at reduced radiation damage to determine quantitative structural information of biological samples.

Structure of a peptide adsorbed on graphene and graphite.

Noncovalent functionalization of graphene using peptides is a promising method for producing novel sensors with high sensitivity and selectivity. Here we perform atomic force microscopy, Raman spectroscopy, infrared spectroscopy, and molecular dynamics simulations to investigate peptide-binding behavior to graphene and graphite. We studied a dodecamer peptide identified with phage display to possess affinity for graphite. Optical spectroscopy reveals that the peptide forms secondary structures both in powder form and in an aqueous medium. The dominant structure in the powder form is α-helix, which undergoes a transition to a distorted helical structure in aqueous solution. The peptide forms a complex reticular structure upon adsorption on graphene and graphite, having a helical conformation different from α-helix due to its interaction with the surface. Our observation is consistent with our molecular dynamics calculations, and our study paves the way for rational functionalization of graphene using biomolecules with defined structures and, therefore, functionalities.

Low bias electron scattering in structure-identified single wall carbon nanotubes: role of substrate polar phonons.

We have performed temperature-dependent electrical transport measurements on known structure single wall carbon nanotubes at low bias. The experiments show a superlinear increase in nanotube resistivity with temperature, which is in contradiction with the linear dependence expected from nanotube acoustic-phonon scattering. The measured electron mean free path is also much lower than expected, especially at medium to high temperatures (>100 K). A theoretical model that includes scattering due to surface polar phonon modes of the substrates reproduces the experiments very well. The role of surface phonons is further confirmed by resistivity measurements of nanotubes on aluminum nitride.

Enabling remote quantum emission in 2D semiconductors via porous metallic networks.

Here we report how two-dimensional crystal (2DC) overlayers influence the recrystallization of relatively thick metal films and the subsequent synergetic benefits this provides for coupling surface plasmon-polaritons (SPPs) to photon emission in 2D semiconductors. We show that annealing 2DC/Au films on SiO2 results in a reverse epitaxial process where initially nanocrystalline Au films gain texture, crystallographically orient with the 2D crystal overlayer, and form an oriented porous metallic network (OPEN) structure in which the 2DC can suspend above or coat the inside of the metal pores. Both laser excitation and exciton recombination in the 2DC semiconductor launch propagating SPPs in the OPEN film. Energy in-/out- coupling occurs at metal pore sites, alleviating the need for dielectric spacers between the metal and 2DC layer. At low temperatures, single-photon emitters (SPEs) are present across an OPEN-WSe2 film, and we demonstrate remote SPP-mediated excitation of SPEs at a distance of 17 µm.

Scattering strength of the scatterer inducing variability in graphene on silicon oxide.

Large variability of carrier mobility of graphene-based field effect transistors hampers graphene science and technology. We show that the number of the scatterer responsible for the observed variability on graphene devices on silicon oxide can be determined by finding the number of hydrogen that can be chemisorbed on graphene. We use the relationship between the number of the scatterer and the mobility of graphene devices to determine that the variability-inducing scatterer possesses scattering strength 10 times smaller than that of adsorbed potassium atoms and 50 times smaller than that of ion-beam induced vacancies. Our results provide an important, quantitative input towards determining the origin of the variability.

The Effect of Preparation Conditions on Raman and Photoluminescence of Monolayer WS2.

We report on preparation dependent properties observed in monolayer WS2 samples synthesized via chemical vapor deposition (CVD) on a variety of common substrates (Si/SiO2, sapphire, fused silica) as well as samples that were transferred from the growth substrate onto a new substrate. The as-grown CVD materials (as-WS2) exhibit distinctly different optical properties than transferred WS2 (x-WS2). In the case of CVD growth on Si/SiO2, following transfer to fresh Si/SiO2 there is a ~50 meV shift of the ground state exciton to higher emission energy in both photoluminescence emission and optical reflection. This shift is indicative of a reduction in tensile strain by ~0.25%. Additionally, the excitonic state in x-WS2 is easily modulated between neutral and charged exciton by exposure to moderate laser power, while such optical control is absent in as-WS2 for all growth substrates investigated. Finally, we observe dramatically different laser power-dependent behavior for as-grown and transferred WS2. These results demonstrate a strong sensitivity to sample preparation that is important for both a fundamental understanding of these novel materials as well as reliable reproduction of device properties.

Dark-field transmission electron microscopy and the Debye-Waller factor of graphene.

Graphene's structure bears on both the material's electronic properties and fundamental questions about long range order in two-dimensional crystals. We present an analytic calculation of selected area electron diffraction from multi-layer graphene and compare it with data from samples prepared by chemical vapor deposition and mechanical exfoliation. A single layer scatters only 0.5% of the incident electrons, so this kinematical calculation can be considered reliable for five or fewer layers. Dark-field transmission electron micrographs of multi-layer graphene illustrate how knowledge of the diffraction peak intensities can be applied for rapid mapping of thickness, stacking, and grain boundaries. The diffraction peak intensities also depend on the mean-square displacement of atoms from their ideal lattice locations, which is parameterized by a Debye-Waller factor. We measure the Debye-Waller factor of a suspended monolayer of exfoliated graphene and find a result consistent with an estimate based on the Debye model. For laboratory-scale graphene samples, finite size effects are sufficient to stabilize the graphene lattice against melting, indicating that ripples in the third dimension are not necessary.

Raman spectroscopy of folded and scrolled graphene.

Here we examine the effects of folding and scrolling on the Raman spectra of mechanically exfoliated single- and bilayer graphene prepared on SiO(2) substrates. We find that incommensurate folding in bilayer graphene results in a shift of the second-order G' band frequency, similar to that observed in folded single-layer graphene due to fold-induced changes in the phonon/electronic energy dispersion. Importantly, we show that the contrasting Raman shifts reported for the G' band frequency in folded graphene can be rationalized by taking into account the relative strength of fold-induced electron/phonon renormalization. More interestingly, we find that curvature in scrolled graphene lifts the degeneracy of the G band and results in a splitting of the G band and the appearance of low-frequency radial breathing-like (RBLM) modes. This study highlights a variety of Raman signatures for fold-induced and curvature-induced graphene and sets the stage for further theoretical and experimental studies of these novel structures.

Photosensitization of carbon nanotubes using dye aggregates.

Ordered assemblies of dye molecules, dye aggregates, possess significantly larger molar optical absorptivity than dye monomers. Yet, aggregates have not been utilized for photosensitizing nanoscale electronic devices. We find that single-walled carbon nanotubes, which are cleaned down to the atomic scale, template the growth of squaraine dye aggregates and these aggregates effectively photosensitize nanotubes. Templating of aggregates by nanotubes and functionalization of nanotubes with ordered molecular films are reported for the first time. The sensitivity achieved by aggregate-functionalized nanotube network devices is approximately an order of magnitude better than those of similar nanotube devices functionalized with dye monomers and photoactive polymers.

Effects of layer stacking on the combination Raman modes in graphene.

We have observed new combination modes in the range from 1650 to 2300 cm(-1) in single-(SLG), bi-, few-layer and incommensurate bilayer graphene (IBLG) on silicon dioxide substrates. A peak at ∼1860 cm(-1) (iTALO-) is observed due to a combination of the in-plane transverse acoustic (iTA) and the longitudinal optical (LO) phonons. The intensity of this peak decreases with increasing number of layers and this peak is absent for bulk graphite. The overtone of the out-of-plane transverse optical (oTO) phonon at ∼1750 cm(-1), also called the M band, is suppressed for both SLG and IBLG. In addition, two previously unidentified modes at ∼2200 and ∼1880 cm(-1) are observed in SLG. The 2220 cm(-1) (1880 cm(-1)) mode is tentatively assigned to the combination mode of in-plane transverse optical (iTO) and TA phonons (oTO+LO phonons) around the K point in the graphene Brillouin zone. Finally, the peak frequency of the 1880 (2220) cm(-1) mode is observed to increase (decrease) linearly with increasing graphene layers.

Intrinsic and extrinsic performance limits of graphene devices on SiO2.

The linear dispersion relation in graphene gives rise to a surprising prediction: the resistivity due to isotropic scatterers, such as white-noise disorder or phonons, is independent of carrier density, n. Here we show that electron-acoustic phonon scattering is indeed independent of n, and contributes only 30 Omega to graphene's room-temperature resistivity. At a technologically relevant carrier density of 1 x1012 cm-2, we infer a mean free path for electron-acoustic phonon scattering of >2 microm and an intrinsic mobility limit of 2 x 105 cm2 V-1 s-1. If realized, this mobility would exceed that of InSb, the inorganic semiconductor with the highest known mobility ( approximately 7.7 x 104 cm2 V-1 s-1; ref. 9) and that of semiconducting carbon nanotubes ( approximately 1 x 105 cm2 V-1 s-1; ref. 10). A strongly temperature-dependent resistivity contribution is observed above approximately 200 K (ref. 8); its magnitude, temperature dependence and carrier-density dependence are consistent with extrinsic scattering by surface phonons at the SiO2 substrate and limit the room-temperature mobility to approximately 4 x 104 cm2 V-1 s-1, indicating the importance of substrate choice for graphene devices.

Atomic structure of graphene on SiO2.

We employ scanning probe microscopy to reveal atomic structures and nanoscale morphology of graphene-based electronic devices (i.e., a graphene sheet supported by an insulating silicon dioxide substrate) for the first time. Atomic resolution scanning tunneling microscopy images reveal the presence of a strong spatially dependent perturbation, which breaks the hexagonal lattice symmetry of the graphitic lattice. Structural corrugations of the graphene sheet partially conform to the underlying silicon oxide substrate. These effects are obscured or modified on graphene devices processed with normal lithographic methods, as they are covered with a layer of photoresist residue. We enable our experiments by a novel cleaning process to produce atomically clean graphene sheets.

Symmetry breaking in boron nitride nanotubes.

We have imaged boron nitride nanotubes with atomic scale resolution using scanning tunneling microscopy. While some nanotubes show the expected triangular lattice pattern, the majority of the nanotubes show unusual stripe patterns which break the underlying symmetry of the boron nitride lattice. We identify the origin of the symmetry breaking and demonstrate that conventional STM imaging analysis is inadequate for boron nitride nanotubes.

Observation of the giant stark effect in boron-nitride nanotubes.

Bias dependent scanning tunneling microscopy and scanning tunneling spectroscopy have been used to characterize the influence of transverse electric fields on the electronic properties of boron-nitride nanotubes (BNNTs). We find experimental evidence for the theoretically predicted giant Stark effect. The observed giant Stark effect significantly reduces the band gap of BNNTs and thus greatly enhances the utility of BNNTs for nanoscale electronic, electromechanical, and optoelectronic applications.

Identifying defects in nanoscale materials.

We have developed a novel iterative experimental-theoretical technique which can identify the atomic structure of defects in many-atom nanoscale materials from scanning tunneling microscopy and spectroscopy data. A given model for a defect structure is iteratively improved until calculated microscopy and spectroscopy data based on the model converge on the experimental results. We use the technique to identify a defect responsible for the electronic properties of a carbon nanotube intramolecular junction. Our technique can be extended for analysis of defect structures in nanoscale materials in general.