All living systems contain naturally occurring nanoparticles with unique structural, biochemical and mechanical characteristics. Specifically, human saliva exosomes secreted by normal cells into saliva via exocytosis, are novel biomarkers showing tumor-antigen enrichment during oral cancer. Here we show the substructure of single human saliva exosomes, using a new ultra sensitive low force Atomic Force Microscopy (AFM) exhibiting sub-structural organization unresolvable in Electron Microscopy. We correlate the data with Field Emission Scanning Electron Microscopy (FESEM) and AFM images to interpret the nanoscale structures of exosomes under varying forces. Single exosomes reveal reversible mechanical deformation displaying distinct elastic, 70-100nm tri-lobed membrane with sub-structures carrying specific trans-membrane receptors. Further, we imaged and investigated, using force spectroscopy with antiCD63 IgG functionalized AFM tips, highly specific and sensitive detection of antigenCD63, potentially useful cancer markers on individual exosomes. The quantitative nanoscale morphological, biomechanical and surface biomolecular properties of single saliva exosomes, are critical for the applications of exosomes for cancer diagnosis and as a model for developing new cell delivery systems.

The application of strain to semiconductors allows for controlled modification of their band structure. This principle is employed for the manufacturing of devices ranging from high-performance transistors to solid-state lasers. Traditionally, strain is typically achieved via growth on lattice-mismatched substrates. For two-dimensional (2D) semiconductors, this is not feasible as they typically do not interact epitaxially with the substrate. Here, we demonstrate controlled strain engineering of 2D semiconductors during synthesis by utilizing the thermal coefficient of expansion mismatch between the substrate and semiconductor. Using WSe2 as a model system, we demonstrate stable built-in strains ranging from 1% tensile to 0.2% compressive on substrates with different thermal coefficient of expansion. Consequently, we observe a dramatic modulation of the band structure, manifested by a strain-driven indirect-to-direct bandgap transition and brightening of the dark exciton in bilayer and monolayer WSe2, respectively. The growth method developed here should enable flexibility in design of more sophisticated devices based on 2D materials.

The mechanical properties of materials depend strongly on crystal structure and defect configuration. Here we measure the strength of suspended single-crystal and bicrystal graphene membranes prepared by chemical vapour deposition. Membranes of interest are first characterized by transmission electron microscopy and subsequently tested using atomic force microscopy. Single-crystal membranes prepared by chemical vapour deposition show strengths comparable to previous results of single-crystal membranes prepared by mechanical exfoliation. Grain boundaries with large mismatch angles in polycrystalline specimens have higher strengths than their low angle counterparts. Remarkably, these large angle grain boundaries show strength comparable to that of single-crystal graphene. To investigate this enhanced strength, we employ aberration-corrected high-resolution transmission electron microscopy to explicitly map the atomic-scale strain fields in suspended graphene. The high strength is attributed to the presence of low atomic-scale strain in the carbon-carbon bonds at the boundary.

Liquid-phase transmission electron microscopy (TEM) can probe and visualize dynamic events with structural or functional details at the nanoscale in a liquid medium. Earlier efforts have focused on the growth and transformation kinetics of hard material systems, relying on their stability under electron beam. Our recently developed graphene liquid cell technique pushed the spatial resolution of such imaging to the atomic scale but still focused on growth trajectories of metallic nanocrystals. Here, we adopt this technique to imaging three-dimensional (3D) dynamics of soft materials instead, double strand (dsDNA) connecting Au nanocrystals as one example, at nanometer resolution. We demonstrate first that a graphene liquid cell can seal an aqueous sample solution of a lower vapor pressure than previously investigated well against the high vacuum in TEM. Then, from quantitative analysis of real time nanocrystal trajectories, we show that the status and configuration of dsDNA dictate the motions of linked nanocrystals throughout the imaging time of minutes. This sustained connecting ability of dsDNA enables this unprecedented continuous imaging of its dynamics via TEM. Furthermore, the inert graphene surface minimizes sample-substrate interaction and allows the whole nanostructure to rotate freely in the liquid environment; we thus develop and implement the reconstruction of 3D configuration and motions of the nanostructure from the series of 2D projected TEM images captured while it rotates. In addition to further proving the nanoconjugate structural stability, this reconstruction demonstrates 3D dynamic imaging by TEM beyond its conventional use in seeing a flattened and dry sample. Altogether, we foresee the new and exciting use of graphene liquid cell TEM in imaging 3D biomolecular transformations or interaction dynamics at nanometer resolution.

The atomic structure of graphene on polycrystalline copper substrates has been studied using scanning tunneling microscopy. The graphene overlayer maintains a continuous pristine atomic structure over atomically flat planes, monatomic steps, edges, and vertices of the copper surface. We find that facets of different identities are overgrown with graphene's perfect carbon honeycomb lattice. Our observations suggest that growth models including a stagnant catalytic surface do not apply to graphene growth on copper. Contrary to current expectations, these results reveal that the growth of macroscopic pristine graphene is not limited by the underlying copper structure.

With the motivation of realizing an all graphene-based circuit for low power, we present a reliable nonvolatile graphene memory device, single-layer graphene (SLG) ferroelectric field-effect transistor (FFET). We demonstrate that exfoliated single-layer graphene can be optically visible on a ferroelectric lead-zirconate-titanate (PZT) substrate and observe a large memory window that is nearly equivalent to the hysteresis of the PZT at low operating voltages in a graphene FFET. In comparison to exfoliated graphene, FFETs fabricated with chemical vapor deposited (CVD) graphene exhibit enhanced stability through a bi-stable current state operation with long retention time. In addition, we suggest that the trapping/de-trapping of charge carriers in the interface states is responsible for the anti-hysteresis behavior in graphene FFET on PZT.

Growth of graphene on copper (100) single crystals by chemical vapor deposition has been accomplished. The atomic structure of the graphene overlayer was studied using scanning tunneling microscopy. A detailed analysis of moiré superstructures present in the graphene topography reveals that growth occurs in a variety of orientations over the square atomic lattice of the copper surface. Transmission electron microscopy was used to elucidate the crystallinity of the grown graphene. Pristine, defect-free graphene was observed over copper steps, corners, and screw dislocations. Distinct protrusions, known as "flower" structures, were observed on flat terraces, which are attributed to carbon structures that depart from the characteristic honeycomb lattice. Continuous graphene growth also occurs over copper adatoms and atomic vacancies present at the single-crystal surface. The copper atom mobility within vacancy islands covered with suspended graphene sheets reveals a weak graphene-substrate interaction. The observed continuity and room-temperature vacancy motion indicates that copper mobility likely plays a significant role in the mechanism of sheet extension on copper substrates. Lastly, these results suggest that the quality of graphene grown on copper substrates is ultimately limited by nucleation at the surface of the metal catalyst.

Single crystals of ReB2 have been prepared from an aluminum flux under inert gas flow. The crystals are typically 1−3 mm in diameter and 500 μm thick, growing along the [002] direction with a distinct hexagonal morphology. Vickers microhardness and nanoindentation testing indicate that the (002) plane possesses the highest hardness with measured values of 40.5 and 36.4 GPa, respectively. The elastic anisotropy was examined and the indentation moduli of the basal plane and an (hk0) plane of unknown indices are 675 and 510 GPa, respectively. Four-probe electrical resistivity measurements demonstrate that ReB2 is the hardest material known to exhibit metallic behavior. Thermogravimetric analysis indicates that the crystals are stable in air up to 1000 °C due to the formation of a protective boron oxide coating.