We use scanning tunneling microscopy and spectroscopy to examine the electronic nature of grain boundaries (GBs) in polycrystalline graphene grown by chemical vapor deposition (CVD) on Cu foil and ...transferred to SiO2 substrates. We find no preferential orientation angle between grains, and the GBs are continuous across graphene wrinkles and SiO2 topography. Scanning tunneling spectroscopy shows enhanced empty states tunneling conductance for most of the GBs and a shift toward more n-type behavior compared to the bulk of the graphene. We also observe standing wave patterns adjacent to GBs propagating in a zigzag direction with a decay length of ∼1 nm. Fourier analysis of these patterns indicates that backscattering and intervalley scattering are the dominant mechanisms responsible for the mobility reduction in the presence of GBs in CVD-grown graphene.
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IJS, KILJ, NUK, PNG, UL, UM
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.
We analyze the optical, chemical, and electrical properties of chemical vapor deposition (CVD) grown hexagonal boron nitride (h-BN) using the precursor ammonia-borane (H3N–BH3) as a function of Ar/H2 ...background pressure (P TOT). Films grown at P TOT ≤ 2.0 Torr are uniform in thickness, highly crystalline, and consist solely of h-BN. At larger P TOT, with constant precursor flow, the growth rate increases, but the resulting h-BN is more amorphous, disordered, and sp3-bonded. We attribute these changes in h-BN grown at high pressure to incomplete thermolysis of the H3N–BH3 precursor from a passivated Cu catalyst. A similar increase in h-BN growth rate and amorphization is observed even at low P TOT if the H3N–BH3 partial pressure is initially greater than the background pressure P TOT at the beginning of growth. h-BN growth using the H3N–BH3 precursor reproducibly can give large-area, crystalline h-BN thin films, provided that the total pressure is under 2.0 Torr and the precursor flux is well-controlled.
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IJS, KILJ, NUK, PNG, UL, UM
Scattering scanning near-field optical microscopy (s-SNOM) has emerged as a powerful nanoscale spectroscopic tool capable of characterizing individual biomacromolecules and molecular materials. ...However, applications of scattering-based near-field techniques in the infrared (IR) to native biosystems still await a solution of how to implement the required aqueous environment. In this work, we demonstrate an IR-compatible liquid cell architecture that enables near-field imaging and nanospectroscopy by taking advantage of the unique properties of graphene. Large-area graphene acts as an impermeable monolayer barrier that allows for nano-IR inspection of underlying molecular materials in liquid. Here, we use s-SNOM to investigate the tobacco mosaic virus (TMV) in water underneath graphene. We resolve individual virus particles and register the amide I and II bands of TMV at ca. 1520 and 1660 cm–1, respectively, using nanoscale Fourier transform infrared spectroscopy (nano-FTIR). We verify the presence of water in the graphene liquid cell by identifying a spectral feature associated with water absorption at 1610 cm–1.
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IJS, KILJ, NUK, PNG, UL, UM
Here we report a technique for transferring graphene layers, one by one, from a multilayer deposit formed by epitaxial growth on the Si-terminated face of a 6H-SiC substrate. The procedure uses a ...bilayer film of palladium/polyimide deposited onto the graphene coated SiC, which is then mechanically peeled away and placed on a target substrate. Orthogonal etching of the palladium and polyimide leaves isolated sheets of graphene with sizes of square centimeters. Repeating these steps transfers additional sheets from the same SiC substrate. Raman spectroscopy, scanning tunneling spectroscopy, low-energy electron diffraction and X-ray photoelectron spectroscopy, together with scanning tunneling, atomic force, optical, and scanning electron microscopy reveal key properties of the materials. The sheet resistances determined from measurements of four point probe devices were found to be ∼2 kΩ/square, close to expectation. Graphene crossbar structures fabricated in stacked configurations demonstrate the versatility of the procedures.
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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.
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Stem cell regulation and hierarchical organization of human skeletal progenitors remain largely unexplored. Here, we report the isolation of a self-renewing and multipotent human skeletal stem cell ...(hSSC) that generates progenitors of bone, cartilage, and stroma, but not fat. Self-renewing and multipotent hSSCs are present in fetal and adult bones and can also be derived from BMP2-treated human adipose stroma (B-HAS) and induced pluripotent stem cells (iPSCs). Gene expression analysis of individual hSSCs reveals overall similarity between hSSCs obtained from different sources and partially explains skewed differentiation toward cartilage in fetal and iPSC-derived hSSCs. hSSCs undergo local expansion in response to acute skeletal injury. In addition, hSSC-derived stroma can maintain human hematopoietic stem cells (hHSCs) in serum-free culture conditions. Finally, we combine gene expression and epigenetic data of mouse skeletal stem cells (mSSCs) and hSSCs to identify evolutionarily conserved and divergent pathways driving SSC-mediated skeletogenesis.
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•PDPN+CD146−CD73+CD164+ marks a self-renewing, multipotent human skeletal stem cell•hSSCs can be isolated from fetal, adult, BMP2-treated human adipose stroma, and iPSCs•hSSCs undergo local expansion in response to acute skeletal injury•Comparison of mouse and human SSCs reveals evolutionary differences in skeletogenesis
Identification of a human skeletal stem cell reveals conserved and species-specific pathways in skeletal development, and response to injury and will guide future regenerative approaches.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP