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 SiO(2) substrates. We find no preferential orientation angle between grains, and the GBs are continuous across graphene wrinkles and SiO(2) 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.

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, 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. * Correspondence should be addressed to lyding@illinois.edu and epop@stanford.edu. Cu has proven the most fruitful platform for large-area graphene growth, as the low carbon solubility promotes monolayer growth. 8 Nevertheless, most applications using CVD-grown graphene require that the films be transferred to insulating substrates. The predominant graphene transfer approach is by using a poly(methyl methacrylate) (PMMA) scaffold. [12][13][14][15][16][17] In this method, the PMMA polymer coats the graphene, supporting it during Cu removal, underside contaminant cleaning, and placement on its destination substrate. 18, 19 However, PMMA removal from graphene after film transfer has proven challenging. 15 Approaches to remove it by high-temperature Ar/H2 forming gas annealing, 14, 20, 21 O2 based annealing, 15, 22, 23 and in situ annealing 16, 24, 25 have been marginally successful in removing PMMA without affecting the graphene. Furthermore, these processes are all at high-temperature, excluding graphene applications with low thermal budgets, including uses in flexible electronics and biomolecule encapsulation. Another process separated the graphene from the PMMA support by an Au interfacial layer, 26 but that process is subject to effective interfacial Au-graphene wetting. Recent transfer results using thermal release tape (TRT), [27][28][29] poly(bisphenol A carbonate) (PC), 30, 31 and sacrificial polymer release layers 26 required elevated temperature (over 100°C) during transfer and differed considerably in terms of surface contamination and graphene area coverage. To exploit the intrinsic properties of large-area graphene, a room temperature transfer process that comes off more cleanly than the established methods is needed. In print atIn this study, we compare the transfer of graphene with the conventional PMMA polymer scaffold with alternative poly(lactic acid) (PLA), poly(phthalaldehyde) (PPA), PC, and bilayer PMMA/PC scaffolds. We choose both PLA and PPA as scaffolds as they can supposedly be removed by modest heating or acid exposure. Further, we choose PC from its heightened reactivity as a condensation polymer and it...

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 .In biological and life sciences, Fourier transform infrared (FTIR) spectroscopy serves as a ubiquitous noninvasive probe of vibrational fingerprints used to identify chemical compounds and molecular species. 1 This information is the basis for nonperturbative and label-free analysis of cell functionality. 2 For example, small changes in frequencies and line shapes of IR absorption bands due to specific proteins or protein conformations can be used to characterize cells and tissues linked to diseases such as Alzheimer's 3 and cancer. 1,4 Detailed databases document molecular absorp- * To whom correspondence should be addressed

We have performed scanning tunneling microscopy and spectroscopy (STM/STS) measurements as well as ab initio calculations for graphene monolayers on clean and hydrogen(H)-passivated silicon (100) (Si(100)/H) surfaces. In order to experimentally study the same graphene piece on both substrates, we develop a method to depassivate hydrogen from under graphene monolayers on the Si(100)/H surface. Our work represents the first demonstration of successful and reproducible depassivation of hydrogen from beneath monolayer graphene flakes on Si(100)/H by electron-stimulated desorption. Ab initio simulations combined with STS taken before and after hydrogen desorption demonstrate that graphene interacts differently with the clean and H-passivated Si(100) surfaces. The Si(100)/H surface does not perturb the electronic properties of graphene, whereas the interaction between the clean Si(100) surface and graphene changes the electronic states of graphene significantly. This effect results from the covalent bonding between C and surface Si atoms, modifying the π-orbital network of the graphene layer. The local density of states shows that the bonded C and Si surface states are highly disturbed near the Fermi energy.

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 (PTOT). Films grown at PTOT ≤ 2.0 Torr are uniform in thickness, highly crystalline, and consist solely of h-BN. At larger PTOT, with constant precursor flow, the growth rate increases, but the resulting h-BN is more amorphous, disordered, and sp 3 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 PTOT if the H3N-BH3 partial pressure is initially greater than the background pressure PTOT 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.* Correspondence should be addressed to lyding@illinois.edu, jkoepkeuiuc@gmail.com, and joshua.wood@northwestern.edu. Films of h-BN have been used as insulating spacers, 1 encapsulants, 2 substrates for electronic devices, 3, 4 corrosion and oxidation-resistant coatings, 5, 6 and surfaces for growth of other 2D nanomaterials such as graphene 7 and WS2. 8 Most of these studies employed small-area (~100 µm 2 ) h-BN pieces exfoliated from sintered h-BN crystals, 9 limiting technological use of h-BN films. Additionally, unlike graphene, h-BN is difficult to prepare in monolayer form by exfoliation. The electronegativity difference between B and N and the reduced resonance stabilization relative to graphene results in electrostatic attractions between layers and in-plane. Consequently, it is more challenging to control h-BN grain size and layer number. Furthermore, partially ionic B-N bonds can form between neighboring BN layers, serving to "spot weld" such layers together. 10 Several groups have sought to overcome these limitations by using chemical vapor deposition (CVD) to grow large-area, monolayer h-BN films. [11][12][13][14][15][16][17][18][19][20][21][22] CVD growth of h-BN has been accomplished using various precursors (e.g., ammonia borane, borazine, and diborane) on transition metal substrates (e.g., Cu, Ni, 23 Fe, 24 Ru, 25, 26 etc.). Of these h-BN growth substrates, we focus on Cu, as Cu has a high catalytic activity, 27 is inexpensive, and is the typical growth substrate 28 for conventional graphene CVD.Regarding h-BN growth precursors, volatile borazine-B3N3H6, isoelectronic with benzene-is far from an ideal choice, as borazine is hazardous and decomposes quickly even at room temperature. While borazine can pyrolyze and dehydrogenate 23, 25,29,30 to generate h-BN films, 13,17,19,20,22,31 partial dehydrogenation is common, [30] resulting in oligomeric BN compounds and aperiodic h-BN grain boundaries. 13,17 Finally, thin films of h-BN can also be grown from mixtures of diborane (B2H6) and ammonia (NH3...