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...

A central issue of nanoelectronics concerns their fundamental scaling limits, that is, the smallest and most energy-efficient devices that can function reliably. Unlike charge-based electronics that are prone to leakage at nanoscale dimensions, memory devices based on phase change materials (PCMs) are more scalable, storing digital information as the crystalline or amorphous state of a material. Here, we describe a novel approach to self-align PCM nanowires with individual carbon nanotube (CNT) electrodes for the first time. The highly scaled and spatially confined memory devices approach the ultimate scaling limits of PCM technology, achieving ultralow programming currents (~0.1 μA set, ~1.6 μA reset), outstanding on/off ratios (~10(3)), and improved endurance and stability at few-nanometer bit dimensions. In addition, the powerful yet simple nanofabrication approach described here can enable confining and probing many other nanoscale and molecular devices self-aligned with CNT electrodes.

The fundamental building blocks of digital electronics are logic gates which must be capable of cascading such that more complex logic functions can be realized. Here we demonstrate integrated graphene complementary inverters which operate with the same input and output voltage logic levels, thus allowing cascading. We obtain signal matching under ambient conditions with inverters fabricated from wafer-scale graphene grown by chemical vapor deposition (CVD). Monolayer graphene was incorporated in self-aligned field-effect transistors in which the top gate overlaps with the source and drain contacts. This results in full-channel gating and leads to the highest low-frequency voltage gain reported so far in top-gated CVD graphene devices operating in air ambient, A(v) ∼ -5. Such gain enabled logic inverters with the same voltage swing of 0.56 V at their input and output. Graphene inverters could find their way in realistic applications where high-speed operation is desired but power dissipation is not a concern, similar to emitter-coupled logic.

Ring oscillators (ROs) are the most important class of circuits used to evaluate the performance limits of any digital technology. However, ROs based on low-dimensional nanomaterials (e.g., 1-D nanotubes, nanowires, 2-D MoS2) have so far exhibited limited performance due to low current drive or large parasitics. Here we demonstrate integrated ROs fabricated from wafer-scale graphene grown by chemical vapor deposition. The highest oscillation frequency was 1.28 GHz, while the largest output voltage swing was 0.57 V. Both values remain limited by parasitic capacitances in the circuit rather than intrinsic properties of the graphene transistor components, suggesting further improvements are possible. The fabricated ROs are the fastest realized in any low-dimensional nanomaterial to date and also the least sensitive to fluctuations in the supply voltage. They represent the first integrated graphene oscillators of any kind and can also be used in a wide range of applications in analog electronics. As a demonstration, we also realized the first stand-alone graphene mixers that do not require external oscillators for frequency conversion. The first gigahertz multitransistor graphene integrated circuits demonstrated here pave the way for application of graphene in high-speed digital and analog circuits in which high operating speed could be traded off against power consumption.

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...