From Growth Surface to Device Interface: Preserving Metallic Fe under Monolayer Hexagonal Boron Nitride.

We investigate the interfacial chemistry between Fe catalyst foils and monolayer hexagonal boron nitride (h-BN) following chemical vapor deposition and during subsequent atmospheric exposure, using scanning electron microscopy, X-ray photoemission spectroscopy, and scanning photoelectron microscopy. We show that regions of the Fe surface covered by h-BN remain in a metallic state during exposure to moist air for ∼40 h at room temperature. This protection is attributed to the strong interfacial interaction between h-BN and Fe, which prevents the rapid intercalation of oxidizing species. Local Fe oxidation is observed on bare Fe regions and close to defects in the h-BN film (e.g., domain boundaries, wrinkles, and edges), which over the longer-term provide pathways for slow bulk oxidation of Fe. We further confirm that the interface between h-BN and metallic Fe can be recovered by vacuum annealing at ∼600 °C, although this is accompanied by the creation of defects within the h-BN film. We discuss the importance of these findings in the context of integrated manufacturing and transfer-free device integration of h-BN, particularly for technologically important applications where h-BN has potential as a tunnel barrier such as magnetic tunnel junctions.

Parameter Space of Atomic Layer Deposition of Ultrathin Oxides on Graphene.

Atomic layer deposition (ALD) of ultrathin aluminum oxide (AlOx) films was systematically studied on supported chemical vapor deposition (CVD) graphene. We show that by extending the precursor residence time, using either a multiple-pulse sequence or a soaking period, ultrathin continuous AlOx films can be achieved directly on graphene using standard H2O and trimethylaluminum (TMA) precursors even at a high deposition temperature of 200 °C, without the use of surfactants or other additional graphene surface modifications. To obtain conformal nucleation, a precursor residence time of >2s is needed, which is not prohibitively long but sufficient to account for the slow adsorption kinetics of the graphene surface. In contrast, a shorter residence time results in heterogeneous nucleation that is preferential to defect/selective sites on the graphene. These findings demonstrate that careful control of the ALD parameter space is imperative in governing the nucleation behavior of AlOx on CVD graphene. We consider our results to have model system character for rational two-dimensional (2D)/non-2D material process integration, relevant also to the interfacing and device integration of the many other emerging 2D materials.

Time Evolution of the Wettability of Supported Graphene under Ambient Air Exposure.

The wettability of graphene is both fundamental and crucial for interfacing in most applications, but a detailed understanding of its time evolution remains elusive. Here we systematically investigate the wettability of metal-supported, chemical vapor deposited graphene films as a function of ambient air exposure time using water and various other test liquids with widely different surface tensions. The wettability of graphene is not constant, but varies with substrate interactions and air exposure time. The substrate interactions affect the initial graphene wettability, where, for instance, water contact angles of ∼85 and ∼61° were measured for Ni and Cu supported graphene, respectively, after just minutes of air exposure. Analysis of the surface free energy components indicates that the substrate interactions strongly influence the Lewis acid-base component of supported graphene, which is considerably weaker for Ni supported graphene than for Cu supported graphene, suggesting that the classical van der Waals interaction theory alone is insufficient to describe the wettability of graphene. For prolonged air exposure, the effect of physisorption of airborne contaminants becomes increasingly dominant, resulting in an increase of water contact angle that follows a universal linear-logarithmic relationship with exposure time, until saturating at a maximum value of 92-98°. The adsorbed contaminants render all supported graphene samples increasingly nonpolar, although their total surface free energy decreases only by 10-16% to about 37-41 mJ/m2. Our finding shows that failure to account for the air exposure time may lead to widely different wettability values and contradicting arguments about the wetting transparency of graphene.

Engineering high charge transfer n-doping of graphene electrodes and its application to organic electronics.

Using thermally evaporated cesium carbonate (Cs2CO3) in an organic matrix, we present a novel strategy for efficient n-doping of monolayer graphene and a ∼90% reduction in its sheet resistance to ∼250 Ohm sq(-1). Photoemission spectroscopy confirms the presence of a large interface dipole of ∼0.9 eV between graphene and the Cs2CO3/organic matrix. This leads to a strong charge transfer based doping of graphene with a Fermi level shift of ∼1.0 eV. Using this approach we demonstrate efficient, standard industrial manufacturing process compatible graphene-based inverted organic light emitting diodes on glass and flexible substrates with efficiencies comparable to those of state-of-the-art ITO based devices.

Fabrication of carbon nanotube-polyimide composite hollow microneedles for transdermal drug delivery.

We introduce a novel method for fabricating hollow microneedles for transdermal drug delivery using a composite of vertically-aligned carbon nanotubes and polyimide. Patterned bundles of carbon nanotubes are used as a porous scaffold for defining the microneedle geometry. Polyimide resin is wicked through the carbon nanotube scaffold to reinforce the structure and provide the prerequisite strength for achieving skin penetration. The high aspect ratio and bottom-up assembly of carbon nanotubes allow the structure of the microneedles to be created in a single step of nanotube fabrication, providing a simple, scalable method for producing hollow microneedles. To demonstrate the utility of these microneedles, liquid delivery experiments are performed. Successful delivery of aqueous methylene blue dye into both hydrogel and swine skin in vitro is demonstrated. Electron microscopy images of the microneedles taken after delivery confirm that the microneedles do not sustain any structural damage during the delivery process.

Physicochemical characteristics and droplet impact dynamics of superhydrophobic carbon nanotube arrays.

The physicochemical and droplet impact dynamics of superhydrophobic carbon nanotube arrays are investigated. These superhydrophobic arrays are fabricated simply by exposing the as-grown carbon nanotube arrays to a vacuum annealing treatment at a moderate temperature. This treatment, which allows a significant removal of oxygen adsorbates, leads to a dramatic change in wettability of the arrays, from mildly hydrophobic to superhydrophobic. Such change in wettability is also accompanied by a substantial change in surface charge and electrochemical properties. Here, the droplet impact dynamics are characterized in terms of critical Weber number, coefficient of restitution, spreading factor, and contact time. Based on these characteristics, it is found that superhydrophobic carbon nanotube arrays are among the best water-repellent surfaces ever reported. The results presented herein may pave a way for the utilization of superhydrophobic carbon nanotube arrays in numerous industrial and practical applications, including inkjet printing, direct injection engines, steam turbines, and microelectronic fabrication.

Reversible tuning of the wettability of carbon nanotube arrays: the effect of ultraviolet/ozone and vacuum pyrolysis treatments.

Among diverse types of synthetic materials, arrays of vertically aligned carbon nanotubes have attracted the most attention, mainly because of their exceptional mechanical, electrical, optical, and thermal properties. However, their wetting properties are yet to be understood. In this present study, oxygenated surface functional groups have been identified as a vital factor in controlling the wetting properties of carbon nanotube arrays. The results presented herein indeed show that a combination of ultraviolet/ozone and vacuum pyrolysis treatments can be used to vary the surface concentration of these functional groups such that the carbon nanotube array can be repeatedly switched between hydrophilic and hydrophobic.