Morris Washington

Stable Aqueous Dispersions of Noncovalently Functionalized Graphene from Graphite and their Multifunctional High-Performance Applications

We present a scalable and facile technique for noncovalent functionalization of graphene with 1-pyrenecarboxylic acid that exfoliates single-, few-, and multilayered graphene flakes into stable aqueous dispersions. The exfoliation mechanism is established using stringent control experiments and detailed characterization steps. Using the exfoliated graphene, we demonstrate highly sensitive and selective conductometric sensors (whose resistance rapidly changes >10,000% in saturated ethanol vapor), and ultracapacitors with extremely high specific capacitance (∼ 120 F/g), power density (∼ 105 kW/kg), and energy density (∼ 9.2 Wh/kg).

Superior Field Emission Properties of Layered WS2-RGO Nanocomposites

We report here the field emission studies of a layered WS2-RGO composite at the base pressure of ~1 × 10−8 mbar. The turn on field required to draw a field emission current density of 1 μA/cm2 is found to be 3.5, 2.3 and 2 V/μm for WS2, RGO and the WS2-RGO composite respectively. The enhanced field emission behavior observed for the WS2-RGO nanocomposite is attributed to a high field enhancement factor of 2978, which is associated with the surface protrusions of the single-to-few layer thick sheets of the nanocomposite. The highest current density of ~800 μA/cm2 is drawn at an applied field of 4.1 V/μm from a few layers of the WS2-RGO nanocomposite. Furthermore, first-principles density functional calculations suggest that the enhanced field emission may also be due to an overalp of the electronic structures of WS2 and RGO, where graphene-like states are dumped in the region of the WS2 fundamental gap.

Optical and Sensing Properties of 1-Pyrenecarboxylic Acid-Functionalized Graphene Films Laminated on Polydimethylsiloxane Membranes

We present fabrication and characterization of macroscopic thin films of graphene flakes, which are functionalized with 1-pyrenecarboxylic acid (PCA) and are laminated onto flexible and transparent polydimethylsiloxane (PDMS) membranes. The noncovalently (π-stacked) functionalization of PCA allows us to obtain a number of unique optical and molecular sensing properties that are absent in pristine graphene films, without sacrificing the conducting nature of graphene. The flexible PCA-graphene-PDMS hybrid structure can block 70-95% of ultraviolet (UV) light, while allowing 65% or higher transmittance in the visible region, rendering them potentially useful for a number of flexible UV absorbing/filtering applications. In addition, the electrical resistance of these structures is found to be sensitive to the illumination of visible light, atmospheric pressure change, and the presence of different types of molecular analytes. Owing to their multifunctionality, these hybrid structures have immense potential for the development of versatile, low-cost, flexible, and portable electronic and optoelectronic devices for diverse applications.

Enhanced field emission properties of doped graphene nanosheets with layered SnS2

We report here our experimental investigations on p-doped graphene using tin sulfide (SnS2), which shows enhanced field emission properties. The turn on field required to draw an emission current density of 1 μA/cm2 is significantly low (almost half the value) for the SnS2/reduced graphene oxide (RGO) nanocomposite (2.65 V/μm) compared to pristine SnS2 (4.8 V/μm) nanosheets. The field enhancement factor β (∼3200 for the SnS2 and ∼3700 for SnS2/RGO composite) was calculated from Fowler-Nordheim (F-N) plots, which indicates that the emission is from the nanometric geometry of the emitter. The field emission current versus time plot shows overall good emission stability for the SnS2/RGO emitter. The magnitude of work function of SnS2 and a SnS2/graphene composite has been calculated from first principles density functional theory (DFT) and is found to be 6.89 eV and 5.42 eV, respectively. The DFT calculations clearly reveal that the enhanced field emission properties of SnS2/RGO are due to a substantial lowe...

Highly Aligned Scalable Platinum-Decorated Single-Wall Carbon Nanotube Arrays for Nanoscale Electrical Interconnects

We present the fabrication and characterization of nanoscale electrical interconnect test structures constructed from aligned single-wall carbon nanotubes using a template-based fluidic assembly process. This CMOS-friendly process enables the formation of highly aligned parallel nanotube interconnect structures on SiO(2)/Si substrates of widths and lengths that are limited only by lithographical limits and, hence, can be easily integrated onto existing Si-based platforms. These structures can withstand current densities of approximately 10(7) A.cm(-2), comparable or better than copper at similar dimensions. Both the nanotube alignment and failure current density improve with decreasing structure width. In addition, we present a novel Pt nanocluster decoration method that drastically decreases the resistivity of the test structures. Ab initio density functional theory calculations indicate that the increase in conductivity of the nanotubes is caused by an increase in conduction channels close to their Fermi levels due to the platinum nanocluster decoration, with a possible conversion of the semiconducting single-wall carbon nanotubes into metallic ones. These results reflect a huge step toward the proposed replacement of copper-based interconnects with carbon nanotubes at gigascale integration levels.

Pressure-enabled phonon engineering in metals

Significance Understanding the pressure response of the electrical properties of metals provides a fundamental way of manipulating material properties for potential device applications. In particular, the electrical resistivity of a metal, which is an intrinsic property determined primarily by the interaction strength between electrons and collective lattice vibrations (phonons), can be reduced when the metal is pressurized. In this article, we show that first-principles calculations of the resistivity, as well as experimental measurements using a solid media piston–cylinder apparatus, predict a significant reduction in the electrical resistivity of aluminum and copper when subject to high pressure due primarily to the reduction in the electron–phonon interaction strength. This study suggests innovative ways of controlling transport phenomena in metals. We present a combined first-principles and experimental study of the electrical resistivity in aluminum and copper samples under pressures up to 2 GPa. The calculations are based on first-principles density functional perturbation theory, whereas the experimental setup uses a solid media piston–cylinder apparatus at room temperature. We find that upon pressurizing each metal, the phonon spectra are blue-shifted and the net electron–phonon interaction is suppressed relative to the unstrained crystal. This reduction in electron–phonon scattering results in a decrease in the electrical resistivity under pressure, which is more pronounced for aluminum than for copper. We show that density functional perturbation theory can be used to accurately predict the pressure response of the electrical resistivity in these metals. This work demonstrates how the phonon spectra in metals can be engineered through pressure to achieve more attractive electrical properties.

Revealing the Crystalline Integrity of Wafer-Scale Graphene on SiO2/Si: An Azimuthal RHEED Approach

The symmetry of graphene is usually determined by a low-energy electron diffraction (LEED) method when the graphene is on the conductive substrates, but LEED cannot handle graphene transferred to SiO2/Si substrates due to the charging effect. While transmission electron microscopy can generate electron diffraction on post-transferred graphene, this method is too localized. Herein, we employed an azimuthal reflection high-energy electron diffraction (RHEED) method to construct the reciprocal space mapping and determine the symmetry of wafer-size graphene both pre- and post-transfer. In this work, single-crystalline Cu(111) films were prepared on sapphire(0001) and spinel(111) substrates with sputtering. Then the graphene was epitaxially grown on single-crystalline Cu(111) films with a low pressure chemical vapor deposition. The reciprocal space mapping using azimuthal RHEED confirmed that the graphene grown on Cu(111) films was single-crystalline, no matter the form of the monolayer or multilayer structure. While the Cu(111) film grown on sapphire(0001) may occasionally consist of 60° in-plane rotational twinning, the reciprocal space mapping revealed that the in-plane orientation of graphene grown atop was not affected. The proposed method for checking the crystalline integrity of the post-transferred graphene sheets is an important step in the realization of the graphene as a platform to fabricate electronic and optoelectronic devices.

van der Waals epitaxy of CdS thin films on single-crystalline graphene

van der Waals epitaxy (vdWE) of three-dimensional CdS thin films on both single-crystalline graphene/Cu(111)/spinel(111) and single-crystalline graphene/SiO2/Si substrates is achieved via thermal evaporation. X-ray and electron backscatter diffraction pole figures reveal that the CdS films are a Wurtzite structure with a weak epitaxy on graphene and accompanied with a fiber texture background. The epitaxial alignment between CdS and graphene is observed to be an unusual non-parallel epitaxial relationship with a 30° rotation between the unit vectors of CdS and graphene. A geometrical model based on the minimization of superlattice area mismatch is employed to calculate possible interface lattice arrangement. It is found that the 30° rotation between CdS and graphene is indeed the most probable interface epitaxial lattice alignment. The vdWE of CdS on graphene, transferrable to arbitrary substrates, may represent a step forward for the growth of quality CdS thin films on arbitrary substrates through a grap...

Decoupling interface effect on the phase stability of CdS thin films by van der Waals heteroepitaxy

Wurtzite (W) and zinc-blende (ZB) polytypism has long been observed in epitaxial CdS thin films. The present work, based on van der Waals epitaxial CdS thin films, is an attempt to explain which crystal modification, W or ZB, is favored under different growth conditions. In this van der Waals epitaxy system where the substrate influence is considered weak, it is found that the substrate temperature plays a crucial role in determining the crystal modification of CdS, that is, W and ZB CdS are more stable at low and high ends of substrate temperature, respectively. We attribute this temperature effect to the entropy difference (SW < SZB), a conclusion well supported by the thermodynamic hard sphere model formulation of the entropy difference between hexagonal close-packed and face-centered cubic structures. By summarizing other works, we find that the entropy difference model can also be applied to large mismatched (≳3%) CdS-substrate chemical epitaxy systems but not for small mismatched (≲3%) ones. In the ...

A two-step dry process for Cs2SnI6 perovskite thin film

ABSTRACT A two-step process for synthesizing stable Cs2SnI6 perovskite thin films is reported in this letter. The two-step process includes the co-evaporation of two precursors SnI2 and CsI onto a glass substrate, followed by a post thermal annealing process in iodine vapor. Using this technique, pure Cs2SnI6 perovskite thin films were successfully synthesized without any wet process. These perovskite thin films are found to be stable under ambient conditions. They also show an electron mobility up to 509 cm2 V−1 s−1, which is higher than the mobilities of films prepared by solution processes reported in the literature. GRAPHICAL ABSTRACT IMPACT STATEMENT A novel two-step dry process to synthesize phase-pure, air-stable Cs2SnI6 perovskite thin film with higher electron mobility than that of the films prepared by the solution process.