Irfan Haider Abidi

Oxidized nitinol substrate for interference enhanced Raman scattering of monolayer graphene

We demonstrate the preparation of a controllable and reproducible active substrate for surface enhanced Raman scattering (SERS) using a facile oxidation method that allows us to obtain a titanium oxide (TiO2) capping layer with the desired thickness on nickel–titanium alloy (NiTi). The carefully tuned oxide layer, which is obtained by controlling the annealing time, exhibits the enhancement of the 2D band intensity of graphene up to ∼50 times in comparison to bare nitinol. The dependence of Raman enhancement upon the oxide thickness can be explained by the interference enhanced Raman scattering (IERS) process, and fitted to a multi reflection model (MRM) of the Raman scattering of graphene on a layered structure. Thus our results provide a facile method to enhance Raman signals of graphene by tuning the thickness of the oxide layer at all three lasers (514 nm, 633 nm and 785 nm). The present method can be adapted to exploit the recent advances in molecular vibration study and biomolecular detection due to the versatility of the proposed substrate.

Recoil Effect and Photoemission Splitting of Trions in Monolayer MoS2

The 2D geometry nature and low dielectric constant in transition-metal dichalcogenides lead to easily formed strongly bound excitons and trions. Here, we studied the photoluminescence of van der Waals heterostructures of monolayer MoS2 and graphene at room temperature and observed two photoluminescence peaks that are associated with trion emission. Further study of different heterostructure configurations confirms that these two peaks are intrinsic to MoS2 and originate from a bound state and Fermi level, respectively, of which both accept recoiled electrons from trion recombination. We demonstrate that the recoil effect allows us to electrically control the photon energy of trion emission by adjusting the gate voltage. In addition, significant thermal smearing at room temperature results in capture of recoil electrons by bound states, creating photoemission peak at low doping level whose photon energy is less sensitive to gate voltage tuning. This discovery reveals an unexpected role of bound states for photoemission, where binding of recoil electrons becomes important.

Engineering sub-100 nm Mo(1−x)WxSe2 crystals for efficient hydrogen evolution catalysis

The edge site of two-dimensional (2D) transition metal dichalcogenides (TMDs) is active towards the hydrogen evolution reaction (HER). Herein, a feasible synthesis of sub-100 nm molybdenum/tungsten diselenide [Mo(1−x)WxSe2] crystals is described. The abundant edge exposure and heteroatom-doping synergistically boost the catalysis of HER by this material. In this work, sub-100 nm Mo(1−x)WxSe2 single crystals were grown on a nitrogen-doped multiwall carbon nanotube before being applied as HER electrocatalysts. At x = 0.13 ± 0.02, the Mo(1−x)WxSe2 shows optimal HER catalytic performance with low overpotentials (70 and 129 mV) required to achieve current densities of −1 and −10 mA cm−2, respectively, along with a Tafel slope of 53.6 mV dec−1 and an exchange current density of 49.5 μA cm−2. Density functional theory (DFT) calculations indicate that the Gibbs free energy of the HER process at the edge site of the crystals reaches a minimum value of 0.06 eV, which is lower than when the reaction is catalysed on Pt active sites. This study provides a general approach to increasing the edge proportion of the catalyst material and activating the terrace of the 2D materials for catalysis, which may be of benefit to the design and fabrication of other TMDs-based compounds.

Recyclable 3D Graphene Aerogel with Bimodal Pore Structure for Ultrafast and Selective Oil Sorption from Water

Development of next-generation porous sorbents to overcome the challenges, such as low uptake capacity, slow sorption rate, and non-recyclability, associated with conventional sorbents is of utmost importance. Herein, we report the synthesis of a highly porous graphene aerogel (GA) with a unique three-dimensional hierarchical bimodal porous network of macro and meso-pores via a facile hydrothermal technique; this aerogel has sorption capacity that is more than 5 times that of conventional commercial sorbents. Fluoroalkyl silane functionalization of the GA surface results in a significant reduction in its water sorption from 20 g g−1 to 5 g g−1 due to the GA surface becoming more hydrophobic, which renders it useful in practical application to selectively remove oil from seawater. Moreover, the sorption rate of the GA for oils and organic solvents has been found to be extremely fast, and saturation of the GA is completed in a few seconds. This is attributed to its unique meso–macro bimodal porous structure with large pore channels called macro-pores or voids of various sizes ranging from 300 nm to over 10 μm, which facilitate mass transport into its inner mesopores of 14–18 nm at high rate. Finally, the GA is shown to be a highly recyclable material due to its good mechanical strength, where the oil- and organic solvent-sorbed GA can be efficiently recovered using thermal or chemical methods for several sorption–desorption cycles without significant loss in its capacity, which also makes the process cost effective and environmentally friendly.

Domain size, layer number and morphology control for graphene grown by chemical vapor deposition

Over the past a few years, high-quality graphene preparation has been evolved from low-yield micromechanical exfoliation in including a wide range of production methods, in particular by chemical vapor deposition (CVD). Here, we review the state-of-the-art on synthesis of graphene using CVD method and the strategies to control the graphene grain size, number of layers and morphology, mainly focusing on the graphene growth that uses Cu as substrate. We highlight the success of the past research in the field and provide a review of the methods that were used for such controlled synthesis.

Molecular Beam Epitaxy of Two-Dimensional In2Se3 and its Giant Electroresistance Switching in Ferroresistive Memory Junction

Ferroelectric thin film has attracted great interest for nonvolatile memory applications and can be used in either ferroelectric Schottky diodes or ferroelectric tunneling junctions due to its promise of fast switching speed, high on-to-off ratio, and nondestructive readout. Two-dimensional α-phase indium selenide (In2Se3), which has a modest band gap and robust ferroelectric properties stabilized by dipole locking, is an excellent candidate for multidirectional piezoelectric and switchable photodiode applications. However, the large-scale synthesis of this material is still elusive, and its performance as a ferroresistive memory junction is rarely reported. Here, we report the low-temperature molecular-beam epitaxy (MBE) of large-area monolayer α-In2Se3 on graphene and demonstrate the use of α-In2Se3 on graphene in ferroelectric Schottky diode junctions by employing high-work-function gold as the top electrode. The polarization-modulated Schottky barrier formed at the interface exhibits a giant electroresistance ratio of 3.9 × 106 with a readout current density of >12 A/cm2, which is more than 200% higher than the state-of-the-art technology. Our MBE growth method allows a high-quality ultrathin film of In2Se3 to be heteroepitaxially grown on graphene, thereby simplifying the fabrication of high-performance 2D ferroelectric junctions for ferroresistive memory applications.

Stacking Modes-Induced Chemical Reactivity Differences on Chemical Vapor Deposition-Grown Trilayer Graphene

Trilayer graphene (TLG) synthesized by chemical vapor deposition (CVD), in particular the twisted TLG, exhibits sophisticated electronic structures that depend on their stacking modes. Here, we computationally and experimentally demonstrate the chemical reactivity differences of CVD-TLG induced by the stacking modes and corroborated by a photoexcited phenyl-grafting reaction. The experimental results show that the ABA stacking TLGs have the most inert chemical property, yet 30°-30° stacking twisted TLGs are the most active. Further, density functional theory calculations have shown that the chemical reactivity difference can be quantitatively explained by the differences in the number of hot electrons generated in their valence band during irradiation. The activity difference is further verified by the calculated adsorption energy of phenyl on the TLGs. Our work provides insight into the chemistry of TLG and addresses the challenges associated with selective functionalization of TLG with phenyl groups. The understandings developed in this project can also guide the future development of TLG-based functional devices.