Zia ur Rehman

Ion Gated Synaptic Transistors Based on 2D van der Waals Crystals with Tunable Diffusive Dynamics

Neuromorphic computing represents an innovative technology that can perform intelligent and energy-efficient computation, whereas construction of neuromorphic systems requires biorealistic synaptic elements with rich dynamics that can be tuned based on a robust mechanism. Here, an ionic-gating-modulated synaptic transistor based on layered crystals of transitional metal dichalcogenides and phosphorus trichalcogenides is demonstrated, which produce a diversity of short-term and long-term plasticity including excitatory postsynaptic current, paired pulse facilitation, spiking-rate-dependent plasticity, dynamic filtering, etc., with remarkable linearity and ultralow energy consumption of ≈30 fJ per spike. Detailed transmission electron microscopy characterization and ab initio calculation reveal two-stage ionic gating effects, namely, surface adsorption and internal intercalation in the channel medium, causing different poststimulation diffusive dynamics and thus accounting for the observed short-term and long-term plasticity, respectively. The synaptic activity can therefore be effectively manipulated by tailoring the ionic gating and consequent diffusion dynamics with varied thickness and structure of the van der Waals material as well as the number, duration, rate, and polarity of gate stimulations, making the present synaptic transistors intriguing candidates for low-power neuromorphic systems.

In situ trapped high-density single metal atoms within graphene: Iron-containing hybrids as representatives for efficient oxygen reduction

Atomically dispersed catalysts have attracted attention in energy conversion applications because their efficiency and chemoselectivity for special catalysis are superior to those of traditional catalysts. However, they have limitations owing to the extremely low metal-loading content on supports, difficulty in the precise control of the metal location and amount as well as low stability at high temperatures. We prepared a highly doped single metal atom hybrid via a single-step thermal pyrolysis of glucose, dicyandiamide, and inorganic metal salts. High-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) revealed that nitrogen atoms doped into the graphene matrix were pivotal for metal atom stabilization by generating a metal-Nx coordination structure. Due to the strong anchoring effect of the graphene matrix, the metal loading content was over 4 wt.% in the isolated atomic hybrid (the Pt content was as high as 9.26 wt.% in the Pt-doped hybrid). Furthermore, the single iron-doped hybrid (Fe@N-doped graphene) showed a remarkable electrocatalytic performance for the oxygen reduction reaction. The peak power density was ∼199 mW·cm−2 at a current density of 310 mA·cm−2 and superior to that of a commercial Pt/C catalyst when it was used as a cathode catalyst in assembled zinc-air batteries. This work offered a feasible approach to design and fabricate highly doped single metal atoms (SMAs) catalysts for potential energy applications.

Synthesis of Ni9S8/MoS2 heterocatalyst for Enhanced Hydrogen Evolution Reaction

We demonstrate a heterostructure Ni9S8/MoS2 hybrid with tight interface synthesized via an improved hydrothermal method. As compared to pure MoS2, the increased surface area and the shorten charge transport pathway in the layered hybrid significantly promote the photocatalytic efficiency for hydrogen evolution reaction (HER). In particularly, the optimized Ni9S8/MoS2 hybrid with 20 wt % Ni9S8 exhibits the highest photocatalytic activity with HER value of 406 μmolg-1h-1, which is enhanced by 70% compared to that of pure MoS2 nanosheets (285.0 μmolg-1h-1). Moreover, the value is 4 times more than the commercial MoS2 (92.0 μmolg-1h-1), indicating the high potential of the hybrid in the catalytic fields.

Ferromagnetism in CVT Grown Tungsten Diselenide Single Crystals with Nickel Doping

Two dimensional (2D) single crystal layered transition materials have had extensive consideration owing to their interesting magnetic properties, originating from their lattices and strong spin-orbit coupling, which make them of vital importance for spintronic applications. Herein, we present synthesis of a highly crystalline tungsten diselenide layered single crystal grown by chemical vapor transport technique and doped with nickel (Ni) to tailor its magnetic properties. The pristine WSe2 single crystal and Ni-doped crystal were characterized and analyzed for magnetic properties using both experimental and computational aspects. It was found that the magnetic behavior of the 2D layered WSe2 crystal changed from diamagnetic to ferromagnetic after Ni-doping at all tested temperatures. Moreover, first principle density functional theory (DFT) calculations further confirmed the origin of room temperature ferromagnetism of Ni-doped WSe2, where the d-orbitals of the doped Ni atom promoted the spin moment and thus largely contributed to the magnetism change in the 2D layered material.

Synergistic effect of an atomically dual-metal doped catalyst for highly efficient oxygen evolution

The oxygen evolution reaction (OER) involving multi-step electron transfer is a challenging approach for water-splitting due to its sluggish kinetics. It is desirable to explore more efficient electro-catalysts with earth-abundant elements. Herein, we employed a high-temperature polymerization method to develop a structure consisting of graphitic carbon nitride (g-C3N4) nanopatch enveloped carbon nanotubes (CNTs), where isolated Ni and Fe atoms were embedded into the tri-s-triazine units of g-C3N4 by forming a metal–Nx structure. The designed dual-metal catalyst exhibited remarkable OER performance with an extremely low overpotential (∼326 mV at 10 mA cm−2) and a small Tafel slope (67 mV per decade), which is superior to those of state-of-the-art electrocatalysts with metal–Nx coordination and the benchmark IrO2/C catalyst. In combination with atomic microscopy observations, our synchrotron-based X-ray absorption spectroscopy results revealed that, as compared to single-metal (Fe or Ni) doped hybrids, the electronic structures of both Ni and Fe atoms were reconfigured in the obtained dual-metal samples. Notably, increase of the oxidative state in Ni sites after multi-metal doping directly contributed to more active sites and favored the OER process, assisted by the porous structure and good electrical contacts between CNTs and g-C3N4. This investigation clearly demonstrated a unique synergistic effect in atomically dual-metal doped catalysts, thus it may provide a versatile route to regulate the electronic structures of single atomic catalysts through engineering of neighboring elements and coordination number.

Electron doping induced semiconductor to metal transitions in ZrSe 2 layers via copper atomic intercalation

Atomic intercalation in two-dimensional (2D) layered materials can be used to engineer the electronic structure at the atomic scale and generate tuneable physical and chemical properties which are quite distinct in comparison with the pristine material. Among them, electron-doped engineering induced by intercalation is an efficient route to modulate electronic states in 2D layers. Herein, we demonstrate a semiconducting to metallic phase transition in zirconium diselenide (ZrSe2) single crystals via controllable incorporation of copper (Cu) atoms. Our angle resolved photoemission spectroscopy (ARPES) measurements and first-principles density functional theory (DFT) calculations clearly revealed the emergence of conduction band dispersion at the M/L point of the Brillouin zone due to Cu-induced electron doping in ZrSe2 interlayers. Moreover, electrical measurements in ZrSe2 revealed semiconducting behavior, while the Cu-intercalated ZrSe2 exhibited a linear current–voltage curve with metallic character. The atomic intercalation approach may have high potential for realizing transparent electron-doping systems for many specific 2D-based nanoelectronic applications.

Magnetic Isotropy/Anisotropy in Layered Metal Phosphorous Trichalcogenide MPS3 (M = Mn, Fe)Single Crystals

Despite the fact that two-dimensional layered magnetic materials hold immense potential applications in the field of spintronic devices, tunable magnetism is still a challenge due to the lack of controllable synthesis. Herein, high-quality single crystals MPS3 (M= Mn, Fe) of millimeter size were synthesized through the chemical vapor transport method. After systemic structural characterizations, magnetic properties were studied on the bulk MPS3 layers through experiments, along with first principle theoretical calculations. The susceptibilities as well as the EPR results evidently revealed unique isotropic and anisotropic behavior in MnPS3 and FePS3 crystals, respectively. It is worth noting that both of these materials show antiferromagnetic states at measured temperatures. The estimated antiferromagnetic transition temperature is 78 K for bulk MnPS3 and 123 K for FePS3 crystals. The spin polarized density functional theory calculations confirmed that the band gap of the antiferromagnetic states could be generated owing to asymmetric response all over the energy range. The ferromagnetic state in MnPS3 and FePS3 is less stable as compared to the antiferromagnetic state, resulting in antiferromagnetic behavior. Additionally, frequency-dependent dielectric functions for parallel and perpendicular electric field component vectors, along with the absorption properties of MPS3, are thoroughly investigated.

Angle-/temperature-dependence of Raman scattering in layered NbSe3 crystal

Distinguishing the lattice vibrational modes of different Raman peaks and further studying the temperature-dependent behaviour of the different Raman modes are fundamental subjects for Raman spectroscopy of single crystal. Herein, we conducted a comprehensive study of angle- and temperature-dependant Raman scattering behaviour in high-crystalline NbSe3 layers prepared by chemical vapour transport method. The polarization experiments performed on NbSe3’s (100) crystal surface revealed that the Raman peaks could be clearly identified as Ag and Bg vibrational modes, indicating significantly anisotropic structure. Meanwhile, the effect of charge density wave (CDW) transition on the lattice vibrational behaviour was studied by investigating temperature-dependent Raman scattering spectra above and below the CDW transition temperature. It was observed that Raman shifts versus temperature for the four prominent Raman peaks of NbSe3 which belonged to Ag vibrational mode exhibited linear softening behaviour as the temperature increased from 83k to 293k. The temperature coefficient of Raman peaks fitted by Gruneisen model further confirmed the anharmonicity of the lattice in NbSe3 crystal, suggesting that the changes of ionic positions across the CDW transition has small effect on its Raman scattering behaviour.