Effect of temperature on polaronic transport in CeO2 thin-film.

The outstanding catalytic property of cerium oxide (CeO2) strongly depends on the polaron formation due to the oxygen vacancy (V̈O) defect and Ce4+ to Ce3+ transformation. Temperature plays an important role in the case of polaron generation in CeO2 and highly influences its electrical transport properties. Therefore, a much needed attention is required for detailed understanding of the effect of temperature on polaron formation and oxygen vacancy migration to get an idea about the improvement in the redox property of ceria. In this work, we have probed the generation of polarons in CeO2 thin-film deposited on a silicon (Si) substrate using the resonance photoemission spectroscopy (RPES) study. The RPES data show an increase in polaron density at the substrate-film interface of the thermally annealed film, indicating the formation of an interfacial Ce2O3 layer, which is, indeed, a phase change from the cubic to hexagonal structure. This leads to a modified electronic band structure, which has an impact on the capacitance-voltage (C-V) characteristics. This result nicely correlates the microscopic property of polarons and the macroscopic transport property of ceria.

D-Band Engineering in Pd-Based Nanowire Networks for Further Enhancement in Ethanol Electrooxidation Reaction.

The development of highly efficient electrocatalysts for the ethanol oxidation reaction (EOR) is essential for the commercialization of direct ethanol fuel cells, yet challenges remain. In this study, a one-pot solution-phase method to synthesize Pd nanowire networks (NNWs) with very high surface-to-volume ratio having numerous twin and grain boundaries is developed. Using the same method, the Pd lattice is further engineered by introducing Ag and Cu atoms to produce AgPd, and CuPd alloy structure which significantly shifts the Pd d-band center upward and downward, respectively due to strain and ligand effects. Theoretical analysis employing density functional theory (DFT) demonstrates that such modification of the d-band center significantly influences the adsorption energies of reactants on the catalytic surface. Owing to their notably high surface-to-volume ratio and the presence of multiple twin and grain boundaries, Pd NNWs demonstrate significantly enhanced electrocatalytic activity toward EOR, ≈7.2 times greater than that of commercial Pd/C. Remarkably, compared to Pd NNWs, AgPd, and CuPd NNWs display enlarged and reduced electrocatalytic activity toward EOR, respectively. Specifically, Ag4Pd7 NNWs achieve a remarkable mass activity of 9.00 A mgpd -1 for EOR, which is 13.6 times higher than commercial Pd/C.

Low-Temperature Synthesis of WSe2 by the Selenization Process under Ultrahigh Vacuum for BEOL Compatible Reconfigurable Neurons.

Low-temperature large-area growth of two-dimensional (2D) transition-metal dichalcogenides (TMDs) is critical for their integration with silicon chips. Especially, if the growth temperatures can be lowered below the back-end-of-line (BEOL) processing temperatures, the Si transistors can interface with 2D devices (in the back end) to enable high-density heterogeneous circuits. Such configurations are particularly useful for neuromorphic computing applications where a dense network of neurons interacts to compute the output. In this work, we present low-temperature synthesis (400 °C) of 2D tungsten diselenide (WSe2) via the selenization of the W film under ultrahigh vacuum (UHV) conditions. This simple yet effective process yields large-area, homogeneous films of 2D TMDs, as confirmed by several characterization techniques, including reflection high-energy electron diffraction, atomic force microscopy, transmission electron microscopy, and different spectroscopy methods. Memristors fabricated using the grown WSe2 film are leveraged to realize a novel compact neuron circuit that can be reconfigured to enable homeostasis.

Improved Alcohol Oxidation through Combined Effects of Tensile Lattice Strain and Twin Defects in Core-Shell Electrocatalysts.

The direct alcohol fuel cells (DAFCs) rely on alcohol oxidation reactions (AORs) to produce electricity, which require catalysts with optimized electronic structure to accelerate the sluggish AORs. Herein, an epitaxial growth of Pd layer onto the pentatwinned Au@Ag core-shell nanorods (NRs) is reported to synthesize highly strained Au@AgPd core-shell NRs. The tensile strain in the AgPd shell of the Au@AgPd nanorods (NRs) arises not only from the core-shell lattice mismatch but also from twinning and lattice distortion occurring at the five twinned boundaries present in the structure. Theoretical simulations prove that the presence of tensile strains in the AgPd layer leads to a significant upward shift of the d-band center of the Pd site toward the Fermi level which remarkably changes the adsorption energy of alcohols on the surface. Highly strained Au@AgPd NRs show exceptional mass activities in electrochemical oxidation of biomass-derived alcohols (ethylene glycol, ethanol, and glycerol) reaching up to 18.66, 15.6, and 7.90 A mgpd -1 , respectively. These values are 23.3, 23.6, and 23.2 times higher than commercial Pd/C catalysts. This strain engineering strategy set the platform for the design and synthesis of highly efficient and versatile catalysts for the construction of high-performance DAFCs.

Green to deep-red emissive carbon dot formation by C+ion implantation on nitrogen beam created self-masked nano-template.

We report the formation of green to red emissive arrays of carbon dot on silicon-nitride nano-templates by successive implantation of nitrogen and carbon broad ion beams. The patterned nano-templates are formed by 14 keV N2+ion-bombardment at grazing incident (70°) on Si. Subsequently, 5 keV C+ions are implanted at the selective sites of the pyramidal nano-template by taking advantage of the self-masking effect. The nano-pyramidal pattern and the implanted carbon dots at the specific sites are confirmed by atomic force microscopy and cross sectional transmission electron microscopy measurements. The developed carbon dots (CDs) are mostly amorphous and consists of SiC and graphitic nitrogen (CN). G-band and D-band carbons are identified by Raman spectroscopy, while the presence of SiC and CN are detected by XPS measurements. A change of band-gap is observed for C-implanted templates by the UV-vis spectroscopy. Excitation wavelength-dependent photoemission from the dots is found in the green to red region. Maximum intense PL is observed in the green-orange region for excitation wavelength of 425 nm and a redshift of PL with decreasing intensity is observed with the increase of excitation wavelength. The observed photoluminescence is described in terms of the combined effects of quantum confinement, graphitic nitrogen and defect induced additional states formation in the carbon dots. The potential applications of CDs are also addressed.

Magnetic-Proximity-Induced Efficient Charge-to-Spin Conversion in Large-Area PtSe2/Ni80Fe20 Heterostructures.

As a topological Dirac semimetal with controllable spin-orbit coupling and conductivity, PtSe2, a transition-metal dichalcogenide, is a promising material for several applications, from optoelectrics to sensors. However, its potential for spintronics applications has yet to be explored. In this work, we demonstrate that the PtSe2/Ni80Fe20 heterostructure can generate large damping-like current-induced spin-orbit torques (SOT), despite the absence of spin-splitting in bulk PtSe2. The efficiency of charge-to-spin conversion is found to be -0.1 ± 0.02 nm-1 in PtSe2/Ni80Fe20, which is 3 times that of the control sample, Ni80Fe20/Pt. Our band structure calculations show that the SOT due to PtSe2 arises from an unexpectedly large spin splitting in the interfacial region of PtSe2 introduced by the proximity magnetic field of the Ni80Fe20 layer. Our results open up the possibilities of using large-area PtSe2 for energy-efficient nanoscale devices by utilizing proximity-induced SOT.

Charge-transfer-driven enhanced room-temperature ferromagnetism in BiFeO3/Ag nanocomposite.

We report observation of more than an order of magnitude jump in saturation magnetization in BiFeO3/Ag nanocomposite at room temperature compared to what is observed in bare BiFeO3nanoparticles. Using transmission electron microscopy together with energy dispersive x-ray spectra (which maps the element concentration across the BiFeO3/Ag interface) and x-ray photoelectron spectroscopy, we show that both the observed specific self-assembly pattern of BiFeO3and Ag nanoparticles and the charge transfer between Ag and O are responsible for such an enormous rise in room-temperature magnetization. The BiFeO3/Ag nanocomposites, therefore, could prove to be extremely useful for a variety of applications including biomedical.

Suberic Acid-Based Supramolecular Metallogels of Ni(II), Zn(II), and Cd(II) for Anti-Pathogenic Activity and Semiconducting Diode Fabrication.

The importance of three synthesized metallogels of suberic acid distinctly with nickel, zinc, and cadmium acetate salts has been uncovered. For the creation of these soft materials, N,N'-dimethyl formamide was utilized as a source of the trapped solvent. The synthesized metallogels display intriguing viscoelasticity, and the interpretation of experimental parameters obtained from rheological results advocates the gel behavior. Microstructural analysis combined with energy-dispersive X-ray confirms the occurrence of individual gel-developing constituents as observed in different hierarchical microstructural patterns. Significant variations in microstructural arrangements with diverse extent of supramolecular non-covalent patterns inside gel networks were perceived through field emission scanning electron microscopy, atomic force microscopy, and transmission electron microscopy analyses. Fourier transform infrared and electrospray ionization-mass spectral analyses and powder X-ray diffraction analysis of metallogel samples of different gel-establishing ingredients help to investigate the possible supramolecular interactions dictating the metallogel scaffolds. Thermogravimetric analysis of xerogel samples was collected from the synthesized metallogels to understand the thermal stability. These gel materials were characterized by their potential antibacterial efficiency. The potency of metallogels against selective Gram-positive and Gram-negative bacteria was visualized via a spectrophotometer. Human pathogens like Klebsiella pneumoniae (MTCC 109), Salmonella typhi (MTCC 733), Vibrio parahaemolyticus, Bacillus cereus (MTCC 1272), Lactobacillus fermentum (NCDO 955), and Staphylococcus aureus (MTCC 96) are employed in this study. Apart from the biological significance, our metallogels demonstrate as incredible diode performance of fabricated semiconducting systems, which exhibit a considerable amount of non-linearity demonstrating a non-ohmic conduction mechanism at room temperature in dark conditions. Device fabrication was achieved from these metallogels employing the sandwich model with indium tin oxide-coated glass substrates/metallogel/Al structure.

Probing Molecular Chirality on the Self-Assembly and Gelation of Naphthalimide-Conjugated Dipeptides.

In this work, 1,8-naphthalimide (NMI)-conjugated three hybrid dipeptides constituted of a ß-amino acid and an α-amino acid have been designed, synthesized, and purified. Here, in the design, the chirality of the α-amino acid was varied to study the effect of molecular chirality on the supramolecular assembly. Self-assembly and gelation of three NMI conjugates were studied in mixed solvent systems [water and dimethyl sulphoxide (DMSO)]. Interestingly, chiral NMI derivatives [NMI-ßAla-lVal-OMe (NLV) and NMI-ßAla-dVal-OMe (NDV)] formed self-supported gels, while the achiral NMI derivative [NMI-ßAla-Aib-OMe, (NAA)] failed to form any kind of gel at 1 mM concentration and in a mixed solvent (70% water in DMSO medium). Self-assembly processes were thoroughly investigated using UV-vis spectroscopy, nuclear magnetic resonance (NMR), fluorescence, and circular dichroism (CD) spectroscopy. A J-type molecular assembly was observed in the mixed solvent system. The CD study indicated the formation of chiral assembled structures for NLV and NDV, which were mirror images of one another, and the self-assembled state by NAA was CD-silent. The nanoscale morphology of the three derivatives was studied using scanning electron microscopy (SEM). In the case of NLV and NDV, left- and right-handed fibrilar morphologies were observed, respectively. In contrast, a flake-like morphology was noticed for NAA. The DFT study indicated that the chirality of the α-amino acid influenced the orientation of π-π stacking interactions of naphthalimide units in the self-assembled structure that in turn regulated the helicity. This is a unique work where molecular chirality controls the nanoscale assembly as well as the macroscopic self-assembled state.

Resultant inward imbalanced seeding force (RIISF)-induced concave gold nanostar (CAuNS) for non-enzymatic electrocatalytic detection of serotonin and Kynurenine in human serum.

CTAC-based gold nanoseed-induced concave curvature evolution of surface boundary planes from concave gold nanocube (CAuNC) to concave gold nanostar (CAuNS) has been achieved by a novel synthetic methodology simply by controlling the extent of seed used and hence the generated 'Resultant Inward Imbalanced Seeding Force (RIISF)'. The resultant CAuNS shows an excellent enhancement in catalytic activity compared to CAuNC and other intermediates as a function of curvature-induced anisotropy. Detailed characterization evaluates the presence of an enhanced number of multiple defect sites, high energy facets, larger surface area, and roughened surface which ultimately results in an increased mechanical strain, coordinately unsaturation, and multifacet-oriented anisotropic behavior suitable for positive influence on the binding affinity of CAuNSs. While different crystalline and structural parameters improve their catalytic activity, the resultant uniform three-dimensional (3D) platform shows comparatively easy pliability and well absorptivity on the glassy carbon electrode surface for increased shelf life, a uniform structure to confine a large extent of stoichiometric systems, and long-term stability under ambient conditions for making this newly developed material a unique nonenzymatic scalable universal electrocatalytic platform. With the help of various electrochemical measurements, the ability of the platform has been established by performing highly specific and sensitive detection of the two most important human bio messengers: Serotonin (STN) and Kynurenine (KYN) which are metabolites of L-Tryptophan in the human body system. The present study mechanistically surveys the role of seed-induced RIISF-modulated anisotropy in controlling the catalytic activity which offers a universal 3D electrocatalytic sensing tenet by an electrocatalytic approach.

Layered SnS2/porous nickel foil based Schottky junction: An excellent ammonia sensor at room temperature.

In recent years, layered materials has gained immense attention in the field of gas sensing owing to their extraordinary electrical, optical and catalytic properties. Their gas sensing performance can further be improved by switching from ohmic to schottky based sensor due to exponential change of conductance in analyte environment. In most of the Schottky based gas sensor, the surface of the sensing material is covered by metal electrode which reduces the sensing performance. Herein, we have fabricated 2D SnS2 (thickness: 5.62 ± 1.26 nm) based Schottky junction for ammonia detection operated at room temperature using porous nickel foil which allows the analyte molecule to maximize the interaction with the sensing material. We have compared the performance of the Schottky junction sensor with that of SnS2 based ohmic sensor. The Schottky junction based sensor has 140.7 times higher response than SnS2 based ohmic sensor at 360 ppm. The response of the sensor exhibits exponential behavior with ammonia concentration which is explained by estimated barrier height modulation from 0.83 eV (in air) to 0.69 eV (at 225 ppm). In addition, the long term stability over six months of the sensor makes it a promising candidate for practical ammonia sensor operated at room temperature.

Spatially varying chemical phase formation on silicon nano ripple by low energy mixed ions bombardment.

We report mixed (CO+and N2+) ion beam induced spatially varying chemical phases formation on Si (100) surface in nanometer length scale. Simultaneous bombardment of carbon, oxygen and nitrogen like three reactive ions leads to well-defined ripple development and spatially varying periodic chemical phases formation. Post bombardment chemical changes of Si surface are investigated by x-ray photoelectron spectroscopy, and spatially resolved periodic variation of chemical phases are confirmed by electron energy loss spectroscopy. The thickness of ion modified amorphous layer, estimated by Monte Carlo simulation (SRIM), is in excellent agreement with the cross-sectional transmission electron microscopy measurements. The formation of such periodic nanoscale ripple having multiple chemical phases at different parts is explained in terms of chemical instability, local ion flux variation and difference in sputtering yield. Potential applications of such newly developed nano material are also addressed.

Single Amino-Acid Based Self-Assembled Biomaterials with Potent Antimicrobial Activity.

The design and development of soft biomaterials based on amino acid and short-peptide have gained much attention due to their potent biomedical applications. A slight alteration in the side-chain of single amino acid in a peptide or protein sequence has a huge impact on the structure and function. Phenylalanine is one of the most studied amino acids, which contains an aromatic phenyl group connected through a flexible -CH2 - unit. In this work, we have examined whether flexibility and aromatic functionality of phenylalanine (Phe) are important in gel formation of model gelator Fmoc-Phe-OH or not. To examine this hypothesis, we synthesized Fmoc-derivatives of three analogues unnatural amino acids including cyclohexylalanine, phenylglycine, and homophenylalanine; which are slightly varied from Phe. Interestingly, all these three new analogues formed hydrogels in phosphate buffer at pH 7.0 having different gelation efficacy and kinetics. This study suggests that the presence of aromatic side-chain and flexibility are not mandatory for the gelation of this model gelator. Newly synthesized unnatural amino acid derivatives have also exhibited promising antimicrobial activity towards gram-positive bacteria by inhibiting cellular oxygen consumption. We further determined the biocompatibility of these amino acid derivatives by using a hemolysis assay on human blood cells. Overall studies described the development of single amino acid-based new injectable biomaterials with improved antimicrobial activity by the slight alteration in the side-chain of amino acid.

Enhanced exciton binding energy, Zeeman splitting and spin polarization in hybrid layered nanosheets comprised of (Cd, Mn)Se and nitrogen-doped graphene oxide: implication for semiconductor devices.

The exciton properties of (Cd,Mn)Se-NrGO (nitrogen doped reduced graphene oxide) hybrid layered nanosheets have been studied in a magnetic field up to 10 T and compared to those of (Cd,Mn)Se nanosheets. The temperature dependent photoluminescence reveals the hybridization of inter-band exciton and intra-center Mn transition with enhancement of the binding energy of exciton-Mn hybridized state (80 meV with respect to 60 meV in (Cd,Mn)Se nanosheets) and increase of exciton-phonon coupling strength to 90 meV (with respect to 55 meV in (Cd,Mn)Se nanosheets). The circularly polarized magneto-photoluminescence at 2 K provides evidence for magnetic field induced exciton spin polarization and the realization of excitonic giant Zeeman splitting withgeffas high as 165.4 ± 10.3, much larger than in the case of (Cd,Mn)Se nanosheets (63.9 ± 6.6), promising for implementation in spin active semiconductor devices.

Correction: Observation of ordered arrays of endotaxially grown nanostructures from size-selected Cu-nanoclusters deposited on patterned substrates of Si.

Correction for 'Observation of ordered arrays of endotaxially grown nanostructures from size-selected Cu-nanoclusters deposited on patterned substrates of Si' by Shyamal Mondal et al., Phys. Chem. Chem. Phys., 2021, 23, 6009-6016 DOI: 10.1039/D0CP06089E.

Observation of ordered arrays of endotaxially grown nanostructures from size-selected Cu-nanoclusters deposited on patterned substrates of Si.

We report the first time observation of endotaxial growth during thermal treatment of size-selected nanoclusters on a patterned substrate, when we fabricate highly ordered and partially embedded 3D crystalline Cu nanostructure arrays of controlled size in Si-substrates. For this purpose, we combine low energy cluster deposition on the ripple-patterned substrate with controlled annealing. We have investigated, in detail, the effect of the substrate pattern on the deposited size-selected clusters upon heat treatment. At the annealing temperature of 400 °C, nanosized islands are found to be organized into regular arrays, following the alignment of the substrate pattern exactly. The formed islands are trapped at the specific sites of the substrate where surface curvature is maximum and concave. It is also observed that the size of the produced nanoislands (or particles) in the direction of the ripple wave vector, i.e., across the ripples, are in congruence with the ripple wavelength. All the formed islands are partially buried in the substrate and the growth inside the substrate exhibits endotaxial growth. Such an embedded size-controlled nanoscale system can be very promising as sinter-resistant heterogenous catalyst with strong potential in clean energy technology and industrial chemical synthesis.

Strain-Controlled Superconductivity in Few-Layer NbSe2.

The controlled tunability of superconductivity in low-dimensional materials may enable new quantum devices. Particularly in triplet or topological superconductors, tunneling devices such as Josephson junctions, etc., can demonstrate exotic functionalities. The tunnel barrier, an insulating or normal material layer separating two superconductors, is a key component for the junctions. Thin layers of NbSe2 have been shown as a superconductor with strong spin orbit coupling, which can give rise to topological superconductivity if driven by a large magnetic exchange field. Here we demonstrate the superconductor-insulator transitions in epitaxially grown few-layer NbSe2 with wafer-scale uniformity on insulating substrates. We provide the electrical transport, Raman spectroscopy, cross-sectional transmission electron microscopy, and X-ray diffraction characterizations of the insulating phase. We show that the superconductor-insulator transition is driven by strain, which also causes characteristic energy shifts of the Raman modes. Our observation paves the way for high-quality heterojunction tunnel barriers to be seamlessly built into epitaxial NbSe2 itself, thereby enabling highly scalable tunneling devices for superconductor-based quantum electronics.

Bimetallic gold-silver nanoparticles mediate bacterial killing by disrupting the actin cytoskeleton MreB.

The actin cytoskeleton is required for the maintenance of the cell shape and viability of bacteria. It remains unknown to which extent nanoparticles (NPs) can orchestrate the mechanical instability by disrupting the cytoskeletal network in bacterial cells. Our work demonstrates that Au-Ag NPs disrupt the bacterial actin cytoskeleton specifically, fluidize the inner membrane and lead to killing of bacterial cells. In this study, we have tried to emphasize on the key parameters important for NP-cell interactions and found that the shape, specific elemental surface localization and enhanced electrostatic interaction developed due to the acquired partial positive charge by silver atoms in the aggregated NPs are some of the major factors contributing towards better NP interactions and subsequent cell death. In vivo studies in bacterial cells showed that the NPs exerted a mild perturbation of the membrane potential. However, its most striking effect was on the actin cytoskeleton MreB resulting in morphological changes in the bacterial cell shape from rods to predominantly spheres. Exposure to NPs resulted in the delocalization of MreB patches from the membrane but not the tubulin homologue FtsZ. Concomitant with the redistribution of MreB localization, a dramatic increase of membrane fluid regions was observed. Our studies reveal for the first time that Au-Ag NPs can mediate bacterial killing and disrupt the actin cytoskeletal functions in bacteria.

Defect-Engineered MoS2 Nanostructures for Reactive Oxygen Species Generation in the Dark: Antipollutant and Antifungal Performances.

Meticulous surface engineering of layered structures toward new functionalities is a demanding challenge to the scientific community. Here, we introduce defects on varied MoS2 surfaces by suitable doping of nitrogen atoms in a sulfur-rich reaction environment, resulting in stable and scalable phase conversion. The experimental characterizations along with the theoretical calculations within the framework of density functional theory establish the impact of nitrogen doping on stabilization of defects and reconstruction of the 2H to 1T phase. The as-synthesized MoS2 samples exhibit excellent dye removal capacity in the dark, facilitated by a synergistic effect of reactive oxygen species (ROS) generation and adsorption. Positron annihilation spectroscopy and electron paramagnetic resonance studies substantiate the role of defects and associated sulfur vacancies toward ROS generation in the dark. Further, on the basis of its ample ROS generation in the dark and in the light, the commendable antimicrobial activity of the prepared MoS2 samples against fungal pathogen Alternaria alternata has been demonstrated. Thus, the present study opens up a futuristic avenue to develop newer functional materials through defect engineering by suitable dopants toward superior performances in environment issues.