Intriguing electronic and optical prospects of FCC bimetallic two-dimensional heterostructures: epsilon near-zero behavior in UV-Vis range.

A higher superconducting critical temperature and large-area epsilon-near-zero systems are two long-standing goals of the scientific community, having an explicit relationship with the correlated electrons in localized orbitals. Motivated by the recent experimental findings of the strongly correlated phenomena in nanostructures of simple Drude metallic systems, we have theoretically investigated some potential bimetallic FCC combinations having close resemblance with the experimental systems. The explored systems include the large-area interface to the embedded and doped two-dimensional (2D) combinatorial nanostructures. Using different effective single-particle first-principles approaches encompassing density functional theory (DFT), time-dependent DFT (TDDFT), phonon and DFT-coupled quantum transport, we propose some interesting correlated prospects of potential bimetallic nanostructures like Au/Ag and Pt/Pd. For the 2D doped and embedded nanostructures of these systems, the DFT-calculated non-trivial band-structures indicate the interfacial morphology-induced band localization. The calculated Fermi-surface topology of the nanostructures and the corresponding nesting behavior may be emblematic to the presence of instabilities, such as charge density waves. The optical attributes extracted from the TDDFT calculations result in near-zero behavior of both real and imaginary parts of the dynamical dielectric response in the ultra-violet to visible (UV-Vis) optical range. In addition, low-energy intra-band plasmonic oscillations, as present for individual metallic surfaces, are completely suppressed for the embedded and doped nanostructures. The TDDFT-derived electron-energy loss spectra manifest the survival of only inter-band transitions. The presence of soft phonons and dynamic instabilities is observed from the phonon-dispersion of the nanostructured systems. Quantum transport calculations on the simplest possible device made out of these bimetallic systems reveal the generation of highly transmitting pockets over the cross-sectional area for some selected device geometry. We envisage that, if scrutinized experimentally, such systems may unveil many fascinating interdisciplinary aspects of orbital chemistry, physics and optics, promoting their relevant applications in many diverse fields.

Combinatorial Large-Area MoS2/Anatase-TiO2 Interface: A Pathway to Emergent Optical and Optoelectronic Functionalities.

The interface of transition-metal dichalcogenides (TMDCs) and high-k dielectric transition-metal oxides (TMOs) had triggered umpteen discourses because of the indubitable impact of TMOs in reducing the contact resistances and restraining the Fermi-level pinning for the metal-TMDC contacts. In the present work, we focus on the unresolved tumults of large-area TMDC/TMO interfaces, grown by adopting different techniques. Here, on a pulsed laser-deposited MoS2 thin film, a layer of TiO2 is grown by atomic layer deposition (ALD) and pulsed laser deposition (PLD). These two different techniques emanate the layer of TiO2 with different crystallinities, thicknesses, and interfacial morphologies, subsequently influencing the electronic and optical properties of the interfaces. Contrasting the earlier reports of n-type doping at the exfoliated MoS2/TiO2 interfaces, the large-area MoS2/anatase-TiO2 films had realized a p-type doping of the underneath MoS2, manifesting a boost in the extent of p-type doping with increasing thickness of TiO2, as emerged from the X-ray photoelectron spectra. Density functional analysis of the MoS2/anatase-TiO2 interfaces, with pristine and interfacial defect configurations, could correlate the interdependence of doping and the terminating atomic surface of TiO2 on MoS2. The optical properties of the interface, encompassing photoluminescence, transient absorption and z-scan two-photon absorption, indicate the presence of defect-induced localized midgap levels in MoS2/TiO2 (PLD) and a relatively defect-free interface in MoS2/TiO2 (ALD), corroborating nicely with the corresponding theoretical analysis. From the investigation of optical properties, we indicate that the MoS2/TiO2 (PLD) interface may act as a promising saturable absorber, having a significant nonlinear response for the sub-band-gap excitations. Moreover, the MoS2/TiO2 (PLD) interface had exemplified better phototransport properties. A potential application of MoS2/TiO2 (PLD) is demonstrated by the fabrication of a p-type phototransistor with the ionic-gel top gate. This endeavor to analyze and perceive the MoS2/TiO2 interface establishes the prospectives of large-area interfaces in the field of optics and optoelectronics.

ZnCl2 loaded TiO2 nanomaterial: an efficient green catalyst to one-pot solvent-free synthesis of propargylamines.

One-pot green synthesis of propargylamines using ZnCl2 loaded TiO2 nanomaterial under solvent-free conditions has been effectively accomplished. The aromatic aldehydes, amines, and phenylacetylene were reacted at 100 °C in the presence of the resultant catalyst to form propargylamines. The nanocrystalline TiO2 was initially synthesized by a sol-gel method from titanium(iv) isopropoxide (TTIP) and further subjected to ZnCl2 loading by a wet impregnation method. X-ray diffraction (XRD) patterns revealed the formation of crystalline anatase phase TiO2. Field emission scanning electron microscopy (FESEM) showed the formation of agglomerated spheroid shaped particles having a size in the range of 25-45 nm. Transmission electron microscopy (TEM) validates cubical faceted and nanospheroid-like morphological features with clear faceted edges for the pure TiO2 sample. Surface loading of ZnCl2 on spheroid TiO2 nanoparticles is evident in the case of the ZnCl2 loaded TiO2 sample. X-ray photoelectron spectroscopy (XPS) confirmed the presence of Ti4+ and Zn2+ species in the ZnCl2 loaded TiO2 catalyst. Energy-dispersive X-ray (EDS) spectroscopy also confirmed the existence of Ti, O, Zn and Cl elements in the nanostructured catalyst. 15% ZnCl2 loaded TiO2 afforded the highest 97% yield for 3-(1-morpholino-3-phenylprop-2-ynyl)phenol, 2-(1-morpholino-3-phenylprop-2-ynyl)phenol and 4-(1,3-diphenylprop-2-ynyl)morpholine under solvent-free and aerobic conditions. The proposed nanostructure-based heterogeneous catalytic reaction protocol is sustainable, environment-friendly and offers economic viability in terms of recyclability of the catalyst.

Large-area high-throughput synthesis of monolayer graphene sheet by Hot Filament Thermal Chemical Vapor Deposition.

We report hot filament thermal CVD (HFTCVD) as a new hybrid of hot filament and thermal CVD and demonstrate its feasibility by producing high quality large area strictly monolayer graphene films on Cu substrates. Gradient in gas composition and flow rate that arises due to smart placement of the substrate inside the Ta filament wound alumina tube accompanied by radical formation on Ta due to precracking coupled with substrate mediated physicochemical processes like diffusion, polymerization etc., led to graphene growth. We further confirmed our mechanistic hypothesis by depositing graphene on Ni and SiO(2)/Si substrates. HFTCVD can be further extended to dope graphene with various heteroatoms (H, N, and B, etc.,), combine with functional materials (diamond, carbon nanotubes etc.,) and can be extended to all other materials (Si, SiO(2), SiC etc.,) and processes (initiator polymerization, TFT processing) possible by HFCVD and thermal CVD.

Laser-induced ultrafast demagnetization in the presence of a nanoscale magnetic domain network.

Femtosecond magnetization phenomena have been challenging our understanding for over a decade. Most experiments have relied on infrared femtosecond lasers, limiting the spatial resolution to a few micrometres. With the advent of femtosecond X-ray sources, nanometric resolution can now be reached, which matches key length scales in femtomagnetism such as the travelling length of excited 'hot' electrons on a femtosecond timescale. Here we study laser-induced ultrafast demagnetization in [Co/Pd](30) multilayer films, which, for the first time, achieves a spatial resolution better than 100 nm by using femtosecond soft X-ray pulses. This allows us to follow the femtosecond demagnetization process in a magnetic system consisting of alternating nanometric domains of opposite magnetization. No modification of the magnetic structure is observed, but, in comparison with uniformly magnetized systems of similar composition, we find a significantly faster demagnetization time. We argue that this may be caused by direct transfer of spin angular momentum between neighbouring domains.

Mechanistic investigation of decolorization and degradation of reactive red 120 by Bacillus lentus BI377.

Bacillus lentus BI377, isolated from textile effluent-contaminated soil, was able to degrade 97% and 92% of Reactive Red 120 dye when 1200 and 1500 mg/l, respectively, of dye was added to nutrient broth (NB) at 35 °C within 12 h. UV-vis spectroscopy, GC-MS, FTIR and 1H NMR revealed the formation of catechol which may be further utilized by the bacterium via the TCA cycle, leading to complete mineralization. Structural analysis of metabolites in conjunction with enzyme activity studies confirmed the involvement of azoreductase, cytochrome P450 monooxygenase and other antioxidant enzymes. Decreases in total organic carbon and in biological and chemical oxygen demand suggest formation of low molecular weight metabolites that could be completely mineralized. These results suggest the potential use of B. lentus BI377 towards online treatment of textile dye effluents by using an appropriate bioreactor over a wide range of pH. This study opens-up a dependable and proficient way to use industrially viable non-pathogenic strains for biotransformation of carcinogenic dyes to ecofriendly compounds.

Evaluation of co-polyaniline nanocomposite thin films as humidity sensor.

Spin coated films of Co-Polyaniline nanocomposite are evaluated for their transmission properties using He-Ne laser for humidity sensing. The thickness (17-29 microm) of the films is varied by multiple deposition of Co-Polyaniline nanocomposite on a glass substrate. The samples exhibit typically two to three regions in their sensitivity curve when tested in the relative humidity (RH) range of 20-95%. The sensitivity ranges from 0.1 mV/%RH to 12.26 mV/%RH for lower to higher thickness. The sensors show quick response of 8s (20-95%RH), and a recovery time of 1 min (95-20%RH) with good repeatability, reproducibility and low hysteresis effect. The sensitivity of the sensor increases with humidity and thickness. Material characterization is done by X-ray diffraction (XRD), scanning electron micrograph (SEM) and Fourier transform infra-red spectroscopy (FTIR).