Synthesis and Characterization of Biotene: A New 2D Natural Oxide From Biotite.

In this work, the synthesis and characterization of ultrathin metal oxide, called biotene, using liquid-phase exfoliation from naturally abundant biotite are demonstrated. The atomically thin biotene is used for energy harvesting using its flexoelectric response under multiple bending. The effective flexoelectric response increases due to the presence of surface charges, and the voltage increases up to ≈8 V, with a high mechano-sensitivity of 0.79 V N-1 for normal force. This flexoelectric response is further validated by density functional theory (DFT) simulations. The atomically thin biotene shows an increased response in the magnetic field and thermal heating. The synthesis of two-dimensional (2D) metal-oxide biotene suggests a wealth of future 2D-oxide material for energy generation and energy harvesting applications.

Spontaneous Time-Reversal Symmetry Breaking at Individual Grain Boundaries in Graphene.

Graphene grain boundaries (GBs) have attracted interest for their ability to host nearly dispersionless electronic bands and magnetic instabilities. Here, we employ quantum transport and universal conductance fluctuation measurements to experimentally demonstrate a spontaneous breaking of time-reversal symmetry across individual GBs of chemical vapor deposited graphene. While quantum transport across the GBs indicate spin-scattering-induced dephasing and hence formation of local magnetic moments, below T≲4 K we observe complete lifting of time-reversal symmetry at high carrier densities (n≳5×10^{12} cm^{-2}) and low temperature (T≲2 K). An unprecedented thirtyfold reduction in the universal conductance fluctuation magnitude with increasing doping density further supports the possibility of an emergent frozen magnetic state at the GBs. Our experimental results suggest that realistic GBs of graphene can be a promising resource for new electronic phases and spin-based applications.

Engineering the Microstructure of Silicon Nanowires by Controlling the Shape of the Metal Catalyst and Composition of the Etchant in a Two-Step MACE Process: An In-Depth Analysis of the Growth Mechanism.

In this work, slanted, kinked, and straight silicon nanowires (SiNWs) are fabricated on Si(111) and (100) substrates using a facile two-step metal-assisted chemical etching nanofabrication technique. We systematically investigated the effect of crystallography, morphology of Ag catalyst, and composition of etchant on the etch profile of Ag catalyst on Si(111) and (100) substrates. We found that the movement of AgNPs inside the Si is determined by physiochemical events such as Ag/Ag interaction, Ag/Si contact, and diffusion kinetics. Further, from detailed TEM and micro-Raman spectroscopy analyses, we demonstrate that the metal catalyst moves in the crystallographically preferred etching direction (viz., <100>) only when the interface effect is not predominant. Further, the metal-assisted chemical etching (MACE) system is highly stable at low-concentration plating and etching solutions, but at high concentrations, the system loses its stability and becomes highly random, leading to the movement of Ag catalyst in directions other than ⟨100⟩. In addition, our studies reveal that Ag nanostructures growth on Si(111) and (100) substrates through galvanic displacement is controlled by substrate symmetry and surface bond density. Finally, we demonstrate that by using an optimized balance between the Ag morphology and concentration of the etchant, the angle in slanted SiNWs, kink position in kinked SiNWs, and aspect ratio of straight SiNWs can be controlled judiciously, leading to enhanced optical absorption in the broadband solar spectrum.

Phase formation and stability of Ag-60 at%Cu alloy nanoparticles synthesized by chemical routes in aqueous media.

The present work reports the nature of the evolution of an array of nanoparticles during the synthesis of alloy nanoparticles of Ag-60 at%Cu by the co-reduction of metal salt precursors using NaBH4 in an aqueous medium. This was achieved by studying samples extracted at different intervals of time from the reaction bath. The microstructural characterization reveals that at the initial stage of synthesis, a single-phase solid solution of alloy nanoparticles of very small sizes was formed; however, as the reaction time increases, a network of chains of nanoparticles evolves containing particles rich in either Ag or Cu. Keeping the particles in the reaction bath for a longer time, the chemistry of the network changes further with the chain containing an Ag-rich core and Cu2O as the shell. In the present study, we tried to rationalize the evolution of the phases from the observed results.

Magnitude and Origin of Electrical Noise at Individual Grain Boundaries in Graphene.

Grain boundaries (GBs) are undesired in large area layered 2D materials as they degrade the device quality and their electronic performance. Here we show that the grain boundaries in graphene which induce additional scattering of carriers in the conduction channel also act as an additional and strong source of electrical noise especially at the room temperature. From graphene field effect transistors consisting of single GB, we find that the electrical noise across the graphene GBs can be nearly 10 000 times larger than the noise from equivalent dimensions in single crystalline graphene. At high carrier densities (n), the noise magnitude across the GBs decreases as ∝1/n, suggesting Hooge-type mobility fluctuations, whereas at low n close to the Dirac point, the noise magnitude could be quantitatively described by the fluctuations in the number of propagating modes across the GB.

Atomic Arrangement Modulation in CoFe Nanoparticles Encapsulated in N-Doped Carbon Nanostructures for Efficient Oxygen Reduction Reaction.

The properties and, hence, the application of materials are dependent on the way their constituent atoms are arranged. Here, we report a facile approach to produce body-centered cubic (bcc) and face-centered cubic (fcc) phases of bimetallic FeCo crystalline nanoparticles embedded into nitrogen-doped carbon nanotubes (NCNTs) with equal loading and almost similar particle size for both crystalline phases by a rational selection of precursors. The two electrocatalysts with similar composition but different crystalline structures of the encapsulated nanoparticles have allowed us, for the first time, to account for the effect of crystal structure on the overall work function of electrocatalysts and the concomitant correlation with the oxygen reduction reaction (ORR). This study unveils that the electrocatalysts with lower work function show lower activation energy to facilitate the ORR. Importantly, the difference between the ORR activation energy on electrocatalysts and their respective work functions are found to be identical (∼0.2 eV). A notable decrease in the ORR activity after acid treatment indicates the significant role of encapsulated FeCo nanoparticles in influencing the oxygen electrochemistry by modulating the material property of overall electrocatalysts.

Investigation on the structure and thermoelectric properties of CuxTe binary compounds.

Cu2Te is a superionic conductor that belongs to the Phonon Liquid Electron Crystal class of thermoelectric (TE) materials. Despite the simple chemical formula, the crystal structures and phases in the Cu2Te system have not been understood properly. In this work, we study the structural and TE properties of Cu2Te (CT2), Cu1.6Te (CT1.6) and Cu1.25Te (CT1.25). The samples were synthesized via a solid-state reaction method. Powder X-ray diffraction analysis revealed that the samples have different crystal structures depending upon the Cu : Te stoichiometry. The elemental compositional analysis showed that all the samples are copper deficient. This is due to the precipitation of metallic copper on the surface of the ingot arising from the thermal dissociation of Cu2Te. The transport properties were measured in the temperature range 300 K-600 K. The electrical conductivity (σ) decreases with an increase in temperature indicating a metal-like behaviour for all the samples. The positive Seebeck coefficients (S) for all the samples indicates that majority charge carriers are holes. The sample CT2 has a higher S (29.5 µV K-1 at 573 K) and a lower σ (2513 S cm-1 at 573 K) due to a lower carrier (hole) concentration compared to the other two samples. With the increase in Cu deficiency, the hole concentration increases, and this leads to higher electronic thermal conductivity in the samples CT1.6 and CT1.25. The maximum thermoelectric figure of merit of 0.03 at 524 K is achieved for the sample CT2 owing to its higher power factor (0.24 mW m-1 K-2) and lower thermal conductivity (3.8 W m-1 K-1). The present study bridges the gap between the theoretical predictions and experimental observations involving the various possible structures in this system. Furthermore, we have shown that the Cu vacancies are detrimental to the thermoelectric performance of Cu2Te.

Phase transformation in nanoscale indium-tin alloy particles embedded in metallic matrices.

The interfaces influence the phase stability of small particles. For embedded indium-tin alloy particles, the interface among the phases present within the particles and the matrix contribute significantly to the free energy and hence influences the phase stability at small sizes. Our results show that upon rapid cooling, we obtain a combination of larger two-phase alloy particles consisting of beta- and y-phases and very fine precipitates of In or Sn. Both beta- and gamma-phases possess an orientation relationship with Al. The in situ results suggest that the beta-rich phase gradually dissolved in the eutectic liquid before melting and the particles retain the facets much above the melting temperature of the alloy particle. We have tried to explain the formation and stability of these phases in terms of favorable nucleation kinetics.

Enhancing elevated temperature strength of copper containing aluminium alloys by forming L12 Al3Zr precipitates and nucleating θ″ precipitates on them.

Strengthening by precipitation of second phase is the guiding principle for the development of a host of high strength structural alloys, in particular, aluminium alloys for transportation sector. Higher efficiency and lower emission demands use of alloys at higher operating temperatures (200 °C-250 °C) and stresses, especially in applications for engine parts. Unfortunately, most of the precipitation hardened aluminium alloys that are currently available can withstand maximum temperatures ranging from 150-200 °C. This limit is set by the onset of the rapid coarsening of the precipitates and consequent loss of mechanical properties. In this communication, we present a new approach in designing an Al-based alloy through solid state precipitation route that provides a synergistic coupling of two different types of precipitates that has enabled us to develop coarsening resistant high-temperature alloys that are stable in the temperature range of 250-300 °C with strength in excess of 260 MPa at 250 °C.

Metal Immiscibility Route to Synthesis of Ultrathin Carbides, Borides, and Nitrides.

Ultrathin ceramic coatings are of high interest as protective coatings from aviation to biomedical applications. Here, a generic approach of making scalable ultrathin transition metal-carbide/boride/nitride using immiscibility of two metals is demonstrated. Ultrathin tantalum carbide, nitride, and boride are grown using chemical vapor deposition by heating a tantalum-copper bilayer with corresponding precursor (C2 H2 , B powder, and NH3 ). The ultrathin crystals are found on the copper surface (opposite of the metal-metal junction). A detailed microscopy analysis followed by density functional theory based calculation demonstrates the migration mechanism, where Ta atoms prefer to stay in clusters in the Cu matrix. These ultrathin materials have good interface attachment with Cu, improving the scratch resistance and oxidation resistance of Cu. This metal-metal immiscibility system can be extended to other metals to synthesize metal carbide, boride, and nitride coatings.

Morphogenesis and mechanostabilization of complex natural and 3D printed shapes.

The natural selection and the evolutionary optimization of complex shapes in nature are closely related to their functions. Mechanostabilization of shape of biological structure via morphogenesis has several beautiful examples. With the help of simple mechanics-based modeling and experiments, we show an important causality between natural shape selection as evolutionary outcome and the mechanostabilization of seashells. The effect of biological growth on the mechanostabilization process is identified with examples of two natural shapes of seashells, one having a diametrically converging localization of stresses and the other having a helicoidally concentric localization of stresses. We demonstrate how the evolved shape enables predictable protection of soft body parts of the species. The effect of bioavailability of natural material is found to be a secondary factor compared to shape selectivity, where material microstructure only acts as a constraint to evolutionary optimization. This is confirmed by comparing the mechanostabilization behavior of three-dimensionally printed synthetic polymer structural shapes with that of natural seashells consisting of ceramic and protein. This study also highlights interesting possibilities in achieving a new design of structures made of ordinary materials which have bio-inspired optimization objectives.

Phase separating bulk metallic glass: a hierarchical composite.

Phase separating systems present a unique opportunity for designing composites with hierarchical microstructure at different length scales. We report here our success in synthesizing phase separating metallic glasses exhibiting the entire spectrum of microstructural possibilities expected from a phase separating system. In particular, we report novel core shell and hierarchical structures of spherical glassy droplets, resulting from critical wetting behavior and limited diffusion. We also report synthesis of a bulk phase separating glass in a metallic glass system. The combination of unique core shell and hierarchical structures in metallic glass systems opens a new avenue for the microstructure design of metallic glasses.