arXiv subjects

S. Assa Aravindh

Publications and source records attributed to S. Assa Aravindh.

9 recordsLinked to original sources

arXiv2025

Suppression of stripe-ordered structural phases in monolayer IrTe$_2$ by a gold substrate

Metal-assisted exfoliation of two-dimensional (2D) materials has emerged as an efficient route to isolating large-area monolayer crystals, yet the influence of the supporting metal substrate on their intrinsic properties remains poorly understood. Here, we demonstrate successful gold-assisted exfoliation of monolayer IrTe$_2$ up to the millimeter scale. Angle-resolved photoemission spectroscopy (ARPES), combined with first-principles calculations, reveals that the low-energy electronic structure closely resembles that of a freestanding monolayer 1T-IrTe$_2$. We find that quasi-covalent hybridization together with substrate-induced strain leads to only modest modifications of the electronic bands. Although strain contributes to phase stability, it is essentially hybridization that drives the stabilization of the 1T-phase of the monolayer IrTe$_2$ by suppressing stripe-ordered phase transitions. These results establish gold-assisted exfoliation as a robust route to prepare a large-area monolayer IrTe$_2$ and highlight the role of metal-substrate interaction in engineering 2D materials with tailored structural phases.

cond-mat.mtrl-sci↗

arXiv2024

Tuning the Electronic Properties of Two-Dimensional Lepidocrocite Titanium Dioxide Based Heterojunctions

Two-dimensional (2D) heterostructures reveal novel physicochemical phenomena at different length scales, that are highly desirable for technological applications. We present a comprehensive density functional theory study of van der Waals (vdW) heterostructures constructed by stacking 2D TiO2 and 2D MoSSe monolayers to form TiO2-MoSSe heterojunction. The heterostructure formation is found to be exothermic, indicating stability. We find that by varying the atomic species at the interfaces the electronic structure can be considerably altered, due to the differences in charge transfer, arising from the inherent electronegativity of the atoms. We demonstrate that the heterostructures possess a type II or type III band alignment, depending on the atomic termination of MoSSe at the interface. The observed charge transfer occurs from MoSSe to TiO2. Our results suggest that Janus interface enables the tuning of electronic properties, providing understanding of the possible applications of the TiO2-MoSSe heterostructure.

cond-mat.mtrl-sci↗

arXiv2024

Tailoring the electronic properties of TiO$_2$ monolayers for solar driven catalysis through transition metal doping

Substitutional doping with transition metals is carried out in the Lepidocrocite phase - the stable monolayer geometry of TiO$_2$, using density functional theory (DFT) methods. The doping is carried out at the differently coordinated O atom cites, producing Janus monolayer geometries. Our results indicate that key fundamental properties for photocatalysis can be tuned via doping. Monolayers doped with Ag, Au, Pd and Pt are thermodynamically stable, amongst all considered doping possibilities, as evident from phonon band structure calculations. Electronic structure of the Janus monolayers alters significantly, compared to pristine TiO$_2$, owing to the emergence of mid-gap states. Reduced band gap arises from upward shift of the valence band, suggesting enhanced visible-light response. Dopant atoms also introduce excess electrons in TiO$_2$ monolayers, which are found to localize at a single Ti site. This induces ferromagnetism in the doped monolayers. Furthermore, charge separation between TiO$_2$ and noble metal dopants is observed which is a key parameter in influencing the selectivity and activity of photocatalytic materials. Compared to the pristine TiO$_2$ monolayer, the Janus structure can promote water adsorption, and the Janus monolayers exhibit significantly improved activity in the hydrogen evolution reaction. These findings suggest that engineering a novel Janus TiO$_2$-based monolayer with a noble metal layer on the other surface can offer a potential approach to improve photocatalytic performance over pristine TiO$_2$.

cond-mat.mtrl-sci↗

arXiv2024

Understanding and Optimizing the Sensitization of Anatase Titanium Dioxide Surface with Hematite Clusters

The presence of small hematite (Fe2O3) clusters at low coverage on titanium dioxide (TiO2) surface has been observed to enhance photocatalytic activity, while excess loading of hematite is detrimental. We conduct a comprehensive density functional theory study of Fe2O3 clusters adsorbed on the anatase TiO2 (101) surface to investigate the effect of Fe2O3 on TiO2. Our study shows that TiO2 exhibits improved photocatalytic properties with hematite clusters at low coverage, as evidenced by a systematic study conducted by increasing the number of cluster adsorbates. The adsorption of the clusters generates impurity states in the band gap improving light absorption and consequently affecting the charge transfer dynamics. Furthermore, the presence of hematite clusters enhances the activity of TiO2 in the hydrogen evolution reaction. The Fe valence mixing present in some clusters leads to a significant increase in H2 evolution rate compared with the fixed +3 valence of Fe in hematite. We also investigate the effect of oxygen defects and find extensive modifications in the electronic properties and local magnetism of the TiO2 - Fe2O3 system, demonstrating the wide-ranging effect of oxygen defects in the combined system.

cond-mat.mtrl-sci↗

arXiv2023

Transport phenomena of TiCoSb: Defects induced modification in structure and density of states

TiCoSb1+x (x=0.0, 0.01, 0.02, 0.03, 0.04, 0.06) samples have been synthesized, employing solid state reaction method followed by arc menting. Theoretical calculations, using Density Functional Theory (DFT) have been performed to estimate band structure and density of states (DOS). Further, energitic calculations, using first principle have been carried out to reveal the formation energy for vacancy, interstitial, anti-site defects. Detail structural calculation, employing Rietveld refinement reveals the presence of embedded phases, vacancy and interstitial atom, which is also supported by the theoretical calculations. Lattice strain, crystalline size and dislocation density have been estimated by Williamson-Hall and modified Williamson-Hall methods. Thermal variation of resistivity [\r{ho}(T)] and thermopower [S(T)] have been explained using Mott equation and density of states (DOS) modification near the Fermi surface due to Co vancancy and embedded phases. Figure of merit (ZT) has been calculated and 4 to 5 times higher ZT for TiCoSb than earlier reported value is obtained at room temperature.

cond-mat.mtrl-sci↗

arXiv2021

Incorporation of Si atoms into CrCoNiFe high-entropy alloy: a DFT study

Density functional theory based computational study has been conducted in order to investigate the effect of substitution of Cr and Co components by Si on the structure, mechanical, electronic, and magnetic properties of the high entropy alloy CrCoNiFe. It is found that the presence of a moderate concentration of Si substitutes (up to 12.5 %) does not significantly reduce the structural and mechanical stability of CrCoNiFe while it may modify its electronic and magnetic properties. Based on that, Si is proposed as a cheap and functional material for partial substitution of Cr or Co in CrCoNiFe.

cond-mat.mtrl-sci↗

arXiv2016

Nature of low dimensional structural modulations and relative phase stability in MoS2/WS2-ReS2 transition metal dichalcogenide alloys

We report on the various types of Peierls like two dimensional structural modulations and relative phase stability of 2H and 1T poly-types in MoS2-ReS2 and WS2-ReS2 alloy system. Theoretical calculation predicts a polytype phase transition cross over at ~50 at.% of Mo and W in ReS2 in both monolayer and bulk form, respectively. Experimentally, two different types of structural modulations at 50% and a modulation corresponding to trimerization at 75% alloy composition is observed for MoS2-ReS2 and only one type of modulation is observed at 50% WS2-ReS2 alloy system. The 50% alloy system is found to be a suitable monolithic candidate for metal semiconductor transition with minute external perturbation. ReS2 is known to be in 2D Peierls distorted 1Td structure and forms a chain like superstructure. Incorporation of Mo and W atoms in the ReS2 lattice modifies the metal-metal hybridization between the cations and influences the structural modulation and electronic property of the system. The results offer yet another effective way to tune the electronic structure and poly-type phases of this class of materials other than intercalation, strain, and vertical stacking arrangement.

cond-mat.mtrl-sci↗

arXiv2015

Defect induced d0 ferromagnetism in a ZnO grain boundary

Several experimental studies have referred to the grain boundary (GB) defect as the origin of the ferromagnetism in ZnO. However, the mechanism of this hypothesis has never been confirmed. Present study investigates the atomic structure and the effect of point defects in a ZnO GB using the GGA+U approximation. The relaxed GB possesses large periodicity and channels with 8 and 10 numbered atoms having 4 and 3 fold coordination. Unlike O vacancy (VO), Zn vacancy (VZn) is preferentially aggregated at the GB, relative to the bulk-like region, indicating the possibility of obtaining p-type conductivity in polycrystalline ZnO. Although no magnetization is obtained from point defect-free GB, VZn induces spin polarization as large as 0.68 μB/atom to the O sites at the GB. Ferromagnetic exchange energy > 150 eV is obtained by increasing the concentration of VZn and by the injection of holes into the system. Electronic structure analysis indicates that the spin polarization without external dopants originates from the O 2p orbitals, a common feature of d0 semiconductors.

cond-mat.mtrl-sci↗

arXiv2013

Studies of FemIrn nano clusters using Density Functional Theory Techniques

The structure, binding energy, magnetic moments and electronic structure of FemIrn clusters are investigated using state of the art density functional theory techniques. Fully unconstrained structural relaxations are undertaken by considering all possible non equivalent cluster structures. The optimized clusters are all compact, indicating a clear tendency to maximize the number of nearest neighbour Fe-Ir pairs. The binding energy shows an increment with cluster size. All the clusters preserve ferromagnetic order after optimization. The average magnetic moment generally shows an increase with Fe concentration. The spin polarized density of states is largely dominated by the contribution of d orbitals. An important enhancement of the local Fe moments in an Ir rich environment is observed due to the charge transfer between Fe and Ir. On the other hand, the Ir moments are already large in the pure Ir clusters and does not show significant enhancement with Fe doping. The HOMO-LUMO gaps show a general reduction with alloying, indicating more metallicity for the doped clusters than the pure ones.

cond-mat.mes-hall↗