Arunava Gupta

A new family of highly uniform, cubic-shaped Cu₃VS_xSe_4−x (CVSSe; 0 ≤ x ≤ 4) nanocrystals based on earth-abundant materials with intermediate bandgaps (IB) in the visible range is reported, synthesized via a hot-injection method. The IB transitions and optical band gap of the novel CVSSe nanocrystals are investigated using ultraviolet-visible spectroscopy, revealing tunable band gaps that span the visible and near-infrared regimes. The composition-dependent relationships among the crystal phase, optical band gap, and photoluminescence properties of the novel IB semiconductors with progressive substitution of Se by S are examined in detail. High-resolution transmission electron microscopy and scanning electron microscopy characterization confirm the high crystallinity and uniform size (~19.7 nm × 17.2 nm for Cu₃VS₄) of the cubic-shaped nanocrystals. Density functional theory (DFT) calculations based on virtual crystal approximation support the experimental findings, showing good agreement in lattice parameters and band gaps across the CVSSe series and lending confidence that the targeted phases and compositions have been successfully realized. A current conversion efficiency, i.e., incident photon-to-current efficiency, of 14.7% was achieved with the p-type IB semiconductor Cu₃VS₄. These novel p-type IB semiconductor nanocrystals hold promise for enabling thin film solar cells with efficiencies beyond the Shockley–Queisser limit by allowing sub-band-gap photon absorption through intermediate-band transitions, in addition to the conventional direct-band-gap transition.

NiFe2O4 has gained significant attention from the scientific community due to its potential applications in microwave integrated devices, magnetoelectric coupling heterostructures, and spintronic devices such as spin filters. In this work, we explore the element specific ultrafast dynamics of NiFe2O4 films grown on ZnGa2O4 and MgAl2O4 with different lattice mismatches. To examine the dynamics, we utilize the transverse magneto optical Kerr effect at the extreme ultraviolet (XUV) regime, which provides access to the Fe and Ni M-edges. The demagnetization is almost concurrent with the pump pulse, suggesting that slower phonon based interactions are not crucial for the demagnetization. The reflectivity of the MAO sample is significantly higher than for the ZGO sample, which correlates well with the increased amount of free carriers. Furthermore, the reflectivity exhibits pronounced oscillations in both the Fe and Ni signals with a period of ∼2.8 ps (0.36 THz). Notably, the onset of the oscillations of the Fe is delayed by about 0.2–0.5 ps with respect to the Ni.

Epitaxial films of BiAlxFe1−xO3 (xBAFO) were grown on SrTiO3 (STO) and SrRuO3 buffered STO substrates using pulsed laser deposition. To understand the effects of Al substitution at the Fe-site of BFO, we systematically investigated its impact on the material’s crystal structure, surface morphology, ferroelectric properties, and magnetic properties. Our x-ray diffraction analysis revealed that phase-pure xBAFO films can be stabilized for Al concentrations between 0% and 35%, without the formation of secondary phases, due to the isotypic crystal structures of BiAlO3 and BiFeO3. This allowed the rhombohedral structure of BAFO to be preserved. We then characterized the ferroelectric properties of xBAFO (0≤x≤0.25 ) by analyzing polarization-voltage hysteresis loops, which exhibited a transition from a nearly square shape to a more slanted shape with increasing Al substitution. Additionally, piezoresponse force microscopy revealed that the domain growth mode, shape, size, dimension, and nucleation play a crucial role in the switching behavior of ferroelectric materials. Furthermore, we observed a modest enhancement in magnetization due to the modified spin ordering of Fe atoms with Al substitution. Notably, the optimal ferroelectric and magnetic properties were achieved at an Al concentration of 15%. These findings suggest that BAFO is a promising magnetoelectric material with desired functionalities for realizing BFO-based next-generation non-volatile memory devices.

We report on the x-ray absorption spectra (XAS) and x-ray magnetic circular dichroism (XMCD) of a series of NiFe2O4 (Ni ferrite) films grown on symmetry matched substrates and measured in two geometries: out-of-plane and near in-plane. The Ni ferrite films, grown by pulsed laser deposition, are epitaxial and the substrates used (ZnGa2O4, CoGa2O4, MgGa2O4, and MgAl2O4) introduce a systematic variation in the lattice mismatch between the substrate and the film. Modeling of the XAS and XMCD spectra, both measured with the surface sensitive total electron yield mode, indicates that the Ni2+ cations reside on the octahedrally coordinated lattice sites in the spinel structure. Analyses of the Fe XAS and XMCD spectra are consistent with Fe3+ cations occupying a subset of the octahedral and tetrahedral sites in the spinel oxide lattice with the addition of a small amount of Fe2+ located on octahedral sites. The Ni2+ orbital to spin moment ratio (μℓ/μs), derived from the application of XMCD sum rules, is enhanced for the substrates with a small lattice mismatch relative to NiFe2O4. The results suggest a path for increasing the orbital moment in NiFe2O4 by applying thin film growth techniques that can maintain a highly strained lattice for the NiFe2O4 film.

Transition-metal chalcogenide nanostructures provide a unique material platform to engineer next-generation energy storage devices such as lithium-ion, sodium-ion, and potassium-ion batteries and flexible supercapacitors. The transition-metal chalcogenide nanocrystals and thin films have enhanced electroactive sites for redox reactions and hierarchical flexibility of structure and electronic properties in the multinary compositions. They also consist of more earth-abundant elements. These properties make them attractive and more viable new electrode materials for energy storage devices compared to the traditional materials. This review highlights the recent advances in chalcogenide-based electrodes for batteries and flexible supercapacitors. The viability and structure–property relation of these materials are explored. The use of various chalcogenide nanocrystals supported on carbonaceous substrates, two-dimensional transition metal chalcogenides, and novel MXene-based chalcogenide heterostructures as electrode materials to improve the electrochemical performance of lithium-ion batteries is discussed. The sodium-ion and potassium-ion batteries offer a more viable alternative to lithium-ion technology as they consist of readily available source materials. Application of various transition metal chalcogenides such as MoS₂, MoSe₂, VS₂, and SnS_x, composite materials, and heterojunction bimetallic nanosheets composed of multi-metals as electrodes to enhance the long-term cycling stability, rate capability, and structural strength to counteract the large volume expansion during the ion intercalation/deintercalation processes is highlighted. The promising performances of layered chalcogenides and various chalcogenide nanowire compositions as electrodes for flexible supercapacitors are also discussed in detail. The review also details the progress made in new chalcogenide nanostructures and layered mesostructures for energy storage applications.

The current need to accelerate the adoption of photovoltaic (PV) systems has increased the need to explore new nanomaterials that can harvest and convert solar energy into electricity. Transition metal dichalcogenides (TMDCs) are good candidates because of their tunable physical and chemical properties. CuCrS₂ has shown good electrical and thermoelectrical properties; however, its optical and photoconductivity properties remain unexplored. In this study, we synthesized CuCrS₂ nanosheets with average dimensions of 43.6 ± 6.7 nm in length and 25.6 ± 4.1 nm in width using a heat-up synthesis approach and fabricated films by the spray-coating method to probe their photoresponse. This method yielded CuCrS₂ nanosheets with an optical bandgap of ~1.21 eV. The fabricated film had an average thickness of ~570 nm, exhibiting a net current conversion efficiency of ~11.3%. These results demonstrate the potential use of CuCrS₂ as an absorber layer in solar cells.