Integrated experimental and theoretical studies on structural and magnetic properties of thin films of double perovskite ruthenates: Ba2DyRuO6 & Sr2DyRuO6.

Thin films of double perovskite ruthenates, viz., Ba2DyRuO6 (BDRO) and Sr2DyRuO6 (SDRO), have been successfully grown on a SrTiO3 substrate using the pulsed laser deposition technique. The BDRO samples crystallizes in cubic structure, while SDRO exhibits monoclinic structure as revealed in their X-Ray diffraction examination. Temperature-dependent magnetization measurements suggest the presence of ferromagnetism in BDRO, while paramagnetism is present for the SDRO thin film. Surprisingly, both films show canted antiferromagnetism at ∼T = 5 K as revealed in their isothermal magnetization curves. The inverse susceptibility has been fitted to the Curie-Weiss law for the SDRO sample, where the Curie temperature (TC ∼ -336.6 K) has been obtained, thus suggesting the prevalence of antiferromagnetic interactions. The existence of the canted magnetism at a lower temperature may be attributed to the Dzyaloshinskii-Moriya (D-M) interactions in the monoclinic SDRO sample due to structural distortion. However, the emergence of canted antiferromagnetism at lower temperatures (5 K) in the BDRO sample with cubic symmetry having no D-M interactions may be attributed to the various modifications at the surface of the thin films. Overall, a comparison made between the magnetic properties of both the thin films i.e., BDRO & SDRO, reveals the suppression of bulk magnetic ordering when compared to their bulk counterparts. The possible reason for the absence of any magnetic ordering in these thin films may be due to any modifications in superexchange interactions, any exchange bias, stress-strain, or uncompensated spins present in these types of thin films. UV-visible measurements for both the samples reveal a direct influence of the A-site element (Sr/Ba) on their band gaps, i.e., 3.66 eV and 2.59 eV for BDRO and SDRO samples, respectively, hence suggesting their insulating nature. We have also carried out first principles calculations with DFT using the CASTEP software to gain more insights into the experimental data. These thin films with insulating-antiferromagnetic properties may be crucial for "spintronics devices".

Lattice defect-formulated ferromagnetism and UV photo-response in pure and Nd, Sm substituted ZnO thin films.

The induction of charge and spin in diluted magnetic semiconductor ZnO is explored for spintronic devices and its wide direct band gap (3.37 eV) and large exciton binding energy (60 meV) exhibit potential in UV photodetectors. We reported the ferromagnetic and optical properties of pure ZnO, Zn0.97Nd0.03O and Zn0.97Sm0.03O thin films. These thin films were synthesized by a metallo-organic decomposition method and annealed at 500 °C for 7 h. Rietveld refinement of the XRD data results in a wurtzite ZnO structure with Nd, Sm doping. The dopants and nanoparticle size are responsible for wurtzite structural deformation, inducing lattice strain effect, which may influence the band gap energy and high-TC ferromagnetism of ZnO. The average size of ZnO nanoparticles with Nd, Sm doping is 10 nm, confirmed with atomic force microscopy. The Raman spectra confirm the wurtzite structure of ZnO with crystalline quality and lattice defect formation with dopant Nd, Sm ions. A near-band-edge emission due to band gap energy is evaluated with photoluminescence spectra, which also involved multiple visible emissions due to oxygen vacancies. The oxygen vacancies-mediated magnetic interactions impart room temperature ferromagnetism in pure ZnO which is enhanced with Nd, Sm doping. The electron paramagnetic resonance spectra revealed the effects of defects and unpaired electrons responsible for observed room temperature ferromagnetism. The zero field cooling and field cooling magnetic measurements include antiferromagnetic interactions without any spin-glass formation. The observed ferromagnetism also correlates with first principle calculations reported for Nd, Sm-doped ZnO and suggests long-range ferromagnetic ordering attributed to defect carriers. The Nd, Sm doping into ZnO thin films significantly enhances absorption in the UV region and suggests its usability for UV detectors. Under UV irradiation (λ = 325 nm), the value of photocurrent in Nd, Sm:ZnO thin films is highly enhanced for possible use in UV sensors.

Mechanistic insights into the interaction between energetic oxygen ions and nanosized ZnFe2O4: XAS-XMCD investigations.

The interactions of energetic ions with multi-cation compounds and their consequences in terms of changes in the local electronic structure, which may facilitate intriguing hybridization between O 2p and metal d orbitals and magnetic ordering, are the subject of debate and require a deep understanding of energy transfer processes and magnetic exchange mechanisms. In this study, nanocrystals of ZnFe2O4 were exposed to O7+ ions with an energy of 100 MeV to understand, qualitatively and quantitatively, the metal-ligand field interactions, cation migration and magnetic exchange interactions by employing X-ray absorption fine structure measurements and X-ray magnetic circular dichroism to get deeper mechanistic insights. Nanosized zinc ferrite nanoparticles (NPs) with a size of ∼16 nm synthesized in the cubic spinel phase exhibited deterioration of the crystalline phase when 100 MeV O7+ ions passed through them. However, the size of these NPs remained almost the same. The behaviour of crystal deterioration is associated with the confinement of heat in this interaction. The energy confined inside the nanoparticles promotes cation redistribution as well as the modification of the local electronic structure. Prior to this interaction, almost 42% of Zn2+ ions occupied AO4 tetrahedra; however, this value increased to 63% after the interaction. An inverse effect was observed for metal ion occupancies in BO6 octahedra. The L-edge spectra of Fe and Zn reveal that the spin and valence states of the metal ions were not affected by this interaction. This effect is also supported by K-edge measurements for Fe and Zn. The t2g/eg intensity ratio in the O K-edge spectra decreased after this interaction, which is associated with detachment of Zn2+ ions from the lattice. The extent of hybridization, as estimated from the ratio of the post-edge to the pre-edge region of the O K-edge spectra, decreased after this interaction. The metal-oxygen and metal-metal bond lengths were modified as a result of this interaction, as determined from extended X-ray absorption fine structure measurements. These measurements further support the observation of cation migration from AO4 tetrahedra to AO6 octahedra and vice versa. The Fe L-edge magnetic circular dichroism spectra indicate that Fe3+ ions occupying sites in AO4 tetrahedra and BO6 octahedra exhibited antiferromagnetic-like ordering prior to this interaction. The NPs that interacted with energetic O ions displayed a different kind of magnetic ordering.

Surface plasmon band tailoring of plasmonic nanostructure under the effect of water radiolysis by synchrotron radiation.

Plasmonic metal nanostructures have a significant impact on a diverse domain of fields, including photocatalysis, antibacterial, drug vector, biosensors, photovoltaic cell, optical and electronic devices. Metal nanoparticles (MNps) are the simplest nanostructure promising ultrahigh stability, ease of manufacturing and tunable optical response. Silver nanoparticles (AgNp) dominate in the class of MNps because of their relatively high abundance, chemical activity and unique physical properties. Although MNps offer the desired physical properties, most of the synthesis and fabrication methods lag at the electronic grade due to an unbidden secondary product as a result of the direct chemical reduction process. In this paper, a facile protocol is presented for fabricating high-yield in situ plasmonic AgNps under monochromatic X-rays irradiation, without the use of any chemical reducing agent which prevents the formation of secondary products. The ascendancy of this protocol is to produce high quantitative yield with control over the reaction rate, particle size and localized surface plasmon resonance response, and also to provide the feasibility for in situ characterization. The role of X-ray energy, beam flux and integrated dose towards the fabrication of plasmonic nanostructures has been studied. This experiment extends plasmonic research and provides avenues for upgrading production technologies of MNps.

MOF/graphene oxide based composites in smart supercapacitors: a comprehensive review on the electrochemical evaluation and material development for advanced energy storage devices.

The surge in interest surrounding energy storage solutions, driven by the demand for electric vehicles and the global energy crisis, has spotlighted the effectiveness of carbon-based supercapacitors in meeting high-power requirements. Concurrently, metal-organic frameworks (MOFs) have gained attention as a template for their integration with graphene oxide (GO) in composite materials which have emerged as a promising avenue for developing high-power supercapacitors, elevating smart supercapacitor efficiency, cyclic stability, and durability, providing crucial insights for overcoming contemporary energy storage obstacles. The identified combination leverages the strengths of both materials, showcasing significant potential for advancing energy storage technologies in a sustainable and efficient manner. In this research, an in-depth review has been presented, in which properties, rationale and integration of MOF/GO composites have been critically examined. Various fabrication techniques have been thoroughly analyzed, emphasizing the specific attributes of MOFs, such as high surface area and modifiable porosity, in tandem with the conductive and stabilizing features of graphene oxide. Electrochemical characterizations and physicochemical mechanisms underlying MOF/GO composites have been examined, emphasizing their synergistic interaction, leading to superior electrical conductivity, mechanical robustness, and energy storage capacity. The article concludes by identifying future research directions, emphasizing sustainable production, material optimization, and integration strategies to address the persistent challenges in the field of energy storage. In essence, this research article aims to offer a concise and insightful resource for researchers engaged in overcoming the pressing energy storage issues of our time through the exploration of MOF/GO composites in smart supercapacitors.

Enhanced electrochemical performance of Ce-MOF/h-CeO2 composites for high-capacitance energy storage applications.

The escalating demand for energy storage underscores the significance of supercapacitors as devices with extended lifespans, high energy densities, and rapid charge-discharge capabilities. Ceria (CeO2), known for its exceptional properties and dual oxidation states, emerges as a potent material for supercapacitor electrodes. This study enhances its capacitance by integrating it with Metal-Organic Frameworks (MOFs), carbon-rich compounds noted for their good conductivity. In our research, hollow ceria (h-ceria) is synthesized via hydrothermal methods and amalgamated with Ce-MOF, employing 2,6-dinaphthalene dicarboxylic acid as a ligand, to fabricate Ce-MOF@h-CeO2 composites. The structural and morphological characteristics of the composite are methodically examined using X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), and Fourier-Transform Infrared (FT-IR) spectroscopy. The band gap of the materials is ascertained through UV-Diffuse Reflectance Spectroscopy (UV-DRS). Electrochemical behavior and redox properties of the Ce-MOF composites are explored using Cyclic Voltammetry (CV), Galvanostatic Charge and Discharge (GCD), and Electrochemical Impedance Spectroscopy (EIS), providing insights into the material's stability. Electrochemical characterization of the composite reveals maximum specific capacitance, energy density and power density are 2643.78 F g-1 at a scan rate of 10 mV s-1, 249.22 W h kg-1, and 7.9 kW kg-1, respectively. Additionally, the specific capacitance of Ce-MOF synthesized with a 2,6-dinaphthalene dicarboxylic acid (NDC) ligand reaches 995.59 F g-1, surpassing that of Ce-MOF synthesized using a 1,3,5-tricarboxylic acid (H3BTC) ligand. These findings highlight the promising economic potential of high-performance, environmentally sustainable, and cost-effective energy storage devices. The innovative Ce-MOF@h-CeO2 composite materials at the core of this research pave the way for advancing the field of energy storage solutions.

Enhancement of Fracture Toughness in carbonate doped Hydroxyapatite based nanocomposites: Rietveld analysis and Mechanical behaviour.

Highly nanocrystalline carbonated hydroxyapatite (CHAp) is synthesized by hydrothermal technique with four different stoichiometric compositions for microstructural and mechanical analysis. HAp is one of the most biocompatible material and addition of carbonate ions lead to increase in fracture toughness highly required in biomedical applications. The structural properties and its purity as single phase is confirmed by X-ray diffraction. Lattice imperfections and structural defects is investigated using XRD pattern model simulation, i.e. Rietveld's analysis. The substitution of CO32- in HAp structure leads to a decrease in crystallinity which ultimately lessens crystallite size of sample as verified by XRD analysis. FE-SEM micrographs confirms the formation of nanorods with cuboidal morphology and porous structure of HAp and CHAp samples. The particle size distribution histogram validates the constant decrease in size due to carbonate addition. The mechanical testing of prepared samples revealed the increase in mechanical strength from 6.12 MPa to 11.52 MPa due to the addition of carbonate content, which leads to a rise in fracture toughness, a significant property of an implant material from 2.93 kN to 4.22 kN. The cumulative effect of CO32- substitution on HAp structure and mechanical properties has been generalized for the application as biomedical implant material or biomedical smart materials.

Charge transfer and X-ray absorption investigations in aluminium and copper co-doped zinc oxide nanostructure for perovskite solar cell electrodes.

This study explores influence of charge transfer and X-ray absorption characteristics in aluminum (Al) and copper (Cu) co-doped zinc oxide (ZnO) nanostructures for perovskite solar cell electrodes. Sol-gel technique was employed to synthesize the nanostructures, and their optical and morphological properties were investigated. X-ray diffraction (XRD) analysis confirmed high crystallinity and also single-phase composition of all the samples, particularly up to 5% Al co-doping. Field emission scanning electron microscopy (FESEM) exhibited the formation of pseudo-hexagonal wurtzite nanostructure and the transition to nanorods at 5% Al co-doping. Diffuse reflectance spectroscopy indicated a reduction in the optical band gap of co-doped zinc oxide from 3.11 to 2.9 eV with increasing Al doping. Photoluminescence spectra (PL) exhibited a decrease in peak intensity, suggesting enhanced conductivity in ZnO, also confirmed from I-V measurements. Near-edge X-ray absorption fine structure (NEXAFS) analysis depicts that charge transfer from Al to oxygen (O) species enhanced the photosensing properties of the nanostructure, which was supported by FESEM micrographs and PL spectra. Furthermore, the study discovered that 5% Al co-doping significantly reduced the density of emission defects (deep-level) in Cu-ZnO nanostructure. These findings highlight the potential of Cu and Al co-doped ZnO materials for perovskite solar cell electrodes, as their improved optical and morphological properties resulting from charge transfer could enhance device performance. The investigation of charge transfer and X-ray absorption characteristics provides valuable insights into the underlying mechanisms and behaviors of the co-doped ZnO nanostructures. However, further research is required to delve into the intricate hybridization resulting from charge transfer and explore the broader impact of co-doping on other properties of the nanostructures, enabling a comprehensive understanding of their potential applications in perovskite solar cells.

In-vitro pH-responsive release of imatinib from iron-supplement coated anatase TiO2 nanoparticles.

Targeted drug delivery is one such precision method of delivering medication inside the human body which can vanquish all the limitations of the conventional chemotherapeutic techniques. In the present study, two types of nanoparticles (NPs) were chosen for the in-vitro pH-responsive release study of the drug, Imatinib, namely anatase Titanium Dioxide nanoparticles (TiO2 NPs) and iron-capped TiO2 NPs, designated as Fe@TiO2 NPs. The novelty of this work lies behind the use of commercially available iron supplement 'Autrin' meant for human consumption, as the material to coat the TiO2 NPs to synthesize Fe@TiO2 NPs. The synthesized NPs were analyzed by XRD, HR-TEM, SAED, EDX and VSM. UV-Vis spectroscopy was performed for absorption studies. Fe@TiO2 NPs showed superparamagnetic behavior and thus they are able to ensure the facile transfer of Imatinib via external magnetic fields. The results obtained from in-vitro drug release studies depicted that both TiO2 NPs and Fe@TiO2 NPs showed a controlled pH-sensitive delivery of the loaded Imatinib molecules. Moreover, both types of NPs do not result in the formation of ROS under human physiological conditions. These results can lay the foundation to the development of efficacious targeted drug delivery systems in the healthcare sector.

Synthesizing and Optimizing Rutile TiO2 Nanoparticles for Magnetically Guided Drug Delivery.

Introduction: Titanium dioxide nanoparticles (TiO2 NPs) have shown tremendous potential in targeted drug-delivery applications. Among various mechanisms, magnetically guided transport of drugs is one such technique for the said purpose. TiO2 NPs being diamagnetic or sometimes exhibiting very weak ferromagnetism can be modified by treating them with suitable magnetic materials. Methods: Rutile TiO2 NPs were synthesized and doped with Iron Supplement FericipXT and rare-earth metals like cerium, erbium and neodymium via sol-gel technique. FericipXT-coated rutile TiO2 NPs were synthesized in three different core-shell ratios (1:3, 1:1 and 3:1). The resulting samples were characterized via X-ray Diffraction (XRD), Vibrating Sample Magnetometer (VSM) and High-Resolution Transmission Electron Microscopy (HR-TEM). Results: XRD of FericipXT-doped TiO2 NPs showed a rutile phase for 1% and 3% doping; however, only a small fraction of the maghemite phase was obtained for 5% doping. The XRD plots of Ce-doped, Er-doped and Nd-doped TiO2 NPs showed a variety of phases of TiO2 NPs (such as anatase/rutile/mixed) along with the oxide phases of the corresponding rare-earth metal. The presence of various iron titanium oxides and iron oxides was found in core-shell NPs. HR-TEM images confirmed the formation of 1:3, 1:1 and 3:1 core-shell TiO2 NPs. VSM studies showed that the resulting NPs depicted magnetism in the form of superparamagnetism, ferromagnetism and even paramagnetism. Discussion: The doping to 3% does not affect the original phase of the resulting TiO2 NPs as depicted from the XRD; however, a doping of 5% and more resulted in extra phases corresponding to the dopant added. FericipXT was loaded over TiO2 NPs in amorphous form. Among all the samples synthesized, FericipXT-coated TiO2 NPs demonstrated the best magnetic ability. It was deduced that coating with a magnetic material drastically improves the magnetic character of the host NPs.

Rapid green-synthesis of TiO2 nanoparticles for therapeutic applications.

Nanoparticles (NPs) with sizes ranging from 2 nm to 1 µm find various applications in the field of theranostics. Moreover, if eco-friendly methods are opted for the synthesis of biocompatible and less toxic NPs, then that's a huge success. Titanium dioxide nanoparticles (TiO2 NPs) have been vigorously studied for their use in medical implants, photodynamic therapy, drug delivery, biosensing and as antimicrobial agents. The present study reports the green-synthesis of TiO2 NPs for the first-time using extracts of black pepper (Piper nigrum), coriander (Coriandrum sativum) and clove (Syzygium aromaticum). All three samples of TiO2 NPs were synthesized via a modified sol-gel method under similar environmental conditions. Similar treatments were given to the samples. The procedure adopted for the synthesis ensures the use of non-toxic materials, no production of toxic by-products and rapid synthesis of the TiO2 NPs. The NPs were characterized by X-ray diffraction, high resolution-transmission electron microscopy, energy dispersive spectroscopy, field emission scanning electron microscopy and selected area electron diffraction which confirmed the formation, morphology, crystallinity and size of the TiO2 NPs. These characterizations displayed the similarity index of all three samples. However, photoluminescence and vibrating sample magnetometer studies highlighted the differences among the three samples. All three samples of NPs obtained had a size range of 5-20 nm. Further, the findings showed that different plant extracts result in TiO2 NPs with moderately different characteristics. Furthermore, the samples were analysed for their drug-encapsulation efficiency using UV-visible spectrophotometry. Among all three samples, the NPs synthesised using black pepper exhibited the maximum encapsulation efficiency. The study concludes that the plant's bio-profile is responsible for bringing about changes in the traits of the resulting nanoparticles. Thus, the extracts from different plants have the ability to manipulate the properties of the synthesized NPs. These findings can help to understand the role and importance of the plants in synthesizing NPs for biomedical applications. A further detailed study in this field can help researchers to understand the influence of the plant's biochemistry in shaping the NPs.

Real-time synthesis and detection of plasmonic metal (Au, Ag) nanoparticles under monochromatic X-ray nano-tomography.

Plasmonic nanostructures are of immense interest of research due to its widespread applications in microelectronics, photonics, and biotechnology, because of its size and shape-dependent localized surface plasmon resonance response. The great efforts have been constructed by physicists, chemists, and material scientists to deliver optimized reaction protocol to tailor the size and shape of nanostructures. Real-time characterization emerges out as a versatile tool in perspective to the optimization of synthesis parameters. Moreover, in the past decades, radiation-induced reduction of metallic-salt to nanoparticles dominates over the conventional direct chemical reduction process which overcomes the production of secondary products and yields ultra-high quality and pure nanostructures. Here we show, the real-time/in-situ synthesis and detection of plasmonic (Au andAg) nanoparticles using single synchrotron monochromatic 6.7 keV X-rays based Nano-Tomography beamline. The real-time X-ray nano-tomography of plasmonic nanostructures has been first-time successfully achieved at such a low-energy that would be leading to the possibility of these experiments at laboratory-based sources. In-situ optical imaging confirms the radiolysis of water molecule resulting in the production of [Formula: see text] and [Formula: see text] under X-ray irradiation. The obtained particle-size and size-distribution by X-ray tomography are in good agreement to TEM results. The effect of different chemical environment media on the particle-size has also been studied. This work provides the protocol to precisely control the size of nanostructures and to synthesize the ultrahigh-purity grade monodisperse nanoparticles that would definitely enhance the phase-contrast in cancer bio-imaging and plasmonic photovoltaic application.

Influence of Cu doping on the local electronic and magnetic properties of ZnO nanostructures.

In this paper, we report the existence of defect induced intrinsic room-temperature ferromagnetism (RTFM) in Cu doped ZnO synthesized via a facile sol-gel route. The wurtzite crystal structure of ZnO remained intact up to certain Cu doping concentrations under the present synthesis environment as confirmed by the Rietveld refined X-ray diffraction pattern with the average crystallite size between 35 and 50 nm. Field emission scanning electron microscopy reveals the formation of bullet-like morphologies for pure and Cu doped ZnO. Diffuse reflectance UV-vis shows a decrease in the energy band gap of ZnO on Cu doping. Further, these ZnO samples exhibit strong visible photoluminescence in the region of 500-700 nm associated with defects/vacancies. Near-edge X-ray absorption fine-structure measurements at Zn, Cu L3,2- and O K-edges ruled out the existence of metallic Cu clusters in the synthesized samples (up to 2% doping concentration) supporting the XRD results and providing the evidence of oxygen vacancy mediated ferromagnetism in Cu : ZnO systems. The observed RTFM in Cu doped ZnO nanostructures can be explained by polaronic percolation of bound magnetic polarons formed by oxygen vacancies. Further, extended X-ray absorption fine-structure data at Zn and Cu K-edges provide the local electronic structure information around the absorbing (Zn) atom. The above findings for ZnO nanostructures unwind the cause of magnetism and constitute a significant lift towards realizing spin-related devices and optoelectronic applications.

Structural and electronic investigation of ZnO nanostructures synthesized under different environments.

An explicit study of comparison on the basis of structure and electronic properties of ZnO nanostructures was discussed. ZnO synthesized by sol-gel and hydrothermal method without using any surfactant leads to the formation of two different morphologies. Rietveld crystal structure refinement of X-ray diffraction patterns confirmed the wurtzite structure of both samples. Raman spectra also confirmed the wurtzite phase formation and improved crystallinity in sample synthesized by hydrothermal route that are concurrent with results obtained from X-ray diffraction. Field-emission scanning electron microscopy revealed the formation of ZnO spherical nanoparticle structure for sol-gel method and flower like µ-structure for ZnO prepared through hydrothermal route. Williamson-Hall equations applied to study the strain and stress parameters present in the material, show the decrease in their values as the crystal size increases. Energy band gap is calculated using diffused reflectance spectroscopy. Near-edge X-ray absorption fine-structure measurements at O K- and Zn L3,2- edges simulated with FEFF9.05 code confirmed the presence of oxygen vacancies. Further extended x-ray absorption fine-structure revealed a similar local atomic structure for both samples despite having different morphologies.

Monochromatic X-Ray Induced Novel Synthesis of Plasmonic Nanostructure for Photovoltaic Application.

It has been universally delineated that the plasmonic metal nanoparticles can enhance the efficiency of photovoltaic cell by increasing the probability of energetic solar photons capturing phenomena using localized surface plasmonic resonance response. In this paper, we developed a novel in-situ simple approach to synthesize noble plasmonic silver nanoparticles (AgNP) from aqueous poly-vinyl-pyrrolidone solution of metal salt using radiolysis of water via synchrotron monochromatic X-ray irradiation without any chemical reducing agent. X-ray irradiation of water produces hydrated electrons (e(-)aq), superoxide (O(-)2) and atom radicals H*, which triggers the reaction and reduces metal salt. X-ray radiolysis based synthesis provides the control over the reaction and prevent the formation of secondary products as occurs in case of chemical reduction route. In the previous studies, synchrotron "white" X-rays had been examined for the synthesis of metal nanoparticles, but that technique limits only upto the material synthesis while in this work we explored the role of "monochromatic" X-rays for the production of bulk amount of nanoparticles which would also provide the feasibility of in-situ characterization. Transmission electron micrographs show that the synthesized AgNP appears spherical with diameter of 2-6 nm and is in agreement with the size estimation from uv-vis spectra by "Mie theory".