New approaches for the synthesis of magnetite (Fe3O4) nanoparticles (NPs) are of considerable interest due to their potential applications in various fields, such as biomedicine, industry, environmental remediation, and catalysis. This study presents a novel approach for synthesizing Fe3O4 NPs using high-energy electron beam (EB) irradiation starting from organic (acetylacetonates) iron precursors. EB irradiation is a challenging nanoparticle synthesis method, being at the same time efficient and rapid. The synthesis is carried out at room temperature and is based on the water radiolysis process. This eliminates the need for chemical-reducing agents and may provide precise control over particle formation. Using high-energy EB irradiation of an organic Fe precursor, we demonstrate the successful synthesis of well-dispersed Fe3O4 NPs with controlled size, morphology and magnetic properties, as proven by morpho-structural, Mössbauer spectroscopy and magnetic investigations. In particular, using organic iron precursors, such as iron acetylacetonates, NPs with distinct surface characteristics and improved thermal stability compared to those synthesized from inorganic precursors were obtained. These findings suggest that integrating organic precursors in EB-assisted synthesis can enhance the functional properties of Fe3O4 NPs, making them more suitable for specific applications. The versatility of this method opens up new avenues for the targeted design of nanomaterials with specific functionalities, paving the way for advanced applications in various technological fields. The current study is also motivated by the lack of literature data on the synthesis of metallic iron or iron oxide NPs mediated by EB radiolysis.
Transition-metal phosphorus trichalcogenides are a class of van der Waals materials having the potential to transform a diverse range of fields, from electronics to energy storage. Among these, nickel phosphorous trisulphide (NiPS3) is particularly interesting with its strongly correlated zig-zag antiferromagnetic insulating state below the Neel temperature, which is, of about 150 K. This study delves into the electronic properties of NiPS3 above the transition temperature, using state-of-the-art synchrotron-based techniques, including x-ray absorption spectroscopy (XAS) combined with x-ray linear dichroism (XLD) and angle-resolved photoemission spectroscopy (ARPES), in order to probe the chemical state and the momentum-resolved band structure. The experimental results, corroborated by density functional theory (DFT) calculations, unveil orbital asymmetries linked to the crystallographic lattice and the orbital content of the electronic structure, which presents a nearly flat band close to the Fermi level. Moreover, the calculated dipole matrix elements reproduce well the polarization dependence observed in valence band ARPES. Our data reveal details on the electronic properties of NiPS3, which could lead to innovative solutions and applications in areas such as advanced computing, photo-electrochemical devices, and photodetectors.
VO2-based thermochromic thin films are promising for energy-efficient smart window applications due to their reversible metal-insulator transition near 68 degrees C. However, practical limitations such as high transition temperature, limited visible transmittance and substrate compatibility remain challenges. In this study, VO2/TiO2 bilayer thin films were deposited by PLD on glass, fused silica, and quartz substrates to investigate the effect of buffer layer, film thickness, and strain on their structural, optical, and electrical properties. Comprehensive characterization using in situ grazing incidence X-ray diffraction, synchrotron GIXRD, and high-resolution Transmission Electron Microscopy revealed that TiO2 buffer layers, in the anatase or brookite phase, significantly influences the growth orientation and strain distribution in VO2 films. Residual strain mapping indicated up to 5 % compressive strain in VO2 and >10 % tensile strain in the TiO2, promoting partial stabilization of the intermediate M2 phase. Thickness-dependent studies showed a strong trade-off between optical transmittance and electrical switching amplitude: thinner films exhibited higher luminous transmittance (up to 30 %) and sharper IR switching, while thicker films yielded larger resistivity switching contrast. These results demonstrate that interfacial strain, film thickness, and substrate choice are critical parameters for tailoring VO2-based coatings and optimizing thermochromic performance for scalable smart window technologies.
Structural and electronic transport features of high quality epitaxial metastable fcc W and beta-W2N thin films compatible with spintronic multilayer nanosystems are reported in a parallel approach. The epitaxial layers have been successfully prepared in a broad range of thicknesses from a few to tens of nanometers. The scalable method of auxiliary plasma assisted substrate magnetron sputtering was used. The epitaxy relationship between the thin films and MgO (100) single-crystal substrate is highlighted by high resolution XRD investigations of the reciprocal space. Electron transport properties are discussed with respect to the striking behavior observed via resistivity over temperature cycles. The chemical stability as active buffer layers of both fcc W and beta-W2N thin films is shown in spintronic configurations, where a thin film of Fe is interposed between W or W2N layers. The reported results show that the obtained high quality W based epitaxial layers are superior template-matched buffers for epitaxial Fe layers, enabling a new class of functional spintronic heterostructures.
This study explores strategies to enhance the ionic conductivity of LiTi2(PO4)(3) (LTP), a promising NASICON-type solid electrolyte for next-generation solid-state batteries. Although LTP exhibits an open-framework structure favorable for Li+ diffusion, its intrinsic low ionic conductivity limits practical application. To address this, this research investigates the impact of co-doping titanium (Ti4+) with iron (Fe3+) and yttrium (Y3+) in Li1+xFeyYx-yTi2-x(PO4)(3) (where x = 0.3 and y = 0.1, 0.15, 0.2), aiming to increase charge carrier concentration and induce structural distortion beneficial for ion transport. Samples were synthesized via solid-state reaction and characterized by X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. The local environment of Fe3+ was further analyzed using electron paramagnetic resonance and Mossbauer spectroscopy. Spark Plasma Sintering (SPS) was employed to obtain dense ceramics and suppress secondary phase formation. The electrical properties were investigated by impedance spectroscopy over the 150K-400K temperature range, and the relaxation dynamics and conduction mechanisms were analyzed using the modulus formalism and a.c. methods conductivity. The Li1.3Fe0.15Y0.15Ti1.7(PO4)(3) composition exhibited the highest room-temperature conductivity of 8.21 x 10(-4) S/cm, confirming the combined effect of Fe3+/Y3+ co-doping and SPS densification in enhancing the ionic transport properties of LTP-based solid electrolytes.
This work presents a comprehensive investigation of the structural, microstructural, magnetic, and magnetocaloric properties of La0.9-xPbxNa0.1MnO3 (x = 0 and 0.1), synthesized through a flash combustion technique and subsequently pressed into pellets. Structural analysis confirms that both samples crystallize in a rhombohedral structure without detectable secondary phases or impurities. Microstructural observations reveal a homogeneous morphology in both compositions, with a noticeable grain growth effect induced by Pb doping. Magnetic measurements show a clear paramagnetic-ferromagnetic phase transition in both samples. The Curie temperature shifts from 179 K for the undoped compound to 309 K for the Pb-doped compounds. Furthermore, the magnetic entropy change and the relative cooling power increase from 3.01 J/kg.K and 184.72 J/kg for La0.9Na0.1MnO3 to 4.56 J/kg.K and 291.29 J/kg for La0.8Pb0.1Na0.1MnO3. Together, these results highlight the beneficial effect of Pb doping in the studied system for room-temperature magnetic refrigeration applications.
This work presents a detailed analysis of the structural and magnetic configuration of bulk Gd₃Fe₅O₁₂ obtained by spark plasma sintering (SPS) at 1100 °C for a dwell time of 1 min. While X-ray diffraction analysis proves formation of the single phase with the gadolinium iron garnet structure, temperature dependent Mössbauer spectroscopy provides more insight on the atomic scale occupancy and local magnetic configurations. It is shown that SPS processing does not alter significantly nor the compound stoichiometry or the compensation temperature, as compared to a reference sample obtained by conventional solid-state reaction and previously reported by our group. In both samples, a limited cationic inversion of about 10
Expression of concern for ‘Iron oxide magnetic nanoparticles with versatile surface functions based on dopamine anchors’ by Mykola Mazur et al., Nanoscale, 2013, 5, 2692–2702, https://doi.org/10.1039/C3NR33506B.
A methodology for the quantitative estimation of the drug loading of iron oxide-based magnetic nanoparticles by corroborating magnetometry and Mössbauer spectroscopy investigations is reported. The proposed methodology is exemplified in the case of two series of nanoparticles, namely Fe3O4 nanoparticles covered with citric acid molecules and further functionalized with doxorubicin, and Fe3O4 nanoparticles covered with L-Cysteine molecules and further functionalized with doxorubicin. The general idea of the proposed methodology is to probe the real magnetic structure of the magnetic core via low-temperature Mössbauer spectroscopy for the correct estimation of the spontaneous magnetization of the magnetic core. It subsequently uses the ratio between the spontaneous magnetization of the covered nanoparticles and that of the magnetic core for the reliable and nondestructive evaluation of the nanoparticle loading by organic molecules. Although the methodology is exemplified in the case of magnetite-based nanoparticles, it can be successfully considered for a large class of medicine-loaded Fe-containing magnetic nanoparticles where 57Fe Mössbauer spectroscopy can be applied.
The field of newly developed two-dimensional (2D) materials with low symmetry and structural in-plane anisotropic properties has grown rapidly in recent years. The phosphorene analog of group IV monochalcogenides is a prominent subset of this group that has attracted a lot of attention because of its unique in-plane anisotropic electronic and optical properties, crystalline symmetries, abundance in the earth’s crust, and environmental friendliness. This article presents a review of the latest research advancements concerning 2D group IV monochalcogenides. It begins with an exploration of the crystal structures of these materials, alongside their optical and electronic properties. The review continues by discussing the various techniques employed for the synthesis of layered group IV monochalcogenides, including both bottom-up methods such as vapor-phase deposition and top-down techniques like mechanical and/or liquid-phase exfoliation. In the final part, the article emphasizes the application of 2D group IV monochalcogenides, particularly in the fields of photocatalysis, photodetectors, nonlinear optics, sensors, batteries, and photovoltaic cells.
The precise control of the magnetic compensation temperature (θc) in ferrimagnetic garnets is essential for the development of cutting-edge ultrafast customizable spintronic devices. In this work we demonstrate how fine variation in stoichiometry and cation distribution in iron gadolinium garnets significanty influences θc. Two samples of Gd3Fe5O112 garnets synthesized via a new hydrothermal method and a conventional solid-state reaction, respectively, were considered. The complex study was carried out using a complex approach combining X-ray diffraction, magnetometry, and Mössbauer spectroscopy. Atomic-scale analysis revealed with unprecedent accuracy a cationic inversion between Fe3+ ang Gd3+ at octahedral and dodecahedral sites in both samples, and their chemical compositions were determined as Gd2.70Fe4.76O11.9 and Gd2.96Fe4.68O11.5, respectively. These local rearrangements have been shown to have a consistent influence on θc (290 K and 317 K, respectively) around room temperature, emphasizing the high sensitivity of exchange interactions to internal atomic order. Results clearly illustrate the strong correlation between the processing, atomic configuration and macroscopic magnetic behavior, establishing a new paradigm for the design of garnet-based materials with tunable θc. The strategy for the accurate determination of cation inversion illustrated in this work exhibits great potential in guiding material innovations for next-generation spintronics.
Electrochemical replication of nanoporous membranes was employed for the fabrication of nickel nanowires. The fabrication process led to uniform arrays of quasi 1 dimensional nanoobjects with low diameters and high aspect ratios. Extensive characterization experiments were carried out for determining the morphological, structural and magnetic properties of the nanostructures. It was found that the working electrode potential employed during the electrochemical deposition fabrication experiments influences both the crystalline structure and the magnetic properties of the nanowires. Accordingly, an in-depth investigation of the correlations between the morpho-structural and the magnetic parameters was performed. It was shown that several structural factors, mainly crystalline texture and grain size and shape, quite sensitive to the deposition potential, influence also the specific magnetic configurations, which can be tuned from 3-dimensional Imry and Ma random anisotropy type to cooperative quasi-1-dimensional superspin type. Consequently, new possibilities in tailoring the magneto-functionalities of polycrystalline magnetic nanowires by adjusting fabrication parameters are revealed.
We report on the Matrix Assisted Pulsed Laser Evaporation, laser technology for depositing biocompatible, antimicrobial, hydrophilic, and biodegradable complex hybrid polymeric system loaded with essential cypress-oil and magnetite nanoparticles as resorbable implants, capable of targeting possible hyperthermia applications, an anticancer moderate field heating therapy. Magnetite nanoparticles based on iron oxide (Fe3O4) coated with Cypress essential oil (denoted: Fe3O4- Cypress) and embedded in PLGA (poly(lactic-co-glycolic acid) (denoted: PLGA-Fe3O4- Cypress-) and PLGA - poly(3,4-ethylene dioxythiophene) doped with poly(styrene sulfonate) anions) (PEDOT: PSS) mixture (denoted: PLGA-Fe3O4- Cypress- PEDOT: PSS) were used as MAPLE targets. The controlled drug delivery of the active Cypress oil, an antimicrobial therapeutic agent from Fe3O4- Cypress nanoparticles could be possible by applying an external radio frequency (RF) magnetic field. The Fe3O4-Cypress-based powders as well as the final hybrid coatings have been characterized in terms of stoichiometry, morphology, magnetic, antimicrobial properties, biocompatibility, and response to external physical stimuli. FTIR analyses confirmed the quasi-stoichiometric laser transfer of organic compounds while the XRD evidenced the semicrystalline structure of deposited thin films. SEM and AFM images evidence that conductive polymer addition led to the films' relief flattening and a decrease in the coatings' thickness and roughness by changing the polymeric packaging. The samples containing conductive polymer exhibited 3 times higher current and corrosion rate values.,. All coatings are hydrophilic and revealed enhanced cellular viability when cultured with osteoblast-like MG-63 cells. The composite structures exhibited significant antimicrobial activity against Gram-positive (Staphylococcus aureus), and Gram-negative (Escherichia coli) bacteria, as well as to the opportunistic yeast Candida albicans.
Non-volatile electronic memory elements are very attractive for applications, not only for information storage but also in logic circuits, sensing devices and neuromorphic computing. Here, a ferroelectric film of guanine nucleobase is used in a resistive memory junction sandwiched between two different ferromagnetic films of Co and CoCr alloys. The magnetic films have an in-plane easy axis of magnetization and different coercive fields whereas the guanine film ensures a very long spin transport length, at 100 K. The non-volatile resistance states of the multiferroic spintronic junction with two-terminals are manipulated by a combined action of small external magnetic and electric fields. Thus, the magnetic field controls the relative orientation of the magnetization of the metallic ferromagnetic electrodes, that leads to different magnetoresistance states. The orientation and the magnitude of the electric field controls the orientation of the polarization of the guanine ferroelectric barrier, that leads to different electroresistance states, respectively. Moreover, we have observed a strong interfacial coupling of the two parameters. Consequently, positive and negative magnetoresistance hysteresis loops corresponding to spin rectification effects and non-hysteretic (erased) resistive states are manipulated with the electric field by switching the orientation of the electrical polarization of the organic ferroelectric.
In the present work, we report the synthesis and investigations of La0.9K0.1MnO3 and La0.8K0.1Pb0.1MnO3 bulk samples which could be potential magnetocaloric materials for magnetic refrigeration close to room temperature. A flash combustion reaction and sintering at 1200 °C for 10 h are used to prepare the bulk materials. Both compounds crystallized into a rhombohedral structure with R 3 c space group confirmed by X-ray powder diffraction results. Scanning electron microscopy analysis, combined with XRD peak profiles is performed to estimate the particle/crystallite size of the samples. Moreover, the Curie temperature, TC, is found to be higher in lead-rich sample due to the enhancement of the grain size and the Mn3+–O–Mn4+ double exchange (DE) interaction. Therefore, the bulk sample La0.8K0.1Pb0.1MnO3 shows a room temperature phase transition of 289 K as well as a higher saturation magnetization. The La0.8K0.1Pb0.1MnO3 bulk compound exhibits a high and sharp peak in magnetic entropy change up to 5.5 Jkg−1 K−1 under 5 T at the magnetic transition temperature TC. To compare the magnetocaloric performances of the studied compounds, relative cooling power (RCP) was employed. The obtained experimental results revealed that the increase in particle size influences severely the magnetocaloric properties.
VO2 based thermochromic thin films can be successfully used for coating usual windows in order to minimize the energy consumption of buildings through a specific temperature driven Metal to Insulator Transition (MIT). A careful analysis on the wide possibilities to optimise such coatings with respect to the desired properties of MIT, followed mainly via the temperature variation of the electron transport properties is reported. Some optimized coatings, investigated by morpho-structural methods as X-Ray Diffraction and Transmission Electron Microscopy and finally by electron transport measurements, have shown stable and reproducible variations of resistivity by about 3 orders of magnitude, over temperatures ranging from 45 ℃ to 65 ℃ and with narrow hysteretic behavior, quite sensitive to processing parameters. The effect of partial pressure of oxygen during the Pulsed Laser Deposition process as well as of the considered substrate are mainly investigated in this work.
Expression of concern for 'Iron oxide magnetic nanoparticles with versatile surface functions based on dopamine anchors' by Mykola Mazur et al., Nanoscale, 2013, 5, 2692-2702, https://doi.org/10.1039/C3NR33506B.
The nanostructural features of VO2 thin films, grown on either LSAT (La0.18Sr0.82)(Al0.59Ta0.41)O3, Si or Quartz substrates have been investigated by transmission electron microscopy (TEM/HRTEM) methods. The overall morphology, film thickness, roughness, VO2 phases and relative percentage, as well as residual strains have been elucidated. The electrical and magnetic characterisation complemented the TEM observations, where a smooth transition of metal to insulator (MIT) has been observed, mainly dependent on the relative percentage of the VO2 polymorphs. The effect of the residual strain has been also discussed, in relation to the MIT effectiveness.
Present work reports a systematic study on the evaluation of magnetic inhomogeneities in non-stoichiometric Mg0 & sdot;5Ca0 & sdot;5Fe2O4 nanoferrite (MCNF) by conducting exhaustive dc -magnetization, ac -susceptibility and Fe-57 Mossbauer spectroscopic measurements and exchange bias investigations using training protocol down to 6 K. Rietveld fitting to PXRD established the formation of anticipated spinel fcc phase of MCNF (non-stoichiometric) along with a minute impurity phase of calcite. Scherrer method and HRTEM micrographs illustrated broad size distribution of MCNF nanoparticles with an average nanocrystallite size of -15 nm. Combined 57Fe Mo center dot ssbauer spectroscopic and dc -magnetization analysis establishes coexistence of ferrimagnetic (67 %) & superparamagnetic (33 %) states at 300 K with notable M-s = 22 emu/g, M-r = 4 emu/g & H-c = 130 Oe and blocking of most of the nanoparticles of MCNF below 300 K. The coercivity followed the size -modified Kneller law for ferrimagnetic nanoparticles and the saturation magnetization abides the Bloch law. Moreover the frequencydependent ac -susceptibility investigations revealed two magnetic transitions: (i) A transition at - 330 K in the low frequency data attributed to the relaxation of blocked particles of bigger sizes under the superparamagnetic (SPM) regime and (ii) an irregularity at low temperatures is assigned to surface spin glass freezing. Surface spin glass freezing was further affirmed by the ageing experiments and dynamic scaling law. Furthermore, even the best fit to the dynamic scaling couldn't assert the existence of conventional spin glass phase due to slower spin -flip time of surface spins. A soft ferrimagnetic core of MCNF is enveloped with disordered surface spins, which manifest spin glass state. Concurrently, the findings of exchange bias at 30 K and training effect at 6 K affirmed that MCNF nanoparticles are presenting themselves as FM core- SG shell system. Our experimental findings suggested magnetic inhomogeneities comprised of superparamagnetism, ferrimagnetism and disordered surface spin glass state in the non-stoichiometric MCNF.
Fe, Co and Si powders were exposed to mechanochemical activation by high-energy ball milling for 0, 2, 4, 8 and 12 h. The samples were subsequently characterized by Mossbauer spectroscopy, X-ray powder diffraction (XRPD), magnetic measurements and optical diffuse reflectance spectroscopy. The room temperature Mossbauer measurements were consistent with the occurrence of FeCo2Si and Fe0.5Co0.5Si crystalline phases. The low temperature Mossbauer spectra confirmed the absence of superparamagnetism up to 44 K in the milled system. XRPD patterns supported the phase sequence derived from Mossbauer spectroscopy. The coercive field was found to increase with the ball milling time (BMT). Zero-field-cooling-field-cooling (ZFC-FC) measurements performed at 200 Oe in the temperature range 5-300 K evidenced the transition to the skyrmion phase of the Fe0.5Co0.5Si material below the critical temperature of 44 K. The optical absorption in the UV-Vis-NIR region of the spectrum was found to increase with BMT.