Temperature Evolution of Composition, Thermal, Electrical and Magnetic Properties of Ti3C2Tx-MXene.

MXenes are a family of two-dimensional nanomaterials. Titanium carbide MXene (Ti3C2Tx-MXene), reported in 2011, is the first inorganic compound reported among the MXene family. In the present work, we report on the study of the composition and various physical properties of Ti3C2Tx-MXene nanomaterial, as well as their temperature evolution, to consider MXenes for space applications. X-ray diffraction, thermal analysis and mass spectroscopy measurements confirmed the structure and terminating groups of the MXene surface, revealing a predominant single OH layer character. The temperature dependence of the specific heat shows a Debye-like character in the measured range of 2 K-300 K with a linear part below 10 K, characteristic of conduction electrons of metallic materials. The electron density of states (DOS) calculations for Ti3C2OH-MXene reveal a significant DOS value at the Fermi level, with a large slope, confirming its metallic character, which is consistent with the experimental findings. The temperature dependence of electrical resistivity of the MXene samples was tested for a wide temperature range (3 K-350 K) and shows a decrease on lowering temperature with an upturn at low temperatures, where negative magnetoresistance is observed. The magnetoresistance versus field is approximately linear and increases its magnitude with decreasing temperature. The magnetization curves are straight lines with temperature-independent positive slopes, indicating Pauli paramagnetism due to conduction electrons.

Graphene removal by water-assisted focused electron-beam-induced etching - unveiling the dose and dwell time impact on the etch profile and topographical changes in SiO2 substrates.

Graphene is one of the most extensively studied 2D materials, exhibiting extraordinary mechanical and electronic properties. Although many years have passed since its discovery, manipulating single graphene layers is still challenging using standard resist-based lithography techniques. Recently, it has been shown that it is possible to etch graphene directly in water-assisted processes using the so-called focused electron-beam-induced etching (FEBIE), with a spatial resolution of ten nanometers. Nanopatterning graphene with such a method in one single step and without using a physical mask or resist is a very appealing approach. During the process, on top of graphene nanopatterning, we have found significant morphological changes induced in the SiO2 substrate even at low electron dose values (<8 nC/µm2). We demonstrate that graphene etching and topographical changes in SiO2 substrates can be controlled via electron beam parameters such as dwell time and dose.

Effects of Ni/Co doping on structural and electronic properties of 122 and 112 families of Eu based iron pnictides.

Superconductivity in high-temperature superconductors such as cuprates or iron pnictides is typically achieved by hole or electron doping and it is of great interest to understand how doping affects their properties leading to superconductivity. To study it we conducted Fe and As K edge x-ray absorption spectroscopy measurements on several electron doped compounds from the 112 and 122 family of Eu-based iron pnictides. XANES and EXAFS results confirm that dopants are located at expected sites. For both families we found an electron charge redistribution between As and Fe occurring with doping. The changes it caused are stronger in the 112 family and they are bigger at As sites, which indicates that doped charges are predominantly localized on the dopant site. However, the results obtained do not provide clues why Ni doping in 122 family does not lead to occurrence of superconductivity.

Ligand Size and Carbon-Chain Length Study of Silver Carboxylates in Focused Electron-Beam-Induced Deposition.

Gas-assisted focused electron-beam-induced deposition is a versatile tool for the direct writing of complex-shaped nanostructures with unprecedented shape fidelity and resolution. While the technique is well-established for various materials, the direct electron beam writing of silver is still in its infancy. Here, we examine and compare five different silver carboxylates, three perfluorinated: [Ag2(µ-O2CCF3)2], [Ag2(µ-O2CC2F5)2], and [Ag2(µ-O2CC3F7)2], and two containing branched substituents: [Ag2(µ-O2CCMe2Et)2] and [Ag2(µ-O2CtBu)2], as potential precursors for focused electron-beam-induced deposition. All of the compounds show high sensitivity to electron dissociation and efficient dissociation of Ag-O bonds. The as-deposited materials have silver contents from 42 at.% to above 70 at.% and are composed of silver nano-crystals with impurities of carbon and fluorine between them. Precursors with the shortest carbon-fluorine chain ligands yield the highest silver contents. In addition, the deposited silver content depends on the balance of electron-induced ligand co-deposition and ligand desorption. For all of the tested compounds, low electron flux was related to high silver content. Our findings demonstrate that silver carboxylates constitute a promising group of precursors for gas-assisted focused electron beam writing of high silver content materials.

In Situ Time-of-Flight Mass Spectrometry of Ionic Fragments Induced by Focused Electron Beam Irradiation: Investigation of Electron Driven Surface Chemistry inside an SEM under High Vacuum.

Recent developments in nanoprinting using focused electron beams have created a need to develop analysis methods for the products of electron-induced fragmentation of different metalorganic compounds. The original approach used here is termed focused-electron-beam-induced mass spectrometry (FEBiMS). FEBiMS enables the investigation of the fragmentation of electron-sensitive materials during irradiation within the typical primary electron beam energy range of a scanning electron microscope (0.5 to 30 keV) and high vacuum range. The method combines a typical scanning electron microscope with an ion-extractor-coupled mass spectrometer setup collecting the charged fragments generated by the focused electron beam when impinging on the substrate material. The FEBiMS of fragments obtained during 10 keV electron irradiation of grains of silver and copper carboxylates and shows that the carboxylate ligand dissociates into many smaller volatile fragments. Furthermore, in situ FEBiMS was performed on carbonyls of ruthenium (solid) and during electron-beam-induced deposition, using tungsten carbonyl (inserted via a gas injection system). Loss of carbonyl ligands was identified as the main channel of dissociation for electron irradiation of these carbonyl compounds. The presented results clearly indicate that FEBiMS analysis can be expanded to organic, inorganic, and metal organic materials used in resist lithography, ice (cryo-)lithography, and focused-electron-beam-induced deposition and becomes, thus, a valuable versatile analysis tool to study both fundamental and process parameters in these nanotechnology fields.

Canted antiferromagnetic order in EuZn2As2 single crystals.

Compounds containing Eu show a vast range of unique physical properties due to the interplay of electronic and magnetic properties, which can lead to a nontrivial electronic topology combined with magnetic order. We report on the growth of trigonal ([Formula: see text] space group) EuZn2As2 single crystals and on the studies of their structural, electronic and magnetic properties. A range of experimental techniques was applied including X-ray diffraction, electron microscopy, magnetic susceptibility, magnetization, heat capacity and Mössbauer spectroscopy in the study. We found that Eu has solely a 2+ valence state and its magnetic moments below TN = 19.2 K form a canted antiferromagnetic structure, tilted from the basal plane.

Carbon Dots/Iron Oxide Nanoparticles with Tuneable Composition and Properties.

We present a simple strategy to generate a family of carbon dots/iron oxide nanoparticles (C/Fe-NPs) that relies on the thermal decomposition of iron (III) acetylacetonate in the presence of a highly fluorescent carbon-rich precursor (derived via thermal treatment of ethanolamine and citric acid at 180 °C), while polyethylene glycol serves as the passivation agent. By varying the molar ratio of the reactants, a series of C/Fe-NPs have been synthesized with tuneable elemental composition in terms of C, H, O, N and Fe. The quantum yield is enhanced from 6 to 9% as the carbon content increases from 27 to 36 wt%, while the room temperature saturation magnetization is improved from 4.1 to 17.7 emu/g as the iron content is enriched from 17 to 31 wt%. In addition, the C/Fe-NPs show excellent antimicrobial properties, minimal cytotoxicity and demonstrate promising bioimaging capabilities, thus showing great potential for the development of advanced diagnostic tools.

Magnetic Properties of Collagen-Chitosan Hybrid Materials with Immobilized Superparamagnetic Iron Oxide Nanoparticles (SPIONs).

The paper presents results of our studies on hybrid materials based on polymers of natural origin containing superparamagnetic iron oxide nanoparticles (SPIONs). Such nanoparticles, coated with the chitosan derivative, were immobilized in a chitosan-collagen hydrogel matrix by crosslinking with genipin. Three types of biopolymer matrices of different collagen-to-chitosan ratios were studied. A thorough magnetic characterization was performed, including magnetic susceptibility, magnetization, and hysteresis loop measurements in a temperature range of 4 K to 300 K and a magnetic field induction up to 8 Tesla. The effect of SPION immobilization and material composition on the magnetic properties of the hybrids was investigated. The results showed that hybrid materials with covalently bounded SPIONs preserved the superparamagnetic character of SPIONs and exhibited promising magnetic properties, which are important for their potential applications.

Selenium-Containing Exopolysaccharides Isolated from the Culture Medium of Lentinula edodes: Structure and Biological Activity.

In continuation of our research on the influence of selenium incorporation on the biosynthesis, structure, and immunomodulatory and antioxidant activities of polysaccharides of fungal origin, we have isolated from a post-culture medium of Lentinula edodes a selenium (Se)-containing exopolysaccharide fraction composed mainly of a highly branched 1-6-α-mannoprotein of molecular weight 4.5 × 106 Da, with 15% protein component. The structure of this fraction resembled mannoproteins isolated from yeast and other mushroom cultures, but it was characterized by a significantly higher molecular weight. X-ray absorption fine structure spectral analysis in the near edge region (XANES) suggested that selenium in the Se-exopolysaccharide structure was present mainly at the IV oxidation state. The simulation analysis in the EXAFS region suggested the presence of two oxygen atoms in the region surrounding the selenium. On the grounds of our previous studies, we hypothesized that selenium-enriched exopolysaccharides would possess higher biological activity than the non-Se-enriched reference fraction. To perform structure-activity studies, we conducted the same tests of biological activity as for previously obtained mycelial Se-polyglucans. The Se-enriched exopolysaccharide fraction significantly enhanced cell viability when incubated with normal (human umbilical vein endothelial cells (HUVEC)) cells (but this effect was absent for malignant human cervical HeLa cells) and this fraction also protected the cells from oxidative stress conditions. The results of tests on the proliferation of human peripheral blood mononuclear cells suggested a selective immunosuppressive activity, like previously tested Se-polyglucans isolated from L. edodes mycelium. The Se-exopolysaccharide fraction, in concentrations of 10-100 µg/mL, inhibited human T lymphocyte proliferation induced by mitogens, without significant effects on B lymphocytes. As with previously obtained Se-polyglucans, in the currently tested Se-polymannans, the selenium content increased the biological activity. However, the activity of selenium exopolysaccharides in all tests was significantly lower than that of previously tested mycelial isolates, most likely due to a different mode of selenium binding and its higher degree of oxidation.

Specific Binding of Novel SPION-Based System Bearing Anti-N-Cadherin Antibodies to Prostate Tumor Cells.

PURPOSE: Epithelial-mesenchymal (EMT) transition plays an important role in metastasis and is accompanied by an upregulation of N-cadherin expression. A new nanoparticulate system (SPION/CCh/N-cad) based on superparamagnetic iron oxide nanoparticles, stabilized with a cationic derivative of chitosan and surface-modified with anti-N-cadherin antibody, was synthetized for the effective capture of N-cadherin expressing circulating tumor cells (CTC). METHODS: The morphology, physicochemical, and magnetic properties of the system were evaluated using dynamic light scattering (DLS), fluorescence spectroscopy, Mössbauer spectroscopy, magnetometry, and fluorescence spectroscopy. Atomic force microscopy (AFM), confocal microscopy and flow cytometry were used to study the interaction of our nanoparticulate system with N-cadherin expressed in prostate cancer cell lines (PC-3 and DU 145). A purpose-built cuvette was used in the cancer cell capture experiments. RESULTS: The obtained nanoparticles were a spherical, stable colloid, and exhibited excellent magnetic properties. Biological experiments confirmed that the novel SPION/CCh/N-cad system interacts specifically with N-cadherin present on the cell surface. Preliminary studies on the magnetic capture of PC-3 cells using the obtained nanoparticles were successful. Incubation times as short as 1 minute were sufficient for the synthesized system to effectively bind to the PC-3 cells. CONCLUSION: Results obtained for our system suggest a possibility of using it to capture CTC in the flow conditions.

Structure, Morphology, Heat Capacity, and Electrical Transport Properties of Ti3(Al,Si)C2 Materials.

A study of Ti3Al1-xSixC2 (x = 0 to x = 1) MAX-phase alloys is reported. The materials were obtained from mixtures of Ti3AlC2 and Ti3SiC2 powders with hot pressing sintering technique. They were characterised with X-ray diffraction, heat capacity, electrical resistivity, and magnetoresistance measurements. The results show a good quality crystal structure and metallic properties with high residual resistivity. The resistivity weakly varies with Si doping and shows a small, positive magnetoresistance effect. The magnetoresistance exhibits a quadratic dependence on the magnetic field, which indicates a dominant contribution from open electronic orbits. The Debye temperatures and Sommerfeld coefficient values derived from specific heat data show slight variations with Si content, with decreasing tendency for the former and an increase for the latter. Experimental results were supported by band structure calculations whose results are consistent with the experiment concerning specific heat, resistivity, and magnetoresistance measurements. In particular, they reveal that of the s-electrons at the Fermi level, those of Al and Si have prevailing density of states and, thus predominantly contribute to the metallic conductivity. This also shows that the high residual resistivity of the materials studied is an intrinsic effect, not due to defects of the crystal structure.

Enhanced Thermal Conductivity of Polyamide-Based Nanocomposites Containing Graphene Oxide Sheets Decorated with Compatible Polymer Brushes.

Polyamide-based nanocomposites containing graphene platelets decorated with poly(acrylamide) brushes were prepared and characterized. The brushes were grafted from the surface of graphene oxide (GO), a thermally conductive additive, using atom transfer radical polymerization, which led to the formation of the platelets coated with covalently tethered polymer layers (GO_PAAM), accounting for ca. 31% of the total mass. Polyamide-6 (PA6) nanocomposites containing 1% of GO_PAAM were formed by extrusion followed by injection molding. The thermal conductivity of the nanocomposite was 54% higher than that of PA6 even for such a low content of GO. The result was assigned to strong interfacial interactions between the brushes and PA6 matrix related to hydrogen bonding. Control nanocomposites containing similarly prepared GO decorated with other polymer brushes that are not able to form hydrogen bonds with PA6 revealed no enhancement of the conductivity. Importantly, the nanocomposite containing GO_PAAM also demonstrated larger tensile strength without deteriorating the elongation at break value, which was significantly decreased for the other coated platelets. The proposed approach enhances the interfacial interactions thanks to the covalent tethering of dense polymer brushes on 2D fillers and may be used to improve thermal properties of other polymer-based nanocomposites with simultaneous enhancement of their mechanical properties.

Modelling of Effective Thermal Conductivity of Composites Filled with Core-Shell Fillers.

An effective model to calculate thermal conductivity of polymer composites using core-shell fillers is presented, wherein a core material of filler grains is covered by a layer of a high-thermal-conductivity (HTC) material. Such fillers can provide a significant increase of the composite thermal conductivity by an addition of a small amount of the HTC material. The model employs the Lewis-Nielsen formula describing filled systems. The effective thermal conductivity of the core-shell filler grains is calculated using the Russel model for porous materials. Modelling results are compared with recent measurements made on composites filled with cellulose microbeads coated with hexagonal boron nitride (h-BN) platelets and good agreement is demonstrated. Comparison with measurements made on epoxy composites, using silver-coated glass spheres as a filler, is also provided. It is demonstrated how the modelling procedure can improve understanding of properties of materials and structures used and mechanisms of thermal conduction within the composite.

High-Entropy Perovskites as Multifunctional Metal Oxide Semiconductors: Synthesis and Characterization of (Gd0.2Nd0.2La0.2Sm0.2Y0.2)CoO3.

Single-phase multicomponent perovskite-type cobalt oxide containing five cations in equiatomic amounts on the A-site, namely, (Gd0.2Nd0.2La0.2Sm0.2Y0.2)CoO3, has been synthesized via the modified coprecipitation hydrothermal method. Using an original approach for heat treatment, which comprises quenching utilizing liquid nitrogen as a cooling medium, a single-phase ceramic with high configuration entropy, crystallizing in an orthorhombic distorted structure was obtained. It reveals the anomalous temperature dependence of the lattice expansion with two weak transitions at approx. 80 and 240 K that are assigned to gradual crossover from the low- via intermediate- to high-spin state of Co3+. The compound exhibits weak ferromagnetism at T ≤ 10 K and signatures of antiferromagnetic correlations in the paramagnetic phase. Ab initio calculations predict a band gap Δ = 1.18 eV in the ground-state electronic structure with the dominant contribution of O_p and Co_d orbitals in the valence and conduction bands, respectively. Electronic transport measurements confirm the negative temperature coefficient of resistivity characteristic to a semiconducting material and reveal a sudden drop in activation energy at T ∼ 240 K from E a ∼ 1 eV in the low-temperature phase to E a ∼ 0.3 eV at room temperature. The possibility of fine tuning of the semiconducting band gap via a subtle change in A-site stoichiometry is discussed.

Correlation of magnetic and magnetoresistive properties of nanoporous Co/Pd thin multilayers fabricated on anodized TiO2 templates.

In this study, we consider a technological approach to obtain a high perpendicular magnetic anisotropy of the Co/Pd multilayers deposited on nanoporous TiO2 templates of different types of surface morphology. It is found that the use of templates with homogeneous and smoothed surface relief, formed on silicon wafers, ensures conservation of perpendicular anisotropy of the deposited films inherent in the continuous multilayers. Also, their magnetic hardening with doubling of the coercive field is observed. However, inhomogeneous magnetic ordering is revealed in the porous films due to the occurrence of magnetically soft regions near the pore edges and/or inside the pores. Modeling of the field dependences of magnetization and electrical resistance indicates that coherent rotation is the dominant mechanism of magnetization reversal in the porous system instead of the domain-wall motion typical of the continuous multilayers, while their magnetoresistance is determined by electron-magnon scattering, similarly to the continuous counterpart. The preservation of spin waves in the porous films indicates a high uniformity of the magnetic ordering in the fabricated porous systems due to a sufficiently regular pores array introduced into the films, despite the existence of soft-magnetic regions. The results are promising for the design and fabrication of future spintronic devices.

Thin-Film Engineering of Mechanical Fragmentation Properties of Atomic-Layer-Deposited Metal Oxides.

Mechanical fracture properties were studied for the common atomic-layer-deposited Al2O3, ZnO, TiO2, ZrO2, and Y2O3 thin films, and selected multilayer combinations via uniaxial tensile testing and Weibull statistics. The crack onset strains and interfacial shear strains were studied, and for crack onset strain, TiO2/Al2O3 and ZrO2/Al2O3 bilayer films exhibited the highest values. The films adhered well to the polyimide carrier substrates, as delamination of the films was not observed. For Al2O3 films, higher deposition temperatures resulted in higher crack onset strain and cohesive strain values, which was explained by the temperature dependence of the residual strain. Doping Y2O3 with Al or nanolaminating it with Al2O3 enabled control over the crystal size of Y2O3, and provided us with means for improving the mechanical properties of the Y2O3 films. Tensile fracture toughness and fracture energy are reported for Al2O3 films grown at 135 °C, 155 °C, and 220 °C. We present thin-film engineering via multilayering and residual-strain control in order to tailor the mechanical properties of thin-film systems for applications requiring mechanical stretchability and flexibility.

Hydrophobically Coated Superparamagnetic Iron Oxides Nanoparticles Incorporated into Polymer-Based Nanocapsules Dispersed in Water.

This paper reports the characterization of iron oxide magnetic nanoparticles obtained via the thermal decomposition of an organometallic precursor, which were then loaded into nanocapsules prepared via the emulsification process in the presence of an amphiphilic derivative of chitosan. The applied synthetic method led to the formation of a hydrophobic layer on the surface of nanoparticles that enabled their loading in the hydrophobic liquid inside of the polymer-based capsules. The average diameter of nanoparticles was determined to be equal to 15 nm, and they were thoroughly characterized using X-ray diffraction (XRD), magnetometry, and Mössbauer spectroscopy. A core-shell structure consisting of a wüstite core and maghemite-like shell was revealed, resulting in an exchange bias effect and a considerable magnetocrystalline anisotropy at low temperatures and a superparamagnetic behavior at room temperature. Importantly, superparamagnetic behavior was observed for the aqueous dispersion of the nanocapsules loaded with the superparamagnetic nanoparticles, and the dispersion was shown to be very stable (at least 48 weeks). The results were analyzed and discussed with respect to the potential future applications of these nanoparticles and nanocapsules based on biopolymers as platforms designed for the magnetically navigated transport of encapsulated hydrophobic substances.

Complex magnetic ordering in nanoporous [Co/Pd]5-IrMn multilayers with perpendicular magnetic anisotropy and its impact on magnetization reversal and magnetoresistance.

We have systematically investigated the magnetization reversal characteristics and magnetoresistance of continuous and nanoporous [Co/Pd]5-IrMn multilayered thin films with perpendicular magnetic anisotropy at different temperatures (4-300 K). For their nanostructuring, porosity was induced by means of deposition onto templates of anodized titania with small (∼30 nm in diameter) homogeneously distributed pores. The magnetization reversal and magnetoresistance of the porous films were found to be closely related to the splitting of the ferromagnetic material into regions with different magnetic properties, in correlation with the complex morphology of the porous system. Independent magnetization reversal is detected for these regions, and is accompanied by its strong impact on the magnetic order in the capping IrMn layer. Electron-magnon scattering is found to be a dominant mechanism of magnetoresistance, determining its almost linear field dependence in a high magnetic field and contributing to its magnetoresistance behavior, similar to magnetization reversal, in a low magnetic field. Partial rotation of IrMn magnetic moments, consistent with the magnetization reversal of the ferromagnet, is proposed as an explanation for the two-state resistance behavior observed in switching between high-resistive and low-resistive values at the magnetization reversal of the porous system studied.

Focused Electron Beam-Induced Deposition and Post-Growth Purification Using the Heteroleptic Ru Complex (η3-C3H5)Ru(CO)3Br.

Focused electron beam-induced deposition using the heteroleptic complex (η3-C3H5)Ru(CO)3Br as a precursor resulted in deposition of material with Ru content of 23 at. %. Transmission electron microscopy images indicated a nanogranular structure of pure Ru nanocrystals, embedded into a matrix containing carbon, oxygen, and bromine. The deposits were purified by annealing in a reactive 98% N2/2% H2 atmosphere at 300 °C, resulting in a reduction of contaminants and an increase of the Ru content to 83 at. %. Although a significant volume loss of 79% was found, the shrinkage was observed mostly for vertical thickness (around 75%). The lateral dimensions decreased much less significantly (around 9%). Deposition results, in conjunction with previous gas-phase and condensed-phase surface studies on the electron-induced reactions of (η3-C3H5)Ru(CO)3Br, provide insights into the behavior of allyl, carbonyl, and bromide ligands under identical electron beam irradiation.

Dynamics of Superparamagnetic Iron Oxide Nanoparticles with Various Polymeric Coatings.

In this article, the results of a study of the magnetic dynamics of superparamagnetic iron oxide nanoparticles (SPIONs) with chitosan and polyethylene glycol (PEG) coatings are reported. The materials were prepared by the co-precipitation method and characterized by X-ray diffraction, dynamic light scattering and scanning transmission electron microscopy. It was shown that the cores contain maghemite, and their hydrodynamic diameters vary from 49 nm for PEG-coated to 200 nm for chitosan-coated particles. The magnetic dynamics of the nanoparticles in terms of the function of temperature was studied with magnetic susceptometry and Mössbauer spectroscopy. Their superparamagnetic fluctuations frequencies, determined from the fits of Mössbauer spectra, range from tens to hundreds of megahertz at room temperature and mostly decrease in the applied magnetic field. For water suspensions of nanoparticles, maxima are observed in the absorption part of magnetic susceptibility and they shift to higher temperatures with increasing excitation frequency. A step-like decrease of the susceptibility occurs at freezing, and from that, the Brown's and Néel's contributions are extracted and compared for nanoparticles differing in core sizes and types of coating. The results are analyzed and discussed with respect to the tailoring of the dynamic properties of these nanoparticle materials for requirements related to the characteristic frequency ranges of MRI and electromagnetic field hyperthermia.