Gordon A. Alanko

Size, surface structure, and doping effects on ferromagnetism in SnO2

The effects of crystallite size, surface structure, and dopants on the magnetic properties of semiconducting oxides are highly controversial. In this work, Fe:SnO2 nanoparticles were prepared by four wet-chemical methods, with Fe concentration varying from 0% to 20%. Analysis confirmed pure single-phase cassiterite with a crystallite size of 2.6 ± 0.1 nm that decreased with increasing. Fe% doped substitutionally as Fe3+. Pure SnO2 showed highly reproducible weak magnetization that varied significantly with synthesis method. Interestingly, doping SnO2 with Fe < 2.5% produced enhanced magnetic moments in all syntheses; the maximum of 1.6 × 10−4 µB/Fe ion at 0.1% Fe doping was much larger than the 2.6 × 10−6 µB/Fe ion of pure Fe oxide nanoparticles synthesized under similar conditions. At Fe ≥ 2.5%, the magnetic moment was significantly reduced. This work shows that (1) pure SnO2 can produce an intrinsic ferromagnetic behavior that varies with differences in surface structure, (2) very low Fe doping results ...

Magnetism of ZnO Nanoparticles: Dependence on Crystallite Size and Surfactant Coating

Many recent reports on magnetism in otherwise nonmagnetic oxides have demonstrated that nanoparticle size, surfactant coating, or doping with magnetic ions produces room-temperature ferromagnetism. Specifically, ZnO has been argued to be a room-temperature ferromagnet through all three of these methods in various experimental studies. For this reason, we have prepared a series of 1% Fe doped ZnO nanoparticle samples using a single forced hydrolysis coprecipitation synthesis method from the same precursors, while varying size (6–15 nm) and surface coating concentration to study the combined effects of these two parameters. Size was controlled by modifying the water concentration. Surfactant coating was adjusted by varying the concentration of polyacrylic acid in solution. Samples were characterized by x-ray diffraction, transmission electron microscopy, x-ray photoelectron spectroscopy, optical absorbance spectroscopy, and magnetometry. No clear systematic effect on magnetization was observed as a function...

Role of oxygen defects on the magnetic properties of ultra-small Sn1−xFexO2 nanoparticles

Although the role of oxygen defects in the magnetism of metal oxide semiconductors has been widely discussed, it is been difficult to directly measure the oxygen defect concentration of samples to verify this. This work demonstrates a direct correlation between the photocatalytic activity of Sn1−xFexO2 nanoparticles and their magnetic properties. For this, a series of ∼2.6 nm sized, well characterized, single-phase Sn1−xFexO2 crystallites with x = 0−0.20 were synthesized using tin acetate, urea, and appropriate amounts of iron acetate. X-ray photoelectron spectroscopy confirmed the concentration and 3+ oxidation state of the doped Fe ions. The maximum magnetic moment/Fe ion, μ, of 1.6 × 10−4 μB observed for the 0.1% Fe doped sample is smaller than the expected spin-only contribution from either high or low spin Fe3+ ions, and μ decreases with increasing Fe concentration. This behavior cannot be explained by the existing models of magnetic exchange. Photocatalytic studies of pure and Fe-doped SnO2 were used to understand the roles of doped Fe3+ ions and of the oxygen vacancies and defects. The photocatalytic rate constant k also showed an increase when SnO2 nanoparticles were doped with low concentrations of Fe3+, reaching a maximum at 0.1% Fe, followed by a rapid decrease of k for further increase in Fe%. Fe doping presumably increases the concentration of oxygen vacancies, and both Fe3+ ions and oxygen vacancies act as electron acceptors to reduce e−-h+ recombination and promote transfer of electrons (and/or holes) to the nanoparticle surface, where they participate in redox reactions. This electron transfer from the Fe3+ ions to local defect density of states at the nanoparticle surface could develop a magnetic moment at the surface states and leads to spontaneous ferromagnetic ordering of the surface shell under favorable conditions. However, at higher doping levels, the same Fe3+ ions might act as recombination centers causing a decrease of both k and magnetic moment μ.

Unusual crystallite growth and modification of ferromagnetism due to aging in pure and doped ZnO nanoparticles

We report the unusual growth of pure and Fe-doped ZnO nanoparticles prepared by forced hydrolysis and the weakening of ferromagnetism due to aging in ambient conditions. More than four dozen nanoparticle samples in the size range of 4–20 nm were studied over 1 to 4 years. The as-prepared samples had significant changes in their crystallite sizes and magnetization as they aged in ambient conditions. Detailed studies using x ray diffraction and transmission electron microscopy (TEM) demonstrated that the crystallite size increased by as much as 1.4 times. Lattice parameters and strain also showed interesting changes. Magnetometry studies of Zn1−xFexO with x = 0–0.2 showed ferromagnetism at room temperature; however, keeping the samples in ambient conditions for one year resulted in modifications in the crystallite size and magnetization. For the Zn0.95Fe0.05O sample, the size changed from 7.9 nm to 9.0 nm, while the magnetization decreased from 1×10–3emu/g (memu/g) to 0.2 memu/g. Both magnetic and structura...

Concentration Dependence of Magnetic Moment in Ce 1-x Fe x O 2

In this study, we examined the impact of iron doping on the structural, chemical, and magnetic properties of ceria (Ce1-xFexO2). Samples were produced in triplicate through a coprecipitation approach in a forced hydrolysis synthesis that yielded consistently sized nanocrystals using three different cerium precursors: cerium chloride, cerium ammonium nitrate, and cerium nitrate. Particles were characterized by x ray diffraction (XRD), x ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR) spectroscopy, and vibrating sample magnetometry (VSM). XPS and EPR data shows iron to be in the Fe3+ state and confirms the nominal dopant concentration. The moment per Fe ion found was largest at the lowest dopant concentrations, and quickly decreased as the concentration was increased. We used XPS to estimate the Ce3+/Ce4+ ratio and observed a linear relation between the saturation magnetization and the Ce3+/Ce4+ ratio.

Correlation between magnetism and electronic structure of Zn1−xCoxO nanoparticles

Zn1−xCoxO nanoparticles (∼9 nm) were produced with x ranging from 0 to 0.2 using a forced hydrolysis method. X-ray diffraction measurements confirm the samples to be single phase, and reveal a systematic change in the lattice parameters upon cobalt doping. The unit cell volume V decreases up to x = 0.025 after which it stays roughly constant. The band gap energy (Eg), determined from the photoluminescence spectra gradually increases from x = 0 to 0.025 and then remains nearly constant for x > 0.025. Room temperature hysteresis loops, obtained using vibrating sample magnetometry, show a similar trend in the saturation magnetization (Ms). Undoped ZnO nanoparticles show a weak magnetic hysteresis; doping causes an increase in Ms up to x = 0.025 and then decreases to lower values for x > 0.025. The magnetic moment per Co ion μ decreases rapidly with x nearly following μ(x) ∝ 1/x, indicating that the moments from the Co ions have little impact on the observed magnetic properties. Electron paramagnetic resonanc...

High-Temperature Corrosion Testing of Uranium Silicide Surrogates

Abstract The corrosion resistance of cerium silicide, a surrogate of uranium silicide, is investigated to gain insight into the reaction of uranium silicide with water. As-received and proton-irradiated Ce3Si2, CeSi2, and CeSi1.x monolithic pellets are subjected to corrosion tests in water at 300°C and 9 MPa for up to 48 h. Results show that an oxide layer composed of Ce4.67 (SiO4)3O forms on the surface of all samples, and it grows thicker with extended exposure times. Irradiated samples corrode to a greater extent than their unirradiated counterparts, which is mainly a result of the existing post-irradiation cerium oxide and the presence of ion-induced defects. Most of the Ce3Si2 samples crack (as-received) or fracture (ion-irradiated) during testing, which is due to the brittleness of the samples and oxide erosion/spallation that occur during testing.