H. Masenda

Paramagnetism in Mn/Fe implanted ZnO

Prompted by the generally poor understanding of the nature of magnetic phenomena in 3d-metal doped ZnO, we have undertaken on-line F57e Mossbauer spectroscopy on ZnO single crystals in an external magnetic field of 0.6 T, following the implantation of radioactive M57n ions at room temperature. The Mossbauer spectra of the dilute Fe impurities are dominated by sextets whose angular dependence rules out an ordered magnetic state (which had been previously proposed) but are well accounted for on the basis of Fe3+ paramagnetic centers on substitutional Zn sites with unusually long relaxation times (>20 ns).

Direct synthesis of carbon nanofibers from South African coal fly ash

Carbon nanofibers (CNFs), cylindrical nanostructures containing graphene, were synthesized directly from South African fly ash (a waste product formed during the combustion of coal). The CNFs (as well as other carbonaceous materials like carbon nanotubes (CNTs)) were produced by the catalytic chemical vapour deposition method (CCVD) in the presence of acetylene gas at temperatures ranging from 400°C to 700°C. The fly ash and its carbonaceous products were characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), laser Raman spectroscopy and Brunauer-Emmett-Teller (BET) surface area measurements. It was observed that as-received fly ash was capable of producing CNFs in high yield by CCVD, starting at a relatively low temperature of 400°C. Laser Raman spectra and TGA thermograms showed that the carbonaceous products which formed were mostly disordered. Small bundles of CNTs and CNFs observed by TEM and energy-dispersive spectroscopy (EDS) showed that the catalyst most likely responsible for CNF formation was iron in the form of cementite; X-ray diffraction (XRD) and Mössbauer spectroscopy confirmed these findings.

Lattice locations and properties of Fe in Co/Fe co-implanted ZnO

The lattice locations and electronic configurations of Fe in 57Co/57Fe implanted ZnO (to (5‐6) × 1014 Fe/cm−2) have been studied by 57Fe Mossbauer emission spectroscopy. The spectra acquired upon room temperature implantation show ∼20% of the probe atoms as Fe2+ on perturbed Zn sites and the remaining fraction as Fe2+ in damage sites of interstitial character. After annealing at 773 K, ∼20% remain on crystalline sites, while the damage fraction has partly disappeared and instead a ∼30% fraction occurs as high‐spin Fe3+, presumably in precipitates. This suggests that precipitation of Co/Fe in ZnO likely takes place at relatively low temperatures, thus explaining some of the discrepancies in the literature regarding magnetic properties of 3d metal‐doped ZnO.

Fe charge state adjustment in ZnO upon ion implantation

The influence of the ion implantation process on the charge state of dilute (57)Fe impurities implanted as radioactive (57)Mn in ZnO is investigated by (57)Fe emission Mössbauer spectroscopy. One sample is additionally implanted with stable (23)Na impurities. Both Fe(2+) and Fe(3+) charge states are observed, and the Fe(3+)/Fe(2+) ratio is found to increase with the fluence of both (57)Mn/(57)Fe and (23)Na ions, demonstrating that the build-up of Fe(3+) is not related to the chemical nature of the implanted ions. The results are interpreted in terms of radiation damage induced changes of the Fermi level, and illustrate that the Fe(3+)/Fe(2+) ratio can be adjusted by ion implantation. The spin-lattice relaxation time for Fe(3+) in ZnO is found to be independent of the implantation fluence, and is evidently an intrinsic property of the system.

Spin–lattice relaxations of paramagnetic Fe3+ in ZnO

The spin–lattice relaxation rate of paramagnetic Fe3+ in single-crystalline ZnO has been determined following low-fluence (Φ<1012 cm−2) 60 keV implantation of 57Mn+ (T1/2=1.5 min) and emission Mossbauer spectroscopy on the 57Fe daughter nucleus in the temperature range from 300 to 664 K. The spin–lattice relaxation of Fe3+ is found to follow a T9 temperature dependence, in contrast to the T2 dependence expected for a two-phonon Raman process determined in both single-crystal MgO and α-Al2O3 using the same analysis method of the Mossbauer spectra measured without an applied external magnetic field. This is an unexpected result since ZnO has a lower Debye temperature than both MgO and α-Al2O3.

Defect annealing in Mn/Fe-implanted TiO2 (rutile)

A study of the annealing processes and charge state of dilute Fe in rutile TiO2 single crystals was performed in the temperature range 143?662?K, utilizing online 57Fe emission M?ssbauer spectroscopy following low concentrations ( ?350?K.

Charge states and lattice sites of dilute implanted Sn in ZnO

The common charge states of Sn are 2+  and 4+. While charge neutrality considerations favour 2+  to be the natural charge state of Sn in ZnO, there are several reports suggesting the 4+  state instead. In order to investigate the charge states, lattice sites, and the effect of the ion implantation process of dilute Sn atoms in ZnO, we have performed 119Sn emission Mössbauer spectroscopy on ZnO single crystal samples following ion implantation of radioactive 119In (T ½  =  2.4 min) at temperatures between 96 K and 762 K. Complementary perturbed angular correlation measurements on 111mCd implanted ZnO were also conducted. Our results show that the 2+  state is the natural charge state for Sn in defect free ZnO and that the 4+  charge state is stabilized by acceptor defects created in the implantation process.

Interstitial Fe in MgO

Copyright: 2014. AIP Publishing. Due to copyright restrictions, only the abstract is available. For access to the full text item, please consult the publishers website. The definitive version of the work is published in Journal of Applied Physics, Vol 115. Issue 2. https://doi.org/10.1063/1.4861403

Atomic-scale study of the amorphous-to-crystalline phase transition mechanism in GeTe thin films

The underlying mechanism driving the structural amorphous-to-crystalline transition in Group VI chalcogenides is still a matter of debate even in the simplest GeTe system. We exploit the extreme sensitivity of 57Fe emission Mössbauer spectroscopy, following dilute implantation of 57Mn (T½ = 1.5 min) at ISOLDE/CERN, to study the electronic charge distribution in the immediate vicinity of the 57Fe probe substituting Ge (FeGe), and to interrogate the local environment of FeGe over the amorphous-crystalline phase transition in GeTe thin films. Our results show that the local structure of as-sputtered amorphous GeTe is a combination of tetrahedral and defect-octahedral sites. The main effect of the crystallization is the conversion from tetrahedral to defect-free octahedral sites. We discover that only the tetrahedral fraction in amorphous GeTe participates to the change of the FeGe-Te chemical bonds, with a net electronic charge density transfer of  ~ 1.6 e/a0 between FeGe and neighboring Te atoms. This charge transfer accounts for a lowering of the covalent character during crystallization. The results are corroborated by theoretical calculations within the framework of density functional theory. The observed atomic-scale chemical-structural changes are directly connected to the macroscopic phase transition and resistivity switch of GeTe thin films.