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Semiconductors, which are ferromagnetic at room temperature (RTFM), are strived after as potential multifunctional materials. For ZnO, RTFM has been achieved by heavy doping with 3d transition metals. However, neither the conditions for nor the origin of the magnetism is as yet understood. Here, by implanting ZnO at temperatures of 300–800K with dilute, radioactive Mn+57 ions, decaying to the Fe57m Mössbauer state, we show that, most likely, Fe atoms, located on Zn sites in a high-spin Fe3+ state at ⩽600K with large magnetic moments, are in a magnetically ordered atomic surrounding with ordering temperatures ⪢600K. The formation/annealing of the ordering is proposed to occur/disappear on an atomic scale upon the association/dissociation of complexes of Mn∕Fe probe atoms with the (mobile) Zn vacancies that are created in the implantation process. These results challenge present concepts to model (ferro)magnetic ordering in 3d-metal doped oxides and suggest this role of vacancies in the magnetism to be a rather general phenomenon.
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.
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.
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