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There is an apparent mismatch between electron paramagnetic resonance and Mössbauer spectroscopy results on the charge and spin states of dilute Fe impurities in NaCl; Mössbauer spectroscopy data have been interpreted in terms of high-spin Fe2+, while electron paramagnetic resonance studies suggest low-spin Fe1+. In the present study, the charge and spin states of dilute substitutional Fe impurities in NaCl and LiF have been investigated with 57Mn→57Fe emission Mössbauer spectroscopy. A scheme is proposed which takes into account the effects of nearest-neighbor distances and electronegativity difference of the host atoms on the Mössbauer isomer shift and allows for the unequivocal differentiation between high-spin Fe2+ and high/low-spin Fe1+ in Mössbauer spectroscopy. From these considerations, the Mössbauer results are found to be consistent with dilute Fe impurities in NaCl and LiF in a low-spin Fe1+ state. These conclusions are supported by theoretical calculations of isomer shifts and formation energies based on the density-functional theory. The experimental results furthermore suggest that charge compensation of dilute Mn2+ dopants in NaCl and LiF is achieved by Na vacancies and F− interstitials, respectively. We acknowledge the support of the ISOLDE Collaboration and technical teams and cluster resources provided by CERN (HTC/Condor). G. Marschick (Vienna University of Technology, Austria; University Duisburg-Essen, Germany & CERN, Switzerland) is acknowledged for experimental help. B. Qi (University of Iceland, Iceland) is acknowledged for fruitful discussions. S.O. acknowledges support from the University of Iceland Research Fund. R.A. acknowledges the funding of the Austrian Science Fund (FWF) through Projects No. P26830 and No. P31423. The Federal Ministry of Education and Research (BMBF) through Grants No. 05K16PGA and No. 05K19SI1 "eMMA" is acknowledged. The European Commission through the Horizon 2020 programme (Grant No. 654002, ENSAR 2) is acknowledged. K.B.-R., H.M., D.N., K.N., and G.P. acknowledge support of the Department of Science & Innovation (South Africa) within the SA-CERN Program. I.U. acknowledges the support of the Ministry of Economy and Competitiveness (MINECO/FEDER) under Project No. RTI2018-094683-B-C55 and Basque Government Grant No. IT-1500-22.

In addition to spectral components due to Fe and Fe, a single line is observed in emission Mössbauer spectra following low fluence (

Conversion electron Mössbauer Spectroscopy measurements have been made on ZnO single crystals implanted with 60 keV Fe to 4 and 8 at.% peak concentrations, and annealed up to 800°C. The spectra show quite strong changes with annealing, but no evidence of magnetic components, thus precluding the formation of large sized precipitates or secondary phases. Above an annealing temperature of 650°C, the dominant spectral component is a doublet with hyperfine parameters typical of Fe , which is attributed to Fe ions in nano-precipitates ~5 nm in size.

solated Fe-57 atoms were studied in MgO single-crystals by emission Mossbauer spectroscopy following implantation of Mn-57 decaying to Fe-57. Four Mossbauer spectral components were found corresponding to different Fe lattice positions and/or charge states. Two components represent Fe atoms substituting Mg as Fe2+ and Fe3+, respectively; a third component is due to Fe in a strongly implantation-induced disturbed region. The fourth component, which is the focus of this paper, can be assigned to Fe at an interstitial site. Comparison of its measured isomer shift with ab initio calculations suggests that the interstitial Fe is located on, or close to, the face of the rock-salt MgO structure. To harmonize such an assignment with the measured near-zero quadrupole interaction a local motion process (cage motion) of the Fe has to be stipulated. The relation of such a local motion as a starting point for long range diffusion is discussed.

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.