Annealing studies combined with low temperature emission Mössbauer spectroscopy of short-lived parent isotopes: Determination of local Debye-Waller factors.

An extension of the online implantation chamber used for emission Mössbauer Spectroscopy (eMS) at ISOLDE/CERN that allows for quick removal of samples for offline low temperature studies is briefly described. We demonstrate how online eMS data obtained during implantation at temperatures between 300 K and 650 K of short-lived parent isotopes combined with rapid cooling and offline eMS measurements during the decay of the parent isotope can give detailed information on the binding properties of the Mössbauer probe in the lattice. This approach has been applied to study the properties of Sn impurities in ZnO following implantation of 119In (T½ = 2.4 min). Sn in the 4+ and 2+ charge states is observed. Above T > 600 K, Sn2+ is observed and is ascribed to Sn on regular Zn sites, while Sn2+ detected at T < 600 K is due to Sn in local amorphous regions. A new annealing stage is reported at T ≈ 550 K, characterized by changes in the Sn4+ emission profile, and is attributed to the annihilation of close Frenkel pairs.

Local increase of the Curie temperature in Mn/Fe implanted Y3Fe5O12 (YIG).

The change in the Curie temperature of single crystalline garnet Y3Fe5O12 (YIG) sample due to lattice damage induced by ion implantation has been investigated in 57Fe emission Mössbauer Spectroscopy (eMS) following implantation of 57Mn (T½ = 1.5 min). The Mössbauer spectra analysis reveal high spin Fe3+ ions substituted on both the octahedral and the tetrahedral sites. Measurements in the temperature range 298 K-798 K show that average values of the magnetic hyperfine field are decreased by the implantation-induced damage on the local lattice structure of the YIG. The Curie temperature, however, is determined to be 651 ± 5 K, considerably higher than the value of bulk YIG (559 K). This is most likely due to lattice damage-induced changes on the spin configurations of YIG through a FeA-O-FeD distortion scheme.

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.

Multipurpose setup for low-temperature conversion electron Mössbauer spectroscopy.

We describe an experimental setup for conversion electron Mössbauer spectroscopy (CEMS) at low temperature. The setup is composed of a continuous flow cryostat (temperature range of 4.2-500 K), detector housing, three channel electron multipliers, and corresponding electronics. We demonstrate the capabilities of the setup with CEMS measurements performed on a sample consisting of a thin enriched 57Fe film, with a thickness of 20 nm, deposited on a silicon substrate. We also describe exchangeable adaptations (lid and sample holder) which extend the applicability of the setup to emission Mössbauer spectroscopy as well as measurements under an applied magnetic field.

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.

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.

H2O at the Phoenix landing site.

The Phoenix mission investigated patterned ground and weather in the northern arctic region of Mars for 5 months starting 25 May 2008 (solar longitude between 76.5 degrees and 148 degrees ). A shallow ice table was uncovered by the robotic arm in the center and edge of a nearby polygon at depths of 5 to 18 centimeters. In late summer, snowfall and frost blanketed the surface at night; H(2)O ice and vapor constantly interacted with the soil. The soil was alkaline (pH = 7.7) and contained CaCO(3), aqueous minerals, and salts up to several weight percent in the indurated surface soil. Their formation likely required the presence of water.

Magnetism at single isolated iron atoms implanted in graphite.

Mössbauer spectra obtained after implantation of 57Fe into highly oriented pyrolytic graphite (HOPG) show a combined magnetic and quadrupole interaction with a magnetic hyperfine field Bhf = 32.6 T at 14 K. Though magnetic effects in nominally diamagnetic HOPG have been reported recently, no experiment has previously shown the existence of magnetism at the atomic scale. The results suggest that magnetic ordering occurs by coupling of the Fe magnetic moment to structural and/or electronic magnetic defects induced by the probe atoms' implantation damage.

Magnetic properties experiments on the Mars exploration Rover Spirit at Gusev Crater.

The magnetic properties experiments are designed to help identify the magnetic minerals in the dust and rocks on Mars-and to determine whether liquid water was involved in the formation and alteration of these magnetic minerals. Almost all of the dust particles suspended in the martian atmosphere must contain ferrimagnetic minerals (such as maghemite or magnetite) in an amount of approximately 2% by weight. The most magnetic fraction of the dust appears darker than the average dust. Magnetite was detected in the first two rocks ground by Spirit.

Magnetic properties experiments on the Mars Pathfinder lander: preliminary results.

Many of the particles currently suspended in the martian atmosphere are magnetic, with an average saturation magnetization of about 4 A. m2/kg (amperes times square meters per kilogram). The particles appear to consist of claylike aggregates stained or cemented with ferric oxide (Fe2O3); at least some of the stain and cement is probably maghemite (gamma-Fe2O3). The presence of the gamma phase would imply that Fe2+ ions leached from the bedrock, passing through a state as free Fe2+ ions dissolved in liquid water. These particles could be a freeze-dried precipitate from ground water poured out on the surface. An alternative is that the magnetic particles are titanomagnetite occurring in palagonite and inherited directly from a basaltic precursor.