Iron nanoparticles in amorphous SiO<Subscript>2</Subscript>: X-ray emission and absorption spectra

The local structure of the chemical bond of iron ions implanted into SiO₂ glasses (implantation energy, 100 keV; fluence, 1 × 10¹⁶ cm^?2) is investigated using x-ray emission and absorption spectroscopy. The Fe L x-ray emission and absorption spectra are analyzed by comparing them with the corresponding spectra of reference samples. It is established that iron nanoparticles implanted into the SiO₂ vitreous matrix are in an oxidized state. The assumption is made that the most probable mechanism of transformation of iron nanoparticles into an oxidized state during implantation involves the breaking of Si-O-Si bonds with the formation of Si-Si and Fe-O bonds.     

Mössbauer studies of mixed-valence spin-crossover iron complexes with a hexadentate tripod ligand

The spin-crossover behaviors of mixed-valence iron compounds [Fe^IIH₃L][Fe^IIIL](NO₃)₂ (1) and [Fe^IIH₃L^Me][Fe^IIIL^Me](NO₃)₂ (2) have been investigated by ⁵⁷Fe Mössbauer spectroscopy, where H₃L is a hexadentate N₆ tripod ligand containing three imidazole groups and H₃L^Me is its 2-methylimidazole derivative. Deconvolution analyses of the Mössbauer spectra revealed that a two-step SCO (LS Fe^II–LS Fe^III→HS Fe^II–LS Fe^III→HS Fe^II–HS Fe^III) proceeds in each compound on elevating the temperature. Compound 2 exhibited lower spin-transition temperatures than 1. “Frozen-in effect” was observed below 120 and 50 K for 1 and 2, respectively.     

The interaction of oxygen molecules with iron films studied with MIES,UPS and XPS

X-ray Photoelectron Spectroscopy (XPS), Metastable Induced Electron Spectroscopy (MIES) and Ultraviolet Photoelectron Spectroscopy (UPS) were applied to study the interaction of oxygen molecules with iron films. Supplementarily, iron oxide was investigated for comparison.With XPS from the Fe 2p_3/2 range contributions of metallic Fe as well as Fe²⁺ and Fe³⁺ can be distinguished. During the interaction with oxygen an oxide film is formed on the iron surface. Nevertheless, XPS still shows metallic contributions even for a surface which is saturated with more than 10⁴ L. The oxide film hinders the dissociation of further impinging oxygen molecules.The interaction of He* atoms with iron oxide surfaces during MIES is dominated by Auger Neutralization. This surprising result follows from the high work function and the fact that intrinsic defects result in a Fermi level pinning to the conduction band.     

Compound synthesis in TiO2 implanted with Rubidium

Rubidium ions, with energy in the range 0.1 MeV, 2.0 MeV have been implanted in TiO₂ single crystals at RT and LNT.

Defects induced by implantation have been studied by optical spectroscopy, X-ray diffraction, RBS, TEM and electrical conductivity.

During implantation, the implanted samples are blue colored after irradiation. This coloration is due to an optical absorption band localized at 900 nm which corresponds to optical transition of intrinsic defects identified as Ti³⁺. These defects are induced by a chemical reaction between the implanted ions and the oxygen of the lattice as in the case of D⁺, H⁺, Li⁺, Na⁺ and K⁺ implanted in rutile.^1-3

The synthesis of a new phase in heavily implanted rutile is exhibited by using a thermal treatment and by combining techniques such as RBS, TEM and X-ray diffraction at glancing angle in the temperature range 300°C-700°C.

This compound does not correspond to metallic precipitates of rubidium which are observed in MgO implanted with Rb ions.

Planar defects have been observed in the implanted area. A correlation is exhibited between these defects and the precipitates of the new phase. From X-ray diffraction measurements and TEM observations, the composition of the synthetized compound is likely Rb₂TiO₃.     

Electron microscopy studies of void swelling and annealing of voids in aluminium irradiated with aluminium ions

Abstract

MgO single crystals implanted with Au⁺ ions (180 keV, 6 10¹⁶-10¹⁷ ions cm^?2) and annealed at temperatures between 25°C and 1100°C, have been analysed—by optical spectrophotometry—by Rutherford back-scattering (to confirm the effective presence and to study the distribution profile of Au atoms), and by TEM and X-ray diffraction (to identify the phases precipitated by thermal treatment).

Thermal annealing between 550°C and 1100°C produced an optical absorption band located between 565 nm and 600 nm. This band can be attributed to a fee Au precipitate with diameter varying from 50 to 200 Å. Larger metallic colloids 1000 Å are in simple orientation with the matrix.

Annealing at temperatures higher than 500°C produces a supplementary optical absorption located at 425 nm. This band can be attributed to Au plasma resonance.

After annealing for 15 min at 1100°C, a new phase is detected by X-ray diffraction and TEM and identified as Au₃Mg alloy with hexagonal structure.     

Synthesis by Coprecipitation of Al-Substituted Hydroxysulphate Green Rust FeII 4FeIII (2−y)AlIII y (OH)12SO4,nH2O

Al-substituted hydroxysulphate green rust (Al-GR{SO₄}) were synthesised by the coprecipitation of Fe^II, Fe^III and Al^III cations. The Al-GR{SO₄} crystals (～50 nm) are significantly smaller than the hydroxysulphate green rust GR{SO₄} crystals (～500 nm). The Mössbauer spectrum of Al-GR{SO₄} was adjusted with two ferrous doublets D₁ and D₃ and one ferric doublet D₂. Doublet D₃ is attributed to Fe^II ions that have Al^III ions as a first neighbour.

     

Dependence of intramolecular valence delocalization on crystal form in mixed-valence trinuclear iron phenylacetate [Fe 2 III FeIIO(PhCH2CO2)6(py)3]

A dependence of intramolecular valence delocalization on crystal form in mixed-valence trinuclear iron phenylacetate [Fe ₂ ^III Fe^IIO(PhCH₂CO₂)₆(py)₃] was found. This complex was obtained in two different crystal forms: a columnar and a needle crystal form. Mössbauer spectra of the columnar crystals show a temperature-dependent valence delocalization, while the needle crystals show a trapped mixed-valence state from a lower temperature up to room temperature.     

Crystal orientation dependence of ferromagnetism in Fe-implanted MgO single crystals

Single crystals of MgO with (100), (110) and (111) orientations were implanted with 64 keV Fe ions at a dose of 1.9×10¹⁷ ions/cm² by using metal-vapor vacuum arc ion source (MEVVA). The magnetic properties were investigated by a superconducting quantum interference device magnetometer and Rutherford backscattering spectrometry (RBS) was used to analyze the Fe concentration and distribution. The presence of Fe nanoparticles in MgO matrix was verified by magnetization measurements. Results show that all the samples behave with ferromagnetism at 5 K and 300 K, and the coercive field, H_C, follow well the relation: at measured temperatures. The orientation dependence of the coercive field may result from the different distribution of Fe nanoparticle size.     

Local states of iron in iron implanted hematite Fe2O3

Powder samples of⁵⁷Fe₂O₃ and⁵⁶Fe₂O₃ were implanted with⁵⁶Fe and⁵⁷Fe ions, respectively. By the use of Conversion Electron Mössbauer Spectroscopy it was possible to observe the local states of implanted ions (⁵⁷Fe in⁵⁶Fe₂O₃) or the states of iron atoms from the target which were displaced during implantation due to the ballistic processes (⁵⁶Fe in⁵⁷Fe₂O₃). The implanted and displaced iron atoms appear in three different states: (i) in regular substitutional positions of Fe₂O₃, (ii) as magnetite Fe₃O₄-type structures and (iii) paramagnetic FeO_1?x state. The observed fractions of each state agree rather well with the calculated values obtained from the local iron atom enrichment at the surface as well as from the analysis of the equilibrium phase diagram for the binary Fe?O system. However, in⁵⁷Fe implanted samples some enhancement of the FeO_1?x fraction was found in comparison with the⁵⁶Fe implanted hematite.     

In-beam implantation of iron into germanium,silicon and diamond studied by the Mössbauer effect

The Mössbauer effect of⁵⁷Fe implanted into diamond structure semiconductors, Ge, Si and C, has been studied by in-beam implantation of⁵⁷Fe ions, which were excited to the 14 keV state by a³⁵Cl beam from a tandem Van de Graaff accelerator. The time between the stopping of the⁵⁷Fe nucleus and the emission of the 14 keV -ray is determined by the lifetime (140 ns) of the 14 keV state. In each material the Mössbauer spectrum exhibits a doublet with velocity coordinates (in mm/s) at room temperature, relative to a sodium ferrocyanide absorber, as follows: diamond (–0.99, 1.10), silicon (–0.80, 0.21), and germanium (–0.88, –0.02). In silicon and germanium crystals the spectra were observed over the temperature range between 13 K and 870 K. The relative line intensities changed dramatically and the positions of the lines shifted systematically with temperature. In addition, channelling studies were made on iron that had been implanted into silicon.     

SiPM-based veto detector for the pion beam at FOPI

Conversion electron M?ssbauer Spectroscopy measurements have been made on ZnO single crystals implanted with 60?keV ⁵⁷Fe 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^3?+?, which is attributed to Fe^3?+? ions in nano-precipitates ～5?nm in size.     

Metallic alloy precipitates in high dose indium implanted MgO

Abstract

MgO implanted at room temperature with 150keV In⁺ ions and doses ranging from 10¹⁵ to 10¹⁷ ions cm^?2 was studied by optical absorption and transmission electron microscopy (TEM). Creation of defects in the anionic sublattice (F-, F⁺-, F₂-centers) and in the cationic sublattice (V^?-centers) are observed. Subsequent annealings of the implanted crystals have shown different behaviours depending on the implanted dose. For medium dose (2 × 10¹⁶ ions cm^?2), the formation of In³⁺ species seems to be the preponderant phenomenon. At higher dose (8 × 10¹⁶ ions cm^?2), metallic precipitates are formed between 400 and 700°C. The identification of these precipitates has been achieved using TEM: they are formed of a metallic alloy Mg₃In with a hexagonal structure and their orientation relationship with respect to the MgO matrix is: (0001)Mg₃In//(111)Mgo and [1120]_Mg3In// [l10]MgO.     

X-ray stimulated luminescence in MgO

Studies have been made of the emission spectrum of MgO crystals induced by X-irradiation at 90 K. Two bands (half-widths ～0.8 eV) were observed to peak at 4.95 and 3.2 eV, respectively, in high purity crystals. Doping with 100 ppm or greater of Fe, Co, Cr, Cu, Mn, and Ni suppressed the luminescence, though in the MgO:Ni crystal the 2.3 eV Ni²⁺ band due to the ¹T_2g→³A_2g transition was observed. In deuterium-doped crystals the ratio of the intensity of 3.2–4.95 eV emission was found to be 1.2 as compared to 8 for the undoped crystals. Prior exposure of the pure crystals to ionizing radiation enhances the 4.95 eV band by a factor of three while not affecting the 3.2 eV band. This enhancement of intensity decays in several stages upon standing at room temperature in a way that reflects the thermal stability of the various components of the composite V-band absorption. These facts together with the observation that the 210 K thermoluminescence peak is composed entirely of 4.95 eV emission indicate that this luminescence band is associated with the recombination of an electron with a hole located in a V-type center, i.e. O?□ + e → (O²?□)1 → O²?□ + 4.95 eV, where the square indicates that the perturbing positive ion vacancy is adjacent to the oxugen ion which has captured the hole. In MgO:Li⁺, which exhibits no V-type centers upon irradiation, the 4.95 eV band was absent and a 2.9 eV emission which may be associated with recombination at the [Li]⁰ center was observe.     

Enhanced photoluminescence of Ar implanted sapphire before and after annealing

In this paper, we studied the changes in the photoluminescence spectra of the Ar⁺ ion implanted mono-crystalline sapphire annealed at different atmospheres and different temperatures. Single crystals of sapphire (Al₂O₃) with the (1 0 1¯ 0) (m-samples) orientation were implanted at 623 K with 110 keV Ar⁺ ions to a fluence of 9.5×10¹⁶ ions/cm². Photoluminescence measurement of the as-implanted sample shows a new emission band at 506 nm, which is attributed to the production of interstitial Al atoms. The intensity of emission band at 506 nm first increased then decreased with increase in annealing temperature. For the same annealing temperature, the intensity of PL peak at 506 nm of the sample annealed in air was higher than the sample annealed in vacuum. The experimental results show that the intensity of the PL peak at 506 nm of Ar-implanted sapphire can be enhanced by subsequent annealing with an enhancement of nearly 20 times. The influence of thermal annealing of the Ar-implanted samples on the new 506 nm emission band was discussed.     

Magnetic properties of substitutional solid solutions of nickel and iron hexacyanoferrate–hexacyanochromate

In order to evaluate the influence of substitution at the central metal ion position in transition hexacyanometallates in some detail, the magnetic studies were carried out on a series of solid solutions of metal hexacyanometallates of the composition M[Fe^II(CN)₆]_{1? x} [Cr^III(CN)₆] _x , where M?=?Ni^II and Fe^III. The temperature and field dependences of magnetization were studied using a superconducting quantum interference device magnetometer. The field dependence of the samples at 5?K shows a hysteresis behaviour. For M?=?Ni^II, the transition temperature increases with increase in the substitution of low-spin Fe(III) by Cr(III) in the hexacyanometallate unit. The saturation magnetization was found to decrease with increase in the iron concentration. The observed variation in the magnetic properties, such as the value of T _C and the nature of magnetic ordering, is attributed to the variation in the composition of the transition-metal ion in the coordination sphere of carbon. On the other hand, for M?=?Fe^III, the transition temperature and saturation magnetization remained almost unchanged, indicating that substitution at the carbon coordination site did not produce any change in the magnetic interaction among the transition-metal ions through the cyanide ions.     

Changes induced by ion implantation in forsterite Sio4 Mg2

Abstract

The various methods of optical absorption spectroscopy, Rutherford back-scattering, transmission electron microscopy and X-ray diffraction, have been associated to study the high-dose ion implantation (150 keV, 10¹⁷ ions cm^?2) phenomena in SiO₄Mg₂ single crystals. After thermal annealing at high temperature under vacuum or in atmosphere, different new phases appear:

For an under vacuum anneal, the formation of solid solution is observed: SiO₄ (Mg, Fe)₂ by X-ray diffraction;

For atmospheric anneal precipitates a spinelle phase of Fe₃O₄ or Mg Fe₂O₄.

Preliminary results on the mechanical properties studied by creep technique will be discussed for these implanted and annealed crystals.     

Observation of phase transition of cesium manganese hexacyanoferrates by X-ray absorption spectroscopy

Cesium manganese hexacyanoferrates exhibit an interesting phenomenon of temperature-induced phase transition accompanied by a variation in the magnetic susceptibility. We observed the variation in the electronic state of Mn during the phase transition by using X-ray absorption spectroscopy. The results of the analyses showed that the content ratio of Fe^II-CN-Mn^III and Fe^III-CN-Mn^II systematically varied during the phase transition. However, the ratio of Fe^II-CN-Mn^II remained constant at almost all temperatures. These results suggest that the charge transfer between Fe and Mn ions in the Fe^III-CN-Mn^II or the Fe^II-CN-Mn^III bond produces the phase transition.     

Electron bombardment induced desorption of oxygen from LiNbO3

Low energy (1 keV) electron bombardment of LiNbO₃ single crystals causes the emission of O⁺ ions with a kinetic energy of 20 eV. The emission process can be identified as a Knotek-Feibelman mechanism, whereby the creation of Nb 4p core-holes is followed by an interatomic Auger process which leaves oxygen in a highly repulsive state. This oxygen subsequently desorbs.     

Structural and Chemical Modification in a Polymer by Metal Ion Implantation

Physical and chemical properties changes in a polymer have been studied for polycarbonate (PC) implanted with 100 keV Ni⁺ ions with varying fluence from 1 × 10¹⁴ to 1 × 10¹⁶ ions/cm². The changes in the surface morphology and composition have been observed with atomic force microscopy (AFM) and X-ray diffraction (XRD). The ions implanted induce changes in topography of PC and indicate that the roughness increases dramatically with ion fluence. Implanted metal ions shows direct evidence of compound formation on the surface. The chemical changes in the surface region have been carried out by Raman Spectroscopy and UV-VIS spectroscopy. UV-VIS absorption analysis indicates a drastic decline in optical band gap from 5.46 eV to 1.76 eV at an implanted dose of 1 × 10¹⁶ ions/cm². It could be shown that the partial destruction of chemical bonding under ion implantation leads to the creation of new amorphous and graphite-like structures, which is confirmed by Raman spectroscopy.     

Magnetic and Mössbauer spectra observed for mixed-metal magnets NBu4 {\bf Fe}^{\bf II}_{\bf n}MA II 1 − n [FeIII(OX)3] (MA=Mn, Fe)

Mixed-metal molecular-based magnets NBu₄ ${\rm Fe}^{\rm II}_{\rm n}$ M_A ^II _1???n[Fe^III(OX)₃] (M_A=Mn, Fe) were investigated by magnetic and Mössbauer measurements. The magnetic susceptibility of NBu₄ ${\rm Fe}^{\rm II}_{0.07}{\rm Mn}^{\rm II}_{0.93}$ [Fe^III(OX)₃] can be fitted to a Curie-Weiss law with a Weiss paramagnetic Curie temperature of θ?=??114.76 K. The negative Weiss constant indicates an intramolecular antiferromagnetic coupling interaction between the adjacent Fe(II) and Fe(III) ions through the oxalate bridge. In the complex NBu₄Fe^II[Fe^III(OX)₃], the Mössbauer results indicate that the Fe^II and Fe^III sublattices experience spontaneous magnetizations. The compound contains two different spin carriers; i.e. Fe^II(S = 2), Fe^III(S = 5/2). Two magnetic sublattices are defined. The appearance of nuclear Zeeman splittings suggests that long range magnetic ordering takes place below 50 K.