A rapid combustion process for the preparation of MgSrAl10O17:Eu phosphor and related luminescence and defect investigations

Blue-emitting europium-ion-doped MgSrAl₁₀O₁₇ phosphor, prepared using the combustion method, is described. An efficient phosphor can be prepared by this method in a muffle furnace maintained at 500 °C in a very short time of few minutes. The phosphor is characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy and BET surface area measurements. Photoluminescence (PL) spectra revealed that europium ions were present in divalent oxidation state. The thermoluminescence (TL) glow curve shows two peaks at around 178 and at 354 °C. The defect centres formed in the phosphor are studied using electron spin resonance (ESR). The ESR spectrum indicates the presence of Fe³⁺ ions in the non-irradiated system. Irradiated MgSrAl₁₀O₁₇:Eu exhibits lines due to radiation-sensitive Fe³⁺ ion and a defect centre. The centre is characterized by an isotropic g-value of 2.0012 and is assigned to a F⁺ centre. The radiation-sensitive Fe³⁺ ion appears to correlate with the main TL peak at 178 °C. During irradiation an electron is released from Fe²⁺ and is trapped at an anion vacancy to form F⁺ centre. During heating, an electron is liberated from the defect centre and recombines with Fe³⁺ emitting light.     

YIG formation in annealed iron implanted YAG

YAG and YIG crystals implanted respectively with 100 keV⁵⁷Fe²⁺ ions (1 × 10¹⁷ ions.cm^?2) and 50 keV²⁷Al ions (1.1 × 10¹⁷ ions.cm^?2) have been studied by conversion electron Mössbauer spectroscopy (CEMS) directly after implantation and after annealings in air at temperatures up to 1100°C. In both as-implanted samples iron is found mainly in three states: Fe²⁺, Fe³⁺ and small metallic precipitates. Annealing behaviour is divided into two stages: (i) up to 400°C the iron has become completely oxidized and (ii) between 400 and 850°C the epitaxial regrowth of the implanted layer takes place. During this process a part of iron ions are incorporated into octahedral and tetrahedral sites, thus making a Y₃ (Al Fe)₅ O₁₂ compound. The remaining iron part precipitates in the form of Fe₂O₃ particles.     

Microstructure of nodular cast iron after excimer laser surface processing

Nodular iron of martensitic structure was treated by means of a XeCl laser prototype. The energy density varied from 0.3 to 5 J/cm² and the number of shots from 4 to 40. Conversion electron Mössbauer spectroscopy, conversion X-ray Mössbauer spectroscopy and grazing incidence X-ray diffraction were used to characterize the irradiated surface. Some Rutherford backscattering spectrometry measurements were performed to control surface oxidation and carbon distribution. It is shown that after irradiation austenite formed in a rather deep heat affected zone (10–20 m) compared to the thickness of the melted zone ( 1 m). The austenite amount as well as its carbon content increase with energy density and number of shots up to a threshold of carbide formation. Beyond the threshold Fe₂C, Fe₃C and Fe₅C₂ formed only in the melted zone. The carbon content as a function of depth is constant in the melted layer, then decreases quickly from the melted layer-heat affected zone interface down its initial value. The carbon content is shown to govern the evolution of phases content in the melted layer depending on the laser treatment conditions.     

Transfert électronique d'intervalence entre sites inéquivalents: Étude de CaFe3O5 par spectrométrie Mössbauer

As in magnetite Fe₃O₄, calcium ferrite CaFe₃O₅ is an oxide in which electron transfer occurs between the iron ions ($\text{Fe}{}^{\mathrm{3+}}\text{Fe}{}^{\mathrm{2+}}\text{= 2}$). This intervalence exchange process has been studied by ⁵⁷Fe Mössbauer spectroscopy and by electrical conductivity measurements. In CaFe₃O₅, the Fe³⁺ and Fe²⁺ ions occupy different crystallographic sites and have a deformed octahedral coordination. Each Fe²⁺O₆ octahedron shares an edge with two Fe³⁺O₆ octahedra. In the antiferromagnetic region (T_N = 282 ± 2 K), the Fe³⁺ and Fe²⁺ ions are well differentiated. Thermally-activated electron transfer is observed above t_n, in the paramagnetic region and is well characterized by the Mössbauer spectra. These are analyzed using the hypothesis of an electron jump limited to a trimer Fe³⁺Fe²⁺Fe³⁺ which leads to a relaxation time of 180 ns at 298 K and 80 ns at 400 K. Within this temperature interval, the process follows the Arrhenius law with an activation energy of 0.10 eV. Electrical conductivity measurements lead to similar results with an activation energy of 0.09 ± 0.02 eV.     

Exchange-coupled pairs of Fe3+ ions in beryl

The EPR spectrum of first nearest neighbour pairs of Fe³⁺ ions substituting for Al³⁺ ions in beryl is reported. The form of the pair spin Hamiltonian is discussed, and operator equivalent factors for fourth-order terms are tabulated. The Fe³⁺ pair interionic coupling corresponds to isotropic antiferromagnetic exchange with J = + 1.7 cm^-1 plus anisotropic dipolar coupling. The pair value of the zero-field splitting parameter D is + 0.0206 cm^-1 and shows a substantial shift from the single-ion value. It is proposed that resonance lines previously attributed to Fe³⁺ ions in Be²⁺ or Si⁴⁺ sites are due to Fe³⁺ pairs.     

Thermo- and photostimulated luminescence and stimulated emission of magnesium oxide crystals irradiated in a nuclear reactor

The luminescence of nominally pure magnesium oxide crystals irradiated in a nuclear reactor is studied. It is shown that, in the entire fluence range (10¹⁵–10¹⁸ n/cm²), the active luminescence centers are chromium impurity ions, which are initially (<10¹⁷ n/cm²) in the form of Cr²⁺ ions and then (>10¹⁷ n/cm²), after the radiation-induced transformation Cr²⁺ → Cr³⁺, are in the form of Cr³⁺ ions. The role played by F centers is also shown. Pulsed stimulated emission is observed in crystals irradiated with a fluence of 10¹⁸ n/cm².     

EPR identification of the iron charge transfer in CuAlS2:Fe

The EPR spectrum of Fe²⁺ has been observed in CuAlS₂. It consists of a single line with g^eff₆ ≈ 9.5 at 34.8 GHz. An analysis yields the following crystal field parameters: 10Dq ≈ 3600 cm^?1, μ ≈ 800 cm^?1 and δ ≈ 900 cm^?1. It is found that Fe³⁺ can be converted into Fe²⁺ by irradiation with light of energies considerably less than the band gap. These results directly confirm the charge transfer model previously suggested for CuAlS₂:Fe.     

Magnetic resonance of metallic nanoparticles in vitreous silicon dioxide implanted with iron ions

Silica glasses exposed to steady-state and pulsed irradiation with Fe⁺ ions are studied using magnetic resonance. The irradiation doses used in experiments are equal to 1 × 10¹⁵, 1 × 10¹⁶, and 1 × 10¹⁷ cm^?2. It is found that, under both steady-state and pulsed irradiation conditions, glass samples exposed at a dose of 1 × 10¹⁷ cm^?2 exhibit a broadband orientation-dependent signal. The shape of inclusions is evaluated under the assumption that the observed spectrum is caused by the ferromagnetic resonance induced in a new phase of metallic iron.     

Gamma-ray induced color centers in Yb:YAG crystals grown by Czochralski method

20 at.% Yb:YAG single crystals have been grown by the CZ method and gamma-ray irradiation induced color centers and valence change of Fe³⁺ and Y b³⁺ ions in Yb:YAG have been studied. One significant 255 nm absorption band was observed in as-grown crystals and was attributed to Fe³⁺ ions. Two additional absorption (AA) bands located at 255 nm and 345 nm, respectively, were produced after gamma irradiation. The changes in the AA spectra after gamma irradiation and air annealing are mainly related to the charge exchange of the Fe³⁺, Fe²⁺, oxygen vacancies and F-type color centers. Analysis shows that the broad AA band is associated with Fe²⁺ ions and F-type color centers. The transition Y b³⁺→Y b²⁺ takes place as an effect of recharging of one of the Y b³⁺ ions from a pair in the process of gamma irradiation.     

Mössbauer and optical investigation of Co3−x Fe x O4 thin films grown by sol–gel process

Structural transformation and the related variation in magnetic and optical properties of Co_3?x Fe _x O₄ thin films grown by a sol–gel method have been investigated as the Fe composition varies up to x?=?2. The normal spinel phase is dominant below x?=?0.55 and the inverse spinel phase grows as x increases further. Conversion electron Mössbauer spectroscopy (CEMS) measurements indicate that the normal spinel phase have octahedral Fe³⁺ ions mostly while the inverse spinel phase contain octahedral Fe²⁺ and tetrahedral Fe³⁺ ions. For higher Fe composition (x?>?1.22), Co²⁺ ions are found to substitute the octahedral Fe²⁺ sites. The measured optical absorption spectra for the Co_3?x Fe _x O₄ films by spectroscopic ellipsometry support the CEMS interpretation.     

Ferromagnetic ordering of iron impurities in the valence-fluctuating semiconductor SmB6

The electron paramagnetic resonance (EPR) of the valence-fluctuating semiconductor SmB₆ doped by 1 at % Fe is studied. The EPR measurements are performed on a SmB₆ single crystal in a temperature range of 1.6–300.0 K. A number of resonance lines whose g factors indicate the presence of iron ions in the Fe⁰, Fe⁺, Fe²⁺, and Fe³⁺ states have been detected. The iron ions are ferromagnetically ordered below a Curie temperature T = 100 K, and this ordering can be caused by the exchange interaction of impurity ions due to matrix polarization (a similar mechanism is observed in PdFe alloys). This exchange interaction is estimated to be significantly higher than that in PdFe; this fact can result from a very high density of states in the narrow f band, which is characteristic of a valence-fluctuating material.     

Thermal evolution of high dose iron implanted sintered alumina

Sintered plates of alumina have been implanted at room temperature with 110 keV⁵⁷Fe⁺ at a dose of 1.2×10¹⁷ ions.cm^?2. The analysis of the Conversion Electron Mössbauer Spectrum indicated that implantation introduces iron in alumina in three charge state: Fe²⁺ (two components), Fe⁴⁺ and Fe⁰ (metallic clusters). The evolution of the iron depth distribution during annealings in oxiding or in neutral atmosphere has been followed using the Rutherford backscattering spectroscopy. Up to 800°C the profile as well as the charge states of iron evolve very slowly. A drastic change occurs' for annealing temperature around 1000°C. The total amount of iron is distributed among α-Fe₂O₃ and α-(Fe_1?x Al _x )₂O₃ precipitates. Some scanning electron micrographs have allowed to locate these precipitates. For highest temperature anneals, up to 1600°C, only substitutional iron remain.     

Photolytic production of Fe3+ in CaS

Calcium sulfide powder containing iron as an impurity was irradiated with 580, 366 or 254 nm light at 77 K. Irradiation enhanced a broad (16 G peak-to-trough) electron paramagnetic resonance (EPR) signal at g = 2.017 and caused six sharp (～1 G) lines to appear in the X-band EPR spectrum at 347, 529, 956, 1963, 3547 and 5376 G. Enrichment of CaS with Fe²⁺ produced samples with similar photochemistry. It is proposed that irradiation causes the reaction Fe²⁺ + trap → Fe³⁺ + trap^?, whose products give rise to six sharp EPR lines assigned to Fe³⁺ and a broad line associated with trap^?. Both hyperfine splitting by ⁵⁷Fe (13 G) and superhyperfine splitting by ³³S (11.4 G) are observed in the six line spectrum. The environment of the photo-generated Fe³⁺ has less than octahedral symmetry. V²⁺ was observed at octahedral sites in unirradiated CaS for the first time, and is characterized by the EPR parameters g = 1.961 and A (hyperfine coupling) = 74.6 × 10^?4 cm^?1. EPR signals due to Mn²⁺ and Cr³⁺ at octahedral sites and Fe³⁺ at a low symmetry site were also observed in unirradiated CaS.     

Mössbauer spectra of Fe3+ and Fe2+ ions in hexagonal ferrite with w-structure

The hexagonal ferrite Fe₂W = BaFe₂²⁺Fe³⁺₁₆O₂₇ exhibits a sharp ⁵⁷Fe Mössbauer spectrum at 300 and 78 K. All seven sublattices in this complicated crystal structure are detected. Fast electron exchange between Fe²⁺ and Fe³⁺ ions gives rise to sharp lines and makes them indistinguishable. At 5 K the exchange is slow and the Fe²⁺ ions are detected from the presence of a weak subspectrum with broadened lines separated from the main spectrum of the Fe³⁺ ions. Analysis shows that the Fe²⁺ ions reside exclusively on one of the seven sublattices, which is occupied statistically by Fe²⁺ and Fe³⁺ ions in the ratio of 2 : 1. For SrFe²⁺₂Fe³⁺₁₆O₂₇ the situation is the same.     

Optical spectra of (CdF2)0.9(InF3)0.1 semiconductor solid solutions

The differences in the optical spectra of CdF₂:In semiconductors with bistable DX centers (concentrated (CdF₂)_0.9(InF₃)_0.1 solid solutions) and “standard” samples with a lower impurity concentration used to record holograms are discussed. In contrast to the standard samples, in which complete decay of two-electron DX states and transfer of electrons to shallow donor levels may occur at low temperatures, long-term irradiation of a (CdF₂)_0.9(InF₃)_0.1 solid solution by UV or visible light leads to decay of no more than 20% deep centers. The experimental data and estimates of the statistical distribution of electrons over energy levels in this crystal give the total electron concentration, neutral donor concentration, and concentration of deep two-electron centers to be ～5 × 10¹⁸ cm^?3, ～9 × 10¹⁷ cm^?3, and more than 1 × 10²⁰ cm^?3, respectively. These estimates show that the majority of impurity ions are located in clusters and can form only deep two-electron states in CdF₂ crystals with a high indium content. In this case, In³⁺ ions in a limited concentration (In³⁺ (～9 × 10¹⁷ cm^?3) are statistically distributed in the “unperturbed” CdF₂ lattice and, as in low-concentrated samples, form DX centers, which possess both shallow hydrogen-like and deep two-electron states.     

3 MeV electron irradiation-induced defects in CuInSe2 thin films

3 MeV electron irradiation induced-defects in CuInSe₂ (CIS) thin films have been investigated. Both of the carrier concentration and Hall mobility were decreased as the electron fluence exceeded 1×10¹⁷ cm⁻². The carrier removal rate was estimated to be about 1 cm⁻¹. To evaluate electron irradiation-induced defect, the electrical properties of CIS thin films before and after irradiation were investigated between 80 and 300 K. From the temperature dependence of the carrier concentration in non-irradiated thin films, we obtained N_D=1.8×10¹⁷ cm⁻³, N_A=1.7×10¹⁶ cm⁻³ and E_D=18 meV from the SALS fitting to the experimental data on the basis of the charge balance equation. After irradiation, a new defect level was formed, and N_T0=1.4×10¹⁷ cm⁻³ and E_T=54 meV were also obtained from the same procedure. From the temperature dependence of Hall mobility, the ionized impurity density was discussed before and after the irradiation.     

Influence of 50 MeV Lithium Ion Irradiation on Hyperfine Interactions of Cr0.5 Li0.5 Fe2O4

Spinel oxide Cr_0.5 Li_0.5 Fe₂O₄ has been irradiated at Nuclear Science Centre, New Delhi, by 50 MeV lithium ions of fluence 5*10¹³ ions/cm² and irradiation effect on hyperfine interactions has been investigated by Mossbauer spectroscopy. The Mossbauer spectrum of irradiated sample shows no paramagnetic doublet contribution and the hyperfine fields corresponding to the Fe³⁺ in the octahedral (B) and the tetrahedral (A) sites are very well separated. That is the observed superimposed A and B sites in unirradiated sample are split into separate lines after Li irradiation. Further an increase of the intensity of the lines (2)–(5) with respect to (1)–(6) signals an orientation of the hyperfine magnetic field towards a direction perpendicular to the ion path due to the irradiation induced strain by the latent tracks. The computer simulation of Mossbauer spectra indicated that the irradiated Fe³⁺-site occupancy of the A-site hyperfine field increased from 43% to 55% whereas the B-site hyperfine field decreased from 57% to 45% compared to unirradiated sample.     

The orange luminescence band in MgO crystals

Nominally pure MgO crystals exhibit a bright orange luminescence when excited with u v or visible laser light This luminescence has been characterized using a variety of measurements with pulsed and cw laser sources Its amplitude increases with temperature to about 400 K. while the lifetime of emission decreases from 270 μs at 290 K to 9 μs at 433 K This emission appears to originate in hole recombination with Fe²⁺ ions Hole trapping at V^?_OH and V^?_Al centers may occur as an intermediate step Bleaching with 514 5-nm Ar⁺ laser light is reversible upon exposure to u v radiation Present data are compared with those obtained previously on the thermoluminescence of irradiated MgO crystals.     

α-Al2O3单晶中Fe3+离子的电子顺磁共振

本文对α-Al₂O₃单晶体中Fe³⁺离子在室温下,X波段进行了电子顺磁共振研究,发现Fe³⁺离子实际上占据四种磁性不等价晶位。在同一氧离子层间的两种晶位上的Fe³⁺离子具有相同的自旋哈密顿参量,而不同氧离子层间的晶位上的Fe³⁺离子具有不同的自旋哈密顿参量,两种自旋哈密顿参量为:(1)g_‖=2.001,g_⊥=2.003,D=1679 关键词：     

The magnetic phase transition in titanium oxide induced by proton irradiation

We have studied the magnetic properties of ⁵⁷Fe-doped TiO₂ compounds irradiated by proton with 0, 5 and 10 pC/μm². We have observed the enhancement of the magnetic moment, measured by superconducting quantum interference device magnetometer, with increasing proton irradiation ranging from 0 to 10 pC/μm². Mössbauer spectra of proton irradiated Ti_0.99⁵⁷Fe_0.01O₂ samples were taken at room temperature. Two sites of the wing (sextet) and the central (doublet) are shown in the spectra, which suggest the magnetically ordered phase and the paramagnetic phase, respectively. With increasing proton irradiation, the part of Fe³⁺ ions was converted to Fe²⁺ ions by compensation charge. This clearly suggests that the enhancement of magnetic moment after proton irradiation is contributed to the moment by the spin-orbit coupling of Fe²⁺ ions.