Mössbauer study on Zn1 − x Fe x O semiconductors prepared by high energy ball milling

We present the preparation of massive Zn_1???x Fe _x O ternary oxides using the mechanical mill. The Fe atom is a particular dopant since it presents two different oxidation states which allow us to vary the starting materials: Fe₂O₃, $\upalpha $ -Fe or FeO. Parameters such as initial concentrations, atmosphere and milling times were varied. X-ray diffraction and ⁵⁷Fe Mössbauer spectrometry (MS) were applied in order to analyze the structure evolution and iron incorporation in the wurtzite crystalline structure with milling time. At final stages, Fe atoms seem to be incorporated in the ZnO structure for those samples milled under Ar atmosphere. In all cases, two paramagnetic components, attributed to Fe atoms in both valence states, were observed by MS.     

Evolution under thermal annealing of Mn-doped iron disilicides obtained by ball milling

Phase formation in the Mn doped $\upbeta $ -FeSi₂ system (Fe_1???x Mn _x Si₂, with 0.00 ≤?x?≤ 0.24) was studied using X-ray diffraction and Mössbauer spectroscopy. Samples were prepared by the simultaneous mill of pure Si, Mn and Fe under Ar atmosphere followed by an annealing at 1,123 K during 4 h at 1 × 10^???7 Torr. After milling, an admixture of $\upbeta $ -FeSi₂, $\upalpha $ -FeSi₂ and $\upvarepsilon $ -FeSi phases was present while $\upalpha $ -FeSi₂ disappeared after annealing, resulting $\upbeta $ -FeSi₂ the main phase. Depending on Mn concentration, small amounts of $\upvarepsilon $ -FeSi and Si segregation were also observed. A preferential substitution of Fe atoms by Mn ones in the Fe_II site of the $\upbeta $ -FeSi₂ regular lattice was inferred from the Mössbauer results.     

Growth of non-polar Zn1−x Mg x O thin films with different Mg contents on r-plane sapphire substrates by plasma-assisted molecular beam epitaxy

We report the growth and characterization of a series of non-polar Zn_1?x Mg _x O thin films with different Mg contents, which have been prepared on r-plane sapphire substrates by plasma-assisted molecular beam epitaxy. Structural properties are anisotropic and surfaces of films show stripes running along the c-axis direction. The films exhibit atomically smooth surface with the minimal root mean square surface roughness of 0.36 nm. Non-polar Zn_1?x Mg _x O thin film is much easier to obtain pure a-plane single crystal orientation when Mg content is high. The quality of the non-polar Zn_1?x Mg _x O thin films is evidenced by X-ray diffraction (XRD) rocking curves full-width at half-maximum of 1,350 arcsec for the ( \( 11\overline{2} 0 \) ) reflection and 1,760 arcsec for the ( \( 10\overline{1} 1 \) ) reflection, respectively. Room temperature photoluminescence peak shifts monotonously from 3.29 to 3.56 eV as Mg content increases from 0 to 0.13. Alloying with Mg is found to widen the bandgap energy of the ZnO.     

Nanoscale distortions of the lattice of a ZnSe crystal doped with 3d elements

The structure of semiconductor crystals Zn_1?x V _x ²⁺ Se (x = 0.0018) and Zn_1?x Cr _x ²⁺ Se (x = 0.0006) was studied for the first time using thermal neutron diffraction at 300 and 120 K. The diffraction patterns of the crystals were revealed to contain diffuse scattering regions near the Bragg reflections of the initial cubic lattice. The experimental results are discussed in combination with earlier obtained data on neutron diffraction and propagation of ultrasonic waves in Zn_1?x Ni _x ²⁺ Se (x = 0.0025) and Zn_1?x Cr _x ²⁺ Se (x = 0.0029). The diffuse scattering is shown to be due to nanoscale shear strains of the ZnSe lattice. The character of these strains is determined by Jahn-Teller 3d ions.     

Search for magnetic interaction in In doped AlN using perturbed angular correlation spectroscopy

The possible presence of a large magnetic field due to spin polarization of a Cd nucleus (decay product of ¹¹¹In) at an Al substitutional site in AlN is investigated with perturbed angular correlation (PAC) spectroscopy. The PAC spectra of ¹¹¹In/¹¹¹Cd in AlN show two probe environments: a weak quadrupole interaction (quadrupole interaction constant, $\nu _{\rm Q}^{\,\,\,\rm lattice} = 30$  MHz) due to ¹¹¹In probes at a defect free Al substitutional site and an unknown large interaction ( $\nu _{\rm Q}^{\,\,\,\rm complex} = 300$  MHz) tentatively attributed to a nearest neighbour pair between ¹¹¹In and a nitrogen vacancy (V_N) aligned along the c-axis. Surprisingly, in density functional theory (DFT) calculations, such a large electric field gradient (EFG) could not be reproduced. However, an inclusion of spin polarization in the calculations indicates a strong magnetic field at ~50 % of the ¹¹¹In/¹¹¹Cd site. An attempt to verify the presence of the strong magnetic field and to explain the origin of the strong interaction is made. Orientation measurements show, the large interaction is not characterised by a magnetic interaction and is predominantly due to the EFG. However, in the presence of an external magnetic field, the strong interaction probe environment becomes more uniform and the EFG increases by ~10 %. This definitely hints towards some sort of magnetic interaction at the strong interaction probe site.     

Fougerite FeII − III oxyhydroxycarbonate in environmental chemistry and nitrate reduction

The identification of the fougerite mineral responsible for the bluish-green shade of gleysols in aquifers as being the Fe^II???III oxyhydroxycarbonate $\text{GR}(\text{CO}_{3}^{2-})^*$ of formula, $[\text{Fe}^{\rm II}_{6x}\text{Fe}^{\rm III}_{6(1 - x)}\text{O}_{12}\text{H}_{2(7-3x)}]^{2+}\bullet[\text{CO}_{3}^{2-}\bullet3\text{H}_{2}\text{O}]^{2-}$ where the ferric molar ratio x = [Fe^III/Fe_total] is restricted to the domain [1/3–2/3] induces to study the reactivity of the synthetic green rust for reducing some major pollutants. The oxidation within the solid compound $\text{GR}(\text{CO}_{3}^{2-})^*$ in the presence of nitrates is followed by miniaturized Mössbauer spectrometer (MIMOS). Ratio x = [Fe^III/Fe_total] increases up to 0.67 where $\text{GR}(\text{CO}_{3}^{2-})^*$ transforms gradually into magnetite. This could well explain the composition variability of fougerite occurrences.     

The N = 16 Spherical Shell Closure in 24O

The unbound excited states of the most neutron-rich dripline oxygen isotope, ²⁴O, have been investigated by using the ²⁴O(p,p′)²⁴O^* reaction at the beam energy of 62 MeV/nucleon in inverse kinematics. The first and second unbound excited states of ²⁴O have been observed at ${E_{\rm x}= 4.63_{-0.14}^{+0.30}}$  MeV and ${E_{\rm x}= 5.13_{-0.24}^{+0.19}}$  MeV (preliminary) along with the evidence for another higher lying state at around 7.3 MeV. The quadrupole deformation parameter ${\beta_{2^+}}$ was deduced to be ${0.15_{-0.03}^{+0.08}}$ (preliminary) for the first time. The systematics of the ${\beta_{2^+}}$ and the ${E_{\rm x}(2_1^+)}$ in the Z = 8 isotopes shows the N = 16 spherical shell closure in ²⁴O.     

Structure of some FeII − III hydroxysalt green rusts (carbonate, oxalate, methanoate) from Mössbauer spectroscopy

The abundances of Fe^II and Fe^III environments within green rusts one, GR1s, that intercalate carbonate, oxalate and methanoate (formate) anions are found from Mössbauer spectra for compositions corresponding to [Fe $^{\rm II}_{6}$ Fe $^{\rm III}_{2}$ (OH)₁₆]^2?+??[CO $_{3}^{2-}$ ?5H₂O]^2???, [Fe $^{\rm II}_{4}$ Fe $^{\rm III}_{2}$ (OH)₁₂]^2?+??[CO $_{3}^{2-}$ ?3H₂O]^2???, [Fe $^{\rm II}_{6}$ Fe $^{\rm III}_{2}$ (OH)₁₆]^2?+??[C₂O $_{4}^{2-}$ ?4H₂O]^2??? and [Fe $^{\rm II}_{5}$ Fe $^{\rm III}_{2}$ (OH)₁₄]^2?+??[2HCOO^????3H₂O]^2???. These formulae correspond to orders α, β and γ where cation distances are (2 × a ₀), ( $\surd 3$ × a ₀) or a mixture of both leading to (7 × a ₀), where ratio x = {[Fe^III]/[Fe_total]} = 1/4, 1/3 and 2/7, respectively. Anion distributions within interlayers are also devised and long-range orders determined accordingly.     

Mössbauer study of magnetism in FeII − III (oxy-)hydroxycarbonate green rusts; ferrimagnetism of FeII − III hydroxycarbonate

Fe^II???III hydroxycarbonate Fe $^{\rm II}_{4}$ Fe $^{\rm III}_{2}$ (OH)₁₂CO₃, green rust GR(CO $_{3}^{2-})$ , reveals a ferrimagnetic behaviour. Moments that lie within two-dimensional cation layers are parallel for same species and antiparallel between Fe^II and Fe^III. Respective ordering temperatures are 5.2 and 7 K. A sextet with distribution from 350 to 580 kOe for Fe^III and an octet reflecting a mixture of states with field of 130 kOe and quadrupole splitting of ?3.0 mm s^???1 for Fe^II are observed at 1.4 K. Ferric oxyhydroxycarbonate Fe $^{\rm III}_{6}$ O₁₂H₈CO₃ is ferromagnetic and displays at 4 K a sextet with field between 400 and 500 kOe (maximum at 480 kOe) and transition at 80 K. GR(CO $_{3}^{2-})$ deprotonation gives magnetic domains with compositions at x?=?1/3, 2/3 and 1 due to long range order.     

Cation distribution of the system Zn1−xCoxFeMnO4 by x-ray,electrical conductivity and Mössbauer studies

Structural, electrical and Mössbauer studies were carried out for the system Zn_1?xCo _x Fe MnO₄. It is observed that forx?0.6, the ionic configuration of the system is Zn _1?x ²⁺ Mn _x ²⁺ [Co _x ³⁺ Mn _1?x ³⁺ Fe³⁺]O ₄ ^2? and forx?0.8 Fe³⁺ ions occupy tetrahedral site also. On the basis of electrical and Mössbauer studies a probable valence distribution of CoMnFeO₄ has been suggested. All the compounds showed positive values of thermoelectric coefficient and electrical conduction takes place by a hopping mechanism. Activation energy and thermoelectric coefficient values decreased with decrease in concentration of Zn²⁺ ions. The compounds possess low mobility values varying between 10^?7 and 10^?9 cm²/V sec.     

35Cl NQR spectra of group 1 and silver dichloromethanesulfonates

The dichloromethanesulfonates of silver and other +1-charged cations, M ^?+?(Cl₂CHSO $_{3}^{-})$ (M = Ag, Tl, Li, Na, K, Rb, Cs) were synthesized and studied by ³⁵Cl NQR. Dichloromethanesulfonic acid was prepared by the methanolysis of dichloromethanesulfonyl chloride, and was then neutralized with the carbonates of the +1-charged cations to produce the corresponding dichloromethanesulfonate salt. This NQR study completed the investigation of the chloroacetates and chloromethanesulfonates of silver, Ag^?+?(Cl _x CH_3???x SO $_{3}^{-})$ and Ag^?+?(Cl _x CH_3???x CO $_{2}^{-})$ , and suggests (1) that the ability of organochlorine atoms to coordinate to silver decreases as the number of electron-withdrawing groups (Cl, SO $_{3}^{-}$ , CO $_{2}^{-})$ attached to the carbon atom increases; (2) that the unusually large NQR spectral width found among M ^?+?(Cl₂CHCO $_{2}^{-})$ salts is not present among M ^?+?(Cl₂CHSO $_{3}^{-})$ salts, and therefore is not generally characteristic of the dichloromethyl group in salts.     

Micro‐Raman investigation of transition‐metal‐doped ZnO nanoparticles

We measured the Raman spectra of ZnO nanoparticles (ZnO‐NPs), as well as transition‐metal‐doped (5% Mn(II), Fe(II) or Co(II)) ZnO nanoparticles, with an average size of 9 nm. A typical Raman peak at 436 cm⁻¹ is observed in the ZnO‐NPs, whereas Zn_1−xMn_xO, Zn_1−xFe_xO and Zn_1−xCo_xO presented characteristic peaks at 661, 665 and 675 cm⁻¹, respectively. These peaks can be related to the formation of Mn₃O₄, Fe₃O₄ and Co₃O₄ species in the doped ZnO‐NPs. Moreover, these samples were analyzed at various laser powers. Here, we observed new vibrational modes (512, 571 and 528 cm⁻¹), which are specific to Mn, Fe and Co dopants, respectively, and ZnO‐NPs did not reveal any additional modes. The new peaks were interpreted either as disorder activated phonon modes or as local vibrations of Mn‐, Fe‐ and Co‐related complexes in ZnO. Copyright © 2007 John Wiley & Sons, Ltd.     

PAC study of dynamic hyperfine interactions at 111In-doped Sc2O3 semiconductor and comparison with ab initio calculations

Time-Differential $\upgamma$ - $\upgamma$ Perturbed-Angular-Correlation (PAC) measurements were performed in ¹¹¹In-difussed Sc₂O₃ polycrystals in order to characterize the electric-field-gradient tensor at ¹¹¹Cd nuclei located at the two non-equivalent cation sites of the host lattice. The experimental data were compared with ab initio calculations performed using the Full-Potential Augmented Plane Wave plus local orbital (FP-APW+lo) method in the framework of the Density Functional Theory. The PAC experiments were carried out in air in the temperature range 10–900 K. The spectra present a strong damping below 650 K. This damping is associated with dynamic hyperfine interactions that were analyzed with the perturbation factor proposed by Bäverstam et al.. A model based in the population of impurity levels that are introduced by the Cd probes (supported by FP-APW+lo results) is proposed in order to explain the origin of the observed dynamic interactions.     

Structural and optical properties of non-polar ZnO/Zn0.81Mg0.19O multiple quantum wells grown on r -plane sapphire substrates by plasma-assisted molecular beam epitaxy

This work investigates the structural and optical properties of non-polar ZnO/Zn_0.81Mg_0.19O multiple quantum wells (MQWs), which have been prepared on $r$ -plane sapphire substrates by plasma-assisted molecular beam epitaxy (MBE). The MQWs are ( $11\bar{2}0$ ) oriented ( $a$ -plane) as identified by the X-ray diffraction pattern. Structural properties are anisotropic and surfaces of MQWs show stripes running along the ZnO $c$ -axis direction. Sharp interfaces between the well layers and barrier layers can be clearly resolved by the secondary ion mass spectroscopy (SIMS) analysis. The room-temperature photoluminescence (PL) resulting from the well regions exhibits a significant blueshift with respect to ZnO single layer. Exciton emission in the ZnO QW is resolved into two components in the temperature dependence of the PL spectra. Two types of excitons are responsible for this feature. The excitons trapped by the potential minima dominate at low temperature, and the excitons localized in the “free exciton states” dominate at relatively high temperature. An activation energy of 7.3 meV for quenching of the exciton emission is in good agreement with the transition of the two types of excitons.     

Localization in the ground state of the ising model with a random transverse field

We study the zero-temperature behavior of the Ising model in the presence of a random transverse field. The Hamiltonian is given by $$H = - J\sum\limits_{\left\langle {x,y} \right\rangle } {\sigma _3 (x)\sigma _3 (y) - \sum\limits_x {h(x)\sigma _1 (x)} } $$ whereJ>0,x,y∈Z ^d, σ₁, σ₃ are the usual Pauli spin 1/2 matrices, andh={h(x),x∈Z ^d} are independent identically distributed random variables. We consider the ground state correlation function 〈σ₃(x)σ₃(y)〉 and prove:

1. Letd be arbitrary. For anym>0 andJ sufficiently small we have, for almost every choice of the random transverse fieldh and everyx∈Z ^d, that $$\left\langle {\sigma _3 (x)\sigma _3 (y)} \right\rangle \leqq C_{x,h} e^{ - m\left| {x - y} \right|} $$ for ally∈Z ^d withC _{x h} <∞.
2. Letd≧2. IfJ is sufficiently large, then, for almost every choice of the random transverse fieldh, the model exhibits long range order, i.e., $$\mathop {\overline {\lim } }\limits_{\left| y \right| \to \infty } \left\langle {\sigma _3 (x)\sigma _3 (y)} \right\rangle > 0$$ for anyx∈Z ^d.

     

Search for ferromagnetic ordering in Pd doped wide band gap semiconductors GaN and ZnO

GaN and ZnO are possible candidates for dilute magnetic semiconductors with Curie temperatures above room temperature. Doping with transition metals like Co, Mn or Fe could be a simple way to create such systems. The perturbed angular correlation (PAC) probe ¹⁰⁰Pd/¹⁰⁰Rh is isoelectronic to cobalt and therefore a perfect tool to investigate the incorporation of transition metals into these compounds as well as the influence of other impurities on internal magnetic fields. The (0001) and (10 $\bar{1}$ 10) surfaces of ZnO single crystals, freestanding GaN films, and GaN thin films (6 μm) on sapphire substrates were recoil-implanted with the ¹⁰⁰Pd/¹⁰⁰Rh probe. The probe was produced using the fusion evaporation reaction ⁹²Zr(¹²C, 4n)¹⁰⁰Pd at a beam energy of 69 MeV. Subsequently, the incorporation of the probe was studied by PAC spectroscopy during an isochronal annealing program. First results without and with an applied external magnetic field are indicative of a strongly disturbed lattice vicinity of Pd impurities in both hosts. No signs of spontaneous ferromagnetic ordering were observed.     

The nucleon structure functions in deep inelastic scattering off deuterium: nuclear shadowing and the Gottfried sum rule

The perturbative QCD is applied to calculation of nuclear shadowing correction to the deuterium structure functionF ₂ ^D (x) atx«1. This correction is shown to be numerically large. It is emphasized that the neglect of nuclear shadowing leads to underestimating of the neutron structure functionF ₂ ⁿ (x) and, as a result, to gross overestimating of the Gottfried integral \(\int_0^1 {\left[ {F_2^P (x) - F_2^n (x)} \right]} dx/x\)      

First-principles study on the electronic and optical properties of Si and Al co-doped zinc oxide for solar cell devices

Electronic and optical properties of co-doped zinc oxide ZnO with silicon (Si) and aluminum (Al), in Zn_1?2x Si _x Al _x O (0 ≤ x ≤ 0.0625) original structure forms, are investigated by the first-principles calculations based on the density functional theory (DFT). The optical constants and dielectric functions are investigated with the full-potential linearized augmented plane wave (FP-LAPW) method and the generalized gradient approximation (GGA) by WIEN2k package. The complex dielectric functions, refractive index and band gap of the pure as well as doped and co-doped ZnO were investigated, which are in good agreement with the available experimental results for the undoped ZnO. Thus, the maximum optical transmittance of the co-doped ZnO of about 95 % was achieved; it is higher than that of pure ZnO. Thus, we showed for the Si–Al co-doped ZnO with x = 0.0315 that the optical transmittance can cover a larger range in the visible light region. In addition, an occurrence of important energy levels around Fermi levels was showed, which is mainly due to doping atoms that lead to an overlap between valence and conduction bands, and consequently to the significant conductor behavior of the Si–Al co-doped ZnO. The original Zn_1?2x Si _x Al _x O structure reveals promising optical and electronic properties, and it can be investigated as good candidates for practical uses as transparent and conducting electrodes in solar cell devices.     

Spin states of cobalt and the thermodynamics of Sm1 − x Ca x CoO3 − δ solid solutions

In the rare-earth SmCoO₃ perovskite, Co³⁺ ions at low temperatures appear to be in the low-spin state with S = 0, t _2g ² e _g ⁰ . If Ca²⁺ ions partially substitute Sm³⁺ ions, oxygen deficient Sm_{1 ? x} Ca _x CoO_{3 ? δ} solid solutions with δ = x/2 appear. The oxygen deficiency leads to the formation of pyramidally coordinated cobalt ions Co _pyr ³⁺ in addition to the existing cobalt ions Co _oct ³⁺ within the oxygen octahedra. Even at low temperatures, these ions have a magnetic state, either S = 1, t _2g ⁵ e _g ¹ or S = 2, t _2g ⁴ e _g ² . At low temperatures, the magnetization of Sm_{1 ? x} Ca _x CoO_{3 ? δ} is mainly determined by the response of Co _pyr ³⁺ ions. Owing to the characteristic features of the crystal structure of the oxygen deficient perovskite, these ions form a set of nearly isolated dimers. At high temperatures, the magnetization of Sm_{1 ? x} Ca _x CoO_{3 ? δ} is mainly determined by the response of Co _oct ³⁺ ions, which exhibit a tendency to undergo the transition from the S = 0, t _2g ⁶ e _g ⁰ state to the S = 1, t _2g ⁵ e _g ¹ or S = 2, tt _2g ⁴ e _g ² state. In addition, the magnetization and specific heat of the solid solutions under study include the contribution from the rare-earth subsystem, which undergoes a magnetic ordering at low temperatures.     

A Weighted Dispersive Estimate for Schrödinger Operators in Dimension Two

Let H = ?Δ + V, where V is a real valued potential on ${\mathbb {R}^2}$ satisfying ${\|V(x)|\lesssim \langle x \rangle^{-3-}}$ . We prove that if zero is a regular point of the spectrum of H = ?Δ + V, then $${\| w^{-1} e^{itH}P_{ac}f\|_{L^\infty(\mathbb{R}^2)} \lesssim \frac{1}{|t|\log^2(|t|)} \| w f\|_{L^1(\mathbb{R}^2)},\,\,\,\,\,\,\,\, |t| \geq 2}$$ , with w(x) = (log(2 + |x|))². This decay rate was obtained by Murata in the setting of weighted L ² spaces with polynomially growing weights.