TDPAC study of Cd-doped SnO

The combination of hyperfine techniques and ab initio calculations has been shown to be a powerful tool to unravel structural and electronic characterizations of impurities in solids. A recent example has been the study of Cd-doped SnO, where ab initio calculations questioned previous TDPAC assignments of the electric-field gradient (EFG) in ¹¹¹In-implanted Sn-O thin films. Here we present new TDPAC experiments at ¹¹¹In-difused polycrystalline SnO. A reversible temperature dependence of the EFG was observed in the range 295–900 K. The TDPAC results were compared with theoretical calculations performed with the full-potential linearized augmented plane wave (FP-LAPW) method, in the framework of the density functional theory. Through the comparison with the theoretical results, we infer that different electronic surroundings around Cd impurities can coexist in the SnO sample.     

PAC measurements in titanium and titanium-hydrogen alloys

Measurements have been performed with the PAC method in pure hcp titanium and highly concentrated titanium hydrogen alloys to investigate the temperature dependence of the electric field gradient (EFG) in both systems. In pure titanium it can be explained by a recent theoretical model; in the titanium hydride the EFG reveals a strong decrease with temperature, which indicates enhanced local vibration amplitudes. Furthermore the interaction of hydrogen and oxygen impurities with the¹¹¹In probe atoms have been studied.     

The quadrupole moments of Cd and Zn isotopes - an apology

In 2010 we presented an update of the nuclear quadrupole moments (Q) for the Cd and Zn isotopes, based essentially on straightforward density functional (DF) calculations (H. Haas and J.G. Correia, Hyperfine Interact 198, 133–137 (2010)). It has been apparent for some years that the standard DF procedure obviously fails, however, to reproduce the known electric-field gradient (EFG) for various systems, typical cases being Cu₂O, As and Sb, and the solid halogens. Recently a cure for this deficiency has been found in the hybrid DF technique. This method is now applied to solid Cd and Zn, and the resultant quadrupole moments are about 15 % smaller than in our earlier report. Also nuclear systematics, using the recently revised values of Q for the long-lived 11/2 isomers in¹¹¹Cd to¹²⁹Cd, together with earlier PAD data for^107,109Cd, leads to the same conclusion. In addition, EFG calculations for the cadmium dimethyl molecule further support the new values: Q(¹¹¹Cd, 5/2⁺) = .683(20) b, Q(⁶⁷Zn, gs) = .132(5) b. This implies, that the value for the atomic EFG in the \(^{3}\textit {P}_{1}\) state of Zn must be revised, as it has been for Cd.     

Hyperfine spectroscopic study of the metal-insulator transition in V2O3

The metal-insulator (M-I) transition in vanadium sesquioxide V₂O₃ has been investigated by time differential perturbed angular correlation measurements of the electric fieldgradient (EFG) and the magnetic hyperfine field at dilute¹¹¹Cd impurities. The EFG undergoes a first-order change at the M-I transition at T_t=160 K, but does not reflect the high temperature resistivity anomaly. The increase of the EFG with temperature in the metallic phase can be attributed to thermal variations of the oxygen sublattice. The temperature dependence of the magnetic hyperfine field in the insulating phase follows a Brioullin function with a saturation value of H_hf(O)=15 KOe and an extrapolated Neel temperature, which, depending on the impurity concentration, varies between 188 and 230 K.     

Hyperfine interactions in 111Cd-doped lutetium sesquioxide

We report here first Perturbed Angular Correlation (PAC) results of the electric field gradient (EFG) characterisation at ¹¹¹Cd impurities located at both non-equivalent cation sites of the bixbyite structure of Lutetium sesquioxide, between room temperature (RT) and 1273 K. The comparison with results coming from a systematic ¹¹¹Cd PAC study in bixbyites and with point-charge model (PCM) predictions shows the presence of a trapped defect at RT in the neighbourhood of the asymmetric cation site, which is completely removed at T > 623 K. The anomalous EFG temperature dependence in Lu₂O₃ can be described in the frame of a “two-state” model with fluctuating interactions, which enables the experimental determination of the acceptor energy level introduced by the Cd impurity in the band-gap of the semiconductor and the estimation of the oxygen vacancy density in the sample. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ab initio study of the EFG tensor at Cd impurities in Sc2O3 semiconductor

We present an ab initio study of diluted Cd impurities localized at both cation sites of the semiconductor Sc₂O₃. The electric-field-gradient (EFG) tensor at Cd impurities located at both cationic sites of the host structure was determined from the calculation of the electronic structure of the doped system. Calculations were performed with the full-potential augmented-plane wave plus local orbitals (APW+lo) method within the framework of the density functional theory. We studied the atomic structural relaxations and the perturbation of the electronic charge density induced by the impurities in the host system in a fully self-consistent way. We showed that the Cd impurity introduces an increase of 8% in the nearest oxygen neighbors bond-lengths, changing the EFG sign for probes located at the asymmetric cation site. The APW+lo predictions for the charged state of the Cd impurity were compared with EFG results existent in the literature, coming from time-differential γ–γ perturbed-angular-correlations experiments performed on ¹¹¹Cd-implanted Sc₂O₃ powder samples. From the excellent agreement between theory and experiment, we can strongly suggest that the Cd acceptor impurities are ionized at room temperature. Finally, we showed that simple calculations like those performed within the point-charge model with antishielding factors do not correctly describe the problem of a Cd impurity in Sc₂O₃.     

Interaction of repulsive impurity pairs in silver

Probe-impurity interactions of In–Cd and In–Zn pairs in silver matrix have been studied using ¹¹¹In-TDPAC measurements. The interactions are repulsive for both the pairs. For 3% alloys, the interaction energy of In–Cd pairs in Ag is 51± 2 meV and that of In–Zn pairs is 19± 1 meV. The Electric Field Gradient (EFG) at ¹¹¹Cd due to a single Cd nn impurity to the In probe is found to be 0.83± 0.04× 10²¹ V/m² while for a Zn impurity is 1.50± 0.05× 10²¹ V/m². Cd–Cd contact interaction in silver is also found to be repulsive. This revised version was published online in August 2006 with corrections to the Cover Date.     

Site occupation of indium and jump frequencies of cadmium in FeGa<Subscript><Emphasis Type="Bold">3</Emphasis></Subscript>

Perturbed angular correlation (PAC) measurements using the In-111 probe were carried out on FeGa₃ as part of a broader investigation of indium site occupation and cadmium diffusion in intermetallic compounds. One PAC signal was observed with hyperfine parameters ω ₁= 513.8(1) Mrad/s and η= 0.939(2) at room temperature. By comparison with quadrupole frequencies observed in PAC measurements on isostructural RuIn₃, it was determined that indium occupies only the 8j site in the FeGa₃ structure, denoted Ga(2) below because two out of the three Ga sites have this point symmetry. PAC spectra at elevated temperature exhibited damping characteristic of electric field gradients (EFGs) that fluctuate as Cd probes jump among Ga(2) sites within the lifetime of the excited PAC level. A stochastic model for the EFG fluctuations based on four conceivable, single-step jump-pathways connecting one Ga(2) site to neighboring Ga(2) sites was developed and used to fit PAC spectra. The four pathways lead to two observable EFG reorientation rates, and these reorientation rates were found to be strongly dependent on EFG orientation. Calculations using density functional theory were used to reduce the number of unknowns in the model with respect to EFG orientation. This made it possible to determine with reasonable precision the total jump rate of Cd among Ga(2) sites that correspond to a change in mirror plane orientation of site-symmetry. This total jump rate was found to be thermally activated with an activation enthalpy of 1.8 ±0.1 eV.     

Study of electric quadrupole interactions at 111Cd on Zn sites in RZn (R = Ce, Gd, Tb, Dy) compounds using the PAC spectroscopy

Nuclear quadrupole interactions at Zn sites in the intermetallic compounds RZn (R = Ce, Gd, Tb, Dy) have been investigated by perturbed gamma-gamma angular correlation (PAC) spectroscopy using ¹¹¹In(¹¹¹Cd) as probe nuclei. Measurements were carried out in the temperature range of 10–295 K. These compounds exhibit CsCl type cubic structure and while CeZn shows antiferromagnetic behaviour, the compounds GdZn, TbZn, DyZn are ferromagnetic. The results show that the EFG in these compounds is sensitive to the distribution of rare-earth 4f-electron charges.     

Atomistic mechanisms of dopant-induced multiple quantum well mixing and related phenomena

We discuss mechanisms of Ga self-diffusion and impurity diffusion in GaAs, and of layer mixing enhancement in GaAs/AlGaAs multiple quantum wells (MQWs). Ga self-diffusion and Ga-Al interdiffusion are governed by the triply negatively charged Ga vacancies, V _Ga ^3– , under intrinsic and n-doping conditions, and by doubly positively charged Ga self-interstitials, I _Ga ²⁺ , under heavy p-doping conditions. The mechanisms responsible for enhancing MQW mixing are the Fermi-level effect for the n-dopants Si and Te, and the combined effects of the Fermi-level and the dopant diffusion-induced nonequilibrium point defects for the p-dopants Zn and Be. For n-type GaAs the donor Si atoms diffuse primarily also via V _Ga ^3– . For p-type GaAs the interstitial-substitutional impurities Zn and Be diffuse via the kickout mechanism and induce a supersaturation and an undersaturation in the concentrations of I _Ga ²⁺ , respectively, under indiffusion and outdiffusion conditions.     

Electric-Field Gradients at Group-III Sites on GaAs and InAs (111)B Surfaces

We report a comparison of electric-field gradients (EFGs) measured at the group-III sites on epitaxially-grown surfaces of 2×2-reconstructed GaAs and InAs crystals. For this purpose, we used ¹¹¹In→¹¹¹Cd perturbed-angular-correlation (PAC) spectroscopy. Sharp spectral lines characterize the perturbation functions corresponding to both surfaces. On GaAs surface, we observe only one well-defined nuclear electric-quadrupole interaction (NQI); and on the InAs surface, we observe a primary and a secondary NQI. Very similar but experimentally-distinguishable values of the EFG-parameters characterize the primary interactions corresponding to the GaAs and InAs surfaces. Specifically, for the GaAs and InAs surfaces, ω _Q =28.0±0.2 Mrad s⁻¹ and η=0.43±0.02 and ω _Q =28.8±0.2 Mrad s⁻¹ and η=0.39±0.02, and the angles between EFG z-axis and the (111) direction are 65°±3° and β=53°±3°, respectively. These unexpected results indicate that the so-called lattice contribution to the EFG is not significant. Moreover, for the primary NQIs on both surfaces, the similar parameter values demonstrate that chemical differences between the ¹¹¹In probe and the indigenous Ga surface atoms cause no large quantitative effects. This information indicates that impurity probes and PAC spectroscopy can be used effectively to investigate III–V surfaces. This revised version was published online in September 2006 with corrections to the Cover Date.     

Pressure dependence of the electric field gradient in Sb and Sb1−x M x (M=ln,Zn, Ge,Pb, Cd,Sn) at the site of111Cd

Using the¹¹¹Cd-TDPAC (time differential perturbated angular correlation) method, the pressure dependence of the electric field gradient (EFG) in Sb and Sb_1–x M _x (M=ln, Zn, Ge, Pb, Cd, Sn) was investigated. The application of a phenomenological ansatz for the parametrisation of the pressure and temperature dependence of the EFG made it possible to combine temperature data gained in former studies [1], [2] with the pressure dependent data presented in this paper. The resulting pressure dependence of –2±0.2 MHz/kbar is shown to be independent of concentration and element of admixture. Results for the volume and explicit temperature dependence agree with existing information on the mixed system Sb_1–x M _x (M=ln, Zn, Ge, Pb, Cd, Sn); the investigation of the EFG in Sb_1–x–y M _x Pb _y showed that the resulting EFG may be interpreted as the weighted sum of the individual contributions of the two metals.This paper is dedicated to Prof. Dr. W. Kreische on the occasion of his 60th aniversary on 02.02.1995     

Electric quadrupole interaction of181Ta in Pd and Zn

A strong electric field gradient (EFG) has been observed at¹⁸¹ Ta in Pd and Zn metals using DPAC technique. The value of the EFG in Pd is found to be 12.5(8)×10¹⁷ V/cm² with an asymmetry parameter () of 0.33(2). The value of the EFG in Zn has the same value as in the Pd metal, but the asymmetry parameter has the value 0.36(3). The variation of EFG in Pd with temperature has shown a weak dependence. The results are interpreted in terms of oxygen trapping at Hf atoms during the sample preparation.     

Electrical transport in a-As2Se3 containing metallic impurities

Significant changes of the hole drift mobility are observed in a-As₂Se₃ containing concentrations less than ～ 10²⁰ cm^?3 of metallic impurities (Mn, Fe, Ni, Cu, Zn, Ga, In, Tl and Na). Depending upon metal concentration the results suggest a modification of the hopping transport channel in Ga, In and Tl doped samples and the buildup of new traps that are either isoenergetic with the intrinsic trap population (Tl, Ga, In, Cu) or lie deeper in the gap (Mn, Fe, Ni, Cu). Trap-limited hopping transport provides a consistent explanation of the experimental data.     

Measurement of Quadrupole Interactions in LaMO3 (M = Cr,Fe, Co) Perovskites by TDPAC

The perturbed angular correlation (PAC) technique has been used to study the electric field gradient (EFG) in LaCoO₃ perovskite. The results are compared with those for LaCrO₃, LaFeO₃ measured earlier. The PAC probe, ¹¹¹In → ¹¹¹Cd, was introduced in the oxide lattice by means of chemical reaction during sample preparation. In the present work, the temperature dependence of the electric quadrupole interaction parameters, for LaCoO₃ was investigated. The resulting systematics of EFG at ¹¹¹Cd, in La(Cr,Fe,Co)O₃ perovskites, reveals a linear dependence with temperature. This revised version was published online in September 2006 with corrections to the Cover Date.     

Electric field gradients in dilute alloys of Cu,Ag and Au

In this paper we present perturbed angular correlation (PAC) measurements on¹⁰⁰Rh and¹¹¹Cd in a number of dilute alloys of Cu, Ag and Au. We discuss the electric field gradient (EFG) values derived from these and other experiments in the framework of a theory of the EFG at nearest neighbours of point defects in metals, essentially based on the screening of a point charge in a free electron gas. We include in our discussion the EFG due to a neighbour monovacancy for a number of fcc metals.     

The electric field gradient and its temperature dependence for indium in beryllium

The electric field gradient (EFG) for¹¹⁷InBe has been determined by a TDPAC measurement to be eq_tot=1.83(1) 10¹⁷V/cm² at room temperature. The sources were prepared by ion — implantation of¹¹⁷Cd in a Be single crystal. The EFG was found to decrease considerably with increasing temperature. The results are compared to those of other impurities in Be.     

Mössbauer Studies on Nanocrystalline Diol Capped γ-Fe2O3

Nanocrystalline indium (nano-In) was prepared with different particle sizes by electrochemical deposition. The temperature dependence of the local electric field gradient (EFG) of nano-In was investigated in a temperature range of 20–300 K using the probe ¹¹¹In for perturbed γγ angular correlation (PAC) experiments. The temperature dependence of the EFG of nano-In can be described by a (1−BT ^3/2) dependence as in bulk-In. It is shown that the low temperature value of the EFG and the proportionality constant B vary systematically with particle size.