Precision PAC measurements in Er2O3 and Ho2O3 single crystals and structure refinement

The structure of C-form Ho₂O₃ and Er₂O₃ single crystals and powder samples was investigated by the electric quadrupole hyperfine interaction of¹¹¹In(EC)¹¹¹Cd probe ions using the perturbed - angular correlation method (PAC). The resulting set of refined atomic coordinates is compared to X-ray data and used to calculate the orientations of the electric field gradients (EFG) which are reproduced by the PAC measurements in single crystals. The temperature dependence of the coordinates was measured for both substances.     

Indium-defect complexes in silicon studied by perturbed angular correlation spectroscopy

The formation of molecule-like complexes, consisting of a defect and a radioactive¹¹¹In atom, is studied using the perturbed angular correlation technique (PAC). The complexes are characterized by their defect specific electric field gradients which also contain information on the geometry of the formed complexes. Whereas the complex is formed with the¹¹¹In atom, its electric field gradient is measured after the decay of the radioactive¹¹¹In atom to¹¹¹Cd. Formation and dissolution of the molecule-like complexes is pursued for a variety of different conditions, such as sample temperature, dopant concentration and position of the Fermi level. In particular, the interaction of In atoms with the following defects in Si was investigated: Intrinsic defects, created by particle irradiation; substitutional donor atoms (P, As, Sb, Bi); and interstitial impurity atoms (Li, H, and an unidentified X defect); especially, the latter ones are known to passivate acceptor atoms in Si. Methodology and specific properties of the PAC technique will be illustrated with the help of these examples.     

Analysis of perturbed angular correlation spectra of metal ions bound to proteins with rotational correlation times in the intermediate region

The formulation by Dattagupta of the strong-collision model, describing the effect on the perturbation function,G ₂(t) by the isotropic tumbling of an electric field gradient, is generalized to electric field gradients with no axial symmetry. The effect on the perturbation function by strong collisions is compared to the effect of rotational diffusion in the adiabatic limit. The comparison is carried out for decays with an intermediate state of spin 5/2 and for non-axially symmetric electric field gradients. It shows that the strong-collision model can be used for interpretation of PAC spectra of molecules with correlation times between the adiabatic and the fast relaxation limits. The strongcollision model is then used to determine the rotational diffusion of the cadmium substituted copper, zinc superoxide dismutase at 3°C and 25°C from^111mCd TDPAC spectra. For these analyses, the model is incorporated into a conventional least-squares fitting routine.     

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.     

Hyperfine interaction of111Cd in In-Pd intermetallic compounds

Perturbed - angular correlation (PAC) spectroscopy was applied to study the hyperfine parameters for¹¹¹In probes in In-Pd intermetallic compounds. The PAC spectra measured in In₃Pd, In₃Pd₂ and InPd₂ compounds reflect the number, population and symmetry of nonequivalent indium probe sites predicted by the crystallographic data. The temperature dependence of the observed electric field gradients was measured in the temperature range 80–873 K.     

Magnetic hyperfine fields in ultrathin Ni films on Cu(100)

The magnetic hyperfine field was measured at ¹¹¹In(¹¹¹Cd) probe atoms in ultrathin Ni films epitaxially grown on Cu(100) utilizing the perturbed -angular correlation (PAC) method. The behaviour of the hyperfine field as a function of temperature was studied for different film thicknesses ranging from 2 up to 10 monolayers. It was found that the strength of the hyperfine fields as well as the critical temperatures are strongly reduced for thin nickel films and approach the bulk value with increasing film thickness. The orientation of the hyperfine field is discussed.     

Growth and melting behaviour of thin in films on Ge(100)

Growth and melting behaviour of thin indium films on Ge(100) have been investigated by Auger-electron spectroscopy (AES), atomic force microscopy (AFM) and perturbed angular correlation (PAC) spectroscopy, respectively. At room temperature inidium is found to grow in three-dimensional islands even at submonolayer coverages. A very rough film surface is observed for thicknesses up to 230 ML. The melting behaviour of such films has been studied by PAC. A reduction of the melting temperature T _m as well as a strong supercooling of the films is observed. The electric field gradient for ¹¹¹In(¹¹¹Cd) in the indium islands is determined as a function of temperature and is used to monitor the local crystalline order of the films up to temperatures just below the melting point.     

PAC investigation of77Br→77Se on silicon surfaces

The perturbed-angular correlation (PAC) method has been applied to investigate the sites occupied by isolated⁷⁷Br-atoms on silicon surfaces. The nuclear quadrupole interaction was used to determine the electric field gradients (efg) acting at the 5/2^– state in⁷⁷Se, populated in the⁷⁷Br decay. For the Si(100)2×1 surface two different field gradients have been observed with the parameters _Q1 = 583(5) MHz, ₁ = 0.0(1) and _Q2=543(5) MHz, ₂ = 0.40(3). Typical values for the Si(111)7×7 surface from preliminary data are _Q=548(9) MHz,=0.54(6). These electric field gradients are identified with adsorption sites of the selenium at dangling bonds of the silicon surfaces.     

Ferromagnetic Semiconductors Studied by Hyperfine Interaction of Nuclear Probes

The ferromagnetic spinels CdCr₂Se₄ and CuCr₂Se₄ were investigated by PAC (perturbed angular correlations) after implantation of the probes ¹¹¹In(¹¹¹Cd), ^111mCd, ¹¹¹Ag(¹¹¹Cd) and ⁷⁷Br(⁷⁷Se). The site occupation of different probes was determined by magnetic and electric hyperfine interactions. Theoretical calculations of hyperfine parameters by the WIEN97 code gave satisfactory efg (electric field gradients) but the magnetic hyperfine fields are inconsistent with the experiments. This revised version was published online in September 2006 with corrections to the Cover Date.     

Pac studies of spin deviations,pressure induced hyperfine field shifts,and temperature variation of supertransferred hyperfine fields

A PAC study of¹¹¹Cd substiuted antiferromagnetic transition metal salts is reported. Supertransferred hyperfine fields at¹¹¹Cd nuclei were used for the first time to observe three effects: zero-point spin deviations, temperature variation, and pressure shift of the hyperfine field. Comparison of KNiF₃ and RbMnF₃ with their corresponding quadraticlayer fluorides K₂NiF₄ and Rb₂MnF₄ yields an estimate for the magnitude of the zeropoint spin deviation in doped antiferromagnets. The temperature dependences of the Cd hyperfine fields in RbMnF₃/Cd and MnF₂/Cd have been determined. The shift in hyperfine field observed for -MnS/Cd under external pressure further supports our model for the origin of the supertransferred hyperfine fields.This work was supported by the US Energy Research and Development Administration.     

Geometrical significance of the orientation of defect-induced electric field gradients

One of the features of defect-induced axial symmetric electric field gradients(efg) is the orientation of their symmetry axis with respect to the crystal lattice. Especially in the case of simple trapped defects(mono-, di-vacancies, single interstitials or single impurity atoms) this orientation should follow the symmetry of the geometrical probe atom defect arrangement. This will be illustrated by PAC measurements at¹¹¹In/¹¹¹Cd for the case of trapped impurity atoms in Cu.This work was supported by the Bundesminister für Forschung und Technologie.     

Semiconductors with structurally determined vacancies – PAC studies

Ternary semiconductors of type □A^IIB ₂ ^III C ₄ ^VI with an ordered array of vacancies were investigated by PAC. Thereby the six probes ¹¹¹Cd, ¹¹⁷Cd(¹¹⁷In), ¹¹¹In(¹¹¹Cd), ¹¹¹Ag(¹¹¹Cd), ⁷⁷Br(⁷⁷Se) and ⁷⁷Kr(⁷⁷Br) were applied. The positions of the different probes are determined and the corresponding electric field gradients by the WIEN 95 code calculated. By ¹¹¹Ag(¹¹¹Cd)-probes the vacancies could be substituted. The electronic charge density distributions are discussed. At elevated temperatures the substances show order–disorder transitions. As compared to the X-ray diffraction patterns the beginning of disorder is observed by PAC at distinctly lower temperatures. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hyperfine interactions of111Cd impurities in Cr2O3

The electric and (antiferro-)magnetic hyperfine interaction of¹¹¹Cd in α-Cr₂O₃ after¹¹¹In implantation was studied via PAC. Two fractions with axially symmetric electric field gradients were observed having antishielding factors of V_zz/V_zz ^pc=79(12) and 106(16), respectively. From the line broadening of the Fourier components of the first fraction its supertransferred magnetic field was estimated as B_loc (20 K)≤0.41 T, about two orders of magnitude smaller than for substitutional¹¹¹Cd in NiO and CoO.     

Magnetic Properties of Grain Boundaries of Nanocrystalline Ni and of Ni Precipitates in Nanocrystalline NiCu Alloys

Perturbed γγ-angular correlation spectroscopy (PAC) was used to investigate nanocrystalline Ni and NiCu alloys, which are prepared by pulsed electrodeposition (PED). Using diffusion for doping nanocrystalline Ni with ¹¹¹In four different ordered grain boundary structures are observed, which are characterized by unique electric field gradients. The incorporation of ¹¹¹In on substitutional bulk sites of Ni is caused by moving grain boundaries below 1000 K and by volume diffusion above 1000 K. The nanocrystalline NiCu alloys prepared by PED are microscopically inhomogeneous as observed by PAC. In contrast, this inhomogeneity cannot be detected by X-ray diffraction. The influence of the temperature of the electrolyte, the current density during deposition, and the optional addition of saccharin to the electrolyte on the homogeneity of nanocrystalline NiCu alloys was investigated. This revised version was published online in September 2006 with corrections to the Cover Date.     

The electric field gradient at111Cd in vanadium oxides

The electric field gradient (efg) of¹¹¹Cd in polycrystalline V₂O₅ was studied using perturbed angular correlation (PAC) spectroscopy, with the¹¹¹In activity ion-implanted at 400 keV. Between the individual steps of an isochronal annealing program, a distinct efg (v _Q 1=88.1(3) MHz, ₁=0.62(2)) was recorded the contribution of which increased with annealing temperature up to 74% at 870 K. Corresponding X-ray analysis of inactive V₂O₅ samples, which underwent the same annealing treatment, proved that the sample always stayed as V₂O₅. Since V₂O₅ has only one equivalent cation site, it is concluded that this efg belongs to¹¹¹Cd at this site. Oxidation of a vanadium foil atT=675 and 800 K at =200 mbar also yielded this efg. From PAC measurements in VO₂, two well-defined efg's were found above and below the metal-semiconductor transition at 340 K, which are tentatively attributed to the monoclinic and the tetragonal phase.Supported by Deutsche Forschungsgemeinschaft and DAAD.On leave from the University of Durban-Westville, South Africa.     

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.     

Vacancy trapping at111In in tungsten

TDPAC measurements were carried out in tungsten foils and single crystals using implanted¹¹¹In as a probe nucleus. After damaging the bcc tungsten lattice by heavy ion implantation, electron- and proton-irradiation the trapping of three different defects in the temperature range 293–1,000 K was observed. They were characterized by quadrupole interaction frequencies of v _Q ¹ = 142(2) MHz, v _Q ² = 181(5) MHz and v _Q ³ = 263(5) MHz. The largest fraction of In nuclei experiencing electric field gradients corresponding to v _Q ¹ and v _Q ² was reached at app. 630 K whereas for v _Q ³ this maximum appeared at app. 850 K. The defect configurations producing the different electric field gradients could be identified as a monovacancy trapped in a nearest neighbour 111 position (v _Q ¹ ), a double vacancy consisting of two adjacent vacancies in the nearest neighbour shell of the probe atom (v _Q ² ) and possibly a larger cluster (v _Q ³ ).     

Temperature dependence of electric field gradient in TbCoO3

The temperature dependence of the electric field gradient (efg) in TbCoO₃ perovskite was measured by perturbed angular correlation (PAC) technique using ¹¹¹Cd and¹⁸¹Ta nuclear probes. The radioactive parent nuclei ¹¹¹In and ¹⁸¹Hf were introduced into the compound through a chemical process during sample preparation. The electric quadrupole interactions at ¹¹¹Cd show two different sites, assigned to probe substituting Tb and Co atoms. The temperature dependence of quadrupole frequencies show sharp discontinuities which have been interpreted as thermally activated spin state transitions from low-spin ground state configuration to the intermediate-spin state and from intermediate-spin to high-spin state of Co^3?+? ion. For ¹⁸¹Ta only one interaction was observed, which was assigned to probe at Co site. Indication of a Jahn–Teller distortion, which stabilizes the intermediate-spin state with orbital ordering, is also pointed out. No magnetic order was observed till 77 K.     

Electric Fields Gradients at 111In Sites in CdIn2O4 Spinel

The perturbed angular correlation (PAC) technique was applied to study the electric field gradients at ¹¹¹In sites in CdIn₂O₄. The measurements were carried out at temperatures in the range 150–1073 K. The aims of the study were both to characterize the quadrupole interactions of the tracers and to determine the distribution of indium ions among the available sites in the spinel structure. Room temperature measurements corresponding to samples cooled at different rates are also reported. ^aAlso at Comisión de Investigasiones Científicas de la Provincia de Buenos Aires, Argentina.     

Vacancy-induced hyperfine interaction in solids detected by perturbed angular distributions

Relaxation effects in time-differential perturbation factors of an implanted nucleus are studied when its environment stochastically changes by fluctuating electric field gradients due to vacancy jumps in the lattice. The average evolution operator can be calculated from easy matrix equations. Special attention is paid to the evolution of a non-equilibrium vacancy distribution around the impurity. Two examples show the validity of approximate solutions for extreme values of the jump frequency and give an insight into the influence of the important parameters. Qualitative agreement with experimental data is reached for the quasistatic case.This work was supported by the Bundesministerium für Technologie and is part of the research program of the Sonderforschungsbereich 161 der Deutschen Forschungsgemeinschaft.