Localized diffusion of helium atoms around indium impurities in aluminium observed by means of perturbed angular correlations

The behaviour of He atoms implanted in ¹¹¹In doped Al has been investigated by means of perturbed angular correlation (PAC) measurements. The onset of He mobility was found to be at about 250K, probably due to vacancy-assisted migration. Mobile helium is effectively trapped at In impurities in small vacancy clusters that accomodate at most 11 He atoms. The PAC spectra taken at temperatures from about 510 K to 670 K exhibit a relaxation effect that is ascribed to hopping of He atoms from one vacancy to another, the saddle-point energy for this localized diffusion being 0.67(5) eV. A tentative model of the cluster is given.     

Intrinsic point defects and light interstitials in metals

Clusters consisting of a radioactive probe atom and various point defects in metallic hosts were studied by means of NMR-ON and PAC. NMR resonance signals were observed for¹³¹IV₂ clusters in Fe and^114mInV₄ clusters in Ni. Decoration of¹¹¹InV₂ clusters by H atoms in W and Mo and by He atoms in W was monitored by PAC. The measurements yield the first reliable data on vacancy-hydrogen binding energies in these metals. The He-decoration results are in excellent agreement with the interpretation of He-desorption data and clearly show the existence of trap mutation.     

Migration and agglomeration of heliumatoms in copper

The magration and agglomeration of Helium atoms in He irradiated Cu was studied between 10 K and 900 K by perturbed γγ angular correlation (PAC) measurements using the radioactive probe atom¹¹¹In. Trapping of interstitial and substitutional He atoms is observed already after irradiation at 10 K. Substitutional He (He-yacancy pair) is bound in the nearest neighbourhood to the¹¹¹In probe atom and seems to be stable up to 725 K (E _He1V1 ^b ≥2.1 eV). The onset of vacancy assisted He agglomeration in Cu is observed at 250 K.     

Feasibilities of nuclear techniques for the study of molecular defects in metals and semiconductors

Nuclear techniques, like Mössbauer effect and perturbed γγ angular correlation spectroscopy (PAC), have proven themselves to be sensitive tools for labelling and identifying probe atom-defect complexes. In these experiments, the “molecular defect” is investigated via the nuclear hyperfine interaction, which is measured at the site of the radioactive probe atom. Here, we shall put the emphasis on the PAC spectroscopy, which often uses¹¹¹In/¹¹¹Cd as radioactive probe atom. In metals, based on the identification of simple probe atom-defect pairs, the agglomeration of defects after cold-working and the interaction of vacancies with He atoms will be discussed. In semiconductors, it will be focussed on the interaction between dopant atoms, which strongly determines the electrical properties of these materials.     

PAC research in biology

In this paper possible applications of the Perturbed Angular Correlations (PAC) technique in Biology are considered. Previous PAC experiments in biology are globally analyzed. All the work that appears in the literature has been grouped in a few research lines, just to make the analysis and discussion easy. The commonly used radioactive probes are listed and the experimental difficulties are analyzed. We also report applications of ¹⁸¹Hf and ¹¹¹In isotopes in life sciences other than their use in PAC. The possibility of extending these studies using the PAC technique is discussed.     

Cavities in silicon investigated with the PAC-probe 111In

The perturbed angular correlation technique (PAC) was used to study the creation and development of He-induced cavities. In order to investigate the interaction of Indium atoms with cavities in Silicon the Bonn isotope separator was used to implant overlapping profiles of He (10 keV) and radioactive ¹¹¹In (160 keV) into undoped FZ-silicon. To get insight into the cavity formation mechanism samples were prepared with various He-doses (0.6, 2 and 6× 10¹⁶ ions/cm²). The samples were measured directly after implantation and after different annealing steps (t_hold= 10 min, T = 500–1100oC). Further, different implantation and annealing sequences were used. At higher He doses (2 and 6× 10¹⁶ ions/cm²) we find a large fraction of ¹¹¹In probe atoms subjected to an electric field gradient (EFG) corresponding to a quadrupole interaction frequency (QIF) of ν_Q= 411(6) MHz with η= 0.25(4). The corresponding defect configuration is formed most effectively after He implantation into annealed, ¹¹¹In doped Si. This and the affinity of In to vacancies leads us to the assumption that, similarly to the situation in metals, the Indium atoms act as nucleation centres for vacancy clusters (cavities) and are situated on the inner walls of the cavities. This revised version was published online in August 2006 with corrections to the Cover Date.     

Donor-acceptor complexes in ZnO

One of the main obstacles to the technical application of the wide-gap semiconductor ZnO represents the difficulty to achieve reliable and sufficient p-type doping. The theoretically proposed concepts of cluster-doping or codoping should lead to an enhanced and stable p-type conductivity of ZnO. We report on PAC results obtained by codoping experiments of ZnO by ion implantation using the donor ¹¹¹In and the group-V acceptors N and P. The formation of In-N and In-P pairs has been observed. Based on these PAC results, there is no evidence for the formation of In-acceptor complexes involving more than one N or P acceptor. Finally, first reports on PAC investigations using ⁷⁷Br as donor in ZnO are presented.     

A perturbed angular correlation spectrometer for material science studies

A four-detector perturbed angular correlation (PAC) spectrometer has been developed with ultra-fast BaF₂ detectors to acquire four coincidence spectra simultaneously, two at 180° and two at 90°. This spectrometer has double efficiency compared to that of a three-detector set-up. Higher efficiency is desirable for PAC studies in solid state physics where large number of coincidences are required to obtain the PAC spectra with good statistics and is particularly useful when the half-lives of the parent probe nuclei used for PAC measurements are ∼2–3 days or less as in ¹¹¹In (2.8 d), ⁹⁹Mo (2.7 d) and ¹⁴⁰La (1.7 d). The performance of the spectrometer has been tested for the HfO₂ monoclinic crystal in the temperature range from 77 to 873 K and for the HfF₄·3H₂O crystal at room temperature. The polycrystalline HfO₂ has been synthesized from Hf metal by heating in air. The hydrated hafnium fluoride has been crystallized by dissolving Hf metal in 40% HF and drying slowly at room temperature.      

Characterization of nanostructured HfO2 films using Perturbed Angular Correlation (PAC) technique

The hyperfine field at ¹⁸¹Ta lattice sites in nanostructured HfO₂ thin films was studied by the Perturbed Angular Correlation (PAC) technique. Thin oxide films were deposited by Electron Beam Evaporation on a silicon substrate. The thickness of the films was ~100 nm and ~250 nm. Radioactive ¹⁸¹Hf nuclei were produced by neutron activation of the film samples in the Brazilian Research Reactor (IPEN IEA-R1) by the reaction ¹⁸⁰Hf(n,γ)¹⁸¹Hf. PAC measurements were carried out after annealing at 1473 K. The PAC technique allows the determination of the electric field gradient (EFG) at the probe sites.     

Low energy γ- γ and e−- γ PAC measurements using APDs and the probe nuclei 83Rb(83Kr) and 83mKr(83Kr)

In the field of Perturbed Angular Correlation (PAC) measurements Avalanche Photo Diodes (APD) are rarely used, despite their favourable properties for fast counting purposes at low energies. This work demonstrates their application in combination with a simple and cheap custom build voltage sensitive preamplifier module. Using the PAC nuclei ⁸³Rb(⁸³Kr) and ^83mKr(⁸³Kr), the time resolution of the set-up is analysed and the feasibility of precise timing measurements is shown.     

Fe-Hydroxysulphates from Bacterial Fe2+ Oxidation

The perturbed angular correlation method (PAC) was applied to investigate the lattice location of implanted ¹¹¹In probe ions in Hf₂Ni and Zr₂Ni intermetallic compounds. It is concluded that the ¹¹¹In/¹¹¹Cd probe nuclei experiencing the highly asymmetric electric field gradient (EFG) occupy the unique hafnium or zirconium 8(h) sites in the investigated phases. Above room temperature, the EFGs decrease linearly with temperature. The results are compared with that of previous PAC measurements with ¹⁸¹Ta probes.     

Electric field gradient in nanostructured SnO2 studied by means of PAC spectroscopy using 111Cd or 181Ta as probe nuclei

Electric quadrupole interactions were studied in pure and Mn-doped powder samples and thin films of SnO₂ using perturbed γγ angular correlation spectroscopy (PAC). The powder samples were prepared by Sol gel method and the thin film were prepared on the Si (100) substrate by sputtering technique using Sn in the oxygen atmosphere. The samples were characterized by x-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy. The thickness of the film was 100 nm. The average particle size of the SnO₂ powder samples was determined to be smaller than 60 nm. The radioactive ¹¹¹In and ¹⁸¹Hf tracers were introduced in the powder samples during the sol gel chemical process. Radioactive ¹¹¹In was implanted on the SnO₂ thin films using the University of Bonn ion implanter (BONIS). PAC measurements were carried out in a four BaF₂ detector spectrometer in the temperature range of 77–973 K for samples annealed at different temperatures. The PAC results for both nuclear probes show the presence of two electric quadrupole interactions. The major fractions in both cases correspond to the substitutional sites in the rutile phase of SnO₂. The results are compared with previous PAC measurements.     

Perturbed angular correlation study of a nanostructured HfO2 film

The hyperfine field at ¹⁸¹Ta lattice sites in a nanostructured HfO₂ thin film was studied by the perturbed angular correlation (PAC) technique. The thin oxide film was deposited by pulsed laser ablation on a silicon substrate kept at 673 K. The thickness was about 25 nm. The radioactive ¹⁸¹Hf ions were produced by neutron activation of the very thin film in the Portuguese research reactor by the reaction ¹⁸⁰Hf(n,γ)¹⁸¹Hf. PAC measurements were carried out at room temperature after annealing at different temperatures up to 1,473 K in air. The PAC technique allows determining the electric field gradient at the ¹⁸¹Ta probe sites. The ¹⁸¹Ta isotopes appear in the sample as disintegration product of ¹⁸¹Hf.     

Dynamic hyperfine interactions in In(Cd)-doped ZnO semiconductor: PAC results supported by ab initio calculations

In this work, we present results of Time-Differential γ–γ Perturbed-Angular-Correlations (PAC) experiments performed in ¹¹¹Cd-doped ZnO semiconductor. The PAC technique has been applied in order to characterize the electric-field-gradient (EFG) tensor at (¹¹¹In (EC)→) ¹¹¹Cd nuclei located, as was later demonstrated, at defect-free cation sites of the ZnO host structure. The PAC experiments were performed in the temperature range of 77–1075 K. At first glance, the unexpected presence of low-intensity dynamic hyperfine interactions was observed, which were analyzed with a perturbation factor based on the Bäverstam and Othaz model. The experimental EFG results were compared with ab initio calculations performed with the Full-Potential Augmented Plane Wave plus local orbital (FP-APW+lo) method, in the framework of the Density Functional Theory (DFT), using the Wien2K code. The presence of the dynamic hyperfine interactions has been analyzed enlightened by the FP-APW+lo calculations of the EFG performed as a function of the charge state of the cell. We could correlate the large strength of the dynamic hyperfine interaction with the strong variation of the EFG due to changes in the electronic charge distribution in the Cd vicinity during the time-window of the PAC measurement. It was also revealed that the Cd impurity decays to a final stable neutral charge state (Cd²⁺) fast enough (in few ns) to produce the nearly undamped observed PAC spectra.     

Pac studies of ZrMn2+x alloys and their hydrides

¹⁸¹Ta PAC and electron diffraction experiments on ZrMn₂ show that the presence of Hf in substitution for Zr at a concentration of 2 at. % can be responsible for distortions from the C14 structure of this intermetallic alloy. The PAC spectra recorded between RT and 50K for the hydride Zr_0.98 Hf_0.02 Mn₂H_3.2 display two successive modifications in the temperature regions 180–150K and 100–50K. In the present state of PAC data analysis, we are not able to claim that such modifications are related to the low-temperature magnetic properties of ZrMn₂ hydrides.     

Multi-photon processes in the Zeeman structure of atomic Cs trapped in solid helium

We report magnetic resonance experiments with optical detection performed on cesium atoms trapped in a crystalline ^Hematrix. Multi-photon transitions, i.e., processes in which several radio-frequency photons are absorbed simultaneously in a given hyperfine Zeeman multiplet of the ground state, were the central topic of these studies. The long relaxation times of spin coherences of Cs in solid He allow such transitions to be spectrally resolved in fields as low as 1 mT. We observed all allowed multi-photon transitions up to the M=8 transition in the F=4 state. We compare the experimental spectra with theoretical spectra obtained from numerical solutions of the Liouville equation that include optical pumping and the interaction with the static and oscillating fields. Multi-photon transitions may find applications in magnetometry, suppress systematic effects in EDM experiments, and allow the study of relaxation phenomena in doped He crystals. The demonstration of these features is still hindered by inhomogeneous line broadening. PACS 76.70.Hb; 32.80.Wr; 32.30.Dx; 32.60.+i     

Electric field gradients at Zr sites and phase transition in the Nasicon-type compound Na5Zr(PO4)3

The quadrupole coupling parameters of the ¹⁸¹Ta probe placed in substitution for zirconium were measured by Perturbed Angular Correlation (PAC) Spectroscopy in a polycrystalline sample of the Na₅Zr(PO₄)₃ composition between R · T and 400°C. The PAC spectra indicate the existence of a transition which spreads out over a rather large temperature range between 90 and 130°C. The results are coherent with the X-ray diffraction data previously reported on this compound. Spin relaxation phenomena are observed, which give evidence that the phase transition induces important modifications on the local motions of Na⁺-ions.     

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.     

The lattice location and hyperfine field of implanted Yb in Fe as a function of annealing temperature

A combined study has been made of the lattice location and hyperfine field of Yb implanted into Fe single crystals. The location has been determined by ion channeling and back-scattering, the hyperfine field by perturbed angular correlation (PAC) measurements on¹⁶⁹Yb (decaying to excited states in¹⁶⁹Tm). The channeling experiments indicate that initially about 60% of the Yb atoms occupy substitutional sites in the Fe lattice, while the remaining atoms are not in any specific crystallographic site. On annealing, Yb migrates from substitutional to non-substitutional sites. No Yb atoms remain substitutional after a 600°C anneal. By making PAC measurements at two temperatures for two - cascades in¹⁶⁹Tm, it is found that the PAC pattern can be described using a combined static and time-dependent magnetic interaction. The PAC results show that the average hyperfine field and relaxation parameter decrease on annealing, and that the field disappears after a 600°C anneal. The correlation between the location and the hyperfine field is discussed. A comparison of the results with previous Mössbauer results for¹⁵¹Gd implanted in Fe, together with relaxation parameter measurements on a¹⁶⁹Yb₂O₃ source, suggests that the non-substitutional Yb is internally oxidized in the Fe host.Work partly carried out while at the Clarendon Laboratory, Oxford, England and Nuclear Physics Division, AERE, Harwell, England.     

The EFG of111Cd in Y2Cu2O5

The perturbed angular correlation (PAC) method was applied to study the “blue-phase” of the high T_c-superconductor YBaCuO.¹¹¹In was implanted at 400 keV into pressed powder of Y₂Cu₂O₅. PAC spectra were taken at measureing temperatures between 23 K and 843 K. Four fractions were observed which show a strong motional narrowing with increasing temperature. Two of these fractions have PAC parameters like Y₂O₃ and the other two are similar to the “Cul-site” in YBaCuO. This work was supported by the BMFT, contract: FKZ 13 N 54930