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.     

Temperature dependence of the electric quadrupole interaction at scandium impurities in zirconium and hafnium

The PAC probe⁴⁴Sc was employed to study the magnitude and temperature dependence of the electric quadrupole interaction at the site of the transition metal Sc in the hexagonal host lattices Zr and Hf. In Zr ∼ 100% of the probe atoms were situated on regular lattice sites and a quadrupole interaction frequency of υ_Q=7.8(1)MHz was measured at room temperature. For Hf the fraction of the probe atoms on regular lattice sites was smaller and a damping of the interaction pattern (υ_Q=9.3(5)MHz at 293 K) could not be excluded. The temperature dependence of the electric field gradient in both host lattices was found to be weak.     

The electric quadrupole interaction of 111Cd in ZrZn2 and Zn in the samples prepared at 8 GPa

The perturbed angular correlation (PAC) measurements with the ¹¹¹In-¹¹¹Cd nuclear probe embedded into the lattice of the cubic (C15) Laves compound ZrZn₂ showed that ¹¹¹Cd nuclei experienced an axially symmetric electric quadrupole interaction with a frequency ν _Q  = 132.4 MHz at room temperature. The samples were synthesized and doped with the probe at a pressure 8 GPa. The temperature dependence of ν _Q was shown to be linear: ν _Q (T) = 147(1 − 0.033 T) MHz. Since the value of ν _Q is very close to that known for ¹¹¹Cd in the lattice of Zn, we have checked if it could be assigned to residual Zn metal in the sample. For the Zn sample melted and doped with ¹¹¹In at 8 GPa we have obtained ν _Q  = 117.3 MHz at 300 K and 127 MHz at 80 K – both values considerably lower than that for ¹¹¹In doped Zn samples prepared at an ambient pressure. These data, and the fact that ν _Q (T) in Zn is known to follow the T ^3/2 law, allow to attribute the ν _Q value quoted above to ¹¹¹Cd nuclei at the substitutional sites with tetrahedral symmetry in the Zn sublattice of ZrZn₂.     

Cavity formation at indium impurities in bcc metals

The defect formation in the bcc metals W and Mo above annealing stage III and the influence of rare gases on this process were investigated by means of the perturbed angular correlation technique using¹¹¹In as radioactive probe. In both metals a relatively high electric field gradient (EFG) could be observed at the indium site, characterized by the quadrupole interaction frequencies υ_Q=263 MHz, ν=0 and υ_Q=220 MHz, ν≈0.15 for W and Mo, respectively. The observations are assigned to the growth of threedimensional vacancy clusters at the probe atoms with the indium atoms situated in the inner surface of this cavities, thus experiencing the corresponding surface EFG.     

Mössbauer and XRD Comparative Study of Host Rock and Iron Rich Mineral Samples from Paz del Rio Iron Ore Mineral Mine in Colombia

The local environment of implanted ¹¹¹Ag (t _1/2 = 7.45 d) in single-crystalline [0001] ZnO was evaluated by means of the perturbed angular correlation (PAC) technique. Following the 60 keV low dose (1 × 10¹³ cm⁻²) ¹¹¹Ag implantation, the PAC measurements were performed for the as-implanted state and following 30 min air annealing steps, at temperatures ranging from 200 to 1050°C. The results revealed that 42% of the probes are located at defect-free S_Zn sites (ν _Q ∼ 32 MHz, η = 0) in the as-implanted state and that this fraction did not significantly change with annealing. Moreover, a progressive lattice recovery in the near vicinity of the probes was observed. Different EFGs assigned to point defects were furthermore measured and a general modification of their parameters occurred after 600°C. The 900°C annealing induced the loss of 30% of the ¹¹¹Ag atoms, 7% of which were located in regions of high defects concentration.     

High Pressure Mössbauer Studies on FCC Fe53Ni47 Alloy

Perturbed angular correlation measurements of the hyperfine interaction of ¹¹¹In in sapphire show, that after implantation and annealing at 1000°C, the fraction of undisturbed probe atoms exhibiting a unique quadrupole interaction with ν _Q = 219(1) MHz (η = 0) varies between 50% at 4 K, 5% at 100 K and 80% at 973 K in a reversible manner. A possible explanation for this surprising behaviour is the influence of so-called ‘after effects’ following the EC-decay of ¹¹¹In to ¹¹¹Cd. Immediately after the decay the ¹¹¹Cd is in an ionized state, then collects electrons from its surroundings and reaches the ground state. The different electronic configurations that arise during this relaxation process affect the amplitude (f _u) and the damping (δ _u) of the unique quadrupole interaction.     

Anomalous Temperature Dependence of the EFG in AlN Measured with the PAC-Probes 181Hf and 111In

¹⁸¹Hf and ¹¹¹In ions were implanted into AlN-layers in order to investigate their immediate lattice site environment and its temperature dependence by means of the Perturbed Angular Correlation (PAC) technique. After rapid thermal annealing at 1273 K up to 50% of the probe atoms were incorporated on undisturbed lattice sites defined by an electric field gradient (EFG) of 33 MHz for In and 572 MHz for Hf for measurement at room temperature. PAC-spectra taken at temperatures between 25 and 1200 K show that the EFG measured at the site of the undisturbed probes changes with temperature. While for Hf it decreases by 3%, for In it increases by 25% within the measured temperature range. Thus, the change cannot be due only to the thermal lattice expansion. In the case of In the fraction of probe atoms on substitutional sites increases with temperature until it reaches nearly 100% at 973 K. These effects are fully reversible. For the Hf probe, an additional EFG was detected at temperatures above 300 K.     

Perturbed Angular Correlation Study of Naturally Occurring Zircon with very Small Impurity Concentrations

We used ¹⁸¹Ta-PAC spectroscopy to characterize the electric field gradient at Zr sites of zircon samples from the Harts Range in Australia. Zircons from this region contain very low levels of radioactive impurities. The PAC spectra between room temperature and 1100°C are axially symmetric and show little damping. The quadrupole frequency decreases linearly with increasing temperature, and the slope of the ν _Q vs. T graph increases above 900°C. This is attributed to a rearrangement of the Si–O coordination, which affects the Zr–O coordination. The spectra of all zircons show a distinct decrease of the anisotropy between 800 and 600°C. This behavior is also seen with samples that do not exhibit the change in slope in the ν _Q vs. T data. We believe that the decrease in the anisotropy is due to an aftereffect following the β-decay of ¹⁸¹Hf.     

Activation of Mg-doped P-GaN by using two-step annealing

One- and two-step rapid thermal annealing (RTA) for activating Mg-doped p-type GaN films had been performed to compare with conventional furnace annealing (CFA). The two-step annealing process consists of two annealing steps: the first step is performed at 750 °C for 1 min and the second step is performed at 600 °C for 5 min in pure O₂ or air ambient. It is found that the samples annealed in air ambient exhibit poor electrical properties as compared to those annealed in pure O₂. Compared to one-step RTA annealing and CFA annealing, the samples with two-step annealing exhibit higher hole concentration and lower resistivity. This means that the two-step annealing is a powerful method to enhance the electrical performance of Mg-doped p-type GaN films. Similar results were also evidenced by photoluminescence (PL) measurement. Possible mechanism was confirmed by secondary ion mass spectrometry analysis.     

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.     

Effects of Zr impurity on microscopic behavior of Hf metal

Hf metal with ∼ 3 wt% Zr impurity has been reinvestigated by perturbed angular correlation (PAC) spectroscopy using a LaBr₃(Ce)–BaF₂ detector set up to understand the microscopic behavior of this metal with temperature. From present measurements, five quadrupole interaction frequencies have been found at room temperature where both pure hcp fraction (∼33%) with 12 nearest neighbor Hf surrounding the probe ¹⁸¹Hf atom and the probe–impurity fraction (∼33%) corresponding to 11 nearest neighbor Hf plus one dissimilar Zr atom are clearly distinguished. At room temperature, the results for quadrupole frequency and asymmetry parameter are found to be ω_Q=51.6(4) Mrad/s, η=0.20(4) for the impurity fraction and ω_Q=46.8(2) Mrad/s, η=0 for the pure fraction with values of frequency distribution width δ=0 for both components. At 77 K, only 1 NN Zr impurity (∼93%) and pure hcp (∼7%) components have been found with a value of δ ∼ 10% for the impurity fraction. A drastic change in microstructural configuration of Hf metal is observed at 473 K where the impurity fraction increases to ∼ 50% and the pure hcp fraction reduces to ∼ 15% with abrupt changes in quadrupole frequencies for both components. The pure fraction then increases with temperature and enhances to ∼50% at 973 K. In the temperature range 473–973 K, quadrupole frequencies for both components are found to decrease slowly with temperature. Using the Arrhenius relation, binding energy (B) for the probe–impurity pair and the entropy of formation are measured from temperature dependent fractions of probe–impurity and pure hcp in the temperature range 473–773 K. The three other minor components found at different temperatures are attributed to crystalline defects.     

The study of the interaction of indium with tellurium in silicon

The perturbed γ–γ angular correlation method has been employed to study indium-impurity pairs in silicon, consisting of the probe atom (¹¹¹In/¹¹¹Cd) and several group-VI donors. Such pairs can be identified via the interaction between the quadrupole moments of the probe nucleus and the electric field gradient (EFG) associated with the formed defect complex. A new quadrupole interaction frequency (QIF) of ν_Q=444(1) MHz (η=0) is measured at T=293 K in Te implanted silicon after annealing the sample above 700 K. The complex is attributed to the In-Te pair along 〈100〉-crystal axis in silicon. In addition, the temperature dependence of the QIF characterizing the pair has also been studied. The implantations of S and Se could not lead to the formation of observable complexes despite similar treatment of all samples. PACS 61.72.-y; 76.80.+y; 61.72.Cc     

Orientation of the oxygen-induced non-axially symmetric electric field gradient at181Ta in Ta

The interaction of dilute¹⁸¹Ta in Ta with interstitial oxygen has been investigated via the γ-γ TDPAC-technique applied to the 482 keV state in¹⁸¹Ta. The trapping of Oxygen leading to a quadrupole interaction frequency ν_Q=580(5) MHz with an asymmetry parameter of η-0.37 (1) has been observed after melting the radioactive parent isotope¹⁸¹Hf with Ta. The temperature dependence of the quadrupole interaction frequency between 17 K and 293 K was found to be very weak whereas η varied by about 10%. In a single crystal experiment the orientation of the three principal axes of the electric field gradient leading to ν_Q was determined. The V_zz-axis points in <110>, the V_yy-axis in <100> and the V_xx-axis in <110> direction. These results can be understood in the charge cloud model, suggested by Wrede et al. /1/ for a similar situation found in the HfNb system.     

Magnetic and quadrupole interaction studies at 111Cd in GdMn2 and TbMn2

The temperature dependence of the electric quadrupole interaction and the magnetic hyperfine field at ¹¹¹Cd probe sites in RMn₂ (R=Gd, Tb) has been studied by TDPAC method. In the paramagnetic region the quadrupole interaction frequency ν_Q in both compounds varies linearly with temperature. Below the Neel temperature, we find an abrupt decrease in the magnitude of ν_Q which is consistent with an expansion of the unit cell. As an important feature, the data near T_N shows the coexistence of localized and itinerant magnetism of Mn atoms. This revised version was published online in August 2006 with corrections to the Cover Date.     

Nuclear Spin Relaxation in Some Non-viscous Media Using the 181Hf Probe

Perturbed angular correlation (PAC) studies have been performed in liquid mercury, HCl media of different acid strengths, H₂O and H₃PO₄ using a ¹⁸¹Hf probe. It is found that, in case of H₂O, interaction between the nucleus and its excited atom following the β⁻ decay of ¹⁸¹Hf is a possible mechanism for the nuclear spin relaxation in this environment. In the liquid mercury and different acid media, however, the perturbations are found to arise due to molecular fluctuations.     

Site occupancy and molecular complex formation of 19F ions in fullerenes C60 and C70 studied by TDPAD

TDPAD spectroscopy measurements have been performed on two fullerene samples, C₆₀ and C₇₀, with recoil implanted ¹⁹F ions as probe nuclei. Quadrupole coupling frequencies of ν_Q= 54(1) MHz for C₆₀ and ν_Q= 57(1) MHz for C₇₀ were observed. These frequencies are associated with a C–F molecular complex formation. The C₇₀ sample was also examined for possible effects due to variation of temperature. No significant changes were observed. An additional frequency of ν_Q= 13(1) MHz registered for both samples has to be attributed to the formation of H–F complexes. Finally, both samples were analysed for proton dose dependent effects, due to the (p,p'γ) implantation process but no effects have shown up. Specifically, computational studies based on quantum chemical methods were performed to assist in the interpretation of the experimental results, using the code MOPAC. This revised version was published online in August 2006 with corrections to the Cover Date.     

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.     

Structure determination of an indium-oxygen-vacancy complex in silver

When bombarding preoxidized silver with α-particles¹¹¹In-oxygen-vacancy complexes are formed. PAC measurements on the most stable complex 6 (ν_q=161 (2) MHz, η=1, δ/ν_q=6(1) %) were performed to determine the structure of this highly asymmetric complex. On the basis of PAC experiments on Ag single crystals and the variation of the oxygen concentration and the measuring temperature a structure model of this complex 6 is proposed.     

Hydrogen and deuterium trapping at nitrogen in tantalum studied by PAC

PAC experiments using¹⁸¹Hf as probe atom were performed in Ta samples containing 1.1 at% of N and loaded with 0.2 at% of H or of 1.6 at% of D. At room temperature only the known frequency due to N is present. Below 100K or 140K, for H and D respectively, the amplitude of this interaction decreases and two new interaction frequencies characterized by V₀=240MHz, η=0.80 and V₀=250 MHz, η=0.40 appear. These frequencies are attributed to H(D) trapped by N in the vicinity of the probe atom¹⁸¹Hf. The disappearance of these interactions at 100K and 140K is interpreted as a release of H (D) from Hf but not from N. From the data the jump rates of H(D) around N in Ta are derived.     

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.