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.     

Incorporation of the transition metal Hf into GaN

The perturbed angular correlation (PAC) technique was applied to study the incorporation of the transition metal Hf into GaN after implantation. To this end the PAC probe ¹⁸¹Hf(¹⁸¹Ta) was implanted into epitaxial Wurtzite GaN layers (1.3 μm on sapphire) with an energy of 160 keV and doses of 7× 10¹² at/cm². PAC spectra were recorded during an isochronal annealing programme, using rapid thermal annealing (RTA) and furnace annealing, in the 300–1000oC temperature range. After implantation the spectra show a damped oscillation corresponding to a quadrupole interaction frequency (QIF) of ν_Q= 340 MHz for 30% of the probe nuclei. Annealing up to 600oC reduces the damping of this frequency without an increase of the probe atom fraction f_s in these sites. Above 600oC f_s grows rapidly until after the 900oC RTA step more than 80% of the Hf probes experience a well defined QIF due to the incorporation of Hf on undisturbed sites of the hexagonal GaN wurtzite lattice. An interaction frequency of ν_Q= 340 MHz is derived. RTA and furnace annealing yield similar results for annealing up to 800oC, where the undisturbed fraction reaches about 60%. Then RTA at higher temperatures increases this fraction, while furnace annealing leads to a decrease down to 22% after annealing at 1000oC. To our knowledge this is the first time that a transition metal probe like Hf is incorporated to such a large extent into a semiconductor lattice. This revised version was published online in August 2006 with corrections to the Cover Date.     

Electric field gradients in Hf2Fe

Perturbed Angular Correlations (PAC) technique was applied to measure the electric field gradients (EFG) at ¹⁸¹Ta sites in Hf₂Fe. The compound has the cubic structure of the Ti₂Ni prototype with two non‐equivalent crystallographic sites for Hf atoms. EFGs for the two sites were measured as a function of the temperature. In addition, one more EFG was observed, which was assigned to the presence of defects in the lattice. The ratio of the measured EFG at the regular lattice sites has been used to assign charges to the ions through a simple calculation using the point charge model and it is shown that the lattice symmetry can explain the very different EFG at both sites. This revised version was published online in August 2006 with corrections to the Cover Date.     

Measurements of the electric field gradient at cadmium in the high Tc superconductor YBa2Cu3O6+x

The electric field gradient (EFG) at¹¹¹Cd probe atoms in YBa₂Cu₃O_6+x has been studied by the perturbed angular correlation (PAC) spectroscopy. After annealing at temperatures below 1000 K the probe atoms are located at the Cu(1) site; above 1100 K they preferentially occupy the Y site, whereas in the intermediate temperature range they also reside on the Ba site. A reduction of the oxygen content from x=1.0 to 0.2 resulted in a decrease of the asymmetry parameter measured at the Ba site, but in an increase of it at the Y site, indicating there a local distortion of the YBa₂Cu₃O_6+x lattice by the Cd impurity. Two different surroundings for the Cd atoms at the Cu(1) site were observed.     

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.     

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.     

Angular correlation studies on 172Lu(172Yb) in GaN and measurements at low temperatures

For optoelectronic devices semiconductors with large band gap doped with rare earth are used. Doping is generally performed during growth but for more structured doping the ion implantation technique is preferable. The perturbed γγ-angular correlation technique is an ideal tool to study the behavior of semiconductors after implantation. An adequate rare earth isotope for such investigations of semiconductors is ¹⁷²Yb. The temperature dependence of the hyperfine fields for ¹⁷²Lu(¹⁷²Yb) in GaN has been analysed. The total electric field gradient (EFG) at the site of this probe is a superposition of the lattice EFG due to the GaN wurtzite structure and the EFG due to the 4f shell of the rare earth probe itself. The latter is strongly temperature dependent and opposed to the lattice EFG which in contrast is nearly constant since the lattice parameters change only negligibly with temperature. At elevated temperatures the sublevels of the 4f shell, split by the crystal electric field, are equally populated. But at low temperatures the lowest level is occupied preferentially. Sign and magnitude of the EFG caused by the 4f shell can be calculated (Tomala et al, J Magn Magn Mater 89(1–2):143, 1990) and the result compared to the experimental data.     

Electric field gradients at Ta in Zr and Hf inter-metallic compounds

Here we calculate the electric field gradient (EFG) at the nucleus of the substitutional Ta impurity site in Zr₂T and Hf₂T (T=Cu, Ag, Au, and Pd) C11_b inter-metallic compounds. We use the ab initio FP-LAPW method as embodied in the Wien97 code in a super-cell approach and include lattice relaxations around the impurity. Our results are compared with EFG values inferred from measurements of the quadrupole coupling constants at the ¹¹¹Ta probe in these compounds performed with the time differential perturbed angular correlation (TDPAC) technique. We also performed EFG calculations for the pure inter-metallic compounds. Through the comparison of theoretical and experimental EFGs in these cases, we elucidate the role played by the Ta probe in the TDPAC measurements of Hf and Zr compounds. Our results show that, although the EFGs at the Hf site are very similar to the EFGs at the Ta impurity, there is no direct correlation between the Zr and Ta EFGs.     

The effects of concentration and temperature on the EFG generated by N.N. Pd impurities in a cubic Ag host

The time differential perturbed angular correlation (TDPAC) method is used to investigate the electric field gradients (EFG) generated by Pd impurity atoms alloyed into the cubic Ag host. As the concentration of the impurity is increased from 0.25 to 2.5 at.% we observed in detail how different near neighbour (n.n.) sites to the probe nuclei are populated, creating different EFG. The temperature dependence of the different EFG for a sample with 0.5 at.% of Pd showed that all follow theT ^3/2 law found previously for other doped cubic systems. In addition we observed that the n.n. population of impurities is strongly related to the thermal treatment of the sample.Work supported in part by Conselho Nacional de Desenvolvimento Científico e Tecnológico and Fianciadora de Estudos e Projectos.     

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.     

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.     

Study of highT c superconductivity in Y1Ba2Cu3O7−x by PAC

HighT _c superconductivity in the YBaCuO superconductor has been investigated through the quadrupole interaction of the probe nuclei⁹⁹Tc. The quadrupole interactions were measured by the TDPAC method from 77 to 296 K. The probe nuclei⁹⁹Tc were introduced into the YBaCuO superconducting specimen by diffusion. The derived electric quadrupole interaction parameters show that the probe nuclei are subject to a unique EFG interaction and occupy a substitutional lattice site in the YBaCuO superconductor. A strong EFG of 10¹⁹ V/cm² was observed. The temperature dependence of the EFG exhibits a linear decrease with temperature increase. Anomalies of both EFG and ν were found in the superconducting transition temperature region. The role of the oxygen vacancies in the Cu−O chains is discussed.     

The internal electric fieldgradient in antiferroelectric PbZrO3 studied by perturbed angular correlations

The internal electric fieldgradient (EFG) at the Zr-site in antiferroelectric polycristalline PbZrO₃ has been investigated as a function of temperature by time differential angular correlation measurements. For the application of this technique PbZrO₃ was doped with small amounts of radioactive¹⁸¹Hf. In the antiferroelectric phase of PbZrO₃ the EFG decreases continously with increasing temperature and exhibits a sharp discontinuity at 230 °C, the Curie point of the compound. In the cubic phase a small remaining EFG is observed which is probably caused by lattice imperfections in the source. The antiferroelectric distortion of the lattice decreases slightly when the temperature approaches the Curie point, as shown by the temperature dependence of the asymmetry parameter of the EFG. The measured EFG at room temperature is compared with the result of a lattice sum calculation.     

Hysteresis and γ-recoil effects in the superconducting compounds HfxZr1−xV2

The anisotropy of the 133–182 keV γ-γ cascade in¹⁸¹Ta measured as a function of temperature between 70K and 298K shows lattice instability, the phenomenon of hysteresis in the vicinity of the lattice transformation temperature (T_L) and a temperature dependent electric field gradient (EFG) at the cubic Hf sites in the superconducting cubic Laves phase (C15) compounds Hf_1?xZr_xV₂ (x=0.0, 0.25 and 0.75). These observations are qualitatively understood by assuming the presence of γ-recoil effects and microdomains fluctuating between the high temperature (T>T_L) and the low temperature (T < T_L) phases of these compounds.     

Electric quadrupole interactions in the CdTiO3 perovskite2

The TDPAC technique has been used to measure the EFG at the Cd site in the perovskite CdTiO₃. The experimental results obtained at 293 K are compared with ionic lattice sum calculations of the EFG. In addition measurements at 16 and 77 K show that no considerable modification of the EFG is observed at the Cd site at temperatures below and above the previously described phase transition at 50 K.     

Lattice Location of 181Ta and 111Cd Probes in Hafnium and Zirconium Aluminides Studied by Perturbed Angular Correlation

The perturbed angular correlation technique was applied to study the lattice location of the ¹¹¹In/¹¹¹Cd and ¹⁸¹Hf/¹⁸¹Ta probe atoms in hafnium and zirconium aluminides. Compounds of different stoichiometries and crystallographic structures were the subject of investigation. According to the expectation, in all investigated compounds ¹⁸¹Hf/¹⁸¹Ta probes occupy the Hf(Zr) crystallographic sites. The ¹¹¹In/¹¹¹Cd probes are placed at the sites of all constituent metals—aluminum, hafnium and zirconium, depending on the crystallographic structure of compound, concentration of the constituent metals and temperature of the sample.     

Thermal properties of high-k Hf_1-xSi_xO₂

Classical atomistic simulations based on the lattice dynamics theory and the Born core-shell model are performed to systematically study the crystal structure and thermal properties of high-k Hf1-xSixO2 . The coefficients of thermal expansion, specific heat, Grneisen parameters, phonon densities of states and Debye temperatures are calculated at different temperatures and for different Si-doping concentrations. With the increase of the Si-doping concentration, the lattice constant decreases. At the same time, both the coefficient of thermal expansion and the specific heat at a constant volume of Hf1-xSixO2 also decreases. The Grneisen parameter is about 0.95 at temperatures less than 100 K. Compared with Si-doped HfO2 , pure HfO2 has a higher Debye temperature when the temperature is less than 25 K, while it has lower Debye temperature when the temperature is higher than 50 K. Some simulation results fit well with the experimental data. We expect that our results will be helpful for understanding the local lattice structure and thermal properties of Hf1-xSixO2 .     

Hyperfine interactions measurements on 181Ta probes in HfV2Hx compounds: (0⩽x≲4)

The electric field gradient (EFG) has been measured on ¹⁸¹Ta probe sites in HfV₂H_x alloys (0?x?4) using the time differential perturbed angular correlation technique. One observes that the main component V_zz of the EFG decreases by a factor of 2 for hydrogen concentrations increasing from x = 0 to x = 4 hydrogen atoms/formula. The opposite behavior was observed on ⁵¹V by using the NMR technique. At T = 4.2 K the EFG tensor is non-axially symmetric. The observed asymmetry factor for x = 0 is η = 0.58(3) and it slightly increases to η = 0.70 for x?4. The system is orthorhombic at low temperatures for all x and the experiments suggest that hydrogen would stabilize a tetragonal phase at higher temperatures. The relaxation effects are absent for x = 0 and vanishingly small for x ? 4 but they are observed at intermediate concentrations supporting the idea of a hydrogen ordering for x = 4.     

The Nonanuclear [Mo(IV){(CN)Fe(III)(3-ethoxy-saldptn)}8]Cl4 Complex Compound Exhibits Multiple Spin Transitions Observed by Mössbauer Spectroscopy

The hyperfine interactions at ¹⁸¹Ta ions on Fe³⁺ sites in α-Fe₂O₃ (hematite) were studied in the temperature range 11–1100 K by means of the perturbed angular correlation (PAC) technique. The ¹⁸¹Hf(β⁻)¹⁸¹Ta probe nuclei were introduced chemically into the sample during the preparation. The hyperfine interaction measurements allow to observe the magnetic phase transition and to characterize the supertransferred hyperfine magnetic field B_hf and the electric field gradient (EFG) at the impurity sites. The angles between B_hf and the principal axes of the EFG were determined. The Morin transition was also observed. The results are compared with those of similar experiments carried out using ¹¹¹Cd probe. ^aAlso at Comisión de Investigaciones Científicas de la Provincia de Buenos Aires, Argentina.     

Mössbauer study of the magnetic and electric hyperfine interaction of dilute57Fe impurities in rare earth metal hosts

The hyperfine interaction of dilute⁵⁷Fe in the rare earth (RE)metals Gd to Lu was investigated by Mössbauer measurements with⁵⁷Co doped RE sources. In all hosts well split, 2-lines spectra were observed at room temperature, with slight asymmetries of the line intensities in some cases. The quadrupole splitting eQV_zz/2 increases from 0.29 mm/sec for Gd to 0.50 mm/sec for Tb, and decreases by less than 10 % between Tb and Lu. Only about 10 % of the corresponding electric fieldgradient (EFG) can be accounted for by the ionic EFG on a substitutional RE site. The temperature dependence of the EFG was measured in the case of Tb. No variation within 3 percent was found between 300 K and 700 K. Measurements of the magnetic hyperfine interaction at low temperatures were carried out in Tb. The saturation field of⁵⁷Fe in this host is H_hf(FeTb;4.2 K)=25(2) KOe. The temperature dependence of the magnetic hyperfine field does not follow the host magnetization (T_c=220K) but vanishes at about 80 K. Similar anomalies of H_hf(T) have previously been observed for other transition element impurities in the RE ferromagnets.