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.     

Momentum dependence of spin polarization for beta emitting nuclei produced through charge exchange reaction at intermediate energy

Hyperfine interactions were studied in the intermetallic compound GdRh₂Si₂ by perturbed angular correlation (PAC) technique using ¹⁸¹Hf(¹⁸¹Ta) probe nuclei. The measurements were performed in the temperature range 15–285 K. The PAC spectra above the antiferromagnetic ordering temperature of the GdRh₂Si₂ compound (T _N ～ 106 K), were analyzed using a model that included only electric quadrupole interactions. The observed major fraction was assigned to the ¹⁸¹Hf(¹⁸¹Ta) probe substituting the Gd atoms. The PAC spectra below Néel temperature were analyzed using combined electric quadrupole and magnetic dipole interactions. The B_hf value at Gd, measured at 15 K was found to be 1.4(1) T which, is smaller, when compared with the values obtained in this compound using other nuclear probes, ¹⁵⁵Gd (B_hf ～ 30 T) and ¹⁴⁰Ce (B_hf ～ 26 T). The present result using ¹⁸¹Hf(¹⁸¹Ta) probe is quite interesting since it shows that the contribution to B_hf at Gd due the host is smaller than other components which contribute to the hyperfine field. The temperature dependence of B_hf shows an anomalous behavior.     

Hf3Al2 and Zr3Al2 Isostructural Aluminides Studied by PAC with 181Ta and 111Cd Probes

The electric quadrupole hyperfine interactions for ¹⁸¹Hf/¹⁸¹Ta and for ¹¹¹In/¹¹¹Cd probes in polycrystalline Zr₃Al₂ and Hf₃Al₂ compounds were measured in the temperature range 24–1100 K. The hyperfine quadrupole interaction parameters were determined after different doping techniques and heat treatments of the samples.¹⁸¹Hf/¹⁸¹Ta was found to substitute the Hf/Zr sites and the ¹¹¹In/¹¹¹Cd impurities appear to substitute both the 8(j) Al sites and the three nonequivalent Hf/Zr sites.     

Electric quadrupole interactions in nano-structured SnO 2 as measured with PAC spectroscopy

Measurements of the electric quadrupole interaction were used to characterize pure and cobalt-doped samples of SnO₂ prepared by the sol-gel method. Perturbed gamma–gamma angular correlation (PAC) spectroscopy using ¹¹¹In–¹¹¹Cd probe nuclei was employed for these measurements. A methodology was developed for sample preparation that were prepared by sol-gel method from pure metallic Sn (99.9999%) and Co (99.9998%) as starting materials. Carrier-free ¹¹¹In was added to the precursor sol-gel solution prior to the formation of gel. PAC measurements were carried out to follow the formation of the SnO₂. PAC measurements were carried out in the temperature range from 10 k to 1123 K and the results show that the electric quadrupole frequency depends on the annealing temperature.     

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.     

Magnetic hyperfine fields at Gd and in sites in GdPdIn compound

Perturbed gamma-gamma angular correlation (PAC) technique was used to measure the hyperfine interactions in the intermetallic compound GdPdIn using ¹¹¹In→ ¹¹¹Cd and ¹⁴⁰La→ ¹⁴⁰Ce probe nuclei at the In and Gd sites, respectively. The PAC results for ¹¹¹Cd show two well-defined electric quadrupole frequencies above T _C assigned to probes occupying Gd and In sites, with ~50% of site occupation each. The fraction corresponding to In sites increases with temperature reaching 95% around 500 K. Below T _C the measurements for ¹¹¹Cd probe showed combined electric quadrupole plus magnetic dipole interaction with sharp increase in the magnetic field below around 80 K. A pure magnetic interaction with lower hyperfine field values was observed at the Gd sites occupied by ¹⁴⁰Ce below 100 K.     

The Electric Field Gradients in (Zr/Hf)Al3 and (Zr/Hf)2Al3 Intermetallic Compounds Studied by 181Ta- and 111Cd-PAC Spectroscopy

The electric quadrupole hyperfine interactions for ¹⁸¹Hf/¹⁸¹Ta and for ¹¹¹In/¹¹¹Cd probes in polycrystalline ZrAl₃ and Zr₂Al₃ compounds were measured in the temperature range 30–1100 K and compared with the results for isostructural hafnium aluminides. On the basis of the similarities of the numbers, sizes and asymmetries of electric field gradients, lattice site allocations were made. In all matrices, ¹⁸¹Hf/¹⁸¹Ta was found to substitute the Hf/Zr site. The ¹¹¹In/¹¹¹Cd impurities were also assigned to the Hf/Zr site in the compounds (Zr/Hf)Al₃, but appear to substitute the two non-equivalent Al sites in the Zr₂Al₃ and Hf₂Al₃ phases. This revised version was published online in September 2006 with corrections to the Cover Date.     

Study of hyperfine interactions in the intermetallic compound CePd2Si2 using PAC technique with 111Cd as probe nuclei

Perturbed γ???γ angular correlation spectroscopy (PAC) has been used to investigate the hyperfine interactions in the intermetallic compound CePd₂Si₂ using ¹¹¹In→¹¹¹Cd probe nuclei. Samples of CePd₂Si₂ were prepared by melting constituent elements in an arc furnace under pure argon atmosphere. Carrier-free ¹¹¹In nuclei were introduced into the samples by thermal diffusion at 800°C in vacuum during 12 h. The measurements were performed in the temperature range of 4.2–300 K. Above the magnetic transition temperature (T _N ?=?10 K), the results show two distinct and well defined quadrupole interactions that were assigned to probe nuclei occupying Ce and Si sites in the compound. The quadrupole frequencies were found to decrease linearly with increasing temperature. The PAC spectra taken below 10 K were analyzed with a model including combined electric quadrupole plus magnetic dipole interactions, from which the hyperfine magnetic field was determined.     

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.     

Investigation of spin transition in GdCoO3 by measuring the electric field gradient at Co sites

In the present work, the time differential perturbed angular correlation (PAC) technique was used to study the temperature dependence of electric field gradient (efg) in GdCoO₃ perovskite using ¹¹¹Cd and ¹⁸¹Ta nuclear probes. The radioactive parent nuclei ¹¹¹In and ¹⁸¹Hf were introduced in the oxide lattice through chemical process during sample preparation and were found to occupy only the Co sites in GdCoO₃. The efg's at ¹¹¹Cd and ¹⁸¹Ta show temperature dependence with two different fractions each that change with temperature. In the case of ¹¹¹Cd the quadrupole frequency slowly decreases, with corresponding increase of the temperature and shows a peak like structure at around 200 K and a discontinuity at 700 K. These changes 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 Co³⁺${\mathrm{Co}}^{3+}$ ion similar to LaCoO₃ compound. Indication of a Jahn–Teller distortion, which stabilizes the intermediate-spin state with orbital ordering, is also pointed out.     

The electric quadrupole interaction of181Ta in the Hf−As system

The temperature dependence of the electric quadrupole interaction of¹⁸¹Ta in the Hf?As system has been investigated using the time-differential perturbed angular correlation technique. The sample was prepared by thermal diffusion of¹⁸¹Hf into arsenic metal and the measurements were made at 77, 300, 423, 573 and 673 K. Two quadrupole interaction frequencies were observed which had considerably high values and showed little variation over the entire temperature range. A TEM analysis of the sample showed the presence of two intermetallic compounds HfAs and HfAs₂ to which the two frequencies were assigned.     

Phase transitions in the SrHfO3 perovskite measured with 111In/111Cd PAC

The temperature dependence of the hyperfine parameters in SrHfO₃ powder samples has been investigated by means of Perturbed Angular Correlation spectroscopy using implanted ¹¹¹In probes. Three quadrupole interactions have been established, with the largest fraction showing a pronounced dynamic interaction. We assign this fraction to ¹¹¹In / ¹¹¹Cd probe atoms on substitutional Hf sites. The temperature dependence of the dynamic interaction has been associated to the Pnma↔Imma phase transition at ∼700 K. We discuss the results in relation to those obtained for ¹⁸¹Hf / ¹¹¹Ta-probes in AHfO₃ (A=Ba, Sr, Ca) and for ¹¹¹In / ¹¹¹Cd-probes in PbZrO₃ and BaTiO₃. This revised version was published online in August 2006 with corrections to the Cover Date.     

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.     

Structural phase transition in cadmium titanate observed by electric quadrupole interaction

The quadrupole interaction at¹¹¹Cd nuclei was measured in the ferroelectric perovskite CdTiO₃ at different temperatures using the PAC method. The interaction parameters indicate a structural phase transition around 50 K.     

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 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.     

PAC detection of oxide formation in zirconium and hafnium hydrides

The formation of HfO₂ and ZrO₂ oxides in Hf and Zr hydrides has been detected by¹⁸¹Ta PAC spectroscopy. The oxides were identified by their¹⁸¹Ta quadrupole frequency and asymmetry parameter. The growth of the oxide contamination in a H₂ atmosphere has been investigated as a function of temperature and time.     

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.     

Perturbed angular correlation studies of Ta hyperfine interactions in Hf-Ni and Zr-Ni compounds

The hyperfine interaction experienced by ¹⁸¹Ta nuclei in the intermetallic compounds ZrNi₅, HfNi₅, and Hf₂Ni₇ has been investigated by perturbed angular correlation (PAC) spectroscopy. At temperatures T≥15 K the ¹⁸¹Ta angular correlation of appropriately annealed ZrNi₅ and HfNi₅ is unperturbed, indicating the absence of a magnetic hyperfine interaction. This observation rules out the possibility of spontaneous magnetic order of ZrNi₅ and HfNi₅ recently proposed in the literature. The temperature dependence of the electric quadrupole interaction of ¹⁸¹Ta in Hf₂Ni₇ suggests the existence of a reversible phase transformation at T≥500 K.     

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.