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.     

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.     

PAC-studies of Sn-doped In2O3: electronic defect relaxation following the 111In(EC)111Cd-decay

Perturbed γ-angular correlation measurements as function of the measuring temperature and the Sn-content have been performed in Sn-doped cubic In₂O₃ using ¹¹¹In(EC)¹¹¹Cd and ^111m Cd probes. By comparing the spectra of both isotopes, electronic relaxation phenomena, socalled decay after-effects, following the electron capture radioactive decay of ¹¹¹In, were established. A time independent loss of the static quadrupole interaction amplitudes was found to be characteristic for the electronic relaxation, and its temperature and doping dependence were measured. The high statistical accuracy of the PAC-data allowed a separation between structural and dynamic effects and the observation of each lattice site’s behaviour. Relaxation rates were extracted from numerical simulations based on Blume’s theory and related to the predominant electron transport mechanisms in In₂O₃, especially, with rising Sn-content, to the transition to metallic conduction.     

Doping of sapphire single crystals with 111In and 111Cd detected by perturbed angular correlation

The electric hyperfine interaction of ion beam implanted ¹¹¹In and ¹¹¹Cd probe atoms in sapphire (Al₂O₃) single crystals has been investigated using perturbed angular correlation spectroscopy. For both probe atoms the same distinctive electric field gradient was found, indicating that nearly all the implanted probe atoms form a stable substitutional configuration in the temperature range between 77 K and 873 K on the aluminum sublattice. A comparative study between ¹¹¹In and ¹¹¹Cd-measurements points to a dynamic interaction initiated by the electron-capture of ¹¹¹In(EC)¹¹¹Cd similar to In₂O₃ and La₂O₃. Size and orientation of the EFG are discussed in comparison to experimental results in Cr₂O₃ single crystals. This revised version was published online in August 2006 with corrections to the Cover Date.     

Investigation of hyperfine interactions in GdCrO3 perovskite oxide using PAC spectroscopy

Perturbed angular correlation (PAC) measurements have been carried out in the antiferromagnetic GdCrO₃ perovskite oxide using ¹¹¹In (¹¹¹Cd) and ¹⁸¹Hf(¹⁸¹Ta) nuclear probes. The radioactive parent nuclei ¹¹¹In and ¹⁸¹Hf were introduced in the compound through a chemical process during sample preparation. The PAC measurements were carried out in the temperature range 20–300 K. Measurements with the ¹⁸¹Ta indicated a unique quadrupole interaction above 170 K and a combined electric quadrupole and magnetic dipole interactions below this temperature. The observed interaction was assigned to the probe nuclei substituting Cr sites. Measurements with ¹¹¹Cd showed two quadrupole interactions. Only one of the fractions however, showed a combined electric and magnetic interaction in the temperature rage 20–170 K which was assigned to ¹¹¹Cd probe substituting Cr site. The other fraction was attributed to the Gd site. The present results are compared with those of LaCrO₃ and NdCrO₃.     

Hyperfine interaction of111Cd in antiferromagnetic cobalt oxide

The temperature dependence of the hyperfine field of substitutional¹¹¹Cd in antiferromagnetic CoO has been measured by means of the perturbed angular correlation technique. The Larmor frequency ω_L is found to obey a power law ω_L(t=ω₀ t ^β) up tot _max=0.4 wheret=1−T/T _N is the reduced temperature withT _N=291.2(3) K and β=0.393 (5) the critical exponent. The results are discussed and compared with PAC experiments on¹¹¹Cd in NiO and Ni and with results obtained by other methods.     

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.     

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.     

Fluctuating Electric Field Gradients at 111Cd in Ice

¹¹¹Cd–PAC measurements have been made using the high specific activity of ¹¹¹In in the methanol–water mixtures of various concentrations at the room temperature. These experiments revealed that the perturbation factors 〈A ₂ G ₂〉 (integrated over two mean lives τ_N) do not follow the dependence of the macroscopic viscosity η. The observed dynamic character of the PAC spectra in ice is explained by the mobility of orientational and ionic defects. The activation energy for the diffusion process was determined to be E _a =0.35(1) eV. This revised version was published online in September 2006 with corrections to the Cover Date.     

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.     

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.     

Influence of the temperature and the ionisation potential on the hyperfine interaction of 111Cd ions in gaseous radioactive indium‐halides

The hyperfine interaction (HFI) of ¹¹¹Cd in different indium‐halides was studied by perturbed angular correlation (PAC). The ¹¹¹Cd ion arises from a ¹¹¹In by electron capture decay (EC) and joined Auger cascade. Coulomb fragmentation of the indium‐halide molecule produces the free excited ¹¹¹Cd ion. The nucleus decays via a γ–γ‐cascade which is perturbed by the HFI. Collisions of the ¹¹¹Cd ion with indium‐halide molecules can strongly change the perturbation. The perturbation was measured by the attenuation coefficient G₂₂(∞) and G₂₂(t). The molecular densities varied between 10¹⁴ and 10²⁰ cm⁻³. The present article shows the temperature dependence of the indium(III)‐halides and a fit for an empirical basic approach. The investigation of the InBr shows the independence of the attenuation coefficient from the temperature by indium(I)‐halides in contrast to the dependence of the indium(III)‐halides. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

TDPAC measurement of quadrupole interaction at111Cd in the nearly heavy fermion system USn2.9

Quadrupole interaction at¹¹¹Cd probe has been studied in the nearly heavy fermion system USn_3– using the TDPAC method. We observe a large quadrupole interaction frequency withv _Q =89.9(10) MHz at 300 K which is much higher than the earlier reported result. The observed frequency shows a linear temperature dependence in the range 25–300 K.     

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.     

Perturbed angular correlation experiments on111In in oxidized AgCd alloy

The hyperfine interaction of¹¹¹Cd probes in preoxidized and α-irradiated Ag_0.94Cd_0.06 alloy has been investigated by PAC measurements and compared with the results for pure Ag. Several probe atom sites were distinguished and characterized by their hyperfine parameters and temperature evolution. The different behavior of In-oxygen and In-oxygen-vacancy complexes in AgCd and Ag was found and discussed. A considerable influence of the irradiation temperature and sample thickness on the different In-oxygen-vacancy complexes formation was evidenced. The parameters of¹¹¹Cd quadrupole interaction measured during isochronal annealing studies in preoxidized and deuteron irradiated AgCd were very similar to the ones observed after α-irradiation.     

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.     

Temperature dependence studies of the EFG at111Cd probes located in some intermetallic compounds

The temperature dependences of the electric field gradient (EFG) at¹¹¹Cd probes in nickel-indium and indium-tellurium intermetallic compounds have been studied by means of the time differential perturbed angular correlation of gamma rays (TDPAC). The room temperature interaction frequencies (e ² Qq/h) in each case were determined as In₂Te₅ (136 MHz), Ni₃In (13.8 MHz), NiIn (252 and 337 MHz) (two sites), and Ni₂In₃ (162 and 266 MHz) (two sites). The TDPAC pattern of¹¹¹Cd in NiIn did not agree with the previous assignment of the crystal structure. A general discussion of the results related to other temperature dependence studies of the EFG is presented and a general trend is discerned.Supported in part by the US Energy and Research Development Administration.     

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.     

Electric field gradients at the 111In site in the ferroelectric and paraelectric phases of LiTaO3

The temperature dependence of the electric-field gradient of ¹¹¹Cd in single crystalline LiTaO₃ was studied from room temperature to 1040 K in the ferroelectric and paraelectric phases. The data taken at room temperature show unambiguously the presence of two quadrupole interaction frequencies, ν_Q1=230 MHz and ν_Q2=242 MHz, with nonzero asymmetry parameters, while above the Curie temperature (T_C=878 K) the data are well described by a unique frequency. The electric field gradient shows a usual temperature dependence, increasing aproximately in a linear fashion until T_C and then decreasing faster. The initial increase is explained mostly by the lattice expansion, while above T_C it is necessary to consider Li and O displacements. This revised version was published online in August 2006 with corrections to the Cover Date.