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.     

Self-radiation damage and recovery in Pu-doped zircon

Abstract

The effects of self-radiation damage due to alpha decay was studied as a function of cumulative decay events in synthetic zircon doped with ²³⁸Pu. The density of the Pu-doped zircon decreased exponentially with dose to a value corresponding to a density change of 14.2% at saturation. The initially crystalline material became fully X-ray amorphous at a dose of 6.7 × 10¹⁸ alpha decays/g. Isochronal annealing indicated that recovery associated with recrystallization of amorphous zircon occurs in two stages, with estimated activation energies of 5.1 ± 0.2 and 6.6 ± 0.3 eV. These results are in good agreement with behavior observed in studies of self-radiation damage over geologic time in natural zircons.     

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.      

Effect of isotope substitution and doping on the Raman spectrum of galena (PbS)

The Raman spectrum of natural PbS has been shown to exhibit features related to the IR-active (Raman forbidden) LO phonons and to allowed scattering by two phonons. In order to confirm the vibrational nature of these features, and their peculiar temperature dependence, we compare here the spectra obtained for natural samples (i.e. mineral as well as synthetic with the natural isotopic abundance) with those measured for crystals prepared from highly enriched ³⁴S. The observed isotopic shifts confirm the vibrational nature of the structures mentioned above. We have also measured the spectra of synthetic samples of PbS annealed at several different pressures of sulphur. Because of their non-stoichiometric sulphur content they have carrier concentrations (either electrons or holes) in the 1×10¹⁷-3×10¹⁸ carriers/cm³ range (as determined from their IR reflection spectra). The measured spectra, as well as their temperature dependence, do not depend on the bulk carrier concentration, a fact that must result from surface pinning of the Fermi level within the fundamental energy gap.We finally discuss the apparent paradox of why the IR spectra reveal coupled LO-phonon-plasmon modes whereas the Raman spectra exhibit the bare LO-phonons.     

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.     

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.     

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     

锆英石的抗γ射线辐照能力和Rietveld结构精修

为研究放射性核素固化介质备选矿物锆英石的抗γ射线辐照结构稳定性,以澳大利亚锆英石为研究对象,通过⁶⁰Co源γ射线辐照装置对样品施以1728 kGy的γ射线辐照.利用X射线荧光光谱仪、扫描电子显微镜和X射线衍射仪对样品的元素含量、γ射线辐照前后的微观形貌及物相变化进行表征,同时利用Rietveld方法对γ射线辐照前后的样品进行了结构精修.结果表明:澳大利亚锆英石经1728 kGy剂量的γ射线辐照后未发生物相变化,射线辐照前后样品的晶胞参数仅发生了10^-4 量级的变 关键词： 锆英石 γ射线 辐照 Rietveld结构精修     

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.     

Influence of gadolinium concentration on the EMR spectrum of Gd in zircon

Electron magnetic resonance (EMR) spectra of gadolinium-doped zircon (ZrSiO₄) powders have been studied at room temperature for gadolinium concentrations between 0.20 and 1.0 mol%. The results suggest that Gd³⁺ ions occupy substitutional sites in the zircon lattice, that the electron magnetic resonance linewidth increases with increasing gadolinium concentration and that the range of the exchange interaction between Gd³⁺ ions is about 1.17 nm, larger than that of the same ion in other host lattices, such as ceria (CeO₂), strontium oxide (SrO) and calcium oxide (CaO). The fact that the electron magnetic resonance linewidth of the Gd³⁺ ion in polycrystalline zircon increases, regularly and predictably, with Gd concentration, shows that the Gd³⁺ ion can be used as a probe to study, rapidly and non-destructively, the crystallinity and degradation of ZrSiO₄.     

Magnetoelastic contribution to the thermal expansion of the rare-earth phosphates TbPO4 and TmPO4

The thermal expansion of the rare-earth phosphates TbPO₄ and TmPO₄ having zircon structure has been investigated experimentally and theoretically. Significant magnetoelastic anomalies of the thermal expansion have been identified and the magnetoelastic contributions have been isolated allowing for corrections to the variation of the phonon contribution along the rare-earth ion series. It is shown that the magnetoelastic contribution to the thermal expansion of terbium and thulium phosphate is well described by the temperature dependence of the quadrupole moments of the rare-earth ions. The fully symmetric magnetoelastic coefficients for Tb³⁺ and Tm³⁺ are determined and a comparison is made of the magnetoelastic anomalies of the thermal expansion and the magnetoelastic coefficients of rare-earth phosphates and vanadates allowing for the differences in the crystal fields of the two isomorphic groups of zircons. Fiz. Tverd. Tela (St. Petersburg) 39, 106–111 (January 1997)     

Anharmonicity in silicate crystals: Temperature dependence of Au type vibrational modes in ZrSiO4 and LiAlSi2O6

Infrared reflection spectra for the extraordinary ray of zircon and spondumene have been obtained in the frequency range from 270 to 1500 cm^?1 and from room temperature up to 1300°K. Using a combination of Kramers-Kronig analysis and a classical dispersion theory, the oscillator parameters of the A_2u modes in zircon and A_u modes in spodumene were determined. The temperature dependence of observed mode damping is analysed on the basis of quantum theoreticall results involving both cubic and quartic anharmonic contributions. The comparison of the present results with other data reported in previously studied silicate crystals, shows that the observed anharmonic behavior of internal and external modes is consistent with simple considerations based on the site vicinity of each ion.     

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.     

Hyperfine interactions at R and In sites in RNiIn (R = Gd, Tb, Dy, Ho) compounds measured by perturbed angular correlation spectroscopy

Perturbed gamma–gamma angular correlation (PAC) technique was used to measure the magnetic hyperfine field (mhf) in RNiIn (R = Gd, Dy, Tb, Ho) intermetallic compounds using the ¹¹¹In→¹¹¹Cd and ¹⁴⁰La→¹⁴⁰Ce probe nuclei. The PAC spectra for ¹¹¹Cd measured above magnetic transition temperature show a major fraction with a well defined quadrupole interaction for all compounds except GdNiIn where a single frequency was observed. PAC measurements below T _C showed a combined electric quadrupole plus magnetic dipole interaction for ¹¹¹Cd probe at In sites, and a pure magnetic interaction for ¹⁴⁰Ce at R sites. The temperature dependence of mhf measured with ¹⁴⁰Ce at R sites shows that the values of fields drop to zero at temperatures around the expected T _C for each compound. However, in the measurements with ¹¹¹Cd at In sites, the mhf values become zero at temperatures which are smaller than T _C . The difference between the temperatures at which mhf is zero for ¹⁴⁰Ce and ¹¹¹Cd probes correlates with T _C . For each compound this difference decreases with T _C . The results are discussed in terms of the RKKY model for magnetic interactions and the existence of two magnetic systems, with distinct exchange interaction energies due to different types of atomic layers in these compounds.     

Hyperfine Interaction of Metamict Zircon Studied by PAC Spectroscopy

Zircon (ZrSiO₄) is a common accessory mineral found in igneous and metamorphic rocks and is generally in an amorphous state due to self-irradiation from radioactive impurities. The crystalline structure may be recovered by annealing. We have studied the annealing behavior of a nearly fully metamict zircon specimen by perturbed angular correlation spectroscopy and powder X-ray diffraction. Our results are consistent with accepted damage accumulation models and point to a two-stage recovery process for the transition from metamict to crystalline zircon. In all of our experiments PAC overestimates the amorphous fraction as compared to that determined by diffraction experiments, and we propose an explanation for this discrepancy. This revised version was published online in September 2006 with corrections to the Cover Date.     

Structural properties of the donor indium in nanocrystalline ZnO

The structural properties of the nanocrystalline semiconductor ZnO (nano-ZnO) doped with the donor Indium were investigated by perturbed γγ angular correlation spectroscopy (PAC) and extended X-ray absorption fine structure measurements (EXAFS). Up to an average concentration of one In atom per nanocrystallite, PAC measurements show that about 12% of the ¹¹¹In atoms are incorporated on substitutional Zn sites. At higher In concentrations, new In defect complexes are visible in the PAC spectra, which dominate the spectra if the average In concentration exceeds one In atoms per nanocrystallite. In addition, the local environment of Zn and In atoms in In doped nano-ZnO was investigated by EXAFS. The measurements at the K edge of Zn show that the crystal structure of nano-ZnO corresponds to bulk ZnO. In heavily In doped nano-ZnO the EXAFS experiments at the K edge of In exhibit an expansion of the first O shell about the In site. Since about four O atoms are detected in this first shell a substitutional incorporation of the In atoms in the ZnO lattice is suggested. The second shell to be occupied by Zn atoms as well as higher shells are almost invisible, which might have the same microscopic origin as the occurrence of defect complexes observed by PAC.     

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.     

Site occupation of indium and jump frequencies of cadmium in FeGa<Subscript><Emphasis Type="Bold">3</Emphasis></Subscript>

Perturbed angular correlation (PAC) measurements using the In-111 probe were carried out on FeGa₃ as part of a broader investigation of indium site occupation and cadmium diffusion in intermetallic compounds. One PAC signal was observed with hyperfine parameters ω ₁= 513.8(1) Mrad/s and η= 0.939(2) at room temperature. By comparison with quadrupole frequencies observed in PAC measurements on isostructural RuIn₃, it was determined that indium occupies only the 8j site in the FeGa₃ structure, denoted Ga(2) below because two out of the three Ga sites have this point symmetry. PAC spectra at elevated temperature exhibited damping characteristic of electric field gradients (EFGs) that fluctuate as Cd probes jump among Ga(2) sites within the lifetime of the excited PAC level. A stochastic model for the EFG fluctuations based on four conceivable, single-step jump-pathways connecting one Ga(2) site to neighboring Ga(2) sites was developed and used to fit PAC spectra. The four pathways lead to two observable EFG reorientation rates, and these reorientation rates were found to be strongly dependent on EFG orientation. Calculations using density functional theory were used to reduce the number of unknowns in the model with respect to EFG orientation. This made it possible to determine with reasonable precision the total jump rate of Cd among Ga(2) sites that correspond to a change in mirror plane orientation of site-symmetry. This total jump rate was found to be thermally activated with an activation enthalpy of 1.8 ±0.1 eV.     

缅甸翡翠中锆石的LA-ICP-MS微量元素U-Pb年龄：对其成因的制约

翡翠产自与俯冲作用相关的HP/LT变质区域,对俯冲作用的研究具有重要意义。锆石常用来确定岩石的年龄,可以用于翡翠成因和形成时代的研究。缅甸是世界上优质翡翠最主要的产地,锆石是缅甸翡翠中常见的副矿物。选择含锆石较多的缅甸翡翠原石,对晶形较好的大颗粒锆石运用阴极发光(CL)图像观察锆石中颜色的分布和韵律环带形态的变化,并根据CL图像特征进一步采用激光剥蚀电感耦合等离子体质谱仪(LA-ICP-MS)对锆石的微量元素和U-Pb年龄进行测定。结果表明具不同颜色和韵律环带形态的锆石,其微量元素分布有一定的差异,但总体却表现为：锆石的标准化球粒陨石稀土配分显示轻稀土元素(LREE)亏损,重稀土元素(HREE)富集,有明显的Ce(Ce/Ce*=19.2～74.2)正异常和微弱的Eu(Eu/Eu*=0.49～0.72)负异常。稀土元素总含量(∑REE)高(810～3 984 μg·g-1),(Yb/Sm)_N值为23.1～195.1(大部分值小于100);Th/U比值为0.28～1.18。研究锆石属于岩浆锆石,形成于俯冲带上覆地幔楔的镁铁质玄武岩浆之中,这类岩浆是陆下地幔橄榄岩受到俯冲过程中释放的流体作用部分熔融形成的。Ti温度计显示锆石的形成温度为762～923 ℃。锆石的206Pb/238U年龄为(157.3±1.3)Ma,这一年龄为锆石的形成时间。CL图像显示锆石中颜色的分布和韵律环带形态的变化与锆石的形成时间无关,是锆石中微量元素差异分布造成的,反映了锆石形成过程中岩浆熔体成分的动态演化。