Development of solar cell material by PAC:111In probes in CuInS2 and related phases

Using metallic indium doped with radioactive¹¹¹In as one of the starting materials samples of stoichiometric CuInS₂, CuInS₂ with excess of indium and sulphur, and stoichiometric CuIn₅S₈ were prepared. Perturbed angular correlations of γ rays emitted by¹¹¹Cd are utilized to analyse the produced crystalline phases.     

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.     

Ionic and electronic transport in In2S3 studied via perturbed angular correlation spectroscopy

We report on Perturbed Angular Correlation measurements in polycrystalline In₂S₃ samples in the temperature range from 8 K to 1000 K where two different crystallographic phases β and α occur. As probes, implanted ¹¹¹In nuclei have been used. The three observed EFGs are attributed to probes residing substitutionally in the different sulfur-octahedra and -tetrahedra of β-In₂S₃. A strong damping between 150 K and 300 K has been attributed to EFG fluctuations following the ¹¹¹In(EC)¹¹¹Cd decay. The α-phase (above 680 K) is characterized by a different dynamical damping of the perturbation functions, caused by mobile In atoms. Therefore, the semiconductor In₂S₃ shows, in two different temperature ranges, dynamical PAC-spectra which correspond to different types of mobile charge carriers. Since ¹¹¹In is a self atom in In₂S₃, this compound is an ideal substance to study the charge transport phenomena by the PAC technique. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and characterization of sol-gel derived Mn2+ doped In2S3 nanocrystallites embedded in a silica matrix

Mn²⁺ doped In₂S₃–SiO₂ nanocomposite thin films were synthesized by sol-gel technique. The films were annealed in air at different temperatures (473–623 K) and characterized by optical, microstructural and electron spin resonance (ESR) study. Optical transmittance study revealed the manifestation of quantum size effect while ESR indicated the presence of manganese in indium sulphide as dispersed dopant rather than manganese cluster.     

Experimental determination of the chemical changes in the electron density on indium nuclei by the γ‐spectrometric ΔIγ/Iγ method

The γ‐spectrometry method for determination of the relative change Δλ_EC/λ_EC in the partial probability λ_EC for the ^114mIn decay branch by the electron capture (EC), when the nucleus is in different chemical environments, was developed. The method is based on an experimental determination of the relative change ΔI_γ/I_γ in the intensity of the γ‐radiation which is emitted by the excited daughter ¹¹⁴Cd nuclei after EC. The ^114mIn decay by EC in indium metal, In₂O₃ and InAs was compared. The largest ΔI_γ/I_γ=(2.5±0.8)·10⁻⁴ has been found for InAs relatively to In₂O₃. The chemical changes in the electron density on the indium nucleus corresponding to the measured ΔI_γ/I_γ values have been determined. This revised version was published online in July 2006 with corrections to the Cover Date.     

Hyperfine Interactions in CeT2Ge2 (T = Mn,Co) Heavy Fermions Compounds Measured by TDPAC

Time Differential Perturbed γ–γ Angular Correlation (TDPAC) technique was used to measure the magnetic hyperfine field at both Ge and Ce sites in CeMn₂Ge₂ and CeCo₂Ge₂ intermetallic compounds. The ¹¹¹In (¹¹¹Cd) probe nuclei was used to investigate the hyperfine interaction at Ge sites, while the ¹⁴⁰La (¹⁴⁰Ce) nuclei was used to measure the magnetic hyperfine field at Ce site. The present measurements cover the temperature ranges from 10–460 K for CeMn₂Ge₂ and 9–295 K for CeCo₂Ge₂, respectively. The result for ¹¹¹Cd probe showed two distinct electric quadrupole frequencies above magnetic transition temperatures, in both compounds and a combined interaction in the magnetic region. The temperature dependence of the magnetic hyperfine field at ¹¹¹Cd at Mn site for the CeMn₂Ge₂ compound showed a transition from ferromagnetic to antiferromagnetic phase around 320 K and from antiferromagnetic to paramagnetic phase at 420 K. While a small magnetic field was measured on ¹¹¹Cd at Co site, no magnetic field on ¹⁴⁰Ce site was observed in CeCo₂Ge₂. This revised version was published online in September 2006 with corrections to the Cover Date.     

Nuclear <Superscript>111</Superscript>Cd probes detect a hidden symmetry change at the γ → α transition in cerium considered isostructural for 60 years

We use the time-differential perturbed angular correlation technique to study nuclear electric quadupole hyperfine interactions of probe ¹¹¹Cd nuclei in cerium lattice sites at room temperature under pressures up to 8 GPa. We have found that the well known γ → α phase transition in cerium is not isostructural. In α-Ce, the probe ¹¹¹Cd nuclei reveal a quadrupole electron charge density component that is absent in γ-Ce. The hidden spacial structure of electronic quadrupoles in α-Ce is triple-q antiferroquadrupolar, as was suggested in [14]. We relate our findings to the current understanding of the γ → α phase transition and also report on nuclear quadrupole interactions in other high-pressure phases of cerium: α″ (C2/m space symmetry) and α′ (α-U structure).     

Electronic Relaxation in Indium Oxide Films Studied with Perturbed Angular Correlations

The electronic relaxation due to the ¹¹¹In → ¹¹¹Cd electron capture process was studied by measuring perturbed γγ-angular correlations after ¹¹¹In-ion implantation into indium oxide films of various compositions and thicknesses and deposited on different substrates. X-ray diffraction, Rutherford backscattering and secondary ion mass spectrometry were used to characterize the microstructure and composition of the samples. The film thickness and type of substrate were found to have much less influence on the after effect than the deposition parameters and impurities.     

Analysis of the nuclear quadrupole interaction of Disulfur Dichloride, S2Cl2

Pure rotational spectra of S₂³⁵Cl₂ and S₂³⁵Cl³⁷Cl have been observed using a Fourier-transform microwave spectrometer. An analysis of the hyperfine structure made by considering the nuclear spin statistics showed that S₂Cl₂ has C₂symmetry, where the hyperfine splittings due to the two Cl nuclei were analyzed precisely. The nuclear quadrupole coupling constants including the off-diagonal (χ_ab, χ_ac, χ_bc) components and the nuclear spin–rotation interaction constants associated with the two Cl nuclei have been determined for the first time. We have shown that the nuclear quadrupole interaction plays an important role in the ortho–para mixing.     

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.     

CuInS2 thin films obtained through the annealing of chemically deposited In2S3-CuS thin films

In this work, we report the formation of CuInS₂ thin films on glass substrates by heating chemically deposited multilayers of copper sulfide (CuS) and indium sulfide (In₂S₃) at 300 and 350 °C in nitrogen atmosphere at 10 Torr. CIS thin films were prepared by varying the CuS layer thickness in the multilayers with indium sulfide. The XRD analysis showed that the crystallographic structure of the CuInS₂ (JCPDS 27-0159) is present on the deposited films. From the optical analysis it was estimated the band gap value for the CIS film (1.49 eV). The electrical conductivity varies from 3 × 10⁻⁸ to 3 Ω⁻¹ cm⁻¹ depending on the thickness of the CuS film. CIS films showed p-type conductivity.     

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.      

Relaxation structure analysis of Li inserted γ-Fe2O3

γ-Fe₂O₃ has a spinel structure with cation vacancy and is expected to perform as a favorable electrode material for secondary lithium-ion battery. When lithium is inserted electrochemically into γ-Fe₂O₃, prolonged potential change is observed after the insertion. In this study, we inserted various amount of Li into γ-Fe₂O₃ (x = 0.66, 1.1, 1.5 in terms of Li_XFe₂O₃), then made the circuit open, measured X-ray diffraction (XRD) patterns at various elapsed time, and analyzed the crystal structure change of γ-Fe₂O₃ with time by the Rietveld method. The X-ray Rietveld analysis revealed that the iron occupancy of 8a site decreased and that of 16c site increased with lithium insertion process and after lithium insertion, the iron occupancy of 8a site increased and that of 16c site decreased gradually with relaxation time. It is indicated that lithium prefer 8a site to occupy kinetically, on the other hand, prefer 16c site thermodynamically.     

The electric field gradient of111Cd in an α-Al2O3 single crystal

Radioactive¹¹¹In⁺ ions were implanted into an α-Al₂O₃ single crystal. The hyperfine parameters of¹¹¹Cd at substitutional Al lattice sites were identified by measuring the perturbed angular correlation for different sample orientations. The electric field gradientV _zz =1.04(17)·10²²V/m² was obtained from the quadrupole coupling constant. This result is compared with the efg values of²⁷Al in α-alumina and¹¹¹Cd in α-Fe₂O₃, which also has the corundum structure. Two additional fractions with broad frequency distributions were observed, one of which is attributed to¹¹¹Cd atoms in a strongly distorted Al₂O₃-lattice.     

Electric-field gradients at Ta donor impurities in Cr2O3(Ta) semiconductor

We report perturbed-angular-correlation (PAC) experiments on ¹⁸¹Hf(→¹⁸¹Ta)-implanted corundum Cr₂O₃ powder samples in order to determine the magnitude and symmetry of the electric-field gradient (EFG) tensor at Ta donor impurity sites of this semiconductor. These results are analyzed in the framework of ab initio full-potential augmented-plane wave plus local orbitals (FP−APW+lo) calculations. The results are also compared with EFG results coming from PAC experiments in isomorphous α-Al₂O₃ and α-Fe₂O₃ doped with ¹¹¹In→¹¹¹Cd and ¹⁸¹Hf→¹⁸¹Ta tracers. This combined analysis enables us to quantify the magnitude of the lattice relaxations induced by the presence of the impurity and to determine the charge state of the impurity donor level introduced by Ta in the band gap of the semiconductor.     

Ab initio study of the EFG tensor at Cd impurities in Sc2O3 semiconductor

We present an ab initio study of diluted Cd impurities localized at both cation sites of the semiconductor Sc₂O₃. The electric-field-gradient (EFG) tensor at Cd impurities located at both cationic sites of the host structure was determined from the calculation of the electronic structure of the doped system. Calculations were performed with the full-potential augmented-plane wave plus local orbitals (APW+lo) method within the framework of the density functional theory. We studied the atomic structural relaxations and the perturbation of the electronic charge density induced by the impurities in the host system in a fully self-consistent way. We showed that the Cd impurity introduces an increase of 8% in the nearest oxygen neighbors bond-lengths, changing the EFG sign for probes located at the asymmetric cation site. The APW+lo predictions for the charged state of the Cd impurity were compared with EFG results existent in the literature, coming from time-differential γ–γ perturbed-angular-correlations experiments performed on ¹¹¹Cd-implanted Sc₂O₃ powder samples. From the excellent agreement between theory and experiment, we can strongly suggest that the Cd acceptor impurities are ionized at room temperature. Finally, we showed that simple calculations like those performed within the point-charge model with antishielding factors do not correctly describe the problem of a Cd impurity in Sc₂O₃.     

Radiation-induced radical ions in calcium sulfite

We have used EPR to study the effect of γ radiation on calcium sulfite. We have observed and identified the radiation-induced radical ions SO ₂ ⁻ (iso) with g = 2.0055 and SO ₂ ⁻ (orth-1) with g₁ = 2.0093, g₂ = 2.0051, g₃ = 2.0020, identical to the initial and thermally induced SO ₂ ⁻ respectively, SO ₃ ⁻ (iso) with g = 2.0031 and SO ₃ ⁻ (axial) with g_⊥ = 2.0040, g_∥ = 2.0023, identical to mechanically induced SO ₃ ⁻ . We have established the participation of radiation-induced radical ions SO ₃ ⁻ in formation of post-radiation SO ₂ ⁻ . __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 467–472, July–August, 2006.     

Determination of the Gamow–Teller strength function for the neutron-deficient isotopes In

The Gamow–Teller β decays of the neutron-deficient indium isotopes ^104–107In have been investigated by using total absorption γ-ray spectrometry on mass-separated sources. The experimental Gamow–Teller strength, deduced as a function of the excitation energy in the daughter nuclei ^104–107Cd, is compared to shell-model predictions.     

Beta decay of the proton-rich nuclei 102Sn and 104Sn

The β decays of ¹⁰²Sn and ¹⁰⁴Sn were studied by using high-resolution germanium detectors as well as a Total Absorption Spectrometer (TAS). For ¹⁰⁴Sn, with three new β-delayed γ-rays identified, the total Gamow-Teller strength (B_GT) value of 2.7(3) was obtained. For ¹⁰²Sn, the γ-γ coincidence data were collected for the first time, allowing us to considerably extend the decay scheme. This scheme was used to unfold the TAS data and to deduce a B_GT value of 4.2(8) for this decay. This result is compared to shell model predictions, yielding a hindrance factor of 3.6(7) in agreement with those obtained previously for ⁹⁸Cd and ¹⁰⁰In. Together with the latter two, ¹⁰²Sn completes the triplet of Z ⩽ 50, N ≥ 50 nuclei with two proton holes, one proton hole and one neutron particle, and two neutron particles with respect to the doubly magic ¹⁰⁰Sn core.     

Structural phase transition of Rh2O3 studied via PAC

The structural phase transition from α-Rh₂O₃ to β-Rh₂O₃ has been studied via the PAC method on dilute¹¹¹Cd impurity atoms implanted into α-Rh₂O₃. The measured antishielding factor β=112 (2) in the α-phase is similar to that found for¹¹¹Cd in other oxides with corundum structure (Al₂O₃. Cr₂O₃, Fe₂O₃). Oxygen with different crystallographic matrices show a pronounced correlation of the electric field gradient with the NN oxygen coordination.