Structural and magnetic properties of RET2Sn2 compounds (RE=La,Ce, Sm; T=Ni,Cu)

The following compounds have been synthesized: LaCu₂Sn₂, CeCu₂Sn₂, SmCu₂Sn₂ and SmNi₂Sn₂. By means of X-ray diffraction their structure was determined to be primitive tetragonal of CaBe₂Ge₂-type (space group P4/nmm) and the lattice parameters were obtained.¹¹⁹Sn Mössbauer measurements were performed in a temperature range between 4.2 K and 300 K. The temperature dependence of the Lamb-Mössbauer factor reveals considerable softening of lattice vibration modes below 160 K. Only SmCu₂Sn₂ orders magnetically above 4.2 K.     

Forced volume magnetostriction in (rare earth) ni2 cubic intermetallic compounds

The forced volume magnetostriction has been measured for the RENi₂ intermetallic compounds (RE = Ce, Pr, Sm, Gd, Tb and Dy). In GdNi₂ both spontaneous and forced magnetostriction originate from pure exchange and it is necessary to invoke short-range spin correlations to explain the peculiar temperature dependence. In PrNi₂, SmNi₂, TbNi₂ and DyNi₂ the magnetostriction is contributed to by strains from both crystalline electric field and exchange, the temperature dependence in TbNi₂ and SmNi₂ being also peculiar. Magnetoelastic coupling parameters for both types of contribution have been determined. At low temperatures a cooperative Jahn-Teller distortion has been identified in PrNi₂ by measuring thermal expansion. The volume magnetostriction of CeNi₂ appears to be anomalous, probably as a consequence of Ce being in an intermediate valence state.     

Sm-Ni二元系合金相图

本文用X射线衍射、差热分析及金相分析方法测定了Sm-Ni二元系合金相图。在此二元系中观察到8个金属间化合物:Sm₃Ni(664℃分解),SmNi(熔点为1079℃),SmNi₂(1034℃分解),SmNi₃(1135℃分解),Sm₂Ni₇(1220℃分解),SmNi₄(1282℃分解),SmNi₅(熔点为1430℃)和Sm₂Ni₁₇(1288℃分解)。发生三个共晶反应:Sm₃Ni-SmNi(570℃,～32at%Ni),SmNi-SmNi₂(809℃,53.5at%Ni)和Sm₂Ni₁₇-Ni(1280℃,94at%Ni)。无论是Sm在Ni中或是Ni在Sm中,均未观察到明显的固溶度。 关键词：     

Search for the stannous ion in a chloride/fluoride matrix: cases of Ba1−x Sn x Cl1+y F1−y and of Ba2SnCl6

With the exception of anhydrous SnCl₂, in divalent tin fluorides and chlorides, tin(II) is always covalent bonded, i.e. its valence orbitals are hybridized and the tin lone pair is located in one of the hybrid orbitals. This lone pair is highly stereoactive and generates a large efg, resulting in a large quadrupole splitting. A doubly disordered Ba_1?x Sn _x Cl_1+y F_1?y solid solution has been prepared and found to contain either ionic tin(II) (Sn²⁺ ions) or a mixture of ionic and covalent tin(II), depending on x, y and the method of preparation. The ionic tin(II) spectrum in Ba_1?x Sn _x Cl_1+y F_1?y gives a Mössbauer single line that is broadened by the lattice efg, like in SnCl₂. Now, Sn²⁺ has been found to be present in an undistorted octahedral coordination in a newly isolated compound, Ba₂SnCl₆. It should be the first example of Sn²⁺ that is fully ionic and has a perfectly spherical lone pair.     

High pressure synthesis of the mixed valent and nonsuperconducting ternary YbRhxSny compound

The ternary compound YbRh_1.4Sn_4.6 with the phase I structure (simple cubic) when subjected to a pressure of 40 kbar at 800°C is found to transform to phase III structure (f.c.c.) with the composition YbRh_1.1Sn₃. The latter compound has a lattice parameter of $\text{a = 13.735}\text{A}\text{?}$ which suggests that the Yb is in an intermediate valence state. The temperature dependence of magnetic susceptibility suggests that the Yb is in a homogeneously mixed valence state in the pressure synthesized product. In the phase I structure YbRh_1.1Sn_4.6 is superconducting at 8.6°K, but in the phase III structure the compound YbRh_1.1Sn₃ is not superconducting down to 0.9°K. It is suggested that superconductivity and mixed valence are incompatible.     

Search for phonon anomalies in the intermediate valence compound CeSn3

The phonon dispersion relations of the intermediate valence compound CeSn₃ and the integral valence reference compound LaSn₃ were measured by inelastic neutron scattering. They are quite similar and no phonon anomalies due to valence fluctuations in CeSn₃ were detected. Likewise no line broadening was observed. Model calculations revealed, that the influence of the “breathing” deformability of the rare earth ions on the lattice dynamics is only moderate; moreover the breathing force constant turned out to be equal for both CeSn₃ and LaSn₃.     

Effect of local cationic environment on the valence state of <Superscript>119</Superscript>Sn probe atoms on the surface of antiferromagnet MnTiO<Subscript>3</Subscript> with ilmenite structure

Annealing in argon of MnTiO₃ impregnated with a SnCl₄ solution leads to the distribution of Sn⁴⁺ ions over sites with different cationic environments in the surface layers of crystallites. The chemical behavior of Sn⁴⁺ ions emerging on the surface upon subsequent annealing in hydrogen depends on the tendency of the neighboring cations to retain the octahedral coordination by O^2? anions. The absence of spin polarization of the Sn²⁺ cations formed on the surface shows that their specific valence state is stabilized by the nearby Ti⁴⁺ cations.     

Effects of SnO2 addition on the magnetic properties of manganese zinc ferrites

SnO₂ was added to high-permeability MnZn ferrites and MnZn ferrites for high-frequency power supplies. The effects of the SnO₂ addition were studied. Sn⁴⁺ ions can dissolve into the spinel lattice and form stable Fe²⁺–Sn⁴⁺ pairs and hence can compensate the magneto-crystalline anisotropy constant K₁ and improve the initial permeability effectively. The initial permeability of ferrites is also improved as abnormal grain growth caused by ion vacancy is controlled with SnO₂ doping. In addition, the SnO₂ doping also leads to a decrease in the relative loss factor and an increase in density. The power loss and minimum power loss temperature decrease with SnO₂ doping.     

An interpretation of the optical properties of Cr-activated pyrochlores, Y2Ti2O7 and Y2Sn2O7

A qualitative model is proposed to explain the differences between the optical properties of the six-coordinated Cr⁴⁺ ion in the pyrochlores, Y₂Sn₂O₇ and Y₂Ti₂O₇. It is shown that polarization of the electron density of the oxygen ions occupying the 48f sites of the pyrochlore lattice is responsible for the observed differences in the optical properties.     

Comparative analysis of crystal field effects and energy level scheme of six-fold coordinated Cr ion in the pyrochlores, Y2B2O7 (B=Ti, Sn)

The electronic energy levels of the six-fold coordinated Cr⁴⁺ ion in the pyrochlores Y₂B₂O₇ (B=Sn⁴⁺, Ti⁴⁺), have been computed using the exchange charge model of crystal field theory. The calculated Cr⁴⁺ energy levels and their trigonal splitting are in good agreement with experimental spectra. Calculations of the crystal field parameters show that the higher crystal field strength in Y₂Sn₂O₇ (in comparison with Y₂Ti₂O₇) arises from increased orbital overlap effects between the Cr⁴⁺ ion and the nearest oxygen ions, which are located at the 48f crystallographic position of the pyrochlore lattice. The increased overlap in Y₂Sn₂O₇ occurs despite the fact that the Cr⁴⁺-O^2- bond distance in Y₂Sn₂O₇ is longer than in Y₂Ti₂O₇. This is attributed to a lack of hybridization (covalent bonding) between the filled 2p orbital of oxygen ion occupying the 48f site of the pyrochlore lattice and the filled Sn⁴⁺ 4d¹⁰ orbital. As a result, a stronger crystal field is experienced by Cr⁴⁺ ions in Y₂Sn₂O₇, even if the Cr⁴⁺-O²⁻ distances are greater in this case, when compared to those in Y₂Ti₂O₇.     

Temperature-Dependent Solid-State 119Sn- MAS NMR of Nd2Sn2O7, Sm2Sn2O7, and Y1.8Sm0.2Sn2O7. Three Sensitive Chemical-Shift Thermometers

The ¹¹⁹Sn MAS NMR resonances of the paramagnetic stannates Ln₂Sn₂O₇ (Ln = Nd, Sm, and Y_1.8Sm_0.2) have been found to be extremely sensitive to temperature, the isotropic resonances varying, at room temperature, by 14 and 1.1 ppm K^−l for Nd₂Sn₂O₇ and Sm₂Sn₂O₇, respectively. This sensitivity has been exploited to develop three chemical-shift thermometers with reciprocal dependences on temperature. Sm₂Sn₂O₇ is suitable for temperature calibration of standard MAS probes and the solid solution Y_1.8Sm_0.2Sn₂O₇ is a shift thermometer with an internal reference. Nd₂Sn₂O₇ is proposed as a high-temperature shift thermometer. These thermometers were used to determine the changes in sample temperature, in a Bruker 7 mm double-bearing probe, as the MAS speed was varied. A change of 8.5 K was observed on increasing the MAS speed from 1 to 5 kHz. The short relaxation times of the ¹¹⁹Sn nuclei enabled short recycle times to be used, and spectra of Sm₂Sn₂O₇ could be obtained in seconds.     

Spin dynamics in LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> low-dimensional helical magnets

Comprehensive NMR investigation of low-frequency spin dynamics of LiCu₂O₂ (LCO) and NaCu₂O₂ (NCO) low-dimensional helical magnets in the paramagnetic state has been carried out for the first time. Temperature dependences of the spin–lattice relaxation rate and anisotropy on various LCO/NCO nuclei have been determined at various orientations of single crystals in an external magnetic field. The spatial asymmetry of spin fluctuations in LCO multiferroic has been discovered. The quantitative analysis of the anisotropy of spin–lattice relaxation in LCO/NCO has allowed estimating the contributions of individual neighboring Cu²⁺ ions to the transferred hyperfine field on Li⁺(Na⁺) ions.     

Cu-site substitution effects onT c in La2CuO4-derived superconductors: A proposal of rationalization

Summary An interpretation of the Cu-site substitution effects on the critical temperature of La₂CuO₄-derived superconductors is presented. We argue that the available data on the dependence ofT _c on the amount of Cu-site substitutions indicate that the integrity of the Cu spin lattice is not fundamental to the superconductivity. A consistent way of systematizing the published data is proposed, by focusing on the interplay of valence fluctuations and accompanying lattice deformations.     

Near-edge X-ray absorption fine structure spectroscopy and structural properties of Ni-doped CeO2 nanoparticles

Ni-doped CeO₂ nanoparticles were prepared by using the co-precipitation method. The prepared nanoparticles were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, field emission scanning electron microscopy (FE-SEM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The XRD results infer that Ni-doped CeO₂ nanoparticles have single phase nature similar to that of pure CeO₂ nanoparticles. We have calculated lattice parameters using Powder-X software, particle size using Scherer’s formula and strain using the Williamson-Hall method for all the synthesized samples. We have observed a systematic decrease in the lattice parameters, particle size and strain with an increase in Ni doping in CeO₂. The FE-SEM micrographs also confirm that Ni-doped CeO₂ have nanocrystalline behavior and particles are spherical shaped. From the Raman spectra, it is observed that the intensity of classical CeO₂ vibration modes first increases then decreases with Ni doping. The NEXAFS spectra measured at Ce M_4,5 and Ni L_3,2 edges clearly indicate that Ce ions are in the +4 valence state and Ni ions are in the +2 valence state.     

Magnetic susceptibility and electrical resistivity of some Th2Zn17-type rare-earth zinc phases

We report measurements of the magnetic susceptibility and electrical resistivity of the iostructural compounds RE₂Zn₁₇ (RE=La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The composition dependence of the lattice parameter and effective moment indicate that all the RE ions are trivalent except Yb which is divalent. Magnetic order is observed in compounds where RE=Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho and Er. A second transition is seen for RE=Pr, Ho, Sm and Tb. Superzone boundary effects are observed in the electrical resistivity of these four alloys as well as in Er₂Zn₁₇. Resistivity measurements reveal concentrated Kondo behavior (or 4f instability) of Ce in Ce₂Zn₁₇.     

High-temperature studies of the magnetic susceptibility of samarium and the Al<Subscript>2</Subscript>Sm compound

The magnetic susceptibility of metallic samarium and the Al₂Sm intermetallic compound has been experimentally studied by the Faraday method in the temperature range of 300–1800 K. It has been shown that the temperature dependences of the magnetic susceptibility of Sm and Al₂Sm in a crystalline state can be described in the framework of Van Vleck paramagnetism theory taking into account variable valence and the contribution from the conduction electrons. Using this theoretical interpretation of the data, the effective valence of samarium in the metallic state and in the Al₂Sm intermetallic compound has been estimated as a function of the temperature.     

Perturbed Angular Correlation Study of Magnetic and Electric Hyperfine Interactions at 111Cd in GdNi2 and SmNi2

The magnetic hyperfine field B _hf of the closed-shell probe nucleus ¹¹¹Cd in the C15 Laves phase RNi₂ (R= Gd, Sm) has been investigated as a function of temperature by perturbed angular correlation (PAC) spectroscopy. The saturation magnetic hyperfine fields at 10 K are B _hf=7.7(2) and 3.9(1) T for GdNi₂ and SmNi₂, respectively. Although the probe nucleus resides on the cubic rare-earth site, a strong axially symmetric electric quadrupole interaction (QI) is observed in the paramagnetic phase at T300 K. The possible relation of this unexpected QI to the structural instability of RNi₂ is discussed.     

Valence fluctuations in La2−xSrxCuO4

Ab-initio electronic band structure calculations are presented for the perovskite La₂CuO₄ and for this material doped with Sr for a supercell of composition La₃SrCu₂O₈. This material is close to the high Tc superconductor La_2−xSr_xCuO₄ discovered recently. The Sr doping gives rise to strong valence fluctuations. We discuss the effect of the valence fluctuations on the stability of the lattice, indicating a small value of U and enhancing the electron-phonon coupling λ, mainly by a mechanism of incipient peroxide formation.     

Effects of the temperature and the pressure on the intermediate valence of Ce(In1−xSnx)3

The curve of the lattice constant of samples Ce(In_1-xSn_x)₃ plotted as a function of the composition x deviates from the linear Vegard's law; the deviation is found to be much more eminent at liquid N₂ temperature than at room temperature. Effects of the pressure on the electrical resistivity was found to be very large for a sample with a composition x = 0.5 which is near to the critical value of the occurence of the intermediate valence state of Ce atoms. The atomic volume of Ce atoms is seen to play an important role for the occurence of the intermediate valence state.     

Latent Fingerprint Imaging Using Dy and Sm Codoped HfO2 Nanophosphors: Structure and Luminescence Properties

The development of latent fingerprints (LFPs) detected at the site of crime is considered as an imperative physical evidence in forensic investigations. Herein, a rapid and cost‐effective approach using nonhazardous Dy and Sm codoped HfO₂ nanophosphors is demonstrated to be utilized for LFP imaging. Sol–gel method can produce Dy and Sm codoped HfO₂ of monoclinic phase with crystallite size ranging from ≈10 to 25 nm. While selected area electron diffraction and lattice spacing calculated from high‐resolution transmission electron microscopy confirm monoclinic phase, Le‐Bail profile refinement of X‐ray diffraction (XRD) patterns demonstrate an exponential increase in lattice volume with incorporating various concentrations of Dy and Sm in HfO₂ lattice. Exciting Dy and Sm codoped HfO₂ with 393 nm photoluminescence spectra show emissions in blue, yellow, and near red regions emerging primarily due to energy transfer from Dy³⁺ to Sm³⁺ through multipolar interaction suggested by time resolved decay spectra. Combining excitation and emission spectra, an energy band diagram is proposed. Owing to excellent emissions, Dy and Sm codoped HfO₂ are explored for LFP imaging with good selectivity and resolution over multivariate surfaces like float glass and aluminum foil. The third‐level details like enclosure and termination–bifurcation are extracted due to nanosized nature of particles.