Crystal structure and magnetic ordering of RNi Si compounds

The element distributions and the magnetic ordering behaviour of compounds RNi₁₀Si₂ (R = Tb, Dy, Ho, Er, Tm) have been studied by neutron powder diffraction down to temperatures of 1.6 K. The compounds crystallize in an ordered variant of the ThMn₁₂ structure type in the tetragonal space group P4/nmm. An ordered 1:1 distribution of Ni and Si on sites 4d and 4e, respectively, corresponds to a modulation vector [0, 0, 1] with respect to the space group I4/mmm of the ThMn₁₂ structure. TbNi₁₀Si₂ orders antiferromagnetically below T _N = 4.5 K with a magnetic propagation vector of [0, 0, 1/2]. The magnetic Tb moments, 8.97(2) /Tb atom at 1.6 K, are aligned along the c-axis. The Ni sites in TbNi₁₀Si₂ do not carry any ordered magnetic moments. The compounds with R = Dy, Ho, Er, and Tm are paramagnetic down to 1.6 K and 3.0 K, respectively. Received 10 July 2002 / Received in final form 12 September 2002 Published online 29 October 2002     

Magnetic properties of RE2Au compounds (RE = Pr,Nd, Gd,Tb, Dy,Ho, Er,Tm and Y)

Magnetic properties of nine RE₂Au compounds have been studied in fields of up to 19 kOe in the temperature range 4.2K–300K. It has been found that all compounds are paramagnetic at room temperature except Gd₂Au. The compounds with Pr, Nd, Ho, Er and Tm exhibit Curie-Weiss behaviour with paramagnetic moments in close agreement with those expected for the free RE³⁺ ion. The moment of gold was found to be zero. The compounds with Pr, Nd, Tb, Dy, Er and Tm are antiferromagnetic at low temperatures. It appears that Ho₂Au is ferromagnetically ordered below 4.5 K. No evidence for magnetic ordering was found for Y₂Au. The compound with Tb exhibits metamagnetic behaviour.     

EPR investigations of oxidation effects in (V1−xMox)2−δO3

Electron paramagnetic resonance (EPR) investigations has been carried out on the new family of molybdenum doped vanadium sesquioxides (V_1−xMo_x)_2−δO₃. The oxidation effects were monitored from the rate of paramagnetic V⁴⁺ created when the sample is exposed to the air. The effects of the oxidation time, sample temperature, and annealing at 1000 °C under a diluted hydrogen atmosphere on the EPR signal features are analyzed. The V⁴⁺ concentration in the oxidized samples is determined and the relaxation effects driven by the conduction electrons are pointed out from the thermal behaviour of the EPR line features. EPR spectra of all the oxidized samples also reveal a small ferromagnetic contribution strongly correlated with the V⁴⁺ content.     

Atomic-scale studies of native point defect and nonstoichiometry in silicon oxynitride

The native point defects and mechanism of accommodating deviations from stoichiometry of Si₂N₂O crystal have been investigated using atomistic simulation techniques. This work firstly provides a reliable classical interatomic potential model derived from density functional theory calculations. The force-field parameters well reproduce the crystal structure, elastic stiffness, and dielectric constants of Si₂N₂O. It is expected that the force-field parameters are useful in future investigations on Si₂N₂O by molecular dynamic simulation. The calculated formation energies for native defects suggest that intrinsic disorder in stoichiometric Si₂N₂O is dominated by antisites and a degree of oxygen Frenkel defect may also exist in this system. In nonstoichiometric Si₂N₂O, the calculated reaction energies indicate that excess SiO₂ or Si₃N₄ is most likely accommodated by the formation of antisite in the lattice. And we also find that SiO₂ excess is energetically more favorable than Si₃N₄ surplus in Si₂N₂O.     

Magnetic and related properties of U4Rh13Si9 and U4Ir13Si9

The compounds U₄Rh₁₃Si₉ and U₄Ir₁₃Si₉ crystallize with the orthorhombic Er₄Ir₁₃Si₉-type structure that contains three non-equivalent positions of uranium atoms. Their magnetic, electrical transport and thermal properties were studied down to liquid helium temperature in magnetic fields up to 9 T. Both compounds have been found to order antiferromagnetically at low temperatures and to exhibit complex magnetic behavior in the ordered state. Some features characteristic of spin fluctuators (U₄Rh₁₃Si₉) and Kondo lattices (U₄Ir₁₃Si₉) indicate that the two ternaries studied are novel strongly correlated electron systems.     

Phase stability and electronic structure of Si2Sb2Te5 phase-change material

On the basis of an ab initio computational study, the present work provide a full understanding on the atomic arrangements, phase stability as well as electronic structure of Si₂Sb₂Te₅, a newly synthesized phase-change material. The results show that Si₂Sb₂Te₅ tends to decompose into Si₁Sb₂Te₄ or Si₁Sb₄Te₇ or Sb₂Te₃, therefore, a nano-composite containing Si₁Sb₂Te₄, Si₁Sb₄Te₇ and Sb₂Te₃ may be self-generated from Si₂Sb₂Te₅. Hence Si₂Sb₂Te₅ based nano-composite is the real structure when Si₂Sb₂Te₅ is used in electronic memory applications. The present results agree well with the recent experimental work.     

Magnetic properties of ternary gallides of type RNi4Ga (R=rare earths)

The magnetic properties of RNi₄Ga (R=La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm and Lu) compounds have been investigated. These compounds form in a hexagonal CaCu₅ type structure with a space group P6/mmm. Compounds with the magnetic rare earths, R= Nd, Sm, Gd, Tb, Dy, Ho, Er and Tm, undergo a ferromagnetic transition at 5, 17, 20, 19, 12, 3.5, 8 and 6.5 K, respectively. The transition temperatures are smaller compared to their respective parent compounds RNi₅. PrNi₄Ga is paramagnetic down to 2 K. LaNi₄Ga and LuNi₄Ga are Pauli paramagnets. All the compounds show thermomagnetic irreversibility in the magnetically ordered state except GdNi₄Ga.     

Influence of Si and Co substitutions on magnetoelastic properties of R2Fe17 (R=Y, Er and Tm) intermetallic compounds

The magnetostriction of the off-stoichiometric R₂Fe₁₇-type intermetallic compounds based on R₂Fe_14−xCo_xSi₂ (R=Y, Er, Tm and x=0, 4) was measured, using the strain gauge method in the temperature range 77-460 K under applied magnetic fields up to 1.5 T. All compounds show sign change and reduction in magnetostriction values compared to the R₂Fe₁₇ compounds by Si substitution. For Y₂Fe₁₄Si₂ and Er₂Fe₁₄Si₂, saturation behaviour is observed near magnetic ordering temperature (T_C), whereas for Tm₂Fe₁₄Si₂, saturation starts from T>143 K. Also, Co substitution has different effects on the magnetostriction of R₂Fe₁₄Si₂ compounds. In Er₂Fe₁₀Co₄Si₂ and Tm₂Fe₁₀Co₄Si₂, saturation occurs below the spin reorientation temperature (T_SR). In addition, in Er₂Fe₁₄Si₂, a sign change occurs in the anisotropic magnetostriction (Δλ) as well as the volume magnetostriction (ΔV/V) at their T_SR values. The volume magnetostrictions of the Tm-containing compounds show an anomaly around their T_SR. In R₂Fe₁₄Si₂ compounds, parastrictive behaviour is also observed in ΔV/V near their T_C values. In addition, the magnetostriction of the sublattices is investigated. Results show that in R₂Fe₁₄Si₂ compounds, the rare-earth sublattice contribution to magnetostriction is negative and comparable to the iron sublattice, whereas, in R₂Fe₁₀Co₄Si₂ compounds, the rare-earth sublattice contribution is positive and larger than Fe sublattice. These results are discussed based on the effect of Si and Co substitutions on the anisotropy field of these compounds. Influence of the spin reorientation transition on the magnetostriction of these compounds is discussed in terms of the anisotropic sublattice interactions.     

Magnetic properties and structural data of ternary silicides: (RE,Th,U) Os2Si2 (RE= rare earth)

New ternary silicides (RE,Th,U) Os₂Si₂ have been synthesized from the elements. All the compounds (RE= Y,La,Ce,Pr,Nd,Sm,Gd,Tb,Dy,Ho,Er,Tm,Yb, Lu) were found to be isotypic and to crystallize with the ordered BaAl₄-type of structure (ThCr₂Si₂-type). Magnetic properties of these alloys — studied in the temperature range 1.5<T<1100 K — reveal a typical Van Vleck paramagnetism of free RE³⁺ ions at temperatures higher than 300 K. The observed effective paramagnetic moment of CeOs₂Si₂, μ(eff)=0.98 BM, is compatible with a rather low concentration (15%) of Ce³⁺. The effective moment of SmOs₂Si₂, μ(eff)=0.47 BM, is in reasonable agreement with a Hund's rule $\text{J=}\text{5}\text{2}$ ground level for free Sm³⁺. For temperatures above 25 K, the magnetic susceptibility as a function of temperature corresponds to the Van Vleck behavior for free Sm³⁺ (closely spaced multiplet, $\text{J=}\text{5}\text{2}$,$\text{J=}\text{7}\text{2}$. Magnetic ordering temperatures of REOs₂Si₂ silicides are generally below 42 K. (Pr,Nd,Ho,Er,Tm) Os₂Si₂ exhibit ferromagnetic ordering whereas (Sm,Gd, Tb,Dy) Os₂Si₂ show antiferromagnetic behavior. Above 1.8 K none of the samples was found to be superconducting.     

Magnetic properties and structural chemistry of ternary silicides (RE,Th, U)Ru2Si2 (RE = RARE EARTH)

Ternary silicides (RE, Th, U)Ru₂Si₂ have been synthesized from the elements. All the compounds (RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were found to be isotypic and to crystallize with the structure type of ThCr₂Si₂ (ordered derivative of the BaAl₄-type). The magnetic behavior of these alloys was studied in the temperature range 1.5 K < T < 1100 K. Magnetic susceptibilities at temperatures T > 300 K closely follow a typical Van Vleck paramagnetism of free RE³⁺-ions. In the case of CeRu₂Si₂ susceptibilities are well described for 20 K < T < 1100 K by a Van Vleck paramagnetism of widely spaced multiplets; the observed effective paramagnetic moment μ_eff = 2.12 BM indicates a high percentage (85%) of Ce³⁺. SmRu₂Si₂ yields an effective moment μ_eff = 0.54 BM, which compares reasonably well with the Hund's rule J = 5/2 ground level for free Sm⁺ and a low-lying excited level with J = 7/2. For temperatures T > 15 K the magnetic susceptibility as a function of temperature follows the “Van Vleck behavior” for free Sm³⁺. At low temperatures ferromagnetic ordering was encountered for (Pr, Nd, Ho, Er, Tm)Ru₂Si₂, whereas antiferromagnetic ordering was observed for (Sm, Gd, Tb, Dy)Ru₂Si₂. The ordering temperatures are generally below 55 K. No superconductivity was found for temperatures as low as 1.8 K.     

Crystal structure and magnetic properties of HoPt2Si2

The crystal structure of HoPt₂Si₂ was determined using powder neutron diffraction data. It is tetragonal, CaBe₂Ge₂ type (space group P4/_n mm). Neutron diffraction and magnetometric measurements indicate that HoPt₂Si₂ remains paramagnetic at the temperature of 2.0 K.     

Electron paramagnetic resonance investigation of K3H(SO4)2 proton conductor doped with Cr ion

The proton arrangement around SO₄ units in K₃H(SO₄)₂ (KHS) was studied in detail by X-band CW EPR spectra of CrO₄³⁻ paramagnetic centre incorporated into KHS during the crystal growth process. The EPR data prove the theoretical model of coherent motion of protons and SO₄ units at the fast-proton conducting phase proposed by Ito and Kamimura.     

TmCu2Si2, a two-singlet magnetic system?

New¹⁶⁹Tm Mössbauer and specific heat data recorded for TmCu₂Si₂ and Tm_1/2Lu_1/2Cu₂Si₂ in the temperature range 1.4K to 20K verify that TmCu₂Si₂ orders magnetically at T_N=3K and support earlier conjecture that TmCu₂Si₂ behaves as a 2-singlet system at low temperatures. However attempts to describe the available data in terms of a single set of parameters suggest that the single-ion and molecular field approximations are an oversimplification of the true situation.     

Electronic and crystal structure of α- and β-CeIr2Si2

We present the results of XRD, magnetization, resistivity and specific heat measurements of CeIr₂Si₂ single crystals for both, the low-temperature α-phase and the high-temperature β-phase, respectively. The α-phase adopts the tetragonal ThCr₂Si₂-type whereas the β-phase forms in the CaBe₂Ge₂-type structure. Both the phases remain paramagnetic down to low temperatures, nevertheless both, the magnetization and resistivity exhibit pronounced anisotropy in the whole temperature range of measurements (2-300 K). Results of fitting the temperature dependence of the susceptibility within the interconfiguration-fluctuation model point to the Ce valence fluctuating between 3+ and 4+. The α-phase behaves as a Fermi-liquid (FL) at low temperatures whereas the β-phase exhibits non-Fermi-liquid (NFL) features. The results are discussed in context of other similar polymorphic compounds.     

Structural study of the Lu2Si2O7-Sc2Si2O7 system

Different compositions in the Lu₂Si₂O₇-Sc₂Si₂O₇ system have been synthesized following the ceramic method. All XRD patterns are compatible with the thortveitite structure (β-RE₂Si₂O₇ polymorph). Unit cell parameters change linearly with composition, which indicates a complete solid solubility of Sc₂Si₂O₇ in Lu₂Si₂O₇. ²⁹Si MAS NMR spectra show a decrease of the ²⁹Si chemical shift with increasing Sc content. A correlation reported in the literature to predict ²⁹Si chemical shifts in silicates is applied here to obtain the theoretical variation in ²⁹Si chemical shift values in the system Lu₂Si₂O₇-Sc₂Si₂O₇ and the results compare favourably with the values obtained experimentally. The FWHM values of the ²⁹Si MAS NMR curves indicate a random distribution of Lu and Sc in the structure of the intermediate members. Finally, the IR study of the system confirms the solubility of Sc₂Si₂O₇ in Lu₂Si₂O₇, showing the splitting of several modes in the intermediate members and a linear shift of the frequency on going from one end-member to the other.     

Magnetic and thermodynamic properties of DyFe2Si2 further investigated with crystal-field theory and two-ion model

We report our theoretical studies on the magnetic and thermodynamic properties of DyFe₂Si₂ using the crystal-field parameters (CFPs) proposed by Chatterji et al. recently [1]. Our calculated magnetization and magnetic specific heat curves obtained with the above CFPs based on the two-ion model we developed recently show reasonable agreement with the experimental data.     

First-principles studies on Ti3Si0.5Ge0.5C2 under pressure

The structural, electronic and elastic properties of Ti₃Si_0.5Ge_0.5C₂ have been investigated by using the pseudopotential plane-wave method within the density-functional theory. Our calculated equation of state (EOS) is consistent with the experimental results. The density of states (DOS) indicates that Ti₃Si_xGe_1−xC₂ (x=0, 0.5, 1.0) are metallic, and these compounds have nearly the same electrical conductivity. The elastic constants for Ti₃Si_0.5Ge_0.5C₂ are obtained at zero pressure, which is compared to Ti₃SiC₂ and Ti₃GeC₂. We can conclude that Ti₃Si_0.5Ge_0.5C₂ is brittle in nature by analyzing the ratio between bulk and shear moduli. There appears to be little effect on the electronic and elastic properties with the Ge substitution to Si atoms in Ti₃SiC₂.     

Magnetic and transport properties of Pr2Pd3Si5

We have investigated the magnetic and transport properties of a new ternary intermetallic compound Pr₂Pd₃Si₅ which forms in U₂Co₃Si₅-type orthorhombic structure (space group Ibam). At low field (0.01 T) magnetic susceptibility exhibits an abrupt increase below 7 K and peaks at 5 K, revealing a magnetic phase transition. The onset of magnetic order is also confirmed by well defined anomalies in the specific heat and electrical resistivity data. Apart from the sharp λ-type anomaly, magnetic part of specific heat also shows a broad Schottky-type hump due to crystal field effect. Magnetoresistance data as a function of temperature exhibits a pronounced peak in paramagnetic state which could be interpreted in terms of crystal field effect and short-range ferromagnetic correlations.     

CO2 laser CVD of a-Si:H: in situ gas analysis and model calculations

4 and disilane Si₂H₆ induced by continuous wave CO₂ laser irradiation has been investigated under the conditions of chemical vapor deposition (CVD) of amorphous hydrogenated silicon a-Si:H. At the very position of depositing the thin film the stationary chemical composition of the processing gas is probed in situ by an effusive molecular beam which passes through a differential pumping stage into a quadrupole mass spectrometer (QMS). With SiH₄ as educt and SF₆ as a sensitizer, SiH₄ and Si₂H₆ are found in the processing gas while Si₃H₈ or higher silanes are lacking. Si₂H₆ and SF₆ lead to SiH₄, Si₂H₆, and Si₃H₈, but higher silanes are missing. The experimentally determined composition of the processing gas is semi-quantitatively reproduced by model calculations based on the assumption of stationary local equilibrium conditions and applying thermodynamic and spectroscopic data (molecular statistics). The mass balance of the processing gas entering and leaving the CVD chamber states an atomic ratio Si:H of 1:2 for the gas phase species forming the solid deposit on the reactor walls. This finding together with theoretical considerations indicates the intermediate Si₂H₄ to be the dominating gas phase species forming the a-Si:H thin films. Received: 17 July 1998/Accepted: 20 July 1998