Electrolytic preparation of CaB<Subscript>6</Subscript> by molten salt technique

Calcium hexaboride (CaB₆) crystals with high melting point (2,235 °C) have been conveniently synthesized at low temperature (900 °C) from molten salt electrolysis. The synthesis was carried out using CaO–B₂O₃–LiF melt under argon atmosphere. Electrochemical experiments were carried out in an inconel reactor to having a high purity graphite crucible, which served as an electrolyte holding vessel as well as the anode. An electropolished molybdenum rod was employed as the cathode. The electrolysis was performed at 900 °C under argon atmosphere at current densities ranging from 0.5 to 1.5 A/cm² at 1:6 M ratios of calcium and boron content. After the electrolysis, the cathode product was removed and cleaned using dilute HCl solution followed by triple distilled water. Characterization of the crystalline product by TG/DTA, XRD, CHNS, EDAX, XPS, EPR, and SEM were reported. From the studies, it has been observed that CaB₆ can be synthesized at all current densities and the products have some impurities.     

ESCA study of electronic structure of SmB6

The electronic structure of SmB₆ was investigated by X-ray photoelectron spectroscopy (XPS or ESCA). The spectrum of each core level of Sm in SmB₆ consists of three peaks. Such a splitting was not observed in Sm₂O₃, SmF₃, and SmB₄. The analysis of the results shows that three kinds of Sm ions — Sm²⁺(4f⁶), Sm²⁺(4f⁵5d^0.86s^0.2), and another Sm²⁺ — are present in SmB₆. The last kind of Sm ions is probably localized in a surface region.     

Radiation effects in samarium-doped calcium fluoride

A study was conducted of the effects of gamma radiation on samarium (Sm)-doped calcium flouride (CaF₂) crystals. Optical absorption measurements indicate that many of the Sm³⁺ ions are converted to Sm²⁺ during irradiation. Heavy doses of 10⁶ rad also modify the trapping structures and enhance certain defects within the crystals. A comparison is provided between unirradiated and heavily irradiated CaF₂ crystals with three Sm concentrations: 0.01, 0.1, and 1.0 molar-percent. Thermoluminescence measurements indicate that the crystals with high Sm content provide less luminescence and that the activation energy is less than seen in the 0.01 molar-percent Sm crystals.     

Raman scattering in intermediate valent SmB6

We have measured the Raman spectra of intermediate valent (IV) SmB₆ and compared it to LaB₆ and EuB₆. Beside the three high energy Raman active phonons we found additional features in the spectra. Most prominent is a peak at 172 cm^-1 for SmB₆, at 214 cm^-1 for LaB₆ and at ～220 cm^-1 for EuB₆. The spectra are analysed in terms of defect induced phonon excitations yielding a weighted phonon density of states. The softening of the line in IV SmB₆ compared to the other hexaborides is unusual since even in the trivalent MB₆ compounds the Raman active phonon modes normally are at lower frequencies than in semiconducting, divalent samples. This phonon softening is explained in analogy with the phonon anomalies in other IV compounds like Sm_1?xY_xS and TmSe.     

Multistep excitation of autoionizing states of the samarium atom

In this work, 4f ⁶6pnl and 4f ⁵5d6snl (l=0,2) autoionizing states of the samarium (Sm) atom, especially those with lower principal quantum number, have been studied, using the isolated-core excitation scheme with three dye lasers. In the energy region between 57 990 and 61 030 cm⁻¹, there are 74 autoionizing states of the Sm atom observed. These states can be classified into the autoionization series converging to four different ionization limits. In most cases, the line shapes of these autoionizing states are nearly symmetric, from which the level energies and widths can be easily obtained by fitting the experimental spectra to the Lorentzian profiles. In addition, several spectroscopic properties of these autoionizing states, such as configuration interaction, are also discussed.     

Imperfection of the Sm sublattice and valence instability in compounds based on SmB6

The magnetic susceptibility, electrical resistance, specific heat, and thermal expansion coefficient of SmB₆, Sm_0.8B₆, and Sm_1–x La_xB₆ (x=0.1 and 0.2) are measured in the temperature range T=4–300 K. The dispersion curves of the acoustic phonon branches in lanthanum-doped samples are studied. A combined analysis of the results confirms the existence of an activation gap in the electron density of states in both nonstoichiometric and lanthanum-doped compounds. The anomalies in the electronic component of the thermal expansion coefficient are associated to a considerable degree with the temperature variation of the valence and, like the magnetic susceptibility, reflect features of the f-electron excitation spectrum. It is found that lanthanum doping does not lead to significant changes in the anomalies in the phonon spectrum of SmB₆. It is established that the homogeneous intermediate-valent state of the samarium ion is fairly stable and is maintained when the perfection of the Sm sublattice is violated. Zh. éksp. Teor. Fiz. 115, 1024–1038 (March 1999)     

A Tunneling Model for Afterglow Suppression in CsI:Tl,Sm Scintillation Materials

Combined radioluminescence, afterglow and thermoluminescence experiments on single-crystal samples of co-doped CsI:Tl,Sm suggest that samarium electron traps scavenge electrons from thallium traps and that electrons subsequently released by samarium recombine non-radiatively with trapped holes, thus suppressing afterglow. Experiments on single crystals support the inference that electrons tunnel freely between samarium ions and are trapped preferentially as substitutional Sm⁺ near V_KA(Tl⁺) centers where non-radiative recombination is the rate-limiting step. Afterglow in microcolumnar films of CsI:Tl,Sm is enhanced by inhomogeneities which impede tunneling between samarium ions, but is partly suppressed by annealing.     

Relaxation studies of bulk samarium doped ceria electrolyte

The nanocrystalline samarium doped ceria powder of phase Ce_0.8Sm_0.2O_1.9 was pelletized and sintered at about 1,623 K for the study of relaxation process. The impedance measurements were done within the frequencies from 1 Hz to 1 MHz for wide temperature range of 529–673 K. The temperature-dependent relaxation frequency found to be shifted towards higher frequency region from 17.26 to 707.96 KHz and the corresponding relaxation time for oxygen ions transport was varied from 9.22 to 0.22 μS. The temperature dependent conductivity and relaxation frequency revealed Arrhenius nature, showing activation energies 1.18 and 1.01 eV, respectively. This difference was attributed to pronounced interference due to the grain boundaries. The effect of sintering on microstructure of the sample was studied by using SEM and X-ray diffractometer (XRD). The structural and phase stability study was done by high-temperature (HT)-XRD. The thermal expansion coefficient of the samarium doped ceria powder determined from HT-XRD was found to be 13.9 × 10⁻⁶ K⁻¹.     

First evidence for a Sm<Superscript>3+</Superscript>-type contribution to the magnetic form factor in the quasielastic spectral response of intermediate valence SmB<Subscript>6</Subscript>

The momentum-transfer dependence of the magnetic form factor associated with the quasielastic spectral component in the dynamic magnetic response of intermediate valence SmB₆ has been measured using inelastic neutron scattering on a double-isotope (¹⁵⁴Sm, ¹¹B) single crystal. The experimental dependence differs qualitatively from those obtained earlier for the inelastic signals, as well as from the field-induced magnetic form factor of SmB₆ obtained by polarized neutron diffraction. This observation is interpreted by specifically considering the Curie-type contributions to the dynamic susceptibility, which arise from the mixing of 4 f⁵ and 4 f⁶J-multiplets into the intermediate valence state wavefunction.     

Localized-electron mechanism for configuration mixing in Sm compounds

A new mechanism for (4f)⁵ - (4f)⁵ 5d configuration mixing in SmB₆ and SmS is described. It involves the simultaneous intra-atomic excitation of two Sm sites.     

Magnetooptical microwave spectroscopy of the coherent magnetic state in the mixed valence compound SmB6 in the frequency range 40–120 GHz

In undoped pure single crystals of the mixed valence compound SmB₆ anomalous ESR absorption is observed in the frequency range v=40–120 GHz at temperatures of 1.8–4.2 K. The ESR for the case of the coherent ground state consists of two components corresponding to g-factors g ₁=1.907±0.003 and g ₂=1.890±0.003. The amplitude of both ESR lines strongly depends on temperature in the temperature range studied: the amplitude of the first line with g=g ₁ increases and the amplitude of the second line decreases with temperature. A model based on consideration of intrinsic defects in the SmB₆ crystalline lattice, with a densit ∼10¹⁵−10¹⁶ cm⁻³, is suggested as an explanation for the anomalous ESR-behavior. In the frequency range v>70 GHz at T=4.2 K, in addition to the main ESR lines, a new magnetic resonance with a hysteretic field dependence is discovered. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 10, 707–712 (25 November 1996) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Study on single domain growth of Ag-doped Sm–Ba–Cu–O bulk using cold seeding technique

Attempts to prepare single grain SmBCO/Ag using NdBa₂Cu₃O_7?δ (Nd123) cold seeding technique have been performed. As silver decreases the melting temperature of SmBa₂Cu₃O_7?δ (Sm123) to approximately 1028 °C, it becomes possible to texture SmBCO/Ag samples with the Nd123 cold seeding technique, and very well textured mono-domain crystals with 15 mm on a side have been successfully obtained. However, the growth rate of SmBCO/Ag system is severely reduced compared with Ag free sample. A series of samples quenched at various lower limit temperatures of slow-cooling process were fabricated to investigate the single domain growth of SmBCO/Ag system. It is found that mono-domain growth exhibits a suppressed tendency within the slow-cooling temperature window considered, and then is hindered significantly by the spontaneous nucleation. The transversal slides of these samples show that large amount of entrapped gas did not escape from the samples during the dwell time at the maximum superheating temperature. During the slow-cooling process, the entrapped gas continued to move towards the edges of the samples, coalesced with each other and very large pores several millimeters in size were formed, which finally were released from the sample. The SEM analysis reveals that the coarsening of Sm₂BaCuO₅ (Sm211) precipitates has occurred during the growth of mono-domain. Large Sm211 cause decreased ability to supply samarium for the growth of Sm123 crystal, resulting in a gradual decrease in the growth rate.     

Jahn-Teller effect on Sm3+ ions in SmB6

Electron spin resonance on samarium ions with stabilized valence Sm³⁺ is investigated in the fluctuating-valence semiconductor SmB₆, both pure and doped with the rare-earth ions Eu²⁺, Er³⁺, and Gd₃₊. The dynamic and static Jahn-Teller effects have been observed for the first time on rare-earth ions. The relation between the Jahn-Teller effect in a fluctuating-valence semiconductor and the excitonic nature of the ground state of such a semiconductor is discussed. Zh. éksp. Teor. Fiz. 115, 1860–1871 (May 1999)     

The study of autoionizing states of the samarium atom

The investigation of the samarium (Sm) atom autoionizing states, belonging to the 4f⁶ 6pnl and 4f⁵ 5d6snl (l=0, 2) configurations, has been carried out by using a three-step isolated-core-excitation (ICE) scheme. Fifty-seven new autoionizing states of the Sm atom have been observed in the energy region between 60,700 and 66,500 cm^?1. These autoionizing states are classified into five autoionization series in the light of different ionization limits. In most cases, the transition profiles of these autoionizing states are nearly symmetric, from which the peak positions and widths can be easily obtained by Lorentzian-profile-fitting procedure. Some autoionizing states have multi-peak profiles whose spectroscopic properties are analyzed in order to understand the complicated structures.     

Intercalation of graphene on iridium with samarium atoms

Intercalation of graphene on Ir (111) with Sm atoms is studied by methods of thermal desorption spectroscopy and thermionic emission. It is shown that adsorption of samarium at T = 300 K on graphene to concentrations of N ≤ 6 × 10¹⁴ atoms cm^–2 followed by heating of the substrate leads to practically complete escape of adsorbate underneath the graphene layer. At N > 6 × 10¹⁴ atoms cm^–2 and increasing temperature, a fraction of adsorbate remains on graphene in the form of two-dimensional “gas” and samarium islands and are desorbed in the range of temperatures of 1000–1200 K. Samarium remaining under the graphene is desorbed from the surface in the temperature range 1200–2150 K. Model conceptions for the samarium–graphene–iridium system in a wide temperature range are developed.     

A general method for preparing lanthanide oxide nanoparticles via thermal decomposition of lanthanide(III) complexes with 1-hydroxy-2-naphthoic acid and hydrazine ligands

Six new lanthanide(III) complexes (i.e., [Ln(L)₂(NA)_1.5]·3H₂O, where Ln=La(III), Pr(III), Nd(III), Sm(III), Gd(III), and Ce(III) and L and NA indicate N₂H₄ and C₁₀H₆(1-O)(2-COO), respectively) with 1-hydroxy-2-naphthoic acid [C₁₀H₆(1-O)(2-COOH)] and hydrazine (N₂H₄) as co-ligands were characterized by elemental, FTIR, UV-visible, and XRD techniques. In the FT-IR spectra, the N-N stretching frequency in the range of 981–949 cm⁻¹ demonstrates evidence of the presence of coordinated N₂H₄, indicating the bidentate bridging nature of hydrazine in the complexes. These complexes show symmetric and asymmetric COO⁻ stretching from 1444 to 1441 cm⁻¹ and 1582 to 1557 cm⁻¹, respectively, indicating bidentate coordination. TG-DTA studies revealed that the compounds underwent endothermic dehydration from 98 to 110 °C. This was followed by the exothermic decomposition of oxalate intermediates to yield the respective metal oxides as the end products. From SEM images, the average size of the metal oxide particles prepared by thermal decomposition of the complexes was determined to be 39–42 nm. The powder X-ray and SEM coupled with energy dispersive X-ray (EDX) studies revealed the presence of the respective nano-sized metal oxides. The kinetic parameters of the decomposition of the complexes were calculated using the Coats-Redfern equation.     

Growth,fabrication, and testing of bismuth tri-iodide semiconductor radiation detectors

Bismuth tri-iodide (BiI₃) is an attractive material for high energy resolution radiation detectors. For the purpose of this research, detectors were fabricated using single crystals grown from ultra-pure BiI₃ powder; synthesized by the Physical Vapor Transport (PVT) technique. This technique yielded powder with total impurity level of 7.9 ppm. Efforts were also made to purify commercial BiI₃ powder using a custom-built Traveling Zone Refining (TZR) system. Initial trial runs were successful in reducing the total impurity level of the commercial powder from 200 ppm to less than 50 ppm. Using the modified vertical Bridgman technique and a customized sharp tip ampoule, a large BiI₃ single crystal was grown. The crystal had a surface area of 2.2 cm² and a thickness of 0.8 cm, which corresponds to a volume of 1.78 cm³. Radiation detectors were fabricated and then tested by measuring their electrical characteristics and radiation response. An alpha particle spectrum (using a ²⁴¹Am α-source) was recorded at room temperature with a BiI₃ detector 0.09 cm thick and with a surface area of 0.16 cm². The electron mobility was estimated to be 433 ± 79 cm²/V.     

Thermally stimulated current measurements in as-grown TlGaSeS layered single crystals

Charge carrier traps in as-grown TlGaSeS layered single crystals were studied using thermally stimulated current measurements. The investigations were performed in temperatures ranging from 10 to 100 K. The experimental evidences were found for the presence of one shallow hole trapping center in TlGaSeS, located at 12 meV from the valence band. The trap parameters have been calculated using various methods of analysis, and these agree well with each other. Its capture cross-section and concentration have been found to be 8.9 × 10⁻²⁶ cm² and 2.0 × 10¹⁴ cm⁻³, respectively. Analysis of the thermally stimulated current data at different light excitation temperatures leads to a value of 19 meV/decade for the shallow hole traps distribution.     

Crystallization of 21.25Gd2O3-63.75MoO3-15B2O3 glass induced by femtosecond laser at the repetition rate of 250 kHz

We report the formation of β′-Gd₂(MoO₄)₃ (GMO) crystal on the surface of the 21.25Gd₂O₃-63.75MoO₃-15B₂O₃ glass, induced by 250 kHz, 800 nm femtosecond laser irradiation. The morphology of the modified region in the glass was clearly examined by scanning electron microscopy (SEM). By micro-Raman spectra, the laser-induced crystals were confirmed to be GMO phases and it is found that these crystals have a strong dependence on the number and power of the femtosecond laser pulses. When the irradiation laser power was 900 mW, not only the Raman peaks of GMO crystals but also some new peaks at 214 cm⁻¹, 240 cm⁻¹, 466 cm⁻¹, 664 cm⁻¹ and 994 cm⁻¹which belong to the MoO₃ crystals were observed. The possible mechanisms are proposed to explain these phenomena.     

Luminescence and defect studies of YAlO3:Dy3+, Sm3+ single crystals exposed to 100 MeV Si7+ ion beam

Ionoluminescence (IL) and photoluminescence (PL) spectra for different rare earth ions (Sm³⁺ and Dy³⁺) activated YAlO₃ single crystals have been induced with 100 MeV Si⁷⁺ ions with fluence of 7.81×10¹² ions cm^?2. Prominent IL and PL emission peaks in the range 550–725 nm in Sm³⁺ and 482–574 nm in Dy³⁺ were recorded. Variation of IL intensity in Dy³⁺ doped YAlO₃ single crystals was studied in the fluence range 7.81×10¹²–11.71×10¹² ions cm^?2. IL intensity is found to be high in lower ion fluences and it decreases with increase in ion fluence due to thermal quenching as a result of an increase in the sample temperature caused by ion beam irradiation. Thermoluminescence (TL) spectra were recorded for fluence of 5.2×10¹² ions cm^?2 on pure and doped crystals at a warming rate of 5 °C s^?1 at room temperature. Pure crystals show two glow peaks at 232 (Tg₁) and 328 °C (Tg₂). However, in Sm³⁺ doped crystals three glow peaks at 278 (Tg₁), 332 (Tg₂) and 384 °C (Tg₃) and two glow peaks at 278 (Tg₁) and 331 °C (Tg₂) in Dy³⁺ was recorded. The kinetic parameters (E, b s) were estimated using glow peak shape method. The decay of IL intensity was explained by excitation spike model.