The surface state of URu2Si2

The ‘hidden-order’ (HO) transition of URu₂Si₂ remains a puzzle after 25 years of research. Using high-resolution angle-resolved photoemission spectroscopy (ARPES) we found that a hole-like band around Γ having its band maximum at E = −35 meV, and previously thought to be a bulk band of the system, is indeed a surface state not related to the HO phase transition. Here we present our detailed investigations to assign that state to a surface feature, and discuss on the possible origins of this surface band.     

Stability, structural, elastic, and electronic properties of polymorphs of the superconducting disilicide YIr2Si2

Using the ab initio approaches, the comparative stability, structural, elastic, and electronic properties of three polymorphs of the superconducting disilicide YIr₂Si₂, which differ in the atomic configurations of [Ir₂Si₂] (or [Si₂Ir₂]) blocks, were examined. For these YIr₂Si₂ polymorphs, the optimized structural data, elastic parameters, electronic bands, total and partial densities of states, Fermi surface topology, and chemical bonding were obtained and analyzed. Our studies showed that although ThCr₂Si₂- and CaBe₂Ge₂-type polymorphs are mechanically stable and relatively hard materials with low compressibility, they will behave as ductile systems. Among them, ThCr₂Si₂-type polymorph will show enhanced elastic anisotropy. In the vicinity of the Fermi energy, the topology of the electronic bands and the Fermi surface for various polymorphs are quite different. Besides, the CaBe₂Ge₂-type polymorph is expected to be anisotropic, i.e. happening mainly in the [Si₂Ir₂] blocks. The inter-atomic bonding for YIr₂Si₂ polymorph phases can be described as an anisotropic mixture of covalent, metallic, and ionic contributions, where inside the [Ir₂Si₂] (or [Si₂Ir₂]) blocks, Ir-Si and Ir-Ir bonds take place, whereas between the adjacent [Ir₂Si₂] (or [Si₂Ir₂]) blocks and Y atomic sheets, Si-Si and Ir-Y, Si-Ir and Si-Y, or mainly Ir-Ir bonds emerge for various polymorphs.     

Field-dependent collective ESR mode in YbRh2Si2

Electron spin resonance (ESR) experiments in YbRh₂Si₂ Kondo lattice at different field/frequencies and H_⊥c revealed: (i) a strong field dependent Yb³⁺ spin-lattice relaxation, (ii) a weak field and T-dependent effectiveg-value, (iii) a suppression of the ESR intensity beyond 15% of Lu-doping, and (iv) a strong sample and Lu-doping (≤15%) dependence of the ESR data. These results suggest that the ESR signal in YbRh₂Si₂ may be due to a coupled Yb³⁺-conduction electron resonant collective mode with a subtle field-dependent spins dynamic.     

Bulk vs. surface effects in ARPES experiment from La2/3Sr1/3MnO3 thin films

Experiments directly probing the electronic states using angle-resolved photoemission (ARPES) were carried out on La_2/3Sr_1/3MnO₃ in order to elucidate its electronic properties. ARPES is a surface sensitive technique where bulk and surface states are usually both present. We present high-resolution ARPES studies in the (1 0 0) and (1 1 0) mirror planes and compare them with simulated ARPES based on GGA + U band structure calculations. In the (1 1 0) mirror plane we identify surface umklapps accounted by surface reconstruction which couple to bulk electronic states. As predicted by the simulated spectra there is additional spectral intensity at the Fermi level detected in ARPES data due to k_⊥-broadening effects in the photoemission final states. We demonstrate that this additional spectral intensity is a convenient spectral marker for determination of the k_F Fermi momenta.     

Luminescence of La3F3[Si3O9]:Ce

The luminescence properties of Ce³⁺ in La₃F₃[Si₃O₉] are reported. Excitation and emission bands corresponding to 4f¹→5d¹ transitions of Ce³⁺ were identified. The center of gravity of the 5d states lies at remarkable high energy (43.2×10³ cm⁻¹) for Ce³⁺ in a silicate compound. This high value is attributed to the combined oxygen/fluoride coordination of the Ce³⁺ ion. Emission from the lowest 4f5d level to the ²F_5/2 and ²F_7/2 levels was found at 32.4×10³ and 30.4×10³ cm⁻¹. These results are compared with literature data on silicates and fluorides. From the values found for Ce³⁺, predictions are made for the positions of the 4f5d bands of Pr³⁺ and Er³⁺ in La₃F₃[Si₃O₉]. For both ions, it is concluded that in this host lattice emission is expected from high lying 4fⁿ energy levels.     

ESR study of the undoped heavy-fermion compound YbRh2Si2

The electron spin resonance (ESR) of the heavy-fermion metal YbRh₂Si₂ has been studied. The angular variation and the temperature dependence of the ESR line width have been measured in YbRh₂Si₂ single crystals in the temperature range of 4–25 K. The characteristic spin-fluctuation temperatureT ^* ～ 17 K estimated from these studies coincides very well with other experimental data. A well-behaved ESR signal due to local Yb³⁺ moments strongly supports the localized moment scenario for heavy-fermion quantum critical points.     

Interplay between unconventional superconductivity and heavy-fermion quantum criticality: CeCu2Si2 versus YbRh2Si2

In this paper the low-temperature properties of two isostructural canonical heavy-fermion compounds are contrasted with regards to the interplay between antiferromagnetic (AF) quantum criticality and superconductivity. For CeCu₂Si₂, fully-gapped d-wave superconductivity forms in the vicinity of an itinerant three-dimensional heavy-fermion spin-density-wave (SDW) quantum critical point (QCP). Inelastic neutron scattering results highlight that both quantum critical SDW fluctuations as well as Mott-type fluctuations of local magnetic moments contribute to the formation of Cooper pairs in CeCu₂Si₂. In YbRh₂Si₂, superconductivity appears to be suppressed at T???10?mK by AF order (T_N?=?70?mK). Ultra-low temperature measurements reveal a hybrid order between nuclear and 4f-electronic spins, which is dominated by the Yb-derived nuclear spins, to develop at T_A slightly above 2?mK. The hybrid order turns out to strongly compete with the primary 4f-electronic order and to push the material towards its QCP. Apparently, this paves the way for heavy-fermion superconductivity to form at T_c?=?2?mK. Like the pressure – induced QCP in CeRhIn₅, the magnetic field – induced one in YbRh₂Si₂ is of the local Kondo-destroying variety which corresponds to a Mott-type transition at zero temperature. Therefore, these materials form the link between the large family of about fifty low-T unconventional heavy – fermion superconductors and other families of unconventional superconductors with higher T_cs, notably the doped Mott insulators of the cuprates, organic charge-transfer salts and some of the Fe-based superconductors. Our study suggests that heavy-fermion superconductivity near an AF QCP is a robust phenomenon.     

Effect of hydrogen-doping on bonding properties of Ti3SiC2

Using the first principles method based on the density functional theory, we investigated the effect of hydrogen-doping on bonding properties of Ti₃SiC₂. The formation energies of hydrogen interstitials in three possible positions were calculated. The results show that hydrogen favors residing near the (0 0 1) Si plane. In these positions, hydrogen is hybridized most with 1s states of lattice atoms (Si and C), instead of Ti. The presence of hydrogen does not substantially influence the bonding nature of Ti₃SiC₂; chemical bonding is characterized by the hybridizations of Ti d-Si p and Ti d-C p states, and yields high strength. This is contrary to hydrogen-doping in transition metals, where the electron of hydrogen fills in the d bands of the metals and, as a consequence, decreases the cohesive strength of the lattice.     

Electronic structure and Fermi surface of new K intercalated iron selenide superconductor KxFe2Se2

Using the ab initio FLAPW-GGA method we examine the electronic band structure, densities of states, and the Fermi surface topology for a very recently synthesized ThCr₂Si₂-type potassium intercalated iron selenide superconductor K_xFe₂Se₂. We found that the electronic state of the stoichiometric KFe₂Se₂ is far from that of the isostructural iron pnictide superconductors. Thus the main factor responsible for experimentally observed superconductivity for this material is the deficiency of potassium, i.e. the hole doping effect. On the other hand, based on the results obtained, we conclude that the tuning of the electronic system of the new K_xFe₂Se₂ superconductor in the presence of K vacancies is achieved by joint effect owing to structural relaxations and hole doping, where the structural factor is responsible for the modification of the band topology, whereas the doping level determines their filling.     

Evaluation of fracture toughness of ZrO2 and Si3N4 engineering ceramics following CO2 and fibre laser surface treatment

The fracture toughness property (K_1C) of Si₃N₄ and ZrO₂ engineering ceramics was investigated by means of CO₂ and a fibre laser surface treatment. Near surface modifications in the hardness were investigated by employing the Vickers indentation method. Crack lengths and the crack geometry were then measured by using the optical microscopy. A co-ordinate measuring machine was used to investigate the diamond indentations and to measure the lengths of the cracks. Thereafter, computational and analytical methods were employed to determine the K_1C. An increase in the K_1C of both ceramics was found by the CO₂ and the fibre laser surface treatment in comparison to the as-received surfaces. The K_1C of the CO₂ laser radiated surface of the Si₃N₄ was over 3% higher in comparison to that of the fibre laser treated surface. This was by softening of the near surface layer of the Si₃N₄ which comprised of lowering of hardness, which in turn increased the crack resistance. The effects were not similar in ZrO₂ ceramic to that of the Si₃N₄ as the fibre laser radiation in this case had produced an increase of 34% compared to that of the CO₂ laser radiation. This occurred due to propagation of lower crack resulting from the Vickers indentation test during the fibre laser surface treatment which inherently affected the end K_1C through an induced compressive stress layer. The K_1C modification of the two ceramics treated by the CO₂ and the fibre laser was also believed to be influenced by the different laser wavelength and its absorption co-efficient, the beam delivery system as well as the differences in the brightness of the two lasers used.     

Electronic band structure and Fermi surface of new low-temperature Ni-based superconductors: 3.3 K (Ni2P2)(Sr4Sc2O6) and 2.7 K (Ni2As2)(Sr4Sc2O6) from first principles

Based on first-principle FLAPW-GGA calculations, we have investigated structural and electronic properties of the recently synthesized tetragonal (space group P4/nmm) nickel-based pnictide oxide superconductors: 3.3 K (Ni₂P₂)(Sr₄Sc₂O₆) and 2.7 K (Ni₂As₂)(Sr₄Sc₂O₆). Optimized structural data, electronic bands, total and partial densities of states, and Fermi surface topology have been obtained and discussed in comparison with available experiments and with their Fe-based (Fe₂P₂)(Sr₄Sc₂O₆) and (Fe₂As₂)(Sr₄Sc₂O₆) analogs.     

Field and temperature induced colossal strain in Gd5(SixGe1−x)4

Gd₅(Si_xGe_1−x)₄, known for its giant magnetocaloric effect, also exhibits a colossal strain of the order of 10,000 ppm for a single crystal near its coupled first-order magnetic-structural phase transition, which occurs near room temperature for the compositions 0.41≤x≤0.575. Such colossal strain can be utilised for both magnetic sensor and actuator applications. In this study, various measurements have been carried out on strain as a function of magnetic field strength and as a function of temperature on single crystal Gd₅Si₂Ge₂ (x=0.5), and polycrystalline Gd₅Si_1.95Ge_2.05 (x=0.487) and Gd₅Si_2.09Ge_1.91 (x=0.52). Additionally a giant magnetostriction/thermally induced strain of the order of 1800 ppm in polycrystalline Gd₅Si_2.09Ge_1.91 was observed at its first order phase transition on varying temperature using a Peltier cell without the use of bulky equipment such as cryostat or superconducting magnet.     

Synthesis,crystal structure and magnetic properties of Yb8Ag18.5Al47.5, Yb2Pd2Cd and Yb1.35Pd2Cd0.65

We report the synthesis of three new Yb-based compounds, Yb₈Ag_18.5Al_47.5 (Yb₈Cu₁₇Al₄₉-type, tetragonal tI74–I4/mmm), Yb₂Pd₂Cd (Mo₂B₂Fe-type, tetragonal tP10-P4/mbm) and Yb_1.35Pd₂Cd_0.65 (MnCu₂Al-type, cubic cF16–Fm3¯m). The crystal symmetry of these compounds has been determined and the complete structural characterisation carried out by single crystal and powder diffraction techniques. Two symmetry in-equivalent sites are available for the Yb ions in Yb₈Ag_18.5Al_47.5 and Yb_1.35Pd₂Cd_0.65. The 4f levels of the Yb ions are appreciably hybridised in Yb₈Ag_18.5Al_47.5 and to a lesser extent in Yb₂Pd₂Cd as inferred from the magnetisation and heat capacity data. Signatures of heavy fermion behaviour are observed in the heat capacity data of Yb₂Pd₂Cd in which the heat capacity, C/T, increases at low temperatures attaining a value of ≈600 mJ/mol K² at 1.8 K. The electrical resistivity of Yb₂Pd₂Cd follows a linear variation with temperature, T, between 1.4 and 5 K, thus indicating a possible non-Fermi liquid behaviour. In contrast, Yb ions are trivalent in Yb_1.35Pd₂Cd_0.65 and order magnetically near 1.4 K.     

Non-Fermi liquid behavior in polycrystalline Ce2PdIn8

We report on the formation of a novel ternary compound Ce₂PdIn₈ that is isostructural with the heavy-fermion superconductors Ce₂CoIn₈ and Ce₂RhIn₈. Its magnetic, electrical transport and thermodynamic properties were studied on polycrystalline samples in wide ranges of temperature and magnetic field strength. The results revealed Ce₂PdIn₈ to be a paramagnetic Kondo lattice with a coherence temperature of about 12 K. The C/T ratio of the specific heat reaches at 350 mK a strongly enhanced magnitude of about per Ce-atom, thus clearly indicating a heavy-fermion nature of this material. Moreover, a logarithmic divergence of C/T vs. T, observed below 3 K, which is accompanied by a linear temperature dependence of the electrical resistivity below 6 K, hint at a non-Fermi liquid character of the electronic ground state in the new compound reported.     

Spectroscopy of X2Y4 (D2h) molecules: tensorial formalism adapted to the O(3)⊃D2h chain, Hamiltonian and transition moment operators

A tensorial formalism adapted to the case of the X₂Y₄ molecules with D_2h symmetry has been developed in the same way as in the previous works on XY₄ (T_d) and XY₆ (O_h) spherical tops and XY₅Z (C_4v) symmetric tops. Here, we use the O(3)⊃D_2h group chain. All the coupling coefficients and formulas for the computation of matrix elements are given for this chain and used in the case of the Hamiltonian and transition moment operators.     

Study of the excitation properties of the Si3O2 cluster under an external electric field

The structure of the Si₃O_x (x=2, 3) cluster is investigated; we find that the geometry of Si₃O₂ is similar to that of Si₃O₃ except for the oxygen-deficient defect structure (Si-Si band) which exists only in the Si₃O₂ cluster. It is known that oxygen-deficient defects are used to explain visible luminescence (especially blue, purple and ultraviolet light) from silicon-based materials, which are directly bound up with the excited states of the molecules. Therefore the excitation properties of the two clusters are also studied. Our results show that the absorption spectrum of Si₃O₂ is concentrated in the visible light region. In contrast, the absorption spectrum of Si₃O₃ is mainly located in the ultraviolet light region. The calculations are perfectly consistent with experimental data and also support the theory of oxygen-deficient defects.     

Luminescence and energy transfer of Ce and Tb in Y3Si2O8Cl

The luminescence properties of Ce³⁺ and Tb³⁺ in Y₃Si₂O₈Cl have been investigated. The Ce³⁺ excitation bands in the region from 220 to are attributed to the transitions from 4f level to the crystal-field splitting levels of 5d. The Tb³⁺ excitation bands in the region from 220 to are due to the 4f-5d transitions. The spectral energy distributions of Tb³⁺ emission strongly depend on the Tb³⁺ concentration, the emissions of Tb³⁺ decrease with increasing Tb³⁺ concentration, this phenomenon is due to the cross-relaxation between Tb³⁺ ions. The efficient energy transfer from Ce³⁺ to Tb³⁺ in the Y₃Si₂O₈Cl is observed and discussed.     

Substrate effects on V2O3 thin films

We apply density functional theory and the augmented spherical wave method to analyze the electronic structure of V₂O₃ in the vicinity of an interface to Al₂O₃. The interface is modeled by a heterostructure setup of alternating vanadate and aluminate slabs. We focus on the possible modifications of the V₂O₃ electronic states in this geometry, induced by the presence of the aluminate layers. In particular, we find that the tendency of the V 3d states to localize is enhanced and may even cause a metal-insulator transition.     

Evolution of the 4f electron localization from YbRh2Si2 to YbRh2Pb studied by electron spin resonance

We report on electron spin resonance (ESR) experiments on the Heusler alloy YbRh₂Pb and compare its spin dynamics with that of several other Yb-based intermetallics. A detailed analysis of the derived ESR parameters indicates the extremely weak hybridization, more localized distribution of the 4f states, and a smaller RKKY interaction in YbRh₂Pb. These findings reveal the important interplay between hybridization effects, chemical substitution, and crystalline electric field interactions that determines the ground state properties of strongly correlated electron systems.     

Microstructural changes in Fe-doped Gd5Si2Ge2

Gd₅Si₂Ge₂-based alloys can exhibit a giant magnetocaloric effect (GMCE); this gives them the potential for use in cooling technologies. It has also been reported that a small addition of iron reduces the hysteresis losses in Gd₅Si₂Ge₂-based alloys, thus increasing the net refrigerating capacity. In this investigation, we have been the first to look at the effect on the microstructure and magnetic properties of Gd₅Si₂Ge₂ resulting from a wide range of substitutions of Si by Fe. The macrostructures of the arc-melted buttons revealed some very unusual surface morphologies, and the analytical results revealed a gradual substitution of the Gd₅(Si,Ge,Fe)₄-type phase by a Gd₅(Si,Ge,Fe)₃-type phase and the presence of three grain-boundary phases, two of which contain substantial amounts of iron. The magnetic measurements indicated that larger amounts of iron reduced the hysteresis losses, but at the same time reduced the Curie temperatures to below lower values that would make the material useful in practice.