Electronic and optical properties of the orthorhombic compounds FeX2 (X = P,As and Sb)

First principles calculations, by means of the full-potential linearized augmented plane wave (FP-LAPW) method within the local density approximation (LDA), were carried out for the structural, electronic and optical properties of the orthorhombic compounds FeP₂, FeAs₂ and FeSb₂. The structural properties are determined through the total energy minimization and the relaxation of the internal parameters. The modified Becke–Johnson (mBJ) method is applied for the electronic structure of FeSb₂. Our LDA-calculation shows that the first two compounds are indirect-gap semiconductors, while for the third one it predicts a small hole-pocket at the R point. The mBJ gives a semiconducting state with an indirect energy gap of 0.248 eV for FeSb₂. The overall shape of the calculated imaginary parts of the dielectric tensor is similar for the three compounds. The assignment of the structures in the optical spectra and band structure transitions are investigated. The electronic dielectric constant along (0 1 0) direction is the largest for the three compounds. For FeAs₂, the calculated components of reflectivity have the same trend of variation as the measured ones in the energy range 1.54–3.1 eV.     

Thermal stability and elastic properties of Mg2X (X = Si, Ge, Sn, Pb) phases from first-principle calculations

Thermal stabilities, elastic properties and electronic structures of Mg₂Si, Mg₂Ge, Mg₂Sn and Mg₂Pb have been determined from first-principle calculations. The calculated heats of formation and cohesive energies show that Mg₂Ge has the strongest alloying ability and Mg₂Si has the highest structural stability. Gibbs free energy, heat capacity and Debye temperature are calculated and discussed. The elastic parameters are calculated, the bulk moduli, shear moduli, Young’s moduli and poisson ratio value are derived, the brittleness and plasticity of these phases are discussed, and the brittle behavior and structural stability mechanism are also explained through the densities of states (DOS) of these intermetallic compounds.     

Non-equilibrium phases in the Fe-Rh system studied by ion beam mixing and ab initio calculation

In the Fe-Rh system, the Fe_100 − xRh_x (x = 40, 50, 65, 70, and 90) multilayered films were prepared and then subjected to ion beam mixing using 200 keV Xe ions. Upon ion beam mixing, amorphous alloy was obtained in the Fe₇₀Rh₃₀ sample, in which an interesting phase transition path was observed as Fe + Rh → fcc → fcc + a →? fcc + bcc → fcc. In addition, a new metastable crystalline fcc phase was observed in the Fe₅₀Rh₅₀ sample together with the solid solutions, and the lattice constants of the ion mixed phases were consistent with those from ab initio calculations. Possible mechanisms for the formation of both amorphous and metastable crystalline phases are discussed in terms of the atomic collision theory.     

Structure and electronic properties of transition metal dichalcogenide MX2 (M = Mo,W, Nb; X = S,Se) monolayers with grain boundaries

Layered transition metal dichalcogenides with unique mechanical, electronic, optical, and chemical properties can be used for novel nanoelectronic and optoelectronic devices. Large-area monolayers synthesized using chemical vapor deposition are often polycrystals with many dislocations and grain boundaries (GBs). In the present paper, atomic structure and electronic properties of MX₂ (M = Mo, W, Nb; X = S, Se) with the GBs were investigated using first principles based on density functional theory. Simulation results revealed that the zigzag-oriented GBs (which consist of pentagon/heptagons (5-7) pairs) were more stable than the armchair-oriented GBs (which consist of pentagon/heptagons (5-7-5-7) pairs). The GBs induced defect levels are located within the band gap for the semiconductor materials of MX₂ (M = Mo, W; X = S, Se) monolayers, and the NbS₂ and NbSe₂ remained as metallic materials with GBs. Results provided a possible pathway to build these nano-layered materials into nanoelectronic devices.     

Electronic structure of CaX (X = O, S, Se) compounds using Compton spectroscopy

The electronic structure of CaO, CaS and CaSe through Compton spectroscopy is reported in this work. Both directional as well as spherically averaged Compton profiles are calculated for all the three compounds employing the CRYSTAL code within the framework of density functional theory (DFT). The anisotropy [1 0 0]-[1 1 0] for CaO is in agreement with the earlier values. The spherically averaged theoretical values are compared with the first ever measurement made on polycrystalline samples using 59.54 keV gamma-rays from Am²⁴¹ source. The calculations are in good agreement with measurements in all cases. Charge transfer in the three compounds has also been estimated following the ionic model. The present study suggests charge transfer from Ca to X (O, S, Se) atom. On the basis of equal-valence-electron-density (EVED) profiles, it is found that CaO is more ionic compared to CaS and CaSe. From the DFT based calculations, we have also determined the cohesive energies, which are compared with other investigations.     

First principles predictions on mechanical and physical properties of HoX (X = As,P)

In this study, the calculated results of the structural, electronic, elastic, lattice dynamic, and thermodynamic properties of HoX (X = As, P) in rocksalt structure (B1) are presented. Ab initio calculations were performed based on density-functional theory using the Vienna Ab initio Simulation Package (VASP). Calculated structural parameters, such as the lattice constant, bulk modulus and its pressure derivative, cohesive energy, second-order elastic constants, electronic band structures and related total and partial density of states, Zener anisotropy factor, Poisson's ratio, Young's modulus, and isotropic shear modulus are presented. In order to gain further information, we investigated the pressure and temperature dependent behavior of the volume, bulk modulus, thermal expansion coefficient, heat capacity, entropy, Debye temperature, and Grüneisen parameter over a pressure range of 0–32 GPa and a wide temperature range of 0–2000 K. The phonon frequencies and one-phonon density of states are also presented.     

Ab initio, crystal field and experimental spectroscopic studies of pure and Ni-doped KZnF3 crystals

Pure and Ni²⁺ doped KZnF₃ single crystals were studied using the combination of the DFT-based ab initio methods, crystal field theory and experimental spectroscopic techniques. The electronic, optical and elastic properties have been calculated and compared with available experimental data and good agreement was achieved. Elastic anisotropy of pure KZnF₃ was modeled; calculations of the sound velocity, Debye temperature, Grüneisen parameter and specific heat capacity were performed. Comparison of the calculated results for the pure and doped material, which is reported for the first time for the considered material, enabled to identify the changes in the optical and electronic properties, which are due to the introduced nickel impurity ions. In particular, it was shown that the lowest Ni 3d states appear in the host's band gap at about 1.0 eV above the valence band. The changes of the electron density distribution after doping were also shown. Microscopic analysis of the crystal field effects based on the performed ab initio calculations of the Ni²⁺ density of states at different external pressures enabled to estimate the constants of the electron–vibrational interaction, Huang-Rhys factor, Stokes shift and local bulk modulus around impurity ions. The crystal field calculations of the Ni²⁺ energy levels were performed to analyze and assign the experimental absorption spectrum. Such a combination of the ab initio and semi-empirical calculating techniques leads to a complementary picture of the physical properties of KZnF₃:Ni²⁺ and can be applied to other doped crystals.     

Superconductivity of p-type diamond (001) and (111) thin films: Ab initio calculations

The surface structure, electronic properties, lattice dynamics, and the electron-phonon coupling for p-doped diamond (001)-(2 × 1) and (111)-(2 × 1) thin films have been extensively investigated using ab initio methods within the virtual crystal approximation. The calculations of p-doped diamond thin films strongly favor dimer reconstruction of diamond surfaces. The physical origin of superconductivity of diamond (001)-(2 × 1), respectively, and (111)-(2 × 1) thin films which is higher than that of bulk diamond is systematically studied. It is showed that surface vibrational modes of diamond (001)-(2 × 1) surfaces give main contributions to superconducting transition temperature T_c, while T_c of diamond (111)-(2 × 1) surfaces is attributed to the combined action of surface and bulk vibrational modes. Therefore, at the highest concentration (13.98 × 10²¹ cm^− 3) T_c ≈ 56.5 K of diamond (111)-(2 × 1) surfaces is about twice as high as that of bulk and diamond (001)-(2 × 1) surfaces.     

Nonlinear optical diagnostic of semimagnetic semiconductors Pb1−xYbxX (X = S, Se, Te)

Nonlinear optical measurements were performed to elucidate the influence of magnetic ions on the behavior of charge carriers in magnetic semiconductors—Pb_1−xYb_xX (X = S, Se, Te at x = 1-3%). It was shown that nonlinear optical methods could be used as sensitive tools for investigations of electron-phonon anharmonicity near low-temperature semiconductor-insulator phase transitions. There exists a difference between surface and bulk-like contributions to the nonlinear optical effects. It was shown that only low-temperature Two Photon Absorption (TPA) oscillator may be related to the number of the electron-phonon anharmonic modes responsible for the observed phase transformation. The explanation of the anomalous temperature dependences is given in accordance with dipole momentum's behaviors determined by low-temperature spin-spin interactions and by electron-phonon anharmonic interactions. We have discovered that low-temperature dependence of specific heat of Pb_1−xR_xTe (R = Yb, Pr with x = 3% and 1.6%, respectively) exhibits a non-magnetic order caused by large electron-phonon contributions and structural disorder effects.     

Phase stabilities of self-organized nc-TiN/a-Si3N4 nanocomposites and of Ti1 − xSixNy solid solutions studied by ab initio calculation and thermodynamic modeling

Bulk properties of stable binary fcc-TiN and hcp(β)-Si₃N₄, hypothetical fcc-SiN and hcp(β)-Ti₃N₄, and ternary Ti_1 − xSi_xN_y phases are calculated by ab initio method. The values of total energies are then used for thermodynamic calculations of the lattice instabilities of hypothetical binary phases of fcc-SiN and hcp-Ti₃N₄, and of the interaction parameters of ternary Ti_1 − xSi_xN_y phases. Based on these data, Gibbs free energy diagrams of the quasi-binary TiN_y-SiN_y system are constructed in order to study the relative phase stability of the metastable ternary fcc- and hcp-Ti_1 − xSi_xN_y phases over the entire range of compositions. The results are supported by the published data from chemical and physical vapor deposition experiments. The constructed Gibbs free energy diagram and phase selection diagram of quasi-binary TiN_y-SiN_y system in fcc structure show that metastable fcc-Ti_1 − xSi_xN coatings should undergo chemically spinodal decomposition into coherent fcc-TiN and fcc-SiN. Due to a high lattice mismatch between fcc-TiN and hcp-Si₃N₄, and to much higher lattice instability of fcc-SiN with respect to stable hcp-Si₃N₄, only about one monolayer of pseudomorphic SiN_y interfacial phase is stable.     

Luminescence excitation spectra of TbX3 (X = Cl, Br, I)

A systematic study of the excitation spectrum of TbX₃ (X = Cl⁻, Br⁻, I⁻) is presented in this work. In general, the excitation spectra of TbX₃ can be divided into three major regions: (1) the short-wave host lattice absorption region, (2) the intermediate absorption region where the Tb³⁺ 4f⁸ → 4f⁷5d¹ interconfigurational excitation transition are located, and (3) the long-wave excitation region where the Tb³⁺ 4f⁸ → 4f⁸ intraconfigurational excitation transition are located. The high spin and the low spin components of the Tb³⁺ interconfigurational excitation transition are clearly identified in the case of TbCl₃. The luminescence of TbX₃ (X = Cl⁻, Br⁻, I⁻) is dominated by emission transitions emanating from the Tb³⁺⁵D₄ state. A comparative study of the optical properties of TbX₃ (X = Cl⁻, Br⁻, I⁻) with the properties of the Tb³⁺ ion in several halide host lattices is presented. Further, a comparative study of the fundamental host lattice optical transitions in terbium halides and other halide materials is also presented.     

DFT study of the coverage effects for Al adsorption on Si(1 1 1) surfaces

Density functional theory (DFT) calculations have been carried out to investigate the interactions between the Si(1 1 1) surface and the Al adatoms. Different adsorption sites and coverage effects have been considered. For low Al coverage, the threefold-filled adsorption site is the most energy favored site. With the increase of Al coverage, adatom-adatom interactions become increasingly important and Al atomic chains or clusters are formed. With the clean Si(1 1 1) surface of metallic feature, we found that 1/3 ML Al adsorption leads to a semiconducting surface. The results for the electronic behavior suggest the formation of the polarized covalent bonding between the Al adatom and the Si(1 1 1) surface.     

Negative thermal expansion and electrical properties of Mn3(Cu0.6NbxGe0.4 − x)N (x = 0.05-0.25) compounds

Bulk materials with the general formula of Mn₃(Cu_0.6Nb_xGe_0.4 − x)N (x = 0.05, 0.1, 0.15, 0.2, 0.25), Mn₃(Cu_0.6Ge_0.4)N and Mn₃(Cu_0.7Ge_0.3)N were fabricated by mechanical ball milling and solid state sintering. Their thermal expansion coefficients and electrical conductivities were investigated in the temperature range of 80-300 K. It is found that the temperature interval of negative temperature expansion behavior is about 95 K in the samples of Mn₃(Cu_0.6Nb_0.15Ge_0.25)N and Mn₃(Cu_0.6 Nb_0.2Ge_0.2)N, which is twice as large as that of Mn₃(Cu_0.7Ge_0.3)N. The negative thermal expansion of Mn₃(Cu_0.6Nb_0.15Ge_0.25)N can reach to − 19.5 × 10⁻⁶ K^− 1 in the temperature range of 165 to 210 K. The electrical conductivity of this series materials is in a level of about 2.5 × 10⁶ (Ω m)^− 1.     

First-principles study of phase transition and elastic properties of XBi (X = Ce, Pr) compounds

The pressure-induced phase transitions of CeBi and PrBi compounds were investigated by using full-potential linearized augmented plane-wave (FP-LAPW) method. The calculations indicate that the transition pressure for CeBi compound from the NaCl-type (B1) structure to the body centered tetragonal (BCT) structure are 11.53 GPa from total energy (E)-volume (V) data and 6.48 GPa from equal Gibbs free energy (G). For PrBi compound, the same phase transition sequence occurred at 10.94 GPa obtained from the slope of the common tangent of E-V curves and 6.04 GPa from the equal G. The detailed structural changes during the phase transition were analyzed. From the elastic constants at zero pressure, we can conclude that B1 phase of XBi (X = Ce, Pr) compounds are mechanical stable, consistent with the experimental observations.     

The adsorption properties of PdZnx alloy on Pd(1 0 0): Preparation and characterization

The formation of PdZn_x alloy on Pd(1 0 0) and its characteristics were investigated by various methods, such as photoelectron, auger-electron, electron energy loss, thermal desorption spectroscopic methods and work-function measurement. The alloy was produced by the decomposition of diethyl zinc on Pd(1 0 0). The alloy surface reacts with O₂ and ZnO_x is formed. The reactivity of alloy to hydrogen is similar to that of K/Pd. The stability of adsorbed CO is lower than on clean Pd(1 0 0).     

Ab initio study of antisite defective layered Ge2Sb2Te5

By means of ab initio calculations, we have investigated the antisite defects in layered Ge₂Sb₂Te₅ (GST). Our results show that both Te_Sb and Sb_Te antisite defective GST alloys are energetically favorable and mechanically stable. Furthermore, the presence of antisite defects results in the decrease in band gaps and hence the increase in the electrical conductivity, while shows slight effect on chemical bonding characters. Based on the present results, increased electrical conductivity and decreased thermal conductivity are expected by introducing antisite defects in GST related layered materials.     

Electronic band-edge properties of rock salt PbY and SnY (Y= S, Se, and Te)

The electronic band-edges of lead chalcogenides PbY and tin chalcogenides SnY (where Y = S, Se, and Te) are investigated by the means of a full-potential linearized augmented plane wave (FPLAPW) method and the local density approximation (LDA). All six chalcogenide binaries have similar electronic structures and density-of-states, but there are differences in the symmetry of the band-edge states at and near the Brillouin zone L-point. These differences give the characteristic composition, pressure, and temperature dependences of the energy gap in Pb_1−xSn_xY alloys.We find that: (1) SnY are zero-gap semiconductors E_g = 0 if the spin–orbit (SO) interaction is excluded. The reason for this is that the conduction band (CB) and the valence band (VB) cross along the Q ≡ LW line. (2) Including the SO interaction splits this crossing and creates a direct gap along the Q-line, thus away from the L symmetry point. Hence, the fundamental band gap E_g in SnY is induced by the SO interaction and the energy gap is rather small E_g ≈ 0.2–0.3 eV. At the L-point, the CB state has symmetric and the VB state is antisymmetric thereby the L-point pressure coefficient ∂E_g(L)/∂p is a positive quantity. (3) PbY have a direct band gap at the L-point both when SO coupling is excluded and included. In contrast to SnY, the SO interaction decreases the gap energy in PbY. (4) Including the SO interaction, the LDA yields incorrect symmetries of the band-edge states at the L-point; the CB state has and the VB state has symmetry. However, a small increase of the cell volume corrects this LDA failure, producing an antisymmetric CB state and a symmetric VB state, and thereby also yields the characteristic negative pressure coefficient ∂E_g(L)/∂p in agreement with experimental findings. (5) Although PbY and SnY have different band-edge physics at their respective equilibrium lattice constants, the change of the band-edges with respect to cell volume is qualitatively the same for all six chalcogenides. (6) Finally, in the discussion of the symmetry of the band edges, it is important to clearly state the chosen unit cell origin; a shift by (a/2,0,0) changes the labeling of the irreducible representations.     

Band alignment of Cd(1 − x)ZnxS produced by spray pyrolysis method

Cd_(1 − x)Zn_xS thin films have been grown on glass substrates by the spray pyrolysis method using CdCl₂ (0.05 M), ZnCl₂ (0.05 M) and H₂NCSNH₂ (0.05 M) solutions and a substrate temperature of 260 °C. The energy band gap, which depends on the mole fraction × in the spray solution used for preparing the Cd_(1 − x)Zn_xS thin films, was determined. The energy band gaps of CdS and ZnS were determined from absorbance measurements in the visible range as 2.445 eV and 3.75 eV, respectively, using Tauc theory. On the other hand, the values calculated using Elliott-Toyozawa theory were 2.486 eV and 3.87 eV, respectively. The exciton binding energies of Cd_0.8Zn_0.2S and ZnS determined using Elliott-Toyozawa theory were 38 meV and 40 meV, respectively. X-ray diffraction results showed that the Cd_(1 − x)Zn_xS thin films formed were polycrystalline with hexagonal grain structure. Atomic force microscopy studies showed that the surface roughness of the Cd_(1 − x)Zn_xS thin films was about 50 nm. Grain sizes of the Cd_(1 − x)Zn_xS thin films varied between 100 and 760 nm.     

First-principles studies of the superconductivity and vibrational properties of transition-metal nitrides TMN (TM = Ti,V, and Cr)

The present paper reports the structural, electronic, phonon and thermodynamical properties of some transition-metal nitrides (TMN: TiN, VN and CrN) by means of first-principles calculations. The computed equilibrium lattice constant and bulk modulus agree well with the available experimental and theoretical data. The electronic band structure and density of states calculations show metallic nature. The phonon frequencies are positive throughout the Brillouin zone for these compounds in rocksalt structure indicating dynamical stability. The calculated electron–phonon coupling constant λ and superconducting transition temperature agree reasonably well with the available experimental data. These compounds behave as a conventional phonon-mediated superconductor. Within the GGA and quasi-harmonic approximation, thermodynamical properties are also investigated.     

Composition dependent thermoelectric properties of sintered Mg2Si1−xGex (x = 0 to 1) initiated from a melt-grown polycrystalline source

Fabrication of Mg₂Si_1−xGe_x (x = 0-1.0) was carried out using a spark plasma sintering technique initiated from melt-grown polycrystalline Mg₂Si_1−xGe_x powder. The thermoelectric properties were evaluated from RT to 873 K. The power factor of Mg₂Si_1−xGe_x with higher Ge content (x = 0.6-1.0) tends to decrease at higher temperatures, and the maximum value of about 2.2 × 10^− 5 Wcm^− 1K^− 2 was observed at 420 K for Mg₂Si and Mg₂Si_0.6Ge_0.4. The coexistence of Si and Ge gave rise to a decrease in the thermal conductivity in the Mg₂Si_1−xGe_x. The values close to 0.02 Wcm^− 1K^− 1 were obtained for Mg₂Si_1−xGe_x (x = 0.4-0.6) over the temperature range from 573 to 773 K, with the minimum value being about 0.018 Wcm^− 1K^− 1 at 773 K for Mg₂Si_0.4Ge_0.6. The maximum dimensionless figure of merit was estimated to be 0.67 at 750 K for samples of Mg₂Si_0.6Ge_0.4.