High thermoelectric performance and low thermal conductivity in K-doped SnSe polycrystalline compounds

SnSe single crystal showed a high thermoelectric zT of 2.6 at 923 K mainly due to an extremely low thermal conductivity 0.23 W m⁻¹ K⁻¹. It has anisotropic crystal structure resulting in deterioration of thermoelectric performance in polycrystalline SnSe, providing a low zT of 0.6 and 0.8 for Ag and Na-doped SnSe, respectively. Here, we presented the thermoelectric properties on the K-doped K_xSn_1−xSe (x = 0, 0.1, 0.3, 0.5, 1.5, and 2.0%) polycrystals, synthesized by a high-temperature melting and hot-press sintering with annealing process. The K-doping in SnSe efficiently enhances the hole carrier concentration without significant degradation of carrier mobility. We find that there exist widespread Se-rich precipitates, inducing strong phonon scattering and thus resulting in a very low thermal conductivity. Due to low thermal conductivity and moderate power factor, the K_0.001Sn_0.999Se sample shows an exceptionally high zT of 1.11 at 823 K which is significantly enhanced value in polycrystalline compounds.     

Intrinsic defect related luminescence in ZrO2

The studies of ZrO₂ and yttrium stabilized ZrO₂ nanocrystals luminescence as well as yttrium stabilized single crystal luminescence and induced absorption showed that the intrinsic defects are responsible for luminescence at room temperature. These defects form a quasi-continuum of states in ZrO₂ band gap and are the origin of the luminescence spectrum dependence on the excitation energy. Luminescence centers are oxygen vacancies related but not the vacancies themselves. At room temperature, in ZrO₂, deep traps for electrons and holes exist. The oxygen vacancies are proposed to be the traps for electrons.     

Charge transport in polycrystalline titanium dioxide☆

This work reports semiconducting properties of undoped polycrystalline TiO₂ studied using the measurements of the electrical conductivity (EC) and thermopower as a function of oxygen partial pressure and temperature in the ranges of p(O₂) between 10 Pa and 70 kPa and temperature 1173–1273 K. The width of the band gap, determined from the minimum of EC, is equal to 3.055±0.012 eV. It was found that the apparent concentration of negatively charged defects, involving both acceptor-type aliovalent ions and Ti vacancies, increases with temperature from 0.6 at% at 1173 K to the level of 0.9–1.4 at% at 1273 K. This effect is considered in terms of Schottky-type defects. It was observed that the minimum of EC at the n–p transition is lower than that for TiO₂ single crystal thus suggesting that grain boundaries are responsible for the formation of conductivity weak links.     

Lattice distortion and corresponding changes in optical properties of CeO2 nanoparticles on Nd doping

Doping of Nd distorts the lattice structure of CeO₂, increases the lattice strain and expands the lattice. Oxygen vacancies and other ceria related defects contribute to the lattice strain. Shifting and broadening of the F_2g Raman peak of doped sample, compared to pure CeO₂, is indicative of local structure distortion on doping. Dopant induced enhancement of oxygen vacancies, in the CeO₂ lattice, is further confirmed by the generation of a new Raman peak at 543 cm^?1 that is otherwise absent in the pure one. UV–vis spectroscopy gives an understanding of the different types of f–f electronic transition of Nd in the crystalline environment of CeO₂. Effective band gap of CeO₂ reduces upto Nd concentration of 2.5%. The band gap, however, increases at 4% of Nd due to Burstein–Moss shift. Photoluminescence intensity of pure CeO₂ decreases with Nd concentration owing to the increase in the number of non radiative oxygen vacancies. These vacancies act as luminescence quencher and reduce the emission intensity. Photoluminescence excitation spectra confirm the presence of these oxygen vacancies in the CeO₂ nanocrystallites.     

Magneto-optical properties of α-Fe2O3@ZnO nanocomposites prepared by the high energy ball-milling technique

Magnetic–fluorescent nanocomposites (NCs) with 10 wt% of α-Fe₂O₃ in ZnO have been prepared by the high energy ball-milling. The crystallite sizes of α-Fe₂O₃ and ZnO in the NCs are found to vary from 65 nm to 20 nm and 47 nm to 15 nm respectively as milling time is increased from 2 to 30 h. XRD analysis confirms presence of α-Fe₂O₃ and ZnO in pure form in all the NCs. UV–vis study of the NCs shows a continuous blue-shift of the absorption peak and a steady increase of band gap of ZnO with increasing milling duration that are assigned to decreasing particle size of ZnO in the NCs. Photoluminescence (PL) spectra of the NCs reveal three weak emission bands in the visible region at 421, 445 and 485 nm along with the strong near band edge emission at 391 nm. These weak emission bands are attributed to different defect – related energy levels e.g. Zn-vacancy, Zn interstitial and oxygen vacancy. Dc and ac magnetization measurements show presence of weakly interacting superparamagnetic (SPM) α-Fe₂O₃ particles in the NCs. ⁵⁷Fe-Mössbauer study confirms presence of SPM hematite in the sample milled for 30 h. Positron annihilation lifetime measurements indicate presence of cation vacancies in ZnO nanostructures confirming results of PL studies.     

Effects of hydroxyls on the structural and room temperature ferromagnetic properties of Co doped SnO2 nanoparticles

Co doped SnO₂ nanoparticles have been prepared via a wet chemical method with different precipitation processes. The structure and morphology of Co doped SnO₂ nanoparticles demonstrate that the nanoparticles are in a rutile single phase and uniform, respectively. X-ray photoelectron spectroscopy shows that the Co dopants are in 2+ oxidation valence state and doped ∼2 atm% in SnO₂ nanoparticles. Moreover, Raman spectroscopy further confirms that Co doped SnO₂ nanoparticles have single phase crystallinity without forming any extra modes related to secondary phases. The magnetic measurements reveal that all nanoparticles exhibit room temperature ferromagnetism (RTFM) due to the presence of disorders and defects introduced by hydroxyls in the crystal structure. In addition, it has been clearly observed that the saturated magnetic moments are strongly affected by the precipitation processes which control the incorporation of hydroxyls into the lattice.     

Studies on structural defects in carbon nanotubes

Structural defects in carbon nanotubes (CNTs) have been paid much attention, because they influence the properties of the CNTs to some extent. Among various defects in CNTs, both single vacancies and Stone-Wales (SW) defects are the simple and common ones. In this paper, we review the progress of research in these two kinds of defects in CNTs. For single vacancies, we first address their different structural features in both zigzag and armchair CNTs, and their stabilities in CNTs with different sizes and different symmetries systematically. The presence of the single vacancies in CNTs not only influences the electronic structures of the systems, but also affects the vibrational properties of the tubes. Nevertheless, being active chemically, the single vacancies in the tubes prefer to interact with adsorbates nearby, of which the interaction of the defects with hydrogen atom, hydrogen molecule and some small hydrocarbon radicals (-CH, -CH₂ and -CH₃) are discussed. The former is associated with H storage and the latter is of merit to improve the local structure of the defect in a CNT. For the Stone-Wales defect, we mainly focus on its stability in various CNTs. The influence of the SW defects on the conductance of CNTs and the identification of such a defect in CNT is described in brief.      

Luminescence characteristics of cobalt doped TiO2 nanoparticles

TiO₂ nanoparticles doped with two different concentrations of Cobalt, 0.02 and 0.04 mol, are prepared by sol–gel method. The crystalline phase of the doped and undoped nanoparticles and particle sizes are observed with X-ray diffraction and transmission electron microscope. FTIR confirms the bonding interaction of Co²⁺ in TiO₂ lattice framework. The UV absorption spectra of the doped material shows two absorption peaks in the visible region related to d–d electronic transitions of Co²⁺ in TiO₂ lattice. Compared to undoped TiO₂ nanoparticles, the cobalt doped samples show a red shift in the band gap. Steady state photoluminescence spectra give emission peaks related to oxygen defects. The decrease in the intensity ratio of UV/visible emission peaks confirms distortion of structural regularity and formation of defects after doping. The intensity ratio of different visible emission peaks is nearly same for undoped and 0.02 Co²⁺. However, this ratio decreases profoundly at 0.04 Co²⁺, due to concentration quenching effect. Photoluminescence excitation spectra, recorded at 598 nm emission wavelength, give different excitation peaks associated with oxygen vacancies and Co²⁺. Time resolved photoluminescence spectra give longer decay time for doped samples, indicating longer relaxation of conduction band electrons on the defect and on dopant sites.     

SnSe分子外场下的基态性质和激发态性质

对Sn原子使用SDB-cc-pVTZ基组, Se原子采用6-311++G^**基组, 利用密度泛函中的B3LYP方法研究了电场强度为-0.04–0.04 a.u.的外电场对SnSe基态分子的几何结构、 电荷布居分布、 HOMO能级、 LUMO能级、 能隙、 费米能级、 谐振频率和红外光谱强度的影响. 继而使用含时密度泛函(TD-B3LYP) 方法研究了SnSe分子在外场下的激发特性. 结果表明, 外电场的大小和方向对SnSe分子基态的这些性质有明显影响. 在所加的电场范围内(-0.04 a.u.–0.04 a.u.), 随着正向电场的增大, 核间距先减小后增大, 在F=0.03 a .u.时取得最小值0.2317 nm; 分子电偶极矩μ近似线性地增大; E_L, E_H、 费米能级E_F和能隙E_g均减小. 随着正向电场逐渐增大, 分子总能量和谐振频率均先增大后减小; 红外谱强度则先减小后增大, 在F=0.03 a.u.时, 取得最小值 0.1138 km·mol^-1. 由基态到第1–10个单重激发态的波长均随着正向电场的增大而增大. 激发能均随着正向电场的增大而减小. 电场的引入可改变SnSe分子激发态出现的顺序并使得一些禁止的跃迁变得可能. 关键词： SnSe 外电场 能隙 激发特性     

Microstructure and dielectric study of pure BST and doped BSTF ceramic materials by broadband dielectric spectroscopy

Pure BST and doped BSTF (with BSTF2: Fe₂O₃ 2 wt % and BSTF4: Fe₂O₃ 4 wt %) ceramics were prepared by solid state reaction. XRD pattern showed the different phases were formed depend on the weight percent of Fe₂O₃. The crystal size and lattice parameters increased while the lattice strain decreased. The topography of the sintered samples shows increase of the grain size with increasing Fe₂O₃ ratio and hence enhances the compaction of ceramics. Broadband dielectric spectroscopy was employed to investigate the effect of magnetite nanoparticle on the dielectric properties of the pure BST ceramic. The interfacial polarization and the conductivity contribution reflect the high values of permittivity and its gradual increase as frequency decreases. The two BSTF samples show relaxation peak dynamic originated from presence of immobile species/electrons at low temperatures and defects/vacancies results from the formation of oxygen vacancies originates from the spontaneous change in oxidation states of Fe ions (Fe ^3+/Fe²⁺) at high temperatures. The relaxation rate obeys Arrhenius law at high temperatures in case of BST sample with activation energy 225 kJ/mol. This high value of activation energy at higher temperatures reflects and confirms the slowed down of the dynamics at the interphase and the decoupling nature of the OH-dynamic and the interfacial polarization.     

Defect-induced ferromagnetism in fullerenes

Based on the ab initio electronic structure calculations the picture of ferromagnetism in polimerized C₆₀ is proposed which seems to explain the whole set of controversial experimental data. We have demonstrated that, in contrast with cubic fullerene, in rhombohedral C₆₀ the segregation of iron atoms is energetically unfavorable which is a strong argument in favor of intrinsic character of carbon ferromagnetism which can be caused by vacancies with unpaired magnetic electrons. It is shown that: (i) energy formation of the vacancies in the rhombohedral phase of C₆₀ is essentially smaller than in the cubic phase, (ii) there is a strong ferromagnetic exchange interactions between carbon cages containing the vacancies, (iii) presence of iron impurities can diminish essentially the formation energy of intrinsic defects, and (iv) the fusion of the magnetic single vacancies into nonmagnetic bivacancies is energetically favorable. The latter can explain a fragility of the ferromagnetism.     

Effect of solution concentration on physicochemical and gas sensing properties of sprayed WO3 thin films

Sub-stoichiometric tungsten trioxide (WO₃) thin films are deposited onto the glass substrates by spray pyrolysis technique using ammonium metatungstate. Effect of solution concentration on structural, morphological, optical, electrical and NO₂ sensing properties of WO₃ thin films is studied. Films are polycrystalline with monoclinic crystal structure and sub-stoichiometric as observed form the XRD and XPS studies, respectively. The SEM and AFM images show micro grained structure and surface roughness increases with increase in solution concentration. The PL studies revealed that the majority of the defects are the oxygen vacancies. From XPS and PL studies it is observed that, oxygen vacancies decrease with increase in solution concentration. The dielectric constant of the films as a function of frequency is in concurrence with resistivity measurements. Films show reproducible and reversible gas response at various operating temperatures and gas concentrations. Highest sensor response (38%) towards 200 ppm NO₂ concentration is observed for the film with 15 mM solution concentration at moderate operating temperature (200 °C). Pd sensitization enhanced gas response to 68% and improved kinetics of the sensor. Films are highly selective towards NO₂ as compared with the various gases such as SO₂, LPG, NH₃ and H₂S.     

Electronic properties of MoS2 nanoribbons with disorder effects

A theoretical study of electronic properties on MoS₂ nanoribbon is made on focusing the calculation of zero bias transport in the presence of disorders. Disorders including intrinsic and extrinsic vacancies and also weak uniform scatter defects are considered. The calculations are based on the tight-binding Green's function formalism by including an iterative procedure. The Slater–Koster transformations are used to determine the parameters. This model reduces the numerical calculation time. The unsaturated atoms at the edge of armchair (zigzag) ribbon induce some mid-gap states with nearly high (low) localization, which act as scattering centers. The antiresonances of created quasi-localized states due to vacancy cause the conductance of the armchair nanoribbon to decrease. Finally, the zigzag ribbon provides the highest sensitivity as well as selectivity between the smaller energy range, in the presence of the single weak scatter with potential value of 2 eV at the edge of the ribbon.     

Ab initio studies of isolated hydrogen vacancies in graphane

We present a density functional study of various hydrogen vacancies located on a single hexagonal ring of graphane (fully hydrogenated graphene) considering the effects of charge states and the position of the Fermi level. We find that uncharged vacancies that lead to a carbon sublattice balance are energetically favorable and are wide band gap systems just like pristine graphane. Vacancies that do create a sublattice imbalance introduce spin polarized states into the band gap, and exhibit a half-metallic behavior with a magnetic moment of 1.00 μ_B per vacancy. The results show the possibility of using vacancies in graphane for novel spin-based applications. When charging such vacancy configurations, the deep donor (+1/0) and deep acceptor (0/−1) transition levels within the band gap are noted. We also note a half-metallic to metallic transition and a significant reduction of the induced magnetic moment due to both negative and positive charge doping.     

Fe doping induced enhancement in room temperature ferromagnetism and selective cytotoxicity of CeO2 nanoparticles

In the present study, structural, optical, magnetic properties as well as cytotoxicity of undoped and Fe doped Ceria (CeO₂) nanoparticles synthesized by simple soft chemical method have been reported. SEM and XRD results have shown that the synthesized samples are comprised of ultrafine spherical nanoparticles having single phase cubic fluorite structure of CeO₂. Raman spectroscopy results have depicted a red shift in F_2g mode with Fe doping which reveals enhancement in the oxygen vacancies. The optical band gap calculated from UV–visible absorption spectra has been found to vary unsystematically with Fe doping which is associated with the creation of impurity level and abundance in oxygen vacancies with Fe doping. The oxygen vacancies have introduced the room temperature ferromagnetism (RTFM) in undoped and Fe doped CeO₂ nanoparticles. The saturation magnetization (M_s) value of pristine CeO₂ nanoparticles has been found to be 0.00083 emu/g which is increased up to 0.0126 emu/g for 7% Fe doped nanoparticles. For cytotoxicity tests, the synthesized nanoparticles induced effects on Neuroblastoma cancer cells & HEK-293 healthy cells have been analyzed via CCK-8 analysis. It has been observed that the prepared undoped and Fe doped CeO₂ nanoparticles have nontoxic nature towards healthy cells while they are extremely toxic towards cancerous cells. Furthermore, the anticancer activity is found to enhance with Fe doping. The selective toxicity and enhancement in anticancer activity with Fe doping has observed to be strongly correlated with reactive oxygen species (ROS) generation.     

Modulation of magnetic properties of bilayer SnSe with transition-metals doping in the interlayer

We investigate the spin-polarized electronic and magnetic properties of bilayer SnSe with transition-metal (TM) atoms doped in the interlayer by using a first-principles method. It shows that Ni dopant cannot induce the magnetism in the doped SnSe sheet, while the ground state of V, Cr, Mn, Fe and Co doped systems are magnetic and the magnetic moment mainly originates from 3d TM atom. Two types of factors, which reduce the magnetic moment of TM atoms doped in bilayer SnSe, are identified as spin-up channel of the 3d orbital loses electrons to SnSe sheet and spin-down channel of the 3d orbital gains electrons from 4s orbital. The spin polarization is found to be 100% at Fermi level for the Mn and Co atoms doped system, while the Ni-doped system is still a semiconductor with a gap of 0.26 eV. These results are potentially useful for development of spintronic devices.     

On the nature of trapped states in an MoS2 two-dimensional semiconductor with sulfur vacancies

ABSTRACT

Molybdenum disulfide (MoS₂) is a common two-dimensional semiconductor that has been highly studied as an emerging material for catalysis and electronics. The most common material defects in MoS₂ are sulfur vacancies. In order to reveal the nature of the trapped states induced by sulfur vacancies, we perform Density Functional Theory (DFT) combined with quantum dynamics calculations. According to our model, we find that the sulfur vacancies create trap states in the original band gap of monolayer MoS₂ that disrupt charge transmission through the monolayer. In addition, we did not find any resonance states among the shallow states in the conduction band continuum.     

Characterization on electron beam evaporated α-MoO3 thin films by the influence of substrate temperature

Electrochromic molybdenum oxide (MoO₃) thin films were prepared by electron beam evaporation technique using the dry MoO₃ pellets. The films were deposited on glass and fluorine doped tin oxide (SnO₂:F or FTO) coated glass substrates at different substrate temperatures like room temperature (RT, 30 °C), 100 °C and 200 °C. The influence of substrate temperature on the structural, surface morphological and optical properties of the films has been studied. The X-ray diffraction analysis showed that the films are having orthorhombic phase MoO₃ (α-MoO₃) with 〈1 1 0〉 preferred orientation. The laser Raman scattering spectrum shows the polycrystalline nature of MoO₃ films deposited at 200 °C. The Raman-active band at 993 cm⁻¹ is corresponding to Mo–O stretching mode that is associated with the unique character of the layered structure of orthorhombic MoO₃. Needle—like morphology was observed from the SEM analysis. The energy band gap of MoO₃ films was evaluated which lies between 2.8 and 2.3 eV depending on the substrate temperature and substrates. The decrease in band gap value with increasing substrate temperature is owing to the oxygen-ion vacancies. The absorption edge shift shows the coloration effect on the films.     

Anisotropic thermoelectric and superconducting properties of the bulk misfit-layered (SnSe)1.17(TaSe2) compound

We present the thermoelectric and superconducting properties of the bulk misfit-layered (SnSe)_1.17(TaSe₂) compound with the critical temperature (T_c ~ 3.8 K). From XRD and electrical resistivity, the anisotropic properties of the misfit-layered compound by the preferred orientation were observed. The zero-temperature-limit upper critical field H_c2(0) and coherence length ξ are obtained by H_c2(0) = 8.94 T and ξ = 6.1 nm. The electron-phonon coupling constant (λ_e-p = 0.735) and the specific heat jump (ΔC_e/γT_c ~ 1.4) imply that the (SnSe)_1.17(TaSe₂) compound is a weak coupled conventional s-wave superconductor. Density functional theory (DFT) calculation results show that some electronic charge transfers from the SnSe layers into the TaSe₂ layers. In addition, the thermoelectric properties of the bulk misfit-layered (SnSe)_1.17(TaSe₂) compound show significant anisotropic properties.     

The role of Co impurities and oxygen vacancies in the ferromagnetism of Co-doped SnO2: GGA and GGA+U studies

The electronic structure and ferromagnetic stability of Co-doped SnO₂ are studied using the first-principle density functional method within the generalized gradient approximation (GGA) and GGA+U schemes. The addition of effective U_Co transforms the ground state of Co-doped SnO₂ to insulating from half-metallic and the coupling between the nearest neighbor Co spins to weak antimagnetic from strong ferromagnetic. GGA+U_Co calculations show that the pure substitutional Co defects in SnO₂ cannot induce the ferromagnetism. Oxygen vacancies tend to locate near Co atoms. Their presence increases the magnetic moment of Co and induces the ferromagnetic coupling between two Co spins with large Co-Co distance. The calculated density of state and spin density distribution calculated by GGA+U_Co show that the long-range ferromagnetic coupling between two Co spins is mediated by spin-split impurity band induced by oxygen vacancies. More charge transfer from impurity to Co-3d states and larger spin split of Co-3d and impurity states induced by the addition of U_Co enhance the ferromagnetic stability of the system with oxygen vacancies. By applying a Coulomb U_O on O 2 s orbital, the band gap is corrected for all calculations and the conclusions derived from GGA+U_Co calculations are not changed by the correction of band gap.