Insights on the origin of the structural phase transition in BaV10O15 from electronic structure calculations and the effect of Ti-doping on its structure and electrical transport properties

Band structure calculations at the level of LMTO-ASA provide insight into the electronic structure of BaV₁₀O₁₅ and the origin of the structural phase transition. A crystal orbital Hamiltonian population/integrated crystal orbital Hamiltonian population analysis provides evidence that the crystallographic phase transition is driven by V-V bond formation. As well, the energy bands near the Fermi level are very narrow, <1 eV, consistent with the fact that the observed insulating behavior can be due to electron localization via either Mott-Hubbard correlation and/or Anderson disorder. The partial solid solution, BaV_10−xTi_xO₁₅, was examined to study the effect of Ti-doping at the V sites on the structure and electronic transport properties. In spite of the non-existence of “BaTi₁₀O₁₅”, the limiting x=8, as indicated by a monotonic increase in the cell volume and systematic changes in properties. This limit may be due to the difficulty of stabilizing Ti²⁺ in this structure. For x=0.5 both the first order structural phase transition and the magnetic transition at 40 K are quenched. The samples obey the Curie-Weiss law to x=3 with nearly spin only effective moments along with θ values which range from −1090 K (x=0.5) to −1629 K (x=3). For x>3 a very large, ∼2×10⁻³ emu/mol, temperature independent (TIP) contribution dominates. Conductivity measurements on sintered, polycrystalline samples show semiconducting behavior for all compositions. Activation energies for Mott hopping derived from high temperature data range from ∼0.1 eV for x=0-1 and fall to a plateau of 0.06 eV for x=3-7. Low temperature data for x=3, 5 and 7 show evidence for Mott variable range hoping (VRH) with a T^1/4 law and in one case between 5 and 17 K, a Efros-Shklovskii correlated hopping, T^1/2 law, was seen, in sharp contrast to BaV₁₀O₁₅ where only the E-S law was observed up to 75 K. Seebeck coefficients are small (<35 μV/K), positive, roughly TIP and increase with increasing x up to x=5. This may point to a Heikes hopping of holes but a simple single carrier model is impossible. The compositions for x>3 are remarkable in that local moment behavior is lost, yet a metallic state is not reached. The failure of this system to be driven metallic even at such high doping levels is not fully understood but it seems clear that disorder induced carrier localization plays a major role.     

Electronic transport study of PbSe pellets prepared from self-assembled 2D-PbSe nanostructures

This work presents a study of the electronic transport properties of PbSe pellets fabricated starting of PbSe nanostructures that exhibited a flake-like 2D morphology, which were synthesized by the co-precipitation method. Seebeck coefficient measurements revealed that the PbSe sample displays n-type conductivity, a maximum Seebeck coefficient of −512.6 μV/K around 380 K, and that the carriers scattering is dominated by acoustic and optical phonons. The Fermi level dependence on the temperature and the band gap energy are also reported. Interestingly, size-dependent confinement effects due probably to the reminiscent PbSe 2D character could be evidenced.     

Li原子掺杂C28单分子器件的热自旋输运性质

利用第一性原理对Li原子掺杂C₂₈的分子器件的热自旋输运性质进行了计算。在不同的温度场下,上下自旋分别为Li原子掺杂C₂₈的分子器件中的空穴和电子提供了输运通道,在MJ₁和MJ₃分子器件中,热自旋电流随着温度增加而增大,但在MJ₂分子器件中,热自旋电流先增大再减小。三种分子器件都出现了自旋塞贝克效应,MJ₂还出现了负微分电阻现象,利用费米-狄拉克分布和自旋输运谱对其物理机理进行了解释。根据Li掺杂C₂₈的单分子器件的热自旋输运性质,可设计新的自旋纳米器件。     

Co掺杂对YBa2 Cu3 O7-δ电阻率与塞贝克系数的影响

用固态反应法制备了YBa2Cu3-xCoxO7-δ(x=0.0,0.1,0.2,0.5)样品,研究了Co掺杂对YBa2Cu3O7-δ高温区的电阻率和塞贝克系数的影响。随着Co含量的增加,样品的电阻率和塞贝克系数逐渐增大,从金属性导电转变为p型半导体导电。x=0.2和0.5样品的电导活化能在500K处发生突变,高温区的活化能大于低温区的活化能。通过塞贝克系数与温度的关系,计算出x=0.2和0.5样品的费米能级分别为0.02和0.12 eV。当温度高于650-700K时,氧脱附显著影响样品的电输运性质,导致电阻率和塞贝克系数随温度增加而增大。     

Effects of process parameters on electrical properties of n-type Bi2Te3 prepared by mechanical alloying and spark plasma sintering

n-Type Bi₂Te₃ thermoelectric materials were prepared by spark plasma sintering (SPS) using mechanically alloyed powders. Seebeck coefficient and electrical conductivity of the resultant materials were measured, with emphasis on the effects of sintering process parameters on the electrical properties. The power factor was improved from 1.5 to 1.6 mW/mK² when the SPS pressure was increased from 20 to 50 MPa at 623 K, and was further increased to 2.1 mW/mK² under 50 MPa by raising the SPS temperature from 623 to 673 K. The maximum power factor was obtained for the sample sintered under optimized SPS process parameters, in which the sintering temperature and the sintering pressure are 673 K and 50 MPa, respectively.     

Synthesis, electronic transport and magnetic properties of Zr1−xYxNiSn, (x=0-0.25) solid solutions

The crystal structure of the Zr_1−xY_xNiSn half-Heusler solid solutions is synthesized and their crystal structure is determined. Electrical resistivity and thermoelectric Seebeck coefficient are measured in the 80-380 K temperature range, whereas magnetic susceptibility is measured at 290 K. It is established that substitution of Zr host atoms by Y in the ZrNiSn intermetallic semiconductor is equivalent to doping by acceptor impurities. Self-consistent ab initio calculations, based on the full potential local orbital (FPLO) minimum basis method, are performed to investigate the electronic and thermoelectric properties of these alloys. Spin polarized within the framework of the coherent potential approximation (CPA) are included.     

p-Type thermoelectric properties of the oxygen-deficient perovskite Ca2Fe2O5 in the brownmillerite structure

Brownmillerite calcium ferrite was synthesized in air at 1573 K and thermoelectric properties (direct current electrical conductivity σ, Seebeck coefficient α, thermal conductivity κ, thermal expansion α_L) were measured from 373 to 1050 K in air. Seebeck coefficient was positive over all temperatures indicating conduction by holes, and electrical properties were continuous through the Pnma-Imma phase transition. Based on the thermopower and conductivity activation energies as well as estimated mobility, polaron hopping conduction was found to dominate charge transport. The low electrical conductivity, <1 S/cm, limits the power factor (α²σ), and thus the figure of merit for thermoelectric applications. The thermal conductivity values of ∼2 W/mK and their similarity to Ruddlesden-Popper phase implies the potential of the alternating tetrahedral and octahedral layers to limit phonon propagation through brownmillerite structures. Bulk linear coefficient of thermal expansion (∼14×10⁻⁶ K⁻¹) was calculated from volume data based on high-temperature in situ X-ray powder diffraction, and shows the greatest expansion perpendicular to the alternating layers.     

泽贝克/佩尔捷效应演示实验

应用半导体温差发电模块制作了半导体温差发电演示装置,该装置可直观演示泽贝克效应及佩尔捷效应,同时还具有测量泽贝克系数等功能.