Electronic and thermoelectric properties of Mg_2Ge_xSn-_(1-x)(x=0.25,0.50,0.75) solid solutions by first-principles calculations

The electronic structure and thermoelectric(TE) properties of Mg_2Ge_xSn_(1-x)(x = 0.25, 0.50, 0.75) solid solutions are investigated by first-principles calculations and semi-classical Boltzmann theory. The special quasi-random structure(SQS) is used to model the solid solutions, which can produce reasonable band gaps with respect to experimental results.The n-type solid solutions have an excellent thermoelectric performance with maximum zT values exceeding 2.0, where the combination of low lattice thermal conductivity and high power factor(PF) plays an important role. These values are higher than those of pure Mg_2Sn and Mg_2Ge. The p-type solid solutions are inferior to the n-type ones, mainly due to the much lower PF. The maximum zT value of 0.62 is predicted for p-type Mg_2Ge_(0.25)Sn_(0.75) at 800K. The results suggest that the n-type Mg_2Ge_xSn_(1-x) solid solutions are promising mid-temperature TE materials.     

Au在Hg_(1-x)Cd_xTe材料中p型掺杂的第一性原理研究

利用基于密度泛函理论的第一性原理方法,研究了Au在Hg1-xCdxTe材料中原位取代Hg的p型掺杂对材料各组分电子结构的影响.通过态密度、形成能和动力学能级的理论分析,系统讨论了分子外延(MBE)和液相外延(LPE)两种生长条件下,Au杂质p型掺杂的稳定性和有效性.结果表明Au原位取代Hg后,Hg1-xCdxTe材料一方面表现出相当好的稳定性,另一方面形成浅杂质能级,是一种有效的p型掺杂剂.讨论了生长气氛对Au在Hg1-xCdxTe(MCT)中p型掺杂效率的影响,发现在MBE生长条件下,富阳离子气氛的所有组分,富Te气氛的0.75x≤1组分以及LPE生长富阳离子条件下的0.75≤x≤1组分的MCT材料中均存在Au杂质的自补偿效应,不适合进行Au的p型掺杂.     

Mg-Al-Ca合金中三元Laves相的稳定性和电子结构

采用基于密度泛函理论的第一性原理方法,应用VASP (Vienna Ab-initio Simulation Package) 计算软件,研究了Mg-Al-Ca合金中三元Laves相,即Ca(Mg1-x,Alx)2和Al2(Ca1-x,Mgx) (x=0, 0.25, 0.50, 0.75, 1)在不同形态结构(C14, C15和C36)下的相稳定性及电子结构。计算所得的晶格常数和实验值吻合很好,形成能和相关能的计算用来研究三元Laves相的合金化能力和稳定性,结果表明：C14-Ca(Mg0.25,Al0.75)2具有很好的合金化能力,而C15- CaAl2具有很好的结构稳定性。态密度和电荷密度的计算用来研究Mg-Al-Ca合金中三元Laves相稳定性的内在微观机制。     

Random alloy-like local structure of Fe(Se, S)(1-x)Te(x) superconductors revealed by extended x-ray absorption fine structure

The local structure of Fe(Se, S)(1-x)Te(x) ternary (11-type) chalcogenides has been studied by temperature dependent Fe K-edge extended x-ray absorption fine structure measurements. We find that the Fe-Se and Fe-Te distances in ternary FeSe(1-x)Te(x) are closer to the respective distances in the binary systems, revealing significant divergence of the local structure from the average one. The mean square relative displacements show a systematic change with Te content, consistent with bond relaxation in the inhomogeneous ternary phases. Also, the Fe-Te and Fe-S distances in the FeS(0.2)Te(0.8) ternary system are found to be different in the crystallographically homogeneous structure. The observed features are characteristic of ternary random alloys, suggesting that a proper consideration should be given to the atomic distribution for describing the complex electronic structure of these multi-band Fe-based chalcogenides.     

Co_(2~-)基Heusler合金Co_2FeAl_(1–x)Si_x(x=0.25,x=0.5,x=0.75)的结构、电子结构及热电特性的第一性原理研究

运用基于密度泛函理论的第一性原理方法,对Co_2FeAl_(1–x)Si_x(x=0.25, 0.5, 0.75)系列Heusler合金的电子结构、四方畸变、弹性常数,声子谱以及热电特性进行了计算研究.结果显示, Co_2FeAl_(1–x)Si_x系列合金的电子结构均为半金属特性,向下自旋态(半导体性)均呈现良好的热电特性,并且随着硅原子浓度的增加功率因子随之增加.计算的声子谱不存在虚频,均满足动力学稳定性条件,弹性常数均满足玻恩稳定性条件,机械稳定性均良好.随着晶格常数c/a的比值变化,体系的能量最低点均出现在c/a=1处,即结构稳定性不随畸变度c/a的变化而变化,说明不存在马氏体相变.此系列合金薄膜的电子结构呈现较高的自旋极化率,在替代浓度x=0.75时自旋极化率达到100%,且当x=0.75时薄膜在畸变度c/a=1.2时存在马氏体相变.随着晶格畸变度的改变,总磁矩也发生变化,且主要由Fe和Co两种过渡金属原子的磁矩变化所决定.     

Nb掺杂导致LaMnO_3绝缘体-金属转变的第一性原理研究

采用基于密度泛函理论(DFT)的第一性原理计算,系统研究了Nb掺杂LaMn_(1-x)Nb_xO_3(x=0,0. 25,0. 5,0. 75)的结构和电磁性质.计算结果表明,所有的LaMn_(1-x)Nb_xO_3都稳定在正交结构. LaMn_(1-x)Nb_xO_3当x 0. 5时为A型反铁磁绝缘体,在x=0. 5和0. 75时为G型反铁磁金属.随着Nb掺杂量增加,当x=0. 5时掺杂电子占据导带的底部,系统产生绝缘体-金属转变.这意味着LaMn_(1-x)Nb_xO_3在电子器件上可能有重要的应用.另外,LaMn_(1-x)Nb_xO_3在x=0. 25和0. 75时出现了自旋玻璃行为.     

Fine grains ceramics of PIN-PT, PIN-PMN-PT and PMN-PT systems: drift of the dielectric constant under high electric field

Lead-based ferroelectric ceramics with (1-x)Pb(B1 B2)O3-xPbTiO3 formula have emerged as a group of promising materials for various applications like ultrasonic sonars or medical imaging transducers. (1-x)PMN-xPT, (1-x)PIN-xPT and ternary solutions xPIN-yPMN-zPT ceramics are synthesised using the solid state reaction method. Our objective is to achieve higher structural transition temperatures than those of PMN-PT ceramics with as good dielectric, piezoelectric and electromechanical properties. Ceramics capacitance and loss tangent are measured when the ac field of measurement increases up to E=500 V/mm. Behaviours of these materials under ac field are related to their coercive field and Curie temperature.     

Concentration-dependent crystal structure,elastic constants and electronic structure of Zr x Ti1−x alloys under high pressure

The physical properties of ZrxTi1-x（x=0.0, 0.33, 0.5, 0.67, 0.75 and 1.00） alloys were sinmlated by virtual crystal approximation （VCA） methods which is generally used for disordered solid solutions modeling. The elastic constant, electronic structure and thermal Equation of state （EOS） of disor- dered ZrxTi1-x alloys under pressure are investigated by plane-wave pseudo-potentia1 method. Our simulations reveal increasement of variations of the calculated equilibrium volumes and decrease- ment of Bulk modulus as a function of the alloy compositions. Lattice parameters a and c of alloys with differentZr concentrations decrease linearly with pressure increasing, but the c/avalues are increasing as pressure increases, indicating no phase transitions under pressure from 0 GPa to 100 GPa. The elastic constants and the Bulk modulus to the Shear modulus ratios （B/G） indicate good ductility of Zr, Zr0.33 Ti0.67 Zr0.5Ti0.5, Zr0.75Ti0.25 and Ti, but the Zr0.67Ti0.33 alloy is brittle under 0 K and 0 GPa. The metallic behavior of these alloys was also proved by analyzing partial and total DOS.     

First-principles investigation of structural,elastic, electronic and magnetic properties of Be0.75Co0.25Y (YS,Se and Te) compounds

We have theoretically investigated the structural, elastic, electronic and magnetic properties of Be_0.75Co_0.25Y (YS, Se and Te) alloys, in their zinc-blend phase. This study is carried out by using the full-potential augmented plane wave plus local orbitals method within the density functional theory. Foe computing the exchange-correlation potential, the Wu and Cohen generalized gradient approximation is employed to calculate structural and elastic properties whereas the modified Becke and Johnson potential local density approximation is utilized to examine electronic and magnetic properties. By minimizing the total energy in paramagnetic (PM) and ferromagnetic (FM) phases, it is found the studied compounds are stable in FM structure. The mechanical behavior of the studied compounds is reported with the calculation of shear modulus, Young's modulus, and Poisson's ratio provides. Such mechanical aspects might be useful for the experimentalists to study the mechanical properties upon alloying BeY compounds with Co. We also compute electronic structures, density of states (total and partial), pd-exchange splitting and magnetic moments. Moreover, bond nature is studied by estimating the spin polarized charge densities of Be_0.75Co_0.25Y (YS, Se and Te).     

Density functional theory investigation on lattice dynamics,elastic properties and origin of vanished magnetism in Heusler compounds CoMnVZ (Z= Al,Ga)

The lattice dynamics, elastic properties and the origin of vanished magnetism in equiatomic quaternary Heusler compounds CoMnVZ (Z=Al, Ga) are investigated by first principle calculations in this work. Due to the similar constituent atoms in CoMnVAl and CoMnVGa compounds, they are both stable in LiMgPdSn-type structure with comparable lattice size, phonon dispersions and electronic structures. Comparatively, we find that CoMnVAl is more structurally stable than CoMnVGa. Meanwhile, the increased covalent bonding component in CoMnVAl enhances its mechanical strength and Vickers hardness, which leads to better comprehensive mechanical properties than those of CoMnVGa. Practically and importantly, structural and chemical compatibilities at the interface make non-magnetic semiconductor CoMnVAl and magnetic topological semimetals Co₂MnAl/Ga more suitable to be grown in heterostructures. Owing to atomic preferential occupation in CoMnVAl/Ga, the localized atoms Mn occupy C (0.5, 0.5, 0.5) Wyckoff site rather than B (0.25, 0.25, 0.25) and D (0.75, 0.75, 0.75) Wyckoff sites in LiMgPdSn-type structure, which results in symmetric band filling and consequently drives them to be non-magnetic. Correspondingly, by tuning localized atoms Mn to occupy B (0.25, 0.25, 0.25) or/and D (0.75, 0.75, 0.75) Wyckoff sites in off-stoichiometric Co-Mn-V-Al/Ga compounds and keeping the total valence electrons as 24, newly compensated ferrimagnetic compounds are theoretically achieved. We hope that our work will provide more choices for spintronic applications.     

Cryopreservation of Quercus robur L. embryogenic calli

Embryogenic calli of pedunculate oak (Quercus robur L.) were cryopreserved using direct immersion in liquid nitrogen. The pretreatment consisted of culture on a solid medium with increasing sucrose concentrations (0.25 M for 1 day, 0.5 M for 1 day, 0.75 M for 2 days, and 1.0 M for 3 days), followed by air desiccation of embryogenic calli to 17.3 percent (fresh weight basis). This method of cryoprotection was compared to a liquid cryoprotection treatment using high concentrations of sucrose solutions, followed by glycerol solutions. Regrowth of frozen tissue pretreated on a solid medium was significantly higher than those pretreated in the liquid solutions.     

CexZr1-xO2固溶体储氧性能与结构的关系

采用加热回流技术制备了系列CexZr1-xO2(0.25≤x≤1)固溶体,通过N2物理吸附、XRD、Raman光谱、UV-Vis漫反射光谱表征了不同铈锆组成的铈锆复合氧化物结构对储氧性能的影响.结果表明,在铈锆组成比不同的样品之间,结构性质相差较大,随着载体中ZrO2 mol%的增加,载体结构从相对的有序经无序再回到相对的有序.Ce0.4Zr0.6O2样品具有最高的储氧性能,而Ce0.25Zr0.75O2样品具有较高的热稳定性.     

Topological surface states in lead-based ternary telluride Pb(Bi(1-x)Sb(x))2Te4

We have performed angle-resolved photoemission spectroscopy on Pb(Bi(1-x)Sb(x))2Te4, which is a member of lead-based ternary tellurides and has been theoretically proposed as a candidate for a new class of three-dimensional topological insulators. In PbBi2Te4, we found a topological surface state with a hexagonally deformed Dirac-cone band dispersion, indicating that this material is a strong topological insulator with a single topological surface state at the Brillouin-zone center. Partial replacement of Bi with Sb causes a marked change in the Dirac carrier concentration, leading to the sign change of Dirac carriers from n type to p type. The Pb(Bi(1-x)Sb(x))2Te4 system with tunable Dirac carriers thus provides a new platform for investigating exotic topological phenomena.     

纳米Ce1-x(Fe0.5La0.5)xO2-δ固溶体的水热合成及光谱分析

采用水热方法合成Ce1-x(Fe0.5 La0.5)xO2-δ固溶体.利用X射线衍射技术(X-ray diffraction technique,XRD)表征样品的相结构,并对固溶体的晶胞参数进行拟合,通过紫外可见漫反射光谱(UV-Vis diffraction spectrum)及拉曼光谱(Raman spectru...     

Luminescence of CdMgTe with CdMnTe ultrathin nanolayers

The luminescence spectra of Cd_0.75Mn_0.25Te/Cd_{1 ? y} Mg _y Te superlattices with narrow-band-gap Cd_0.75Mn_0.25Te nanolayers having nominal thicknesses of 0.5, 1.5, and 3.0 monolayers (MLs) exhibit exciton emission bands of Cd_{1 ? y} Mg _y Te barriers and nanolayers, as well as intracenter luminescence of Mn²⁺ ions. For all samples, the luminescence spectra of Cd_0.75Mn_0.25Te nanolayers consist of two bands. From analyzing the dependences of the luminescence intensity on the nanolayer thickness and temperature, these bands are assigned to excitons localized at two-and zero-dimensional potentials. The intracenter emission of Mn²⁺ in 3.0-ML-thick Cd_0.75Mn_0.25Te clearly reveals excitation migration.     

BiOCl1-xIx及BiOBr1-xIx固体溶液的制备、表征及性能研究

在太阳光照射下,利用半导体光催化去除污染物是最绿色、有效的方法之一,其核心问题是获得高效光催化剂。目前研究最多的光催化剂是TiO₂和ZnO等,但由于其禁带宽度大故不能充分利用太阳光,从而限制了其实际使用。除了对TiO₂等改性以改进其可见光催化活性外,开发其他材料作为光催化剂也是解决的重要途径。铋基化合物半导体由于原材料丰富、种类多、太阳光响应性好及优良的光催化活性而成为重要研究对象。其中卤氧铋系化合物[BiOX, X=Cl, Br, I]由于层状结构特点而具有良好的光催化活性,但单独使用时光催化效率较低。研究表明,BiOX间能通过形成固体溶液(即彼此呈分子分散的固体混合物)进一步改善其光催化降解污染物的能力。本文利用低温湿化学法,以Bi₂O₃为铋源,在醋酸溶液中加入一定比例的KI/KBr或KI/KCl水溶液,室温下反应0.5 h,分别得到片状结构的BiOCl_1-xI_x和BiOBr_1-xI_x固体溶液。X射线衍射(X-ray diffraction, XRD)分析结果表明,所合成的BiOCl_1-xI_x和BiOBr_1-xI_x样品结晶性良好,且能在x=0～1的范围内形成固体溶液。透射电子显微镜(transmission electron microscope, TEM)测得所制备的固体溶液呈不规则的薄片状。X射线光电子能谱(X-ray photoelectron spectroscopy, XPS)测试进一步证明了其表面元素组成及化学状态。紫外-可见漫反射光谱(diffuse reflectance spectroscopy, DRS)分析表明,随着碘元素含量的增加,固体溶液的吸收边界发生红移、禁带宽度减小,故可见光吸收能力增强、产生的载流子数目将增加。在可见光激发下对甲基橙(methyl orange, MO)降解的光催化性能研究表明,BiOCl_0.25I_0.75及BiOBr_0.25I_0.75拥有最高的光催化活性。循环实验表明,BiOCl_0.25I_0.75及BiOBr_0.25I_0.75都具有较高稳定性。光催化机理研究发现,这些卤氧铋样品光催化降解MO过程中的活性物种主要为空穴和超氧离子自由基。结合其能带结构,认为固体溶液的形成不但增加了可见光吸收能力,而且调变了其能带结构,相对于BiOI而言,固体溶液的形成降低了价带电位,提高了导带电位,因而增强了光生电子的还原能力及空穴的氧化能力,故催化性能提高。该工作的创新之处在于：采用的固体溶液制备方法,避免了高温水热法或加入表面活性剂等,而且所制备的BiOCl_1-xI_x和BiOBr_1-xI_x固体溶液,尤其是BiOCl_0.25I_0.75和BiOBr_0.25I_0.75,在可见光激发下对MO具有良好的降解能力,且催化剂的重复使用及稳定性良好,有望在环境治理中得到应用。     

几种三元过渡金属碳化物弹性及电子结构的第一性原理研究

基于密度泛函理论平面波方法研究了六方WC型Re_xW_1－xC(x=1, 0.25, 0.75, 0),Re_0.5Os_0.5C和Os_0.5W_0.5C的晶体结构、弹性和电子结构性质.研究发现Re_0.25W_0.75C晶体具有优异的弹性性能及稳定性,其剪切模量(312 GPa)超过了所有其他实验合成和     

Structural properties of Pb2MnW(1-x)Re(x)O6 double perovskites

Pb2MnW(1-x)Re(x)O6 samples have been synthesized and their structure determined by powder x-ray diffraction. These samples undergo a first order structural phase transition between 413 and 445 K depending on the composition. Above this temperature, the samples are cubic. Below the transition temperature, solid solutions are found for x ≤ 0.2 and x ≥ 0.5. The W-rich samples adopt an orthorhombic cell whereas the Re-rich compounds are monoclinic. In the intermediate region, 0.2 < x < 0.5, both phases coexist. X-ray absorption spectra did not reveal significant changes in the local structure for Pb, Mn or Re atoms across the structural phase transition. All the atoms exhibit distorted environments in the whole series. In the case of Pb and W(Re) atoms, the local distortion remains in the high temperature phase. Samples with x ≤ 0.2 also show a sharp discontinuity in the dielectric permittivity at the phase transition temperature indicating the presence of a concomitant electrical ordering in the bulk grains. Such an anomaly in the dielectric constant is not observed for the x ≥ 0.5 samples, compatible with the lack of dipole ordering for this composition range. The different electrical behaviours also explain the differences in the entropy content for the two types of transition.