氟掺杂钛酸钡的电子结构和磁性的第一性原理研究

基于密度泛函理论的第一性原理平面波赝势方法,计算了F掺杂立方相BaTiO3的稳定性、电子结构和磁性.结果表明F掺杂BaTiO3体系结构稳定,掺杂体系的磁耦合作用与F原子间距密切相关.当F原子间距为0.6468nm时具有很强的铁磁耦合作用,其磁性机制可归结为未配对的Ti 3d电子自旋极化,且一个F原子替代产生1.0μB磁矩.当F原子间距为0.4933 nm时为反铁磁耦合,而间距大于0.7511 nm时为顺磁态.由于F掺杂立方相的BaTiO3可以获得比较好的铁磁性而且其稳定性很高,故有望在自旋电子器件方面发挥重要的作用.     

Ba7(BO3)3F5晶体结构及热分析

采用高温溶液法从BaCO3,BaF2及H3BO3混合体系中生长出了一种氟硼酸钡晶体,Ba7(BO3)3F5晶体属六方晶系,空间群为P63mc,晶胞参数:a=1.11562(15) nm,c=0.72415(14) nm,Z=2,V=0.7805(2) nm3.Ba7(BO3)3F5晶体结构是由Ba(1)O7F3基团,Ba(2)O4F3基团,Ba(3)O6F4基团和独立的BO3基团相互连接形成的三维空间网络结构.Ba7(BO3)3F5的热分析分析结果表明Ba7(BO3)3F5在1070℃同成份熔化.     

B掺杂BaTiO3的电子结构和磁性的第一性原理研究

利用基于第一性原理的自旋极化密度泛函理论计算了B掺杂BaTiO3的稳定性、电子结构和磁学性质.结果表明B掺杂BaTiO3体系稳定,并表现为铁磁性.B替位掺杂BaTiO3体系的磁性机制可归结为部分B2p电子的自旋极化和B2p/O2p与Ti3d电子的p-d耦合作用,B间隙掺杂BaTiO3体系中磁性源于未配对Ti3d电子的自旋极化.     

Ce掺杂与O空位对锐钛矿相TiO2磁学和光学性能影响的第一性原理研究

基于第一性原理计算,建立了含有不同Ce与O空位配比的锐钛矿TiO2模型.对各个体系的稳定性、磁性、电子结构及吸收光谱进行了计算.结果表明:Ce与近邻O空位间的自旋电子交换是锐钛矿TiO2净磁矩的来源,因此体系的磁性与Ce和O空位的相对位置有关.Ce或O空位浓度增加在费米能级附近形成的施主能级使得带隙宽度进一步减小,因此体系对可见光的吸收系数进一步增加.与局域性更强的Ce-4f电子相比,Ti-3d电子更易受激参与光催化反应,因此Ce掺杂引起的O空位及其浓度是影响锐钛矿TiO2光催化性能的主要因素.     

Na掺杂和空位对ZnO磁性及电子结构的影响

通过第一性原理,对Na掺杂(NaZn)与Zn空位(VZn)及Na掺杂与O空位(VO)共存的ZnO体系的形成能、电子结构及磁性机理进行了研究.结果表明,Na原子与空位(VZn或VO)空间位置最近时,掺杂体系的形成能最低;与诱导VZn相比,Na掺杂在ZnO体系中更易诱导VO,并且过量的Na掺杂必然导致VO的形成.另外,磁性研究发现,Na掺杂与空位(VZn或VO)共存的体系都具有磁性.并且Na掺杂与VZn共存的ZnO体系磁性源于VZn的本征缺陷,而Na掺杂与VO共存的ZnO体系的磁性源于Na原子与VO的电子关联交互作用.     

磁性Fe3O4@TiO2/ZnO的制备及光催化性能研究

通过水热法制备磁性Fe3O4@C纳米微球,分别将TiO2和ZnO负载到微球上得到磁性Fe3O4@TiO2/ZnO催化剂.利用扫描电镜、红外光谱和紫外漫反射光谱表征催化剂的形貌和结构性能.紫外漫反射光谱显示磁性Fe3O4@TiO2/ZnO的吸收带边红移,表明催化剂可以在更高的波长范围内吸收光波,且禁带宽度变大表明光生电子和空穴具有更强的氧化还原能力,因此具有更强的光催化活性.相比于磁性Fe3O4@TiO2,磁性Fe3O4@TiO2/ZnO催化剂对罗丹明B的降解率从65.33;增加到98.11;.循环使用5次后,磁性Fe3O4@TiO2/ZnO催化剂对罗丹明B的降解率仍保持92.05;,说明该催化剂具有易于回收和良好的循环稳定性.     

ZnO掺杂对PVK∶Ir(ppy)3体系发光特性的影响

以无机纳米颗粒ZnO作为电子传输材料,并以不同质量比掺杂到PVK∶ Ir(ppy)3体系作为发光层制成一系列磷光器件,器件结构为:ITO/PVK∶ Ir(ppy)3∶ ZnO(100∶ 1∶ x)/ BCP/Alq3/Al, ZnO的掺杂浓度x分别为0;,1;,2;,5;,10;,研究了它们的电致发光特性.结果表明:合适比例ZnO掺杂可以改善器件的发光特性,ZnO的最佳掺杂量为1;,此时器件的相对发光强度是未掺杂的器件的4倍,器件的启亮电压也由未掺杂时的15.5 V降到了10.5 V.当掺杂浓度较大时,电子传输过多在电极另一侧形成漏电流,没有在发光层内进行电子与空穴有效复合,没有对发光起到作用,导致器件的发光性能下降.     

LaAlO3晶体点缺陷的电子结构和磁性的第一性原理研究

利用密度泛函理论计算了LaAlO3晶体点缺陷的电子结构和磁学性质.结果表明,LaAlO3中La,Al空位缺陷具有铁磁性,O空位缺陷没有磁性.La,Al空位磁性源于体系中所有O原子2p轨道的部分极化.     

溶胶-凝胶法合成3LiMnPO4·Li3V2(PO4)3及其电化学性能研究

以柠檬酸为络合剂,聚乙二醇(PEG)为表面活性剂,偏钒酸铵、乙酸锰、磷酸二氢铵、氢氧化锂为原料,采用溶胶-凝胶法合成了xLiMnPO4·yLi3V2(PO4)3锂离子电池复合正极材料.采用X射线衍射(XRD)、扫描电镜(SEM)对其晶体结构和微观形貌进行表征,结果表明在700℃下烧结15 h合成的3LiMnPO4·Li3V2(PO4)3为结晶良好的两相结构,颗粒粒径相对较小且分布均匀.电化学性能研究表明,3LiMnPO4·Li3V2(PO4)3在室温0.2C倍率下首次充放电容量分别为148.2 mAh/g和141.5 mAh/g,循环50次后放电容量为136.7 mAh/g.     

Mn掺杂BaTiO3多铁性的第一性原理研究

本文基于第一性原理方法,对过渡金属元素Mn掺杂四方相BaTiO3体系进行了系统的研究.通过对掺杂前后的电子结构改变及所引起的磁学性能的分析发现,过渡金属元素Mn的掺入可以使BaTiO3产生较大的铁磁性,这一磁性主要源于Mn离子局域磁矩的贡献,且随着Mn掺杂量的增加,材料体系的磁性增强;同时发现掺杂体系在001方向存在畸变,仍然保持BaTiO3原有的自发极化,即掺杂后体系仍具备铁电性.研究结果表明,进一步优化的Mn掺杂BaTiO3有望成为一种性能优越的新型多铁性材料.     

Structure and lithium ion diffusion in lithium silicate glasses and at their interfaces with lithium lanthanum titanate crystals

Solid state lithium ion electrolytes are important to the development of next generation safer and high power density lithium ion batteries. Lithium containing glasses such as lithium silicate glasses have been widely studied due to their high ionic conductivity. Recently, lithium silicate glasses were introduced in polycrystalline lithium lanthanum titanate (LLT) ceramics as intergranular thin films between the crystalline grains to achieve higher lithium ion conductivities in these solid state electrolytes. In this work, we present investigations of the structure and diffusion behavior of lithium silicate glasses and their interfaces with LLT crystals using molecular dynamics simulations. The short and medium range structures of the lithium silicate glasses were characterized and the ceramic/glass interface models were obtained using MD simulations. Lithium ion diffusion behaviors in the glass and across the glass/ceramic interfaces, as well as the effect of atomic structure on diffusion behaviors, were investigated. It was found that there existed a minor segregation of lithium ions at the glass/crystal interface. The interface lithium ion diffusion energy barrier was found to be dominated by the glass phase.     

Effect of external field on bond energy and activation barrier for surface diffusion

Surface diffusion is one of the most common phenomena during the thin-film growth. The microstructure of the thin film depends on the rate of surface diffusion of the adatoms. In this paper, we theoretically show the effect of external field on surface diffusion barrier using gallium nitride as an example. We show, via density functional calculation, that the desorption energy of surface adsorbed atom and activation barrier for surface diffusion process can be altered by application of external field. Finally, based on the arguments of the electronic effect, we analyze the origin of the effect of the external field and its orientation on desorption energy and activation barrier for surface diffusion.     

CeO2对CaTiO3陶瓷烧结性能以及微观结构的影响

以CaO和TiO2为原料,采用固相反应烧结法合成钛酸钙陶瓷.以CeO2为添加剂,重点研究CeO2掺杂对合成钛酸钙陶瓷烧结性能及微观结构的影响.利用XRD、SEM、EDS等手段对试样的物相组成、显微形貌以及元素分布进行表征.通过X'pert High score Plus软件研究CeO2添加量和煅烧温度对合成钛酸钙的相组成、晶胞参数、缺陷反应的影响.结果表明:随着CeO2加入量的增大,Ce4+与Ti4+及Ce3+与Ca2+之间发生取代,致使钛酸钙的晶体结构发生畸变,晶格常数以及晶胞体积出现了先增大后减小的趋势.CaTiO3结构中取代位置的改变,是造成晶胞体积呈非线性变化趋势的原因.形成的结构缺陷加速了固相烧结反应,钛酸钙晶粒由发育不完全的台阶状转变为规则的多边形.过量的CeO2会抑制晶粒的生长,减小晶粒尺寸.随着煅烧温度的升高,结构中热缺陷浓度增大,促进了钛酸钙的烧结.     

Magnonic excitations versus three‐dimensional structural periodicity in magnetic composites

The study deals with the spin wave spectrum in magnetic macrostructure (composed of two ferromagnetic materials) showing a 3D periodicity; the structure considered consists of spherical ferromagnetic grains disposed in the nodes of a simple cubic crystal lattice and embedded in a matrix with different ferromagnetic properties. It is shown that the magnonic spectrum of this composite structure exhibits frequency regions forbidden for magnon propagation, and the energy gaps are sensitive to the exchange contrast between the constituent materials as well as to the magnetization contrast. The widths of the respective magnonic gaps are studied as functions of parameters characterizing the magnetic structure. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of EuTe islands on SnTe by molecular beam epitaxy

Semiconductor magnetic quantum dots are very promising structures, with novel properties that find multiple applications in spintronic devices. EuTe is a wide gap semiconductor with NaCl structure, and strong magnetic moments S=7/2 at the half filled 4f⁷ electronic levels. On the other hand, SnTe is a narrow gap semiconductor with the same crystal structure and 4% lattice mismatch with EuTe. In this work, we investigate the molecular beam epitaxial growth of EuTe on SnTe after the critical thickness for island formation is surpassed, as a previous step to the growth of organized magnetic quantum dots. The topology and strain state of EuTe islands were studied as a function of growth temperature and EuTe nominal layer thickness. Reflection high energy electron diffraction (RHEED) was used in-situ to monitor surface morphology and strain state. RHEED results were complemented and enriched with atomic force microscopy and grazing incidence X-ray diffraction measurements made at the XRD2 beamline of the Brazilian Synchrotron. EuTe islands of increasing height and diameter are obtained when the EuTe nominal thickness increases, with higher aspect ratio for the islands grown at lower temperatures. As the islands grow, a relaxation toward the EuTe bulk lattice parameter was observed. The relaxation process was partially reverted by the growth of the SnTe cap layer, vital to protect the EuTe islands from oxidation. A simple model is outlined to describe the distortions caused by the EuTe islands on the SnTe buffer and cap layers. The SnTe cap layers formed interesting plateau structures with easily controlled wall height, that could find applications as a template for future nanostructures growth.     

Te溶剂Bridgman法CdMnTe晶体核辐射探测器的制备和表征

碲锰镉(CdMnTe)作为性能优异的室温核辐射探测器材料,可用于环境监测和工业无损检测领域。本文中采用Te溶剂Bridgman法生长In掺杂Cd_0.9Mn_0.1Te晶体,制备成10 mm×10 mm×2 mm大小的室温单平面探测器,研究了该探测器对²⁴¹Am@59.5 keV γ射线源的能谱响应。通过表征红外透过率、电阻率以及探测器能谱响应等参数,综合评定了探测器用CdMnTe晶体的质量、电学和探测器性能。结果表明,晶片的红外透过率均在55%以上,最好可达到60%。采用湿法钝化,100 V偏压下的漏电流由钝化前的9.48 nA降为钝化后的7.90 nA,钝化后的电阻率为2.832×10¹⁰ Ω·cm。在-400 V反向偏压下,CdMnTe探测器对²⁴¹Am@59.5 keV γ射线源的能量分辨率在钝化前后分别为13.53%和12.51%,钝化后的电子迁移率寿命积为1.049×10^-3 cm²/V。研究了探测器的能量分辨率随电压的变化特性,当偏压≤400 V时,探测器的能量分辨率主要由载流子的收集效率决定,而当偏压>400 V时,能量分辨率由漏电流决定。本文研究结果表明,Te溶剂Bridgman法生长的CdMnTe晶体质量较好,电阻率和电子迁移率寿命积满足探测器制备需求。     

Investigation of the ultrasonic wave influence on magnetic ordering in a 20 × [Fe(20 Å)/Cr(12 Å)]/MgO layered structure

A 20 × [Fe(20 Å)/Cr (12 Å)]/MgO structure excited by an ultrasonic wave was investigated by polarized neutron reflectometry. It was found that magnetic domains oscillate and their effective size decreases in weak magnetic fields. In close-to-saturation fields, a magnetic lattice is formed in the layered structure; the interplanar spacings in this lattice change with an increase in the field strength and as a result of the excitation of the structure by an ultrasonic wave.     

Features of the magnetic state of the layered Fe-V nanostructure of the superconductor-ferromagnet type

The magnetic state of the V(39 nm)/20 [V(3 nm)/Fe(3 nm)] nanostructure has been investigated by polarized neutron reflectometry in the temperature range from 1.6 to 30 K in magnetic fields from 0.2 to 15 kOe. The data obtained indicate that the superconductivity of vanadium layers may affect magnetic ordering both over the depth of the structure and in its plane.     

Analysis of the structure of an amorphous sediment obtained upon decomposition of potassium oxofluroniobate in water

An amorphous sediment was prepared by the decomposition of potassium oxofluoroniobate K_{2 ? x} Nb₄O₃(O, F)₃F in water. For this sediment, the atomic radial distribution function was analyzed with the use of a fragment model, which allows one to interpret expanded coordination spheres as being formed by first several strongest diffusion maxima. These spheres carry the most reliable information on the structure. It is shown that the amorphous sediment consists of the randomly packed Nb(O,F)₆-octahedra with interatomic distances close to those observed in the ordered region in the N-Nb₂O₅ structure. During decomposition in water, the initial K_{2 ? x} Nb₄O₃(O, F)₃F phase loses KF-layers, whereas Nb₆ clusters with metal bonds are destroyed.     

Simulation of ion transport in layered cuprate La2SrCu2O6

Oxygen diffusion in layered cuprate La₂SrCu₂O₆ has been simulated by the molecular dynamics method in the temperature range of 300–2500 K. The lattice is found to transform at temperatures above 1550 K; this transformation is accompanied by a change in the pair correlation functions. The abrupt change in the oxygen diffusion coefficient in the range of 1500–1550 K may indicate the presence of a phase transition to the superionic state. The motion of oxygen anions could be traced at the microscopic level. It has been proven for the first time that the La₂SrCu₂O₆ crystal lattice allows, along with displacements of O1 ions within the CuO₂ layer, their migration from the crystallographic positions to the intermediate unoccupied O3 positions. The motion of O2 anions is also fairly complicated: they move not only in their layer over the O2 positions but they also jump to the neighboring layer to occupy the O1 positions. The oxygen diffusion coefficient in layered cuprate La₂SrCu₂O₆ exceeds that in cuprates with perovskite structure and structure of the K₂NiF₄ type (at the same temperatures), which indicates that this material has good prospects for electrodes with mixed ionic-electronic conductivity.