单相Na0.5Bi0.5Ti1-xMnxO3陶瓷中的多铁性

溶胶凝胶法制备了Na0.5Bi0.5Ti1-xMnxO3(x=0,0.02,0.04)陶瓷样品,X射线衍射(XRD)分析表明陶瓷样品均形成了单一的钙钛矿(ABO3)型结构且没有杂质相的形成.随着Mn含量的增加,XRD峰向高角度方向移动,表明Mn离子进入Na0.5Bi0.5TiO3晶格.掺杂样品均表现出室温铁磁性和铁电性.磁测量表明样品中存在复杂的磁相互作用,包括铁磁,反铁磁和顺磁相互作用.以上结果表明,通过Mn的掺杂可以使铁电材料Na0.5Bi0.5TiO3转变为多铁材料.     

Bi2Te3 基花状纳米片粉体的制备及热电性能研究

本文通过选用不同乙二胺四乙酸(EDTA) 的用量采用水热法制备出了具有花状纳米片形貌的碲化铋(Bi2Te3 ) 纳米粉体, 研究了不同 EDTA 的用量对 Bi2Te3 纳米粉体花状纳米片形貌的影响, 结果表明 EDTA 的用量对粉体的成相和形貌有很大的影响. EDTA 用量为0.2 g 是最佳值, 有助于形成纯相的 Bi2Te3 花状纳米片. 并以 Y元素掺杂为例, 研究了 EDTA 用量对元素掺杂 Bi2Te3 纳米粉体花状形貌的影响, 研究发现元素掺杂后对 Bi2Te3粉体的微观形貌有一定的影响. 为了保持元素掺杂 Bi2Te3 纳米粉体的花状形貌,EDTA 合适的用量至关重要. 以Y0 .2Bi1 .8Te3 为例, 研究了 EDTA 用量对样品的热电性能的影响. 结果表明, 花状纳米片形貌有利于在降低样品电阻率的同时有效降低样品的热导率, 从而大大增加了样品的ZT 值.     

纳米TiO2的表面能态及光生电子-空穴对复合过程的研究

以液相法制备了水溶态纳米TiO2,并通过X射线衍射(XRD)、X射线光电子能谱(XPS)和傅里叶红外光谱仪(FTIR)对纳米TiO2的结构和组成作了细致分析.并对其紫外-可见光谱(UY-Vis spectrum)和荧光发光光谱(PL spectrum)进行了分析.结果发现纳米TiO2呈现较好的锐钛矿型,平均粒径为5 nm.水溶态纳米TiO2由于吸附而在表面形成了Ti-OH和Ti-H2O的表面态,其能级位于其价带以上约0.6和0.54eV;500℃热处理后样品的表面吸附水基本消失,但OH-仍然存在,同时在纳米TiO2晶格中出现了氧空位,其能级位于价带以上3.13 eV.对于水溶态纳米TiO2,表面复合是电子-空穴对的主要复合过程;热处理后的样品,由于表面态遭到破坏,粒子半径变大,直接复合成为电子-空穴对的主要复合过程,同时还伴随有通过氧空位的间接复合和通过Ti-OH的表面复合.     

Bi2Sr2CaCu2-xSnxO8+δ系列超导体的XRD和XPS研究

实验研究了Bi2 Sr2 CaCu2 -xSnxO8 δ的X射线衍射 (XRD)和光电子能谱 (XPS) .实验发现随着掺杂 (Sn)量的增加 ,晶格参数a和c都有所变化 ,O1s和Cu2 p芯能级谱也发生了变化 .实验结果表明 :在低掺杂量时 ,Sn主要呈二价态 ;而在高掺杂浓度时呈四价态 ;掺Sn对超导电性的影响与其他元素的掺杂不同 .这些实验结果支持化学环境在高温超导样品的电子结构中起着重要作用的结论 .     

Bi_(3.15)Nd_(0.15)Ti_3O_(12)纳米棒的拉曼和紫外吸收光谱研究

以Bi(NO3)3.5H2O,Nd(NO3)3.6H2O和Ti(OC4H9)4为原料,加入聚乙烯醇(PVA-124),采用水热法在200℃经48 h合成了铋层状钙钛矿结构掺钕钛酸铋(Bi3.15Nd0.85Ti3O12,BNdT)纳米棒,纳米棒直径约10~200 nm,长度达十几微米。利用Raman散射研究了掺钕对钛酸铋晶格结构的影响。掺钕钛酸铋和钛酸铋的Raman光谱表明,Nd取代了类钙钛矿层中A位的Bi,掺Nd改善了BTO的对称性和减小了TiO6八面体的畸变。利用UV-vis光谱研究了BNdT纳米棒的光吸收特性,BNdT纳米棒存在A(400 nm),B(275 nm),C(210 nm),D(196 nm)四个吸收带,分别对应于电子从Bi3+的基态1S0到激发态3P1,3P2,1P1的跃迁和电子从阴离子团TiO6八面体到带正电的Bi3+离子的跃迁。BNdT的带隙为4.3 eV,大的带隙归因于纳米结构的量子尺寸效应。     

(Bi1-x Agx)2(Te1-ySey)3粉体的机械合金化制备及其放电等离子烧结体的热电输运特性

采用机械合金化制备了n型(Bi1-x Agx)2(Te1-y Sey)3合金粉体,对其进行XRD分析表明Bi,Te,Ag,Se单质粉末,经2 h球磨后实现了合金化;SEM分析表明随着机械合金化时间延长粉体颗粒变得均匀、细小,颗粒尺寸在微米至哑微米数量级.采用放电等离子烧结制备了块体样品,研究了合金成分和球磨时间对热电件能的影响.结果表明材料的热电性能与掺杂元素有密切关系.Ag有利于提高功率因子和降低晶格热导率,球磨10 h的(Bi0.99Ag0.01)2(Te0.96Se0.04)3合金粉末的烧结块体具有最大的功率因子和最低的晶格热导率,并在323 K取得最高ZT值0.52.     

纳米晶硅的掺杂及表面改性研究(英文)

采用基于密度泛函理论的第一性原理方法(DMOL3程序),在广义梯度近似(GGA)下,计算了硅纳米晶(Si75H76)在B和P掺杂和乙基(—CH2CH3)、异丙基(—CH(CH3)2)表面改性等情形下态密度、结合能及能隙的变化。结果表明:掺杂对体系的禁带宽度(约3.12eV)几乎没有影响,但会引入带隙态;三配位的B掺杂,在禁带中靠近导带约0.8eV位置引入带隙态,三配位的P掺杂在禁带中靠近价带0.2eV位置引入带隙态;四配位的B掺杂,在禁带中靠近价带约0.4eV位置引入带隙态,四配位的P掺杂在禁带中靠近导带约1.1eV位置引入带隙态;且同等掺杂四配位时体系能量要低于三配位;适当的乙基或异丙基表面覆盖可以降低体系的总能量,且表面覆盖程度越高体系能量越低,但在表面嫁接有机基团过多将导致过高位阻,计算时系统不能收敛。     

熔体旋甩法合成n型(Bi_(0.85)Sb_(0.15))_2(Te_(1-x)Se_x)_3化合物的微结构及热电性能

采用熔体旋甩结合放电等离子烧结(MS-SPS)技术制备了单相n型四元(Bi0.85Sb0.15)2(Te1-xSex)3(x=0.15,0.17,0.19,0.21)化合物,并对所得样品的微结构和热电传输性能进行了系统研究.样品自由断裂面的场发射扫描电子显微镜及抛光面的背散射电子成分分析表明:块体材料晶粒细小,晶粒排列紧密,成分分布均匀且相结构单一,样品中存在大量10—100nm的层状结构.随着Se含量x的增加,样品的电导率和热导率逐渐增加,而Seebeck系数逐渐降低.相比商业应用的区熔材料,MS-SPS方法合成的高Se组成的样品均在425K后表现出更高的ZT值,其中(Bi0.85Sb0.15)2(Te0.83Se0.17)3样品具有最高的ZT值,在360K可达到0.96,并在320—500K均保持较高的ZT值,500K时其ZT值相比区熔材料提高了48%.此外,通过调节Se的含量,可以有效地调控材料的ZT峰值出现的温度段,这对多级或梯度热电器件的制备具有重要意义.     

Fe、Ni共掺杂ZnO基稀磁半导体光学性能与铁磁性研究

采用水热法成功制备了不同掺杂浓度的Zn1-2x Fe x Ni x O(x=0,0.025,0.05,0.1)稀磁半导体材料,利用X射线衍射(XRD)、透射电子显微镜(TEM)和X射线能量色散分析仪(XEDS)对样品进行表征,并结合拉曼(Raman)光谱、光致发光光谱(PL)和振动样品磁强计(VSM)研究样品的光学性能和磁学性能。结果表明,水热法制备的样品具有结晶性良好的纤锌矿结构,没有杂峰出现,形貌为纳米棒状结构,分散性良好。Fe2+、Ni2+是以替代的形式进入ZnO晶格中,Fe和Ni的掺杂使得晶体中的缺陷和应力增加,拉曼光谱峰位发生红移,光致发光光谱发生猝灭现象。另外,共掺杂样品在室温条件下存在明显的铁磁性,饱和磁化强度随着掺杂量的增加而增强。     

V族元素掺杂的单层二维铁电α-In2Se3中的带隙异常增大现象

基于第一性原理密度泛函理论计算, 我们探索了 V 族元素(P,As 和Sb) 掺杂的单层二维铁电α-In2Se3 的电子结构. 由于本征的α-In2Se3 中存在两个不等价的In 原子层,V 族元素掺杂在不同的In 原子层会表现出不同的能带结构, 对于带隙变化尤为明显. 当掺杂元素位于α-In2Se3 的四面体配位的In 原子层时, 其带隙相比于本征的单层α-In2Se3 的带隙明显增大, 这与通常半导体或绝缘体中杂质掺杂的物理图像相反. 利用α-In2Se3 的铁电特性, V族元素掺杂的单层α-In2Se3 的带隙可以通过施加外电场翻转α-In2Se3 电极化的方向来调控. 这项工作为在二维材料中构建具有不同电子性质的非易失双态提供了一种实际有效的方法.     

Nonlinear optical probe of tunable surface electrons on a topological insulator

We use ultrafast laser pulses to experimentally demonstrate that the second-order optical response of bulk single crystals of the topological insulator Bi(2)Se(3) is sensitive to its surface electrons. By performing surface doping dependence measurements as a function of photon polarization and sample orientation we show that second harmonic generation can simultaneously probe both the surface crystalline structure and the surface charge of Bi(2)Se(3). Furthermore, we find that second harmonic generation using circularly polarized photons reveals the time-reversal symmetry properties of the system and is surprisingly robust against surface charging, which makes it a promising tool for spectroscopic studies of topological surfaces and buried interfaces.     

STUDY OF DOPING EFFECT ON THE Bi2Sr2Ca2Cu3Oy SUPERCONDUCTOR

We have systematically investigated the doping effect on the Bi₂Sr₂Ca₂Cu₃O_y superconductive material. After entering into the crystal lattice, Pb and/or Sb atoms cause not only variations of the temperature condition during the sample preparation process, but also variations of structures and superconductivity. By analyzing the experimental results, we have come to the conclusion that the Pb and/or Sb atoms enter into the Bi-O planes, preferably occupy the sites of Bi ions, regulate the crystal structures and the distribution of oxygen ions in Bi-O planes and nearby lattice sites, thus benefiting the formation of the high-T_c phase and improving the superconductivity.     

高压烧结制备Tb掺杂n型(Bi1–xTbx)2(Te0.9Se0.1)3合金及其微结构和热电性能

采用高压烧结技术制备了稀土元素Tb掺杂的n型Bi2Te2.7Se0.3基纳米晶块体热电材料.将高压烧结成型的样品于633 K真空退火36 h.研究了Tb掺杂量对样品的晶体结构和热电性能的影响.结果表明,高压烧结制备的样品为纳米结构, Tb掺杂使样品的晶胞体积变大,功率因子增大,热导率降低,从而使ZT值提高.Tb掺杂量为x=0.004是最优的掺杂量,该掺杂量的高压烧结样品经退火处理后,于373 K时ZT值达到最大为0.99,并且在323-473 K范围内, ZT值均大于0.8,这对用于温差发电领域具有重要意义.     

STUDY OF DOPING EFFECT ON THE Bi2Sr2Ca2Cu3Oy SUPERCONDUCTOR

We have systematically investigated the doping effect on the Bi₂Sr₂Ca₂Cu₃O_y superconductive material. After entering into the crystal lattice, Pb and/or Sb atoms cause not only variations of the temperature condition during the sample preparation process, but also variations of structures and superconductivity. By analyzing the experimental results, we have come to the conclusion that the Pb and/or Sb atoms enter into the Bi-O planes, preferably occupy the sites of Bi ions, regulate the crystal structures and the distribution of oxygen ions in Bi-O planes and nearby lattice sites, thus benefiting the formation of the high-T_c phase and improving the superconductivity.     

First-principles calculations of nitrogen-doped antimony triselenide: A prospective material for solar cells and infrared optoelectronic devices

This study is focused on calculation of the electronic structure and optical properties of non-metal doped Sb2Se3 using the first-principles method. One and two N atoms are introduced to Sb and Se sites in a Sb₂Se₃ crystal. When one and two N atoms are introduced into the Sb₂Se₃ lattice at Sb sites, the electronic structure shows that the doping significantly modifies the bandgap of Sb₂Se₃ from 1.11 eV to 0.787 and 0.685 eV, respectively. When N atoms are introduced to Se sites, the material shows a metallic behavior. The static dielectric constants ε1(0) for Sb₁₆Se₂₄, Sb₁₅N₁Se₂₄, Sb₁₄N₂Se₂₄, Sb₁₆Se₂₃N₁, and Sb₁₆Se₂₂N₂ are 14.84, 15.54, 15.02, 18.9, and 39.29, respectively. The calculated values of the refractive index n(0) for Sb₁₆Se₂₄, Sb₁₅N₁Se₂₄, Sb₁₄N₂Se₂₄, Sb₁₆Se₂₃N₁, and Sb₁₆Se₂₂N₂ are 3.83, 3.92, 3.86, 4.33, and 6.21, respectively. The optical absorbance and optical conductivity curves of the crystal for N-doping at Sb sites show a significant redshift towards the short-wave infrared spectral region as compared to N-doping at Se sites. The modulation of the static refractive index and static dielectric constant is mainly dependent on the doping level. The optical properties and bandgap narrowing effect suggest that the N-doped Sb₂Se₃is a promising new semiconductor and can be a replacement for GaSb due to its very similar bandgap and low cost.     

Pr含量对Bi_5Fe_(0.5)Co_(0.5)Ti_3O_(15)室温多铁性的影响

采用改良的固相烧结工艺制备了Bi5-xPrxFe0.5Co0.5Ti3O15(BPFCT-x,x=0.25,0.50,0.75,0.80)陶瓷样品.X射线衍射结构分析表明:镨(Pr)含量对样品微观结构产生了影响,但所有样品均为层状钙钛矿结构;BPFCT-x样品的剩余极化强度(2Pr)随着掺杂量的增加呈现出先增大后减小的变化趋势,当Pr含量为0.75时,样品的2Pr达到最大值,为6.43μC/cm2.样品的磁性与铁电性能具有相同的变化规律,室温下样品的剩余磁化强度(2Mr)也呈现出先增大后减小的趋势,并且也在x=0.75时达到最大为0.097 emu/g.随着Pr掺杂量增大,样品的室温下铁电和铁磁性能得到明显改善,并且当掺杂量为0.75时,样品室温多铁性最好.Pr掺杂降低了样品中的缺陷浓度,从而提高了样品铁电畴动性,这有助于提高样品铁电性能.而样品铁磁性能的改善可能与Pr对样品晶格畸变产生的影响有关.     

Structure Sensitive Reaction Channels of Molecular Hydrogen on Silicon Surfaces

The ability of the Si(001) surface to adsorb H2 molecules dissociatively increases by orders of magnitude when appropriate surface dangling bonds are terminated by H atoms. Through molecular beam techniques the energy dependent sticking probability at different adsorption sites on H-precovered and stepped surfaces is measured to obtain information about the barriers to adsorption, which decrease systematically with an increase in coadsorbed H atoms. With the help of density functional calculations for interdimer adsorption pathways, this effect is traced back to the electronic structure of the different adsorption sites and its interplay with local lattice distortions.     

太阳电池用YVO_4∶Eu~(3+)下转换材料的掺杂改性研究

为进一步提高YVO_4材料的下转换发光性能,在改进后的溶胶-凝胶法制备的YVO_4∶Eu~(3+)中,通过掺入Bi~(3+)来拓宽其在紫外波段的光谱吸收并提高其发光强度,通过掺入P~(5+)达到以PO_4~(3-)部分取代VO_4~(3-)来改善YVO_4∶Eu~(3+)的光输出稳定性及温度猝灭特性的目的。研究表明,掺入的Bi~(3+)和P~(5+)可成功取代YVO_4晶格中的Y~(3+)和V~(5+)。当Bi~(3+)掺入量较少时,样品仍然为四方晶系,Bi~(3+)较好地取代了Y~(3+)的晶格位置,形成单相的晶体结构。而在掺入少量的P~(5+)之后,YVO_4与YPO_4之间形成了均匀的固溶体。在350 nm激发光源作用下,当Bi~(3+)和P5+掺杂摩尔分数分别为0.04和0.10时,发光强度达到最大,特别是YV0.90P0.10O4∶0.05Eu~(3+)在619 nm处的发光强度要比YVO_4∶0.05Eu~(3+)的发光强度增大1.9倍。     

Doping Mn into(Li_(1-x)Fe_x)OHFe_(1-y)Se superconducting crystals via ion-exchange and ion-release/introduction syntheses

We report the success in introducing Mn into(Li_(1-_x)Fe_x)OHFe_(1-y) Se superconducting crystals by applying two different hydrothermal routes, ion e_xchange(1-step) and ion release/introduction(2-step). The micro-region _x-ray diffraction and energy dispersive _x-ray spectroscopy analyses indicate that Mn has been doped into the lattice, and its content in the 1-step fabricated sample is higher than that in the 2-step one. Magnetic susceptibility and electric transport properties reveal that Mn doping influences little on the superconducting transition, regardless of 1-step or 2-step routes. By contrast, the characteristic temperature T*, at which the negative Hall coefficient reaches its minimum, is significantly reduced by Mn doping.This implies that the hole carriers contribution is obviously modified, and hence the hole band might have no direct relationship with the superconductivity in(Li_(1-_x)Fe_x)OHFe_(1-y) Se superconductors. Our present hydrothermal methods of ion e_xchange and ion release/introduction provide an efficient way for elements substitution/doping into(Li_(1-_x)Fe_x)OHFe_(1-y) Se superconductors, which will promote the in-depth investigations on the role of multiple electron and hole bands and their interplay with the high-temperature superconductivity in the FeSe-based superconductors.