Co掺杂β-FeSi2化合物的热电性能及电子结构的第一性原理研究

采用机械合金化结合后续热处理成功制备出Fe1-xCoxSi2化合物,探讨Co掺杂对化合物热电性能的影响;利用基于密度泛函理论赝势平面波方法对Co掺杂前后β-FeSi2的电子结构进行计算。结果表明:Co元素掺杂量x应控制在0～0.05之间;β-FeSi2的费米面位于价带顶,其电阻率随温度升高而降低,为非简并半导体;Co掺杂后费米面进入导带底,使其成为n型简并半导体,电阻率较掺杂前大幅度降低;本实验条件下,热电性能检测发现,当x=0.03,温度873 K时,试样的功率因子达到最大值为60μW.m-1.K-2。     

Tb掺杂CaMnO3氧化物材料热电输运性能的研究

采用溶胶-凝胶法结合陶瓷烧结工艺制备了Tb掺杂CaMnO3基氧化物热电材料,系统研究了Tb掺杂材料物相组成、微观组织和和电输运性能.结果表明,Tb掺杂试样均为单一物相的CaMnO3晶体材料.随着Tb掺杂量的增加,试样晶粒逐渐细化.所得CaMnO3基材料内部晶粒互连,试样结构较为致密.所有Tb掺杂试样电阻率随温度升高而降低,呈明显的半导体传输特性,其中Tb掺杂量为0.14的试样电阻率最低.Tb掺杂试样Seebeck系数绝对值随掺杂量的增加而降低,这是由于Tb掺杂引入的电子型载流子造成的.所有试样功率因子均随温度升高而逐渐增加,并且所有Tb掺杂试样的功率因子均大于未掺杂试样.其中Tb掺杂量为0.08的块体试样功率因子在测试温度最高点973 K时达到最大值2.0×10-4 W·m-1·K-2,远高于未掺杂试样,通过稀土元素Tb掺杂可以优化CaMnO3基过渡金属氧化物材料的电性能.     

Al掺杂ZnO多晶的热电输运性质研究

采用固相反应法制备了六方纤锌矿结构Zn1-xAlxO(0≤x≤0.03)系列多晶,探究了Al掺杂对ZnO多晶的微观形貌和热电输运性质的影响.结果表明,Al掺杂促使ZnO晶粒长大联结,晶界减少,x＞0.003时出现在晶界分布的ZnAl2O4尖晶石相.掺杂后样品由ZnO的半导体行为转变为电阻率显著下降的金属行为,且x=0.003有最小的室温电阻率～1.7 mΩ·cm,主要由于掺杂使样品载流子浓度和迁移率显著提高,x=0.003时载流子浓度和迁移率为最高,分别为1.05×1021 cm-3和20 cm2/V·s;300 ～900 K下掺杂样品热电势的绝对值和功率因子均随温度升高而增大,x =0.003时有最大的室温功率因子～0.4mW/m·K2.综合得到ZnO中Al掺杂的饱和固溶度x≈0.003.     

Bi掺杂量对Mg-Si-Sn-Bi材料热电性能的影响

利用粉末冷压成型及真空烧结制备了不同Bi掺杂量的Mg-Si-Sn-Bi材料,并对制备材料组成和热电性能进行研究.结果表明,制备材料由Mg2Sn、Mg2Si和Mg2(Si,Sn)固溶体相组成.随测试温度的增加,制备材料的电阻率都急剧减小,这是典型的半导体特征.在研究范围内,掺杂Bi元素含量增加,制备材料的电阻率开始逐渐减小,但Bi掺杂量增加到一定值后,材料的电阻率又增加,而且掺杂后的材料电阻率都低于未掺杂的.制备材料的Seebeck系数是负值,表明这些材料都为n型半导体.对于掺杂Bi的材料,随着测试温度由室温增加到730 K,测得的Seebeck系数绝对值开始时轻微增加,约在240～270 K达到最大值,再随着温度增加,Seebeck系数绝对值又显著单调减小.对于掺杂Bi元素的材料,随Bi掺杂量的增加,Seebeck系数的绝对值先减少后增加,这是掺杂造成载流子浓度增加和散射过程加大相互竞争的结果.掺杂Bi的Mg-Si-Sn材料的功率因子都高于未掺杂的材料,且Bi掺杂量增加,制备材料的功率因子显著增加.对于1.29at; Bi和1.63at; Bi掺杂量的材料,功率因子分别在500 K和530 K存在一个极大值.     

Sr3YCo4-xMgxO10.5+δ(0≤x≤0.04)多晶的制备和热电输运性质研究

采用固相反应法制备Sr3YCo4-xMgxO10.5+δ(0≤x≤0.04)系列多晶,研究了Mg掺杂对体系结构、电输运和热电性质的影响.结果表明系列多晶为四方晶系,由于掺入的Mg2+(0.066 nm)部分替代了Co3+/4+(0.053 nm/0.061 nm),使晶格膨胀;多晶热电势在340~830 K随温度升高而下降,且Mg掺杂对热电势影响不大,表明Mg掺杂对体系载流子浓度影响不大;多晶电阻率在100~300 K随温度升高而降低,且随着掺杂量增加电阻率降低,结合扫描电镜观察到多晶的气孔数目减少、晶粒连接紧密和热电势的结果认为Mg掺杂对体系电输运性质的影响机制主要是使气孔、晶界散射作用减弱、载流子迁移率变大,而Mg掺杂对载流子浓度的影响是次要的.     

n型Ge基Ba_8Ga_(16-x)Zn_xGe_(30) I-型笼合物的制备及电传输特性

用熔融法结合放电等离子体烧结技术,采用Zn掺杂制备了具有半导体传导特性的n型Ba_8Ga_(16-x)Zn_xGe_(30) I-型笼合物,研究了Zn部分置换Ga对化合物电传输特性的影响.研究表明所制备的化合物为单相的具有空间群Pm3-n的I-型笼合物.Zn掺杂前对应化合物表现为金属传导特性,Zn掺杂后对应化合物表现为典型的杂质半导体传导特性.室温下,随Zn掺杂量的增加,化合物的载流子浓度和载流子有效质量逐渐降低;Zn掺杂对室温载流子迁移率无明显影响.在300～900 K温度范围内,随Zn掺杂量的增加对应化合物的电导率逐渐降低,Seebeck系数逐渐增加.Zn掺杂后对应化合物的功率因子与掺杂前相比有所降低,且达到最大值的温度都向低温方向偏移.     

硫铁矿烧渣制备导电陶瓷的工艺研究

采用全铁含量21.89;,Fe2O3含量29.80;的硫铁矿烧渣,在高温还原气氛下以少量还原剂还原,制备了电阻率较低的高强导电陶瓷.研究了烧结温度、保温时间、矿化剂种类及掺杂量对导电陶瓷强度及电阻率的影响.结果表明:导电陶瓷的强度随烧结温度的升高而增加,保温时间的延长而降低,矿化剂掺杂量的增加而增加;而电阻率的变化趋势正好与强度变化相反.当还原剂与硫铁矿烧渣比值为0.1,1400℃保温60 min,萤石掺杂量5.4;,导电陶瓷电阻率达到58 Ω·cm,强度87 MPa;而当Na2O掺杂量达到4;,电阻率为88 Ω·cm,强度为84MPa.     

Bi掺杂对Ca3-xBixCo4O9氧化物微观结构和热电性能的影响

采用固态反应法制备Ca3-xBixCo4O9 (0.0≤x≤0.45)样品,并研究了Bi掺杂对样品的微观结构和热电性能的影响.XRD与SEM结果显示,在含Bi样品中形成了c轴取向的结构,x=0.3和x=0.45样品具有大的晶粒取向度和晶粒尺寸,这就导致了这两个样品具有较高的电导率.由于Bi3+替代Ca2+降低了载流子浓度,样品的塞贝克系数随Bi含量的增加而增加.在1000 K,x=0.3样品的功率因子可达2.77×10-4 W/m·K2,这一数值与利用热压法制备的Ca3Co4O9样品的功率因子相当.     

室温铁磁Sr4-xErxCo4O10.5+δ(0.6≤x≤1.2)多晶电输运和磁性能

采用固相反应法制备Sr4-xErxCo4O10.5+δ(0.4≤x≤1.2)多晶,系统研究了Er掺杂对体系结构、电输运和磁性质的影响.X射线衍射结果表明室温下x=0.4时多晶为立方晶系,空间群为P3m3,0.6≤x≤1.2时,为四方晶系,空间群为I4/mmm,四方相晶格常数随着Er含量增加而减小.扫描电子显微镜结果表明,随着Er掺杂量增加,晶粒细化,晶界增加.采用四探针法测量多晶的电阻率-温度曲线,结果表明多晶样品在80～ 300 K为半导体电输运行为,且随Er化学计量比增加样品电阻率和热激活能增大.采用超导量子干涉仪测量多晶的磁化强度-温度曲线和磁滞回线,结果表明0.6≤x≤1.2时Sr4-xErxCo4O10.5+δ多晶具有室温铁磁性,Tc≈320 ～ 335 K,室温铁磁性可能源于A位Sr和Er离子有序及CoO4.5+δ层中Co离子自旋倾斜净磁矩不为零.     

Y、V共掺杂CaBi4Ti4O15陶瓷的结构及电性能研究

采用固相烧结法制备了Y、V共掺杂的CaBi4Ti4O15陶瓷(简称CYBTV).Y、V共掺杂有利于陶瓷晶粒沿c轴方向生长,提高瓷体致密度.测量和分析了不同频率下CYBTV陶瓷的交流电导率σ.c和直流电导率σdc随温度(300～ 1150 K)的变化以及陶瓷的复阻抗谱.σac在不同温区表现出不同程度的频率和温度相关性:在低温区,σac随着频率的升高而增大;在高温区,σac随着温度的升高而增大.CBT基材料的复阻抗响应主要与晶粒电阻电容有关,Y、V共掺杂后,陶瓷的晶粒电阻率显著增大,从而导致材料电阻率的提高.     

Thermodynamic modeling of the system As–Fe combined with first-principles total energy calculations

A thermodynamic model has been developed for the system As–Fe by combining the Calphad approach and the first-principles total energy calculations. Our first-principles calculations are based on the projector augmented wave method within the generalized gradient approximation. We performed these calculations because the experimental values for the enthalpy of formation of the compounds As₂Fe, AsFe and AsFe₂ may have a large uncertainty. Our results indicate significantly more negative values for the enthalpy of formation of these compounds relative to the experimentally established values. We demonstrate that applying our first-principles results in a thermodynamic analysis based on the Calphad approach leads to a calculated phase diagram and thermodynamic properties which are not significantly different from experimental data.     

Mn掺杂半金属铁磁体Fe2Si电磁特性的第一性原理计算

采用基于密度泛函理论第一性原理的贋势平面波方法,计算了不同比例Mn掺杂Fe2-xMnxSi体系的电子结构和磁学特性,分析了不同比例Mn掺杂对Fe2-xMnxSi体系电磁特性的影响.计算结果表明:不同比例Mn掺杂Fe2-xMnxSi体系是铁磁体,自旋向上的能带结构穿过费米面表现金属特性,未掺杂Fe2Si的半金属隙为0.164eV;掺杂比例为8.3;时,自旋向下部分转变为L间的直接带隙半导体,Fe2-xMnxSi(x=0.17)体系呈现半金属特性;掺杂比例为12.5;时,自旋向下部分转变为A间的直接带隙半导体,Fe2-xMnxSi(x=0.25)体系呈现半金属特性;掺杂比例为25;时,自旋向下部分的带隙值接近于0,Fe2-xMnxSi(x=0.5)体系呈现金属特性.Mn掺杂使Fe2-xMnxSi体系的能带结构和电子态密度向低能方向移动,费米能级落入自旋向下的禁带之中,使得自旋极化率达到100;.Fe2-xMnxSi体系的半金属性和磁性主要来源于Fe-3d电子与Mn-3d电子之间的d-d交换,Si-3p电子与Fe-3d电子之间的p-d杂化.这些结果为半金属铁磁体Fe2Si的电磁调控提供了有效的理论指导.     

Electrophysical properties of Ni/V and Cr/Fe multilayer films

Results of experimental researches of electrophysical properties of Multilayer film systems Ni/V, and Cr/Fe which was formed on the basis of nanocrystals (V, Cr and Fe) and high dispersed Ni films are presented. It is carried out comparisons of experimental and calculated on the basis ratio for films alloy (Cr/Fe) and semiphenomenological model (Ni/V) results. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

First-principles study on structural and electronic properties of Prussian blue cathode material for sodium-ion battery

Abstract

Prussian blue, Fe[Fe(CN)₆] currently attracts a huge attention as a promising material in the application of large-scale energy storage because of its cost-effective and environmental friendly material. Besides, open framework structure and stability are the main causes for PB performance. In this study, effects of sodium cation insertion/deinsertion toward the structural and electronic properties were analyzed. The use of Hubbard U method successfully delivered a good approximation on electronic properties of the transition-metal ions in PB. The calculated band gap of 1.84?eV was in good agreement with theoretical and experimental results. Upon the insertion of the sodium cation, volume of the cathode material expanded between 2% and 4% showing that this cathode material has good cycle retention. From partial density of states, Fe 3d dominated the conduction and valence band. Furthermore, the redox reaction mechanism of Prussian blue can also be depicted. The voltage obtained from energy calculation for the first and second insertion of cation was 3.32 and 3.42?V, respectively.     

LEED-Intensitätsspektren verschiedener Oberflächen des kubisch-raumzentrierten α-Eisens

LEED intensity spectra of clean Fe(100)-, Fe(110)- and Fe(111)-surfaces are calculated and compared with experimental curves of various authors. The Layer KKR method succesfully used for fcc-lattices was applied to bcc-lattices up to electron energies of 500 eV. Good conformity of theoretical and experimental spectra was established by taking into consideration a sufficient number of beams (up to 61) and a sufficient number of phase shifts (up to 8).     

Low Dimensional Triangular Magnetic Systems in Transition Metal Intercalates of Misfit Layer Compounds

Abstract

Low dimensional triangle magnetism was studied for transition metal intercalates of incommensurate misfit layer compounds (RS)^x[M^0.33(NbS²)²] (R = La, Ce, M = Fe, Mn). Magnetization measurements for the single crystals of the Fe intercalated compounds (RS)^x[Fe^0.33(NbS²)²] show the successive magnetic transition at 14 K and 22 K. The strong frustration appears between two transition temperatures as quasi two-dimensional antiferro-magnetic triangular Ising spin system. In contrast, the Mn compounds (RS)^x[Mn^0.33(NbS²)²] has very low transition temperature of 3.0 K due to the nature of quasi two-dimensional Heisenberg spin system.     

57Fe Mössbauer effect studies in Y66(FExTM1−x)34 metallic glasses

⁵⁷Fe Mössbauer effect (ME) measurements in a variety of Y based metallic glasses are reported. The spectra are best described in terms of a model which assumes two Fe sites having nearly equal intensities. We find that the ME parameters are smooth and monotonic functions of composition (x) for the glasses Y₆₆(Fe_xTM_1?x)₃₄ (TM = Mn, Fe, Co, Ni, Cu Zn) leading to the conclusion that Fe randomly substitutes for the various TM in these glasses. The nature of the two sites we observe is radically different depending on whether TM is to the right or left of Ni. Those glasses containing Mn, Fe, Co, and Ni display a degree of chemical ordering. In these glasses (TM = Mn, Fe, Co, Ni) we identify site 1 as a Y-dominated Fe environment and site 2 as an Fe environment having a larger number of Fe(TM) near neighbors. A correlation between the isomer shifts [IS] of site 2 and Fe impurities in the corresponding crystalline compounds PTYM₂ is noted and discussed in terms of a volume dependence of IS.     

Dependence of pharmacokinetic properties of 1,4-dihydropyridine calcium antagonists on agglomeration in crystals

With the aim of validating the hypothesis that the pharmacokinetic properties of drugs depend on molecular agglomeration, crystal-chemical analysis was performed for the following representatives of 1,4-dihydropyridine calcium antagonists: nifedipine, felodipine, and nitrendipine. These compounds belong to the structural class P2₁/c, Z = 4(1). The energy of intermolecular interactions was calculated with the use of the CCA program designed for the conventional crystal-chemical analysis. The structural subclasses for the compounds in question were determined. On the basis of the published data, the relationship between the pharmacokinetic properties of these compounds and molecular agglomeration was revealed.     

高压相立方氮化物的硬度预测

硬度是一个复杂的物理量,用第一性原理难以描述,我们基于固体硬度等于单位面积上所有键对压头的抵抗力之和的观点,从化学键理论出发定义了物质的硬度.本文利用复杂晶体的化学键理论计算了立方氮化物高压相的化学键参数,结果表明这些氮化物具有高的共价成键特性.利用硬度的化学键理论预测了立方氮化物高压相的硬度,通过与实验值的比较说明了结果的合理性.     

On Peculiarities of Chemical Bond in the Zn?P System from the Magnetic Susceptibility Data

The measurements of magnetic susceptibility of the Zn-P system compounds have been performed and their Langevin diamagnetic component has been calculated. The influence of the degree of covalency of bonding on the value of diamagnetic constituent of the compounds has been investigated. It is shown that the semiconductor compounds of the Zn-P system have preferably covalent character of chemical bond.