Sr掺杂对CaMnO_3基氧化物电子性质及热电输运性能的影响

采用密度泛函理论计算分析的方法研究了Ca位Sr掺杂的CaMnO_3基氧化物的电子性质和电性能;采用柠檬酸溶胶-凝胶法结合陶瓷烧结制备工艺制备了Ca位Sr掺杂的CaMnO_3基氧化物块体试样,分析研究了所得试样的热电传输性能.结果表明,Sr掺杂CaMnO_3氧化物仍然呈间接带隙型能带结构,带隙宽度由0.756 eV减小到0.711 eV.Sr掺杂CaMnO_3氧化物费米能级附近的载流子有效质量均得到调控,载流子浓度也有所增大.Sr比Ca具有更强的释放电子能力,其掺杂在CaMnO_3氧化物中表现为n型.Sr掺杂的CaMnO_3基氧化物材料电阻率大幅度降低,Seebeck系数绝对值较本征CaMnO_3基氧化物材料有一定程度的增大,Sr掺杂量为0.06和0.12的Ca_(1-x)Sr_xMnO_3(x=0.06,0.12)试样,其373 K的电阻率分别降低至本征CaMnO_3基氧化物材料的25%和21%,其373 K的Seebeck系数绝对值分别是本征CaMnO_3基氧化物材料的112.9%和111.1%,Sr掺杂有效提高了CaMnO_3基氧化物材料的热电性能.     

Cu_2O/ZnO氧化物异质结太阳电池的研究进展

介绍了近年来低成本Cu_2O/ZnO氧化物异质结太阳电池方面的研究进展.应用于光伏器件的吸收层材料Cu_2O是直接带隙半导体材料,天然呈现p型;其原材料丰富,且对环境友好.Cu_2O/ZnO异质结太阳电池结构主要有平面结构和纳米线/纳米棒结构.纳米结构的Cu_2O太阳电池提高了器件的电荷收集作用;通过热氧化Cu片技术获得的具有大晶粒尺寸平面结构Cu_2O吸收层在Cu_2O/ZnO太阳电池应用中展现出了高质量特性.界面缓冲层(如i-ZnO,a-ZTO,Ga_2O_3等)和背表面电场(如p~+-Cu_2O层等)可有效地提高界面处能级匹配和增强载流子输运.10 nm厚度的Ga_2O_3提供了近理想的导带失配,减少了界面复合;Ga_2O_3非常适合作为界面层,其能够有效地提高Cu_2O基太阳电池的开路电压V_(oc)(可达到1.2 V)和光电转换效率.p~+-Cu_2O(如Cu_2O:N和Cu_2O:Na)能够减少器件中背接触电阻和形成电子反射的背表面电场(抑制电子在界面处复合).利用p型Na掺杂Cu_2O(Cu_2O:Na)作为吸收层和Zn_(1-x)Ge_x-O作为n型缓冲层,Cu_2O异质结太阳电池(器件结构:MgF_2/ZnO:Al/Zn_(0.38)Ge_(0.62)-O/Cu_2O:Na)光电转换效率达8.1%.氧化物异质结太阳电池在光伏领域展现出极大的发展潜力.     

Al掺杂SnO2 材料电子结构和光学性质

采用基于第一性原理的线性缀加平面波方法(FP-LAPW),研究Al掺杂SnO₂材料Sn_1-xAl_xO₂ (x= 0,0.0625,0.125,0.1875,0.25)的电子结 构和光学性质,包括能带结构、电子态密度、介电函数和其他一些光学性质.计算结果表明,掺杂Al之后价带上部分折叠态增加,价带宽度发生收缩,对导带底起作用的Sn 5s态减少,使得带隙增宽,且态密度整体向高能方向发生移动.随着Al掺杂量的增加带隙越来越宽,Al杂质能级在导带部分与Sn 5p态电子相互作用逐渐增强,虚部谱中的第一介电峰的强度随掺杂Al浓度增大而减弱.同时,吸收谱及其他光学谱线与介电函数虚部谱线相对应,各谱线均发生蓝移现象,对应带隙增宽,从理论上指出了光学性质与电子结构之间的内在关系. 关键词： 能带结构 态密度 光学性质 介电函数     

Mg,Al掺杂对LiCoO2体系电子结构影响的第一原理研究

为了研究Mg ,Al掺杂对锂二次电池正极材料LiCoO2 体系的电子结构的影响 ,进而揭示Mg掺杂的LiCoO2 具有高电导率的机理 ,对Li(Co ,Al)O2 和Li(Co,Mg)O2 进行了基于密度泛函理论的第一原理研究 .通过对能带及态密度的分析 ,发现在Mg掺杂后价带出现电子态空穴 ,提高了电导 ,并且通过歧化效应 (disproportionation)改变了Co 3d电子在各能级的分布 ,而Al掺杂则没有这些作用 .O2 - 的离子性在掺杂后明显增强 .     

Ga掺杂ZnO的电子结构与电性能的研究

采用密度泛函理论广义梯度近似第一性原理计算的方法研究了n型Ga掺杂的纤锌矿结构氧化物ZnO的晶格结构、能带结构和态密度,在此基础上分析了其电性能.计算结果表明,掺杂ZnO氧化物晶格a,b轴增大,c轴略有减小;Ga掺杂ZnO氧化物两能带之间具有0.6eV的直接带隙,需要载流子(电子)跃迁的能隙宽度较未掺杂的ZnO氧化物减小;掺杂体系费米能级附近的态密度大大提高,其能带主要由Gas态、Zns态和Os态电子构成,且他们之间存在着强相互作用,其中Gas态电子对导带贡献最大.电输运性能分析结果表明,Ga掺杂ZnO氧化物导电机构由Znp-Op电子在价带与导带的跃迁转变为Gas-Znd-Os电子在价带与导带的跃迁,这也表明Gas态电子在导电过程中的重要作用;掺杂体系费米能级附近的载流子有效质量较未掺杂体系增大,且价带中的载流子有效质量较大,导带中的载流子有效质量较小.     

Fe，Ag掺杂单层MoSe2光电性质的第一性原理计算

本文基于第一性原理分别计算了Fe, Ag掺杂对单层MoSe₂电子结构和光电效应的影响,结果表明:与本征单层MoSe₂相比,Fe, Ag掺杂体系的能带更加密集,且费米能级附近均出现了较多杂质能带;通过对分波态密度进行分析,发现其分别是由Fe-3d、Se-4p轨道和Se-4p、Mo-4d轨道所贡献.在近乎整个可见光范围内,Fe, Ag掺杂有效加强了单层MoSe₂的光响应能力,其中Ag掺杂效果最好;这可以归结于掺杂显著改变了单层MoSe₂费米能级附近的能带结构.即掺杂进一步减小了体系的带隙,更有利于电子跃迁,进而产生较大的光响应.研究结果可为单层MoSe₂在光电器件的实际应用提供一定的理论参考.     

Pb掺杂对Cd_2Ru_2O_7反常金属态的调控

具有烧绿石结构的Cd_2Ru_2O_7在形成长程反铁磁序的同时进入反常的金属态.采用高压高温方法制备了一系列Pb掺杂的Cd_(2-x)Pb_xRu_2O_7(0≤x≤2)多晶样品,并系统研究了其晶体结构和电阻率、磁化率、热电势等物理性质.尽管Pb_2Ru_2O_7是泡利顺磁金属,但少量Pb~(2+)掺杂的样品Cd1.8Pb0.2Ru2O7却呈现出明显的金属-绝缘体转变,与施加静水压和少量Ca~(2+)掺杂的效果类似.通过与类似的烧绿石Ru~(5+)氧化物进行对比,提出Cd_2Ru_2O_7中的Ru~(5+)-4d~3电子态恰好处于巡游到局域过渡的区域,少量Pb~(2+)掺杂造成的晶格无序增强了电子的局域性,使得形成反铁磁序的同时伴随出现了金属-绝缘体转变.这表明具有烧绿石结构的Ru~(5+)氧化物是研究巡游-局域电子转变的理想材料体系.     

Mg掺杂对Li(Co,Al)O2电子结构影响的第一原理研究

基于密度泛函理论的第一原理赝势法,研究了Mg在Li(Co,Al)O2中掺杂前后的电子结构的变化.通过能带和态密度的分析,发现Mg掺杂后在价带中引入了电子空穴,同时价带展宽,这两个电子结构的显著变化是引起Li(Co,Al)O2导电率提高的主要机理.通过对Co3d电子态密度的分析发现,在二价Mg掺杂后,Li(Co,Al)O2中的Co价态升高,介于Co3+和Co4+之间.从能带计算出发,进一步定量给出了Co和O的平均价态的变化.     

Al和O间隙原子对α-Al_2O_3热力学性质影响的第一性原理计算

Al粒子作为铝热剂中的主要金属还原剂,通常会自发氧化而在表面形成Al_2O_3钝化层.Al和O原子的扩散渗透将使Al_2O_3壳层的结构和热力学性质发生变化进而对铝热剂的点火过程产生影响.采用基于密度泛函理论的第一性原理方法,结合准简谐徳拜模型和晶格动力学理论,计算并比较了α-Al_2O_3,Al原子掺杂α-Al_2O_3以及O原子掺杂α-Al_2O_3在高温高压下的相关热力学性质,讨论了Al和O原子掺杂对其热力学性质的影响.结果表明:在研究的温度和压力范围内,Al和O间隙原子的掺杂将使α-Al_2O_3的体模量减小,热容和热膨胀系数增大.这一结果意味着对于外表面包覆Al_2O_3的纳米Al粒子而言,高温高压下Al和O原子在Al_2O_3壳层中的扩散将使得Al_2O_3更具延展性而不利于发生剧烈散裂.     

同时具有CuO_2层和Fe_2Se_2O层的新型结构Pr_4CuO_7Fe_2Se_2的设计与电子结构研究

铜氧化物高温超导体和铁基高温超导体的发现,打破了基于电声耦合机理的BCS所预测的超导转变温度极限,使得人们对于超导材料的研究进入新的阶段.两者具有相似的层状结构,在掺杂引入载流子的情况下能够产生超导现象.本文报道基于已有的铜氧化物超导体Pr2CuO_4和具有类超导体结构的Pr2O_3Fe_2Se2系列化合物,设计出一系列超导候选材料Pr_4CuO_7Fe_2Se_2,并对其电子结构进行了基于密度泛函理论的第一性原理计算研究.计算的能带结构和态密度表明,Pr_4CuO_7Fe_2Se_2整体表现出弱导电性,与已有超导体类似;具有明显的各项异性,同样为层状结构,Fe_2Se_2O层和CuO_2层均表现出导电性,被Pr2O_2层分离开,其中费米能级附近Fe_2Se_2O层对态密度的贡献较大,Pr2O_2层几乎无导电性,z轴方向则表现出绝缘体特性.新设计结构的整体表现如同Pr2CuO_4和Pr2O_3Fe_2Se2的结合,但是CuO_2层和Fe_2Se_2O层的活跃能级区域又有所不同,这就使得同一环境下,单一物质中,对比研究两种层状结构的物理表现成为一种可能.     

Electron-hole asymmetry in GdBaCo2O(5+x): evidence for spin blockade of electron transport in a correlated electron system

In RBaCo2O(5+x) compounds (R is rare earth), the variability of the oxygen content allows precise doping of CoO2 planes with both types of charge carriers. We study transport properties of doped GdBaCo2O(5+x) single crystals and find a remarkable asymmetry in the behavior of holes and electrons doped into a parent insulator GdBaCo2O(5.5). The doping dependencies of resistivity, Hall response, and thermoelectric power reveal that the doped holes greatly improve the conductivity, while the electron-doped samples always remain poorly conducting. This doping asymmetry provides strong evidence for a spin blockade of the electron transport in RBaCo2O(5+x).     

Mg掺杂对Li(Co,Al)O2电子结构影响的第一原理研究

基于密度泛函理论的第一原理赝势法，研究了Mg在Li(Co，Al)O2中掺杂前后的电子结构的变化.通过能带和态密度的分析,发现Mg掺杂后在价带中引入了电子空穴，同时价带展宽，这两个电子结构的显著变化是引起Li(Co，Al)O2导电率提高的主要机理.通过对Co3d电子态密度的分析发现，在二价Mg掺杂后，Li(Co，Al)O2中的Co价态升高，介于Co3+和Co4+之间.从能带计算出发，进一步定量给出了Co和O的平均价态的变化. 关键词： Li(Co Al)O2 电子结构 第一原理 电导     

Thermoelectric power of HoBaCo2O5.5: possible evidence of the spin blockade in cobaltites

Thermoelectric power measurements have been performed for an ordered oxygen-deficient perovskite, HoBaCo2O5.5, in which the alternative layers of CoO6 octahedra and of [CoO(5)](2) bipyramids are occupied by Co3+ species. The T-dependent Seebeck coefficient S shows a clear change of the conduction regime at the metal-insulator (MI) transition (T(MI) approximately 285 K). The sign change of S from S<0 to S>0 can be explained assuming that a spin state transition occurs at T(MI). In the metallic state, Co2+ e(g) electrons are moving in a broad band on the background of high or intermediate spin Co3+ species. In contrast, the insulating behavior may result from the Co3+ spin state transition to a low-spin Co3+ occurring in the octahedra. In this phase the transport would occur by hopping of the low-spin Co(4+)t(2g) holes, whereas the high-spin Co2+ electrons become immobilized due to a spin blockade.     

Electronic model for CoO2 layer based systems: chiral resonating valence bond metal and superconductivity

Takada et al. have reported superconductivity in layered Na(x)CoO(2)yH(2)O (T(c) approximately equal to 5 K). We model a reference neutral CoO2 layer as an orbitally nondegenerate spin-1/2 antiferromagnetic Mott insulator on a triangular lattice and Na(x)CoO(2)yH(2)O as electron doped Mott insulators described by a t-J model. It is suggested that at optimal doping chiral spin fluctuations enhanced by the dopant dynamics lead to a gapful d-wave superconducting state. A chiral resonating valence bond (RVB) metal, a parity and time (PT) reversal violating state with condensed RVB gauge fields, with a possible weak ferromagnetism, and low temperature p-wave superconductivity are also suggested at higher dopings.     

Role of hybridization in NaxCoO2 and the effect of hydration

Density functional theory is used to understand the electronic properties of Na(1/3)CoO2 and Na(1/3)CoO2(H2O)(4/3). Comparing the charge density of CoO2 and the Na doped phases indicates that doping does not simply add electrons to the t(2g) states. In fact, the electron added in the t(2g) state is dressed by hole density in the e(g) state and electron density in the oxygen states via rehybridization. In order to fully understand this phenomenon, a simple extension of the Hubbard Hamiltonian is proposed and solved using the dynamical mean-field theory. This model confirms that the rehybridization is driven by a competition between the on-site Coulomb interaction and the hybridization, and results in an effective screening of the low-energy excitations. Finally, we show that hydration causes the electronic structure to become more two dimensional.     

Sc掺杂SnO2稀磁半导体的第一性原理研究

采用第一性原理方法,对Sc掺杂SnO2以及含有O空位的Sc掺杂SnO2的电子结构和磁学性质进行了计算。结果表明SnO2晶格中存在两种本征磁性来源,分别为Sc掺杂诱导的未配对O-2p态电子的自旋极化和O空位诱导的未配对Sn-5p态电子的自旋极化。由于两种未配对的弱束缚电子分别由电离施主和受主诱导产生,因此二者之间存在电荷补偿效应,在特定配比下能够使SnO2晶格出现磁性猝灭。     

(Zn,Al)O电子结构第一性原理计算及电导率的分析

采用第一性原理平面波赝势方法和广义梯度近似计算了ZnO与(Zn,Al)O的电子结构.结合分子轨道理论,从原子布居、键布居、能带结构和态密度角度分析了掺Al前后ZnO的成键情况及对电子间相互作用的影响.利用第一性原理计算结果理论推导计算了(Zn,Al)O的载流子浓度并进一步分析了ZnO电导率的变化情况.与实验结果比较可知,掺Al后ZnO载流子浓度增加,并且ZnO的电导率比未掺杂时有了显著的提高. 关键词： 第一性原理 电子结构 电导率 (Zn Al)O     

Analysis of electronic structures of 3d transition metal-doped TiO2 based on band calculations

The electronic structures of titanium dioxide (TiO₂) doped with 3d transition metals (V, Cr, Mn, Fe, Co and Ni) have been analyzed by ab initio band calculations based on the density functional theory with the full-potential linearized-augmented-plane-wave method. When TiO₂ is doped with V, Cr, Mn, Fe, or Co, an electron occupied level occurs and the electrons are localized around each dopant. As the atomic number of the dopant increases the localized level shifts to lower energy. The energy of the localized level due to Co is sufficiently low to lie at the top of the valence band while the other metals produce midgap states. In contrast, the electrons from the Ni dopant are somewhat delocalized, thus significantly contributing to the formation of the valence band with the O p and Ti 3d electrons. Based on a comparison with the absorption and photoconductivity data previously reported, we show that the t_2g state of the dopant plays a significant role in the photoresponse of TiO₂ under visible light irradiation.     

Influences of Al doping on the electronic structure of Mg(0001) and dissociation properties of H2

By using the density functional theory method, we systematically study the effects of the doping of an Al atom on the electronic structures of the Mg(0001) surface and on the dissociation behaviors of H₂ molecules. We find that for the Al-doped surfaces, the surface relaxation around the doping layer changes from expansion of a clean Mg(0001) surface to contraction, due to the redistribution of electrons. After doping, the work function is enlarged, and the electronic states around the Fermi energy have a major distribution around the doping layer. For the dissociation of H₂ molecules, we find that the energy barrier is enlarged for the doped surfaces. In particular, when the Al atom is doped at the first layer, the energy barrier is enlarged by 0.30 eV. For different doping lengths, however, the dissociation energy barrier decreases slowly to the value on a clean Mg(0001) surface when the doping layer is far away from the top surface. Our results well describe the electronic changes after Al doping for the Mg(0001) surface, and reveal some possible mechanisms for improving the resistance to corrosion of the Mg(0001) surface by doping of Al atoms.