ZnO氧化物的电子结构与热学性能的研究

采用密度泛函理论基础上的平面波超软赝势第一性原理计算的方法研究了纤锌矿结构热电氧化物ZnO的电子结构和热学性能。电子结构计算结果表明,纤锌矿结构的ZnO存在着约1.0eV的直接带隙,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;靠近价带顶的能带中的电子主要为p态电子,靠近导带底的能带中的电子主要为p,d态电子。体系分态密度计算结果表明,费米能级附近的能带主要由Znp,Znd和Op态电子构成,且Znp和Op态电子之间存在着很强的杂化作用。声子态密度及分布计算结果表明,体系晶格振动频率主要集中在3～10THz和10～12THz范围之内,其中振动频率约为11THz的振动模式在体系中数量较多,主要为光学波声子。热电性能理论分析结果表明,ZnO基热电氧化物应该具有较高的Seebeck系数和热电性能。     

Al和S共掺杂金红石型TiO2第一性原理研究

利用密度泛函理论体系下的第一性原理平面波超软赝势法,研究Al单掺杂和S单掺杂以及Al/S共掺杂金红石相TiO_2的能带结构、态密度和光学性质。结果表明:Al单掺杂导致禁带宽度减小为1.79eV,并且在价带上方形成了一条杂质能带;S单掺杂导致费米能级上移靠近导带,直接带隙减小为0.816eV;Al/S共掺杂导致能带结构中出现了3条杂质能带,直接带隙约0.841eV,杂质能级主要由Al原子的3p轨道和S原子的3p轨道组成。Al/S共掺杂后使TiO_2的吸收带产生红移,在可见光区具有较大的吸收系数,能够增强电子传输能力和抑制电子空穴对复合。     

Ti3SnC2电子结构的第一性原理研究

采用密度泛函数理论框架下的第一性原理研究了Ti3SnC2的电子结构,利用GGA-PW91基组对Ti3SnC2晶体结构进行了优化,并计算了Ti3SnC2的能带结构、总态密度和各原子的分态密度.对能带和总态密度的计算结果表明,Ti3SnC2在费米能级处电子态密度较高,材料表现出较强的金属性,同时材料的导电性为各向异性.Ti3SnC2各原子的分态密度图的计算结果表明,其导电性主要由Ti2的3d电子决定,Ti1的3d态电子、Sn的5p态电子和C的2p态电子也有少量贡献.决定材料电学性质的主要是Ti的3d、Sn的5p和C的2p态电子的p-d电子轨道杂化,而p-d电子轨道杂化成键则使材料具有比较稳定的结构.     

Mg2Si电子结构及光学性质的研究

采用基于第一性原理的赝势平面波方法系统地计算了Mg2Si基态的电子结构、态密度和光学性质。计算结果表明Mg2Si属于间接带隙半导体，禁带宽度为0．2994eV；其价带主要由Si的3p以及Mg的3s、3p态电子构成，导带主要由Mg的3s、3p以及Si的3p态电子构成；静态介电常数ε1（0）=18．89；折射率n0=4．3460；吸收系数最大峰值为356474．5cm^-1；并利用计算的能带结构和态密度分析了Mg2Si的介电函数、折射率、反射率、吸收系数、光电导率和能量损失函数的计算结果，为Mg2Si的设计与应用提供了理论依据。     

多相ZrO2几何结构及电子结构第一性原理研究

采用基于第一性原理的密度泛函理论投影缀加平面波,使用广义梯度近似处理交换关联势能,深入研究了弛豫多相 ZrO2几何结构特征及电子结构。研究发现,单斜、四方和立方 ZrO2能带间隙分别约为3.47 eV、3.96 eV 和3.36 eV。近费米能级态密度分析结果表明,多相 ZrO2的基本性质均由 O 2p 态电子和 Zr 4d 态电子决定。     

Ta2N3电子结构与光学性质的第一性原理研究

基于密度泛函第一性原理的GGA方法计算研究了Ta2N3的能带结构、态密度、分态密度和光学性质.计算结果表明,Ta2N3具有明显的金属能带结构特征,且在费米能级附近,Ta的5d态与N的2p态杂化,Ta-N以共价键相互作用.Ta2N3的静态介电常数为77.428,静态的折射率n0为8.88,而介电函数的虚部随能量的增加而减小.Ta2N3多晶体的反射系数在0～1.65eV区域随能量的增加而逐渐减小,在1.65eV附近达极小值,此后随能量的增加而增大,但在15eV时发生陡降.Ta2N3多晶体的吸收系数数量级达105 cm-1,且在高能区对光子的吸收较少,其电子能量损失谱(EELS)的共振峰在15eV处,与此能量时反射系数的陡降相对应.     

金红石型TiO2(110)表面吸附TiCl4的微观机理

采用密度泛函理论平面波赝势方法研究了TiCl₄分子在TiO₂(110)表面桥位氧上的吸附,对稳定吸附构型的吸附能、电荷密度、差分电荷密度、电子态密度、Mulliken电荷布居等进行计算和分析。研究结果表明,TiCl₄在完整晶胞表面不能吸附;在有氧空位的晶胞表面,TiCl₄以面心向下吸附最稳定,吸附过程为放热。当表面氧空位密度为12.5%、25%时,面心向下吸附方式的吸附能分别为-29.780 9 kJ·mol-1和-48.641 9 kJ·mol-1,表明氧空位密度越高,吸附强度越强;带隙从1.304 eV分别减小到0. 074 eV、0.015 eV,能带结构的带隙宽度变窄,表明氧空位密度越高,带隙宽度越窄;TiCl₄分子向晶胞表面转移的电荷分别为0.2 eV、0.26 eV,说明随着表面氧空位密度增加,TiCl₄分子向晶胞表面转移的电荷量增加,表面对分子的氧化作用越强。     

CoSi_2合金电子结构和光学性质的理论研究

采用基于密度泛函理论框架的第一性原理计算方法,利用LSDA+U方法计算了CoSi2合金材料的电子结构和光学性质。计算结果表明,CoSi2合金能带结构的导带和价带在费米能级附近存在明显的交叠,表现出半金属特性。随着U值的增加,费米能级处的能级逐渐分裂,导带部分和价带部分分别向高能和低能方向移动,当U=8时,CoSi2合金出现自旋劈裂现象。电荷密度计算结果显示Co—Si键是一种以共价键为主且含有部分离子键成分的混合价合金材料,载流子具有明显的由Si原子向Co原子的电荷转移特性。光学吸收谱分析表明,随着U值的增大,CoSi2材料的吸收峰发生蓝移现象,吸收峰强度逐渐减弱。这些结果表明,CoSi2合金材料是一种很好的具有一定发光性能的热电材料。     

Nb掺杂浓度对SrTiO3的电子结构和光学性能的影响

用第一性原理计算不同Nb掺杂浓度的n型Nb掺杂SrTiO3,研究了Nb掺杂浓度对SrTiO3的形成焓、电子结构和光学性能的影响.在Nb掺杂SrTiO3中Nb替位Ti原子,与实验结果一致.Nb掺杂SrTiO3的费米能级进入导带底部,Nb掺杂SrTiO3呈现n型半导体特征.从微观角度分析了Nb掺杂浓度对导电性的影响,1.11at％ Nb掺杂SrTiO3在可见光范围有强吸收,是一种有潜在应用的光催化材料;而1.67at％和2.5at％Nb掺杂SrTiO3是潜在的透明导电材料.     

单晶硅和纳米晶硅空带的NEXAFS理论研究

利用多重散射团簇方法（MSC）计算了单晶硅的K边NEXAFS谱，研究显示NEXAFS谱包含了导带态密度的信息。同时在模拟C－Si的团簇中引入一定数量的空位，构造了纳米晶硅的模型，MSC计算证实吸收边位置上升约0．5eV，说明纳米晶硅的禁带比c-Si的展宽了。     

First-Principle Investigation of O2 Adsorption on the NiTi Alloy (110) Surface

The discrete-variational method within the framework of density functional theory was used to investigate the process of O2 adsorption occurring on the surface of NiTi alloy. The calculated results showed that O2 exhibits the adsorption state of O2δ-(0.36<δ <0.70). O2 only interact with one nearest surface Ti atom, and the Ti atom only adsorbs one oxygen atom of the O2 molecule.Other cluster atoms would not be influenced in the adsorption process. The density of state analysis showed that the interaction between Ti and O atom is mainly contributed to 2p (O) and 4s (Ti) orbitals.     

SrTiO_3/CaCu_3Ti_4O_(12)复合陶瓷材料的介电性能

本文采用固相反应法制备了xSrTiO_3/(1-x)CaCu_3Ti_4O_(12)(x=0,0.2,0.4,0.6,0.8,1)复合陶瓷,研究了复合材料的物相、微观结构和宽温度宽频率范围内的介电性能。结果表明:在1348~1600K的温度范围内烧结能够得到致密性良好的xSrTiO_3/(1-x)CaCu_3Ti_4O_(12)(x=0,0.2,0.4,0.6,0.8,1)复合陶瓷。频率为100kHz时,样品的室温介电常数随SrTiO_3含量的增加而减少,从71358(x=0)单调减少至270(x=1),其变化规律遵循Lichtenecker法则。介电损耗随SrTiO_3含量的增加先增大后减少。当x=0.2时,样品与CaCu_3Ti_4O_(12)陶瓷的介电性能相似,存在低温的介电弛豫和巨介电常数平台。随着SrTiO_3含量的增加,复合陶瓷的低温介电弛豫激活能增大,介电响应被抑制,而高温介电响应由于高温电导的影响而增强,使得CaCu_3Ti_4O_(12)特有的巨介电常数平台随着SrTiO_3的增加逐渐消失,xSrTiO_3/(1-x)CaCu_3Ti_4O_(12)复合材料的温度依赖性增强。     

L10-TiAl基本物性的计算与比较研究

为了从理论上进一步揭示L10型TiAl金属间化合物的本征物性,采用第一原理赝势平面波方法,计算了L10型TiAl金属间化合物的平衡晶格常数、合金结合能、形成热、弹性常数以及点缺陷形成能,并与其他计算方法和实验测试的结果进行了比较.点缺陷形成能的分析结果表明,富Ti合金易出现Ti反位缺陷,富Al合金易出现Al反位缺陷;双空位形成能的分析结果表明,Ti-Ti最近邻双空位形成能最低,表明这种Ti-Ti最近邻双空位最稳定.基于晶体总电子态密度与各原子分波态密度等电子结构信息,对上述计算结果进行了初步分析.     

First-principles investigation of B2 partial disordered structure,martensitic transformation,elastic and magnetic properties of all-d-metal Ni-Mn-Ti Heusler alloys

In this work,the B2 partial disordered structure of the austenitic parent phase,martensitic transformation,elastic and magnetic properties of the Ni8 Mn4+xTi4-x(x=0,1 and 2) Heusler alloys have been systematically investigated by the first-principles calculations.The preferential atomic occupation of B2 structure is one Ti atom exchange with the nearest neighboring Mn atom from the view of lowest energy principle.This disordered exchange sites(Mn-Ti) and the excess Mn atoms occupying the Ti sites(MnTi)could reduce the nearest Mn-Mn distance,resulting in the anti ferromagnetic state in the austenitic and martensitic phases of the alloys.The total magnetic moment of the alloy decreases with the increasing Mn content;it is ascribed to the antiferromagnetic magnetic moments of the excess Mn atoms.When x=0,the alloy does not undergo martensitic transformation since the austenite has absolute phase stability.The martensitic transformation will occur during cooling process for x=1 or 2,owing to the energy difference between the austenite and the martensite could provide the driving force for the phase transformation.The elastic properties of the cubic austenitic phase for the Ni2 MnTi alloy is calculated,and the results reveal the reason why Ni-Mn-Ti alloy has excellent mechanical properties.The origin of martensitic transformation and magnetic properties was discussed based on the electronic density of states.     

Ab-initio calculations of synergistic chromium–nitrogen codoping effects on the electronic and optical properties of anatase TiO2

Electronic and optical properties of compensated and noncompensated (Cr, N) codoped TiO₂ have been investigated using density functional theory with plane wave basis set and pseudopotential. To investigate the formation of defect pair in the codoped models, defect pair binding energy was calculated. Compensated codoped model has two Cr atoms doped at Ti sites, one N atom at O sites along with an oxygen vacancy that gave stable configuration, better electronic and optical properties. Defect pair binding energy of this model showed that, individual defects would bind each other leading to stable configuration compared to mono-doped models. Band structure results showed that compensated (Cr, N) codoping introduced substantially broaden intermediate states in the forbidden band along with narrowed band gap. Furthermore, the Fermi level was shifted from top of the valence band to middle of the forbidden band describing half metallic character. Cr doping changed the nature of N 2p states from unoccupied to occupied which will improve electron–hole pair separation. Optical properties comparison showed that all doped models effectively shifted the absorption edge of TiO₂ towards visible light. Compensated (Cr, N) codoped TiO₂ has better optical properties and covered wide absorption band in the visible light region, attributed to the stable configuration, narrowed band gap and widely distributed states in the band gap. Our results provide reasonable explanation of the experimental findings.     

第一原理研究LuPO4中氧空位的性质

磷酸结构的晶体在掺杂二价阳离子后容易形成产生焦磷酸结构(P₂O₇) ^4-, 这种含有焦磷酸结构的氧化物材料十分适合做质子导体、燃料电池、气体传感器以及陶瓷膜等。本文利用第一性原理研究了LuPO₄晶体中氧空位的结构性质, 结果显示当氧空位带二价正电时, 会引发氧空位周围原子奇特的畸变, 形成焦磷酸结构。为了解释这种结构畸变的机理, 本文利用过渡态搜索计算了结构变化过程中势能面的变化情况, 正一价氧空位形成焦磷酸 结构需要越过2.4 eV的势垒, 而正二价氧空位形成焦磷酸结构则不需要越过任何势垒, 因此很容易形成焦磷酸 结构。最后给出氧空位不同带电态的晶格结构、电子态密度以及电荷密度分布等基本物理性质, 氧空位处于正二价态结构下, 氧空位附近的P原子与O原子成键, 又由于O原子有较强的电负性, P的s轨道电子向O的p轨道转 移。P的s、p轨道在禁带中出现了与总态密度对应的缺陷能级, 结果表明带正二价氧空位的晶体性质发生了明显变化。     

Ferromagnetic properties,electronic structures,and formation energies of Zn vacancy monodoping and (Zn vacancy,Li) codoped ZnO by first principles study

Using the first-principles method based on the density functional theory, we investigated the ferromagnetic properties, electronic structures, and formation energies of Zn vacancy monodoping and (Zn vacancy, Li) codoped ZnO. The results indicate that both cases prefer the ferromagnetic ground state. It was found that the Zn vacancy defect brings a spin polarized state in the nearest neighbor oxygen atoms, and the magnetic moments mainly come from the O atoms surrounding the defect centers, which are different from the conventional diluted magnetic semiconductor. In addition, we found that the spin polarized oxygen atoms have a metallic feature in both spin states and the ferromagnetic exchange interaction among oxygen atoms is mediated by Zn 3d state. Furthermore, it was observed that the replacement of one Zn atom in the system of Zn₁₅O₁₆ by one Li atom can generate holes and reduce the formation energy of Zn vacancy, and then stabilizes the zinc vacancy-including system, resulting in a larger magnetic moment.     

A comparative study of the atomic and electronic structure of F centers in ferroelectric KNbO3: Ab initio and semi-empirical calculations

The linear muffin-tin-orbital method combined with density functional theory (in a local density approximation) and the semi-empirical method of the intermediate neglect of the differential overlap (INDO) based on the Hartree-Fock formalism are used for the supercell study of the F centers (O vacancy with two electrons) in cubic and orthorhombic ferroelectric KNbO₃ crystals. The two electrons are found to be considerably delocalized even in the ground state of the defect. Their wave functions extend over the two Nb atoms closest to the O vacancy and over other nearby atoms. Thus, the F center in KNbO₃ resembles much more electron defects in the partly covalent SiO₂ crystal (the so-called E₁′ center) rather than usual F centers in ionic crystals like MgO and alkali halides. This covalency is confirmed by the analysis of the electronic density distribution. The absorption energies were calculated by means of the INDO method using the ΔSCF scheme after a relaxation of atoms surrounding the F center. For the orthorhombic phase three absoprtion bands are predicted, the first one is close to that observed experimentally under electron irradiaton.     

Ho掺杂对Bi4-xHoxTi3O12陶瓷结构与铁电性能的影响

以Ho为掺杂元素,采用热压烧结方法制备Bi4-xHoxTi3O12陶瓷,重点研究了Ho掺杂量对其物相组成、致密度、微观结构和铁电性能的影响.首先以Bi2O3、TiO2和Ho2O3微粉为原料,利用固相反应在900℃合成出主晶相为Bi4Ti3O12的Bi4-xHoxTi3O12(x=0～0.8)粉体;然后,将合成粉体在850℃、30 MPa条件下热压烧结,当Ho掺杂量x=0～0.4得到了物相单一、整体致密(>99%)的Bi4-xHoxTi3O12陶瓷.随Ho掺杂量的增加,Bi4-xHoxTi3O12陶瓷的剩余极化强度呈现先增大后减小的趋势,主要与氧空位浓度和不同掺杂浓度引起的掺杂位置的不同有关.在Ho掺杂量x=0.4时,其剩余极化强度最大(2Pr=13.92μC/cm2),远大于未掺杂的Bi4Ti3O12陶瓷,说明适量Ho掺杂能有效改善其铁电性能.     

Rare earth elements in α-Ti: A first-principles investigation

The interaction energies between substitutional rare earth (RE) atoms, between RE and interstitial C, N, O, H atoms, as well as between RE and vacancies in α-Ti are calculated via first-principles density-functional theory with projector augmented-wave (PAW) pseudopotentials. The results show that the RE–vacancy and RE–RE interactions are attractive due to the weaker RE–Ti bond than the host Ti–Ti bond. All of the RE atoms investigated in this paper are repulsive to C and N, but attractive to H. RE–O interactions are repulsive for the light RE atoms, though the interactions are very weak for the heavy RE atoms. The mechanism underlying the interactions and their possible influence on the properties of Ti alloys are discussed.