基于第一性原理的含空位a-Fe和H原子相互作用研究

氢致裂纹是制约超高强度钢应用的关键问题,掌握扩散氢的分布行为有助于弄清氢致裂纹的形成机理.本文采用第一性原理方法计算了H原子占据α-Fe晶格间隙和空位时的情况,得到了晶体的稳定构型及能量,并据此分析了H原子在晶格间隙和空位中的溶解倾向;从Mulliken布居、电子密度分布、态密度分布等角度分析了H原子与α-Fe晶体间隙和空位之间的相互作用.结果表明:间隙H原子倾向占据α-Fe四面体间隙位,其1s轨道电子与Fe的4s轨道电子呈微弱共轭杂化;空位是强氢陷阱, H原子倾向占据空位内壁附近的等电荷面.在真空0 K条件下单空位最多稳定溶解3个H原子,且H原子之间未表现出自发形成H2的倾向;间隙和空位中的H原子溶入改变了Fe晶格内电子分布导致原子结合力弱化,并在局部区域形成反键.基于第一性原理能量计算结果开展热力学分析,分析结果表明大多数情况下间隙H原子都是H主要的固溶形式, H平衡溶解度计算结果与实际符合良好.     

LiAl中空位形成能的第一原理计算

LiAl是一种非常典型和有重要用途的金属间化合物.采用平面波展开和第一原理赝势法，计算了LiAl化合物中Li空位和Al空位的形成能和空位周围的原子弛豫，讨论了空位形成时电荷密度的重新分布、相应的电子态密度以及能带结构等性质. 关键词： LiAl 空位形成能 第一原理计算     

稀土La对bcc-Fe中Cu扩散行为影响的第一性原理研究

采用基于密度泛函理论的第一性原理,研究了稀土La对bcc-Fe中Cu析出行为的影响.计算了α-Fe中La原子和Cu原子与空位之间,以及La原子和Cu原子之间的点缺陷结合能;在此基础上,讨论了α-Fe中La对Cu扩散激活能的关系.结果表明:La原子与空位之间有较强的相互吸引作用,且对近邻Cu原子也有一定的束缚.此外,La的加入使Cu原子近邻的空位形成能显著升高,这表明La,Cu偏聚区形成空位较为困难.与此同时,由于La原子对近邻空位和Cu原子的吸引作用,使Cu原子向近邻空位跳跃的迁移能有所升高.迁移能与空位形成能变化的计算结果显示,La原子的加入能够使α-Fe中Cu的扩散激活能显著升高,从而延缓了铁素体区富铜相的偏聚和析出.     

运用第一性原理研究氧化锌电阻阀片中氧空位与掺杂条件下ZnO晶体电学性质

为了比较Nb_2O_5、MnO_2、MgO三种添加剂对氧化锌电阻阀片电学性能影响,在微观层面模拟Nb、Mn、Mg三种元素分别掺杂ZnO完整超晶胞和带有氧空位缺陷的ZnO超晶胞,并运用第一性原理分析掺杂晶胞的特性.本文计算了晶体结构、掺杂形成能、氧空位形成能、能带结构、态密度、载流子迁移率、电导率等.结果表明,掺入Nb原子的掺杂体系晶格体积最大,Mg掺杂体系的形成能最大,稳定性最弱,Nb掺杂氧空位形成能最低,更容易引入氧空位.Nb掺杂的ZnO超晶胞禁带宽度最小,氧空位缺陷增大掺杂晶体的禁带宽度.在相同掺杂浓度和同等条件下,Mn掺杂的晶体电导率最高.     

NiAl中Ni空位对杂质C原子的多重俘获及温度效应的第一性原理研究

本文应用基于密度泛函理论的第一原理方法,研究了NiAl金属间化合物中Ni空位对杂质C元素的多重俘获.研究结果表明:在Ni空位存在时,单个C原子最易于存在于空位中心附近的富Ni八面体间隙位置且与邻近的Ni原子和Al原子之间存在共价键形式的相互作用.多个C原子在NiAl中倾向于以"Sequential"的方式被Ni空位俘获,进而形成CnVNi(n=1,2,3,4)团簇.通过电荷密度和差分电荷密度分析得到,当Ni空位俘获多个C原子后,C原子之间有着优先于自身成键的特性.进一步,我们应用热力学模型计算了温度对于C_nV_(Ni)(n=1,2,3,4)团簇浓度及空位浓度的影响.研究表明本征Ni空位的浓度会随着温度的升高而升高.在NiAl金属间化合物中,大多数的杂质C原子会被Ni空位俘获而不是存在于远离Ni空位的八面体间隙位置.由于C原子被Ni空位俘获的过程是一个放热过程,使得体系温度升高,因此会进一步激发更多的Ni空位产生.但是在一定的温度范围内(温度小于700 K时),Ni空位均以C_nV_(Ni)团簇的形式存在.     

LiF中空位形成能的第一性原理计算

采用平面波展开和基于密度泛函理论框架下的第一性原理赝势法,计算了102GPa下LiF化合物中Li空位和F空位的形成能及空间周围的原子弛豫,讨论了空位形成时电荷密度的重新分布,相应的电子态密度以及能带结构等性质.结果表明:LiF晶体中F空位的形成能比大于Li空位的形成能;F空位对LiF晶体的电子结构等性质的影响要比Li空位的大.     

LiF中空位形成能的第一性原理计算

采用平面波展开和基于密度泛函理论框架下的第一性原理赝势法,计算了102GPa下LiF化合物中Li空位和F空位的形成能及空间周围的原子弛豫,讨论了空位形成时电荷密度的重新分布,相应的电子态密度以及能带结构等性质.结果表明:LiF晶体中F空位的形成能比大于Li空位的形成能;F空位对LiF晶体的电子结构等性质的影响要比Li空位的大.     

LiF中空位形成能的第一性原理计算

采用平面波展开和基于密度泛函理论框架下的第一性原理赝势法,计算了102GPa下LiF化合物中Li空位和F空位的形成能及空间周围的原子弛豫,讨论了空位形成时电荷密度的重新分布,相应的电子态密度以及能带结构等性质.结果表明:LiF晶体中F空位的形成能比大于Li空位的形成能;F空位对LiF晶体的电子结构等性质的影响要比Li空位的大.     

氧空位浓度对ZnO电子结构和吸收光谱影响的研究

目前,氧空位对ZnO形成杂质能级的研究结果存在相反的结论,深杂质能级和浅杂质能级两种实验结果均有文献报道,并且,在实验中高温加热的条件下,氧空位体系ZnO中导带自由电子增加的来源认识不足.为了解决此问题,本文采用密度泛函理论框架下的第一性原理平面波超软赝势方法,建立了纯的与两种不同氧空位浓度ZnO超胞模型,分别对模型进行了几何结构优化、态密度分布、能带分布、布居值和差分电荷密度的计算.结果表明,氧空位浓度越大,系统能量越上升、稳定性越下降、形成能越高、氧空位越难、导带越向低能方向移动、电子跃迁宽度越减小、吸收光谱越红移.这对设计制备新型氧空位ZnO体系光学器件有一定的理论指导作用.     

第一性原理研究氧空位对Ag在MgO(001)面吸附的影响

采用基于密度泛函理论的第一性原理研究方法,应用Vienna Ab-initio Simulation Package (VASP),计算了氧空位对Ag原子在MgO(001)面吸附的影响．通过成键过程中电荷密度的变化以及电荷转移的讨论,从原子尺度上分析了MgO(001)面空位点Fs和Fs+对其吸附、聚集与成核属性的影响以及吸附的能量属性.结果表明,相对清洁的MgO表面而言,Ag原子吸附在O空位时,能够更牢固地与MgO表面结合,并吸引更多的Ag原子聚集在一起,形成一个个独立的Ag原子岛.     

金属中空位的形成能

从固体的表面张力出发,求得空位的形成能。发现由这理论计算得到的空位形成能的数值与实验值符合,金属的空位形成能与自扩散激活能以及熔化温度各成正比关系,这些关系中之一表明,空位形成能与自扩散激活能的比值为0.43。另外,空位形成能也是原子序数的周期性函数。     

GaN中与C和O有关的杂质能级第一性原理计算

用局域密度泛函线性丸盒轨道大型超原胞方法(32个原子),对纯纤锌矿结构的GaN用调节计算参数(如原子球与“空球”的占空比)在自洽条件下使Eg的计算值(323eV)接近实验值(35eV).然后以原子替代方式自洽计算杂质能级在Eg中的相对位置.模拟计算了六角结构GaN中自然缺陷以及与C和O有关的杂质能级位置,包括其复合物.计算结果表明,单个缺陷如镓空位VGa、氮空位VN、氧代替氮ON、炭代替氮CN、炭代替镓CGa等与已有的计算结果基本一致.计算结果表明杂质复合物会导致单个杂质能级位置的相对变化.计算了CNON,CGaCN,CNOV和CGaVGa,其中CNON分别具有深受主与浅施主的特征,是导致GaN黄光的一种可能的结构. 关键词： GaN 杂质能级 电子结构     

FS and FS(OH) defect centers at the MgO(1 0 0) surface: cluster and periodic calculations

We present a model of a new paramagnetic defect center which results from the interaction of atomic hydrogen with the MgO(1 0 0) surface. DFT calculations have been performed using periodic supercells and embedded cluster models where long-range polarization effects are included explicitly. The H atom promotes the creation of an oxygen vacancy (F center) by formation of the F_S⁺(OH⁻) defect where an hydroxyl group is adsorbed near an electron trapped in an oxygen vacancy. This new center has some characteristics similar to those of the classical F_S⁺ centers but a smaller formation energy; furthermore, being globally neutral, it can be treated also with supercell methods.     

First-principles calculation of defect formation energy in chalcopyrite-type CuInSe2, CuGaSe2 and CuAlSe2

In order to quantitatively evaluate the formation energies of Cu, In/Ga/Al and Se vacancies in chalcopyrite-type CuInSe₂ (CIS), CuGaSe₂ (CGS) and CuAlSe₂ (CAS), first-principles pseudopotential calculations using plane-wave basis functions were performed. All calculations were performed using a supercell with 64 atoms, which was eight times greater than the number of atoms in a primitive cell with eight atoms. The formation energies of point defects were calculated as a function of the atomic chemical potentials of constituent elements. Atomic arrangements around the vacancy were optimized allowing relaxation of the first- and second-nearest-neighbor atoms of the vacancy. The obtained results were as follows: (1) the formation energy of Cu vacancy was smaller than those of the other vacancies in CIS, CGS and CAS. Under the Cu-poor condition, the formation energy of Cu vacancy in CIS was lowest among those in them; (2) the formation energy of Se vacancy in CIS was relatively lower than those in CGS and CAS; (3) the formation energy of (2V_Cu+In_Cu) pair in CIS was greatly dependent on the chemical potential of the constituent elements, i.e. Cu, In and Se. On the other hand, the formation energies of (2V_Cu+Ga_Cu) in CGS and (2V_Cu+Al_Cu) in CAS were not largely dependent on the chemical potential of the constituent elements. Under the Cu-poor condition, the formation energy of (2V_Cu+In_Cu) pair in CIS was much lower than those of (2V_Cu+Ga_Cu) in CGS and (2V_Cu+Al_Cu) in CAS.     

Atomic and electronic structures of p-type dopants in 4H-SiC

Using hybrid density functional calculation,we study the atomic and electronic structures of p-type dopants,B,Al and Ga,in 4 H-SiC.For B,depending on the growth condition,it can occupy both Si and C sites.In contrast,Al and Ga on the C sites exhibit too high formation energy to exist in a significant amount.In 4 H-SiC,there exist two types of Si sites in wurtzite-like and zincblende-like local coordination,respectively.Our calculations suggest that the dopant atoms have negligible preference occupying the two sites.In neutral charge state,all the dopants exhibit significant distortions from the structure in the negatively charged state.For most cases,our calculations yield three distorted structures,in which the most stable one has the dopant atom displaced along its bond with one of the surrounding equatorial Si or C atoms,lowering the C_(3 v) symmetry to Cs symmetry(i.e.,a mirror symmetry only).Among the three dopant elements,Al on Si sites exhibits overall the lowest formation energy and the shallowest acceptor level.Nevertheless,it is not a hydrogenic dopant with the acceptor level 0.12 eV above the valence band maximum based on calculation using a 400-atom supercell.Its corresponding defect state exhibits apparent localization along the [0001] direction,but it is relatively delocalized in the(0001) plane.     

Simulation of the short-range order in disordered cubic titanium monoxide TiO1.0

A model of the atomic structure with the short-range order in the vacancy distribution for the disordered cubic phase of titanium monoxide TiO_1.0 has been proposed. The effect of the short-range order on the electronic structure and the stability of the compound has been studied by the supercell method within the DFT-GGA approximation with the use of pseudopotentials. It has been established that the appearance of the short-range order considerably decreases the total energy. The decrease in the energy is comparable with the energy gain during the ordering of the vacancies according to the type of monoclinic superstructure Ti₅O₅ to the long-range order parameter η = 0.7. It has been shown that the discrepancies between the theoretical and experimental electronic spectra of titanium monoxide can be explained by allowance for the short range order.     

面心立方金属的空穴松弛能和空穴形成能的计算

本文利用纯金属的Morse势计算了五种面心立方金属(Pb,Ag,Ni,Cu,Al)的空穴松弛能和空穴形成能。计算松弛能时,除了考虑原子重新分布外,还特别考虑了电子云重新分布所引起的效应。如此求得的松弛能分别为1.27—1.36,>1.73,1.93—2.29,1.52—1.84,>1.09eV,比没有考虑电子云重新分布求得的松弛能大一个多电子伏。这表明电子云重新分布对松弛能的贡献是很重要的。由于求得了比较合理的松弛能,因而找到了一种模型比较简单,充分考虑到松弛效应的、适合于计算所有立方金属空穴形成能的方法。最后,求得上述金属的空穴形成能分别为0.64—0.74,<1.22,1.78—2.15,1.52—1.85,<1.67eV,比实验值大一些;它给出了上述实际金属的合理的理论上限值。     

Interactions between vacancies and prismatic Σ3 grain boundary in α-Al_2O_3:First principles study

Interactions between vacancies and Σ3 prismatic screw-rotation grain boundary in α-Al_2O_3 are investigated by the first principles projector-augmented wave method.It turns out that the vacancy formation energy decreases with reducing the distance between vacancy and grain boundary(GB) plane and reaches the minimum on the GB plane(at the atomic layer next to the GB) for an O(Al) vacancy.The O vacancy located on the GB plane can attract other vacancies nearby to form an O–O di-vacancy while the Al vacancy cannot.Moreover,the O–O di-vacancy can further attract other O vacancies to form a zigzag O vacancy chain on the GB plane,which may have an influence on the diffusion behavior of small atoms such as H and He along the GB plane of α-Al_2O_3.     

Contributions of different mechanisms of self-diffusion in face-centered cubic metals under equilibrium conditions

The contributions of different mechanisms of self-diffusion in face-centered cubic metals Ni, Cu, and Al at thermodynamic equilibrium have been analyzed using the molecular dynamics method. The vacancy, divacancy, and cyclic mechanisms of self-diffusion, as well as the mechanisms involving the vacancy migration to the second coordination sphere and the formation and recombination of Frenkel pairs, have been considered. It has been shown that the second in contribution to the self-diffusion after the vacancy mechanism in the metals under consideration is the migration of divacancies. The third is the mechanism involving the formation and recombination of dynamic Frenkel pairs. The cyclic mechanisms (with simultaneous atomic displacements) and the vacancy migration directly to the second coordination sphere in face-centered cubic metals are unlikely.