Fe-Cr-Al合金高温氧化行为电子理论研究

从电子层面系统研究Fe-Cr-Al合金氧化膜的形成机理,杂质硫对氧化膜黏附性的影响,稀土元素在改善氧化膜黏附性方面的作用,揭示合金氧化的物理本质.研究表明氧使Al在合金表层的环境敏感镶嵌能最低,促使Al原子从合金内部向合金表面扩散,最终在合金表面偏聚.由于氧与Al间的亲和力较大,氧原子易与Al结合生成Al2O3保护膜.杂质S在基体/氧化膜界面的环境敏感镶嵌能较低,可通过扩散偏聚在基体/氧化膜界面,削弱氧化膜与合金基体的结合力.当合金中加入Y后,Y易与S结合形成稳定的硫化物,阻碍S向基体/氧化膜界面的偏聚,显著提高氧化膜的黏附性,提高合金抗高温氧化能力.     

Nb掺杂对TiO2/NiTi界面电子结构影响的第一性原理计算

采用基于密度泛函理论的第一性原理平面波超软赝势方法,计算了Nb掺杂对TiO2/NiTi界面电子结构的影响.体系生成能的计算结果表明,4种TiO2/NiTi界面结构中,NiTi中Ti原子和TiO2中O原子相邻的界面,即Ti/O界面的生成能最大,结构最稳定.在Ti/O界面结构优化的基础上,态密度、电荷分布以及集居数的计算结果均表明:Nb原子取代界面上的Ti原子后,界面原子之间的结合力增强,且界面附近的基体和氧化层中原子之间的相互作用也增加,有利于促进NiTi合金抗氧化性能的提高.     

掺杂Fe对VH2解氢性能影响的第一性原理研究

采用密度泛函理论(DFT)的第一性原理的平面波超软赝势方法,研究了Fe掺杂对VH₂的电子结构和解氢性能的影响.通过计算Fe掺杂VH₂前后体系的合金形成热、V-H之间的重叠布居数、电子态密度、电子密度,发现Fe掺杂VH₂后,随着Fe含量增加,合金体系的晶胞参数和晶胞体积逐渐减少;体系的负合金形成热逐渐减少,且掺杂后体系的负合金形成热都比VH₂的负合金形成热小,体系的稳定性降低;电子态密度计算也显示Fe掺杂后费米能级处的电子浓度增加,体系稳定性降低;重叠布居数和电子密度计算表明掺杂后V-H之间的重叠布居数由0.1减小为0.08或0.09,V-H之间的电子密度减少,说明V和H原子之间的相互作用减弱,提高了VH₂的解氢性能.计算结果解释了实验现象. 关键词： Fe掺杂 电子结构 解氢性能 第一性原理计算     

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.     

氧化锌电阻阀片中ZnO(002)/β-Bi_2O_3(210)界面结构的第一性原理研究

为了从物质微观结构上了解氧化锌避雷器阀片的性能,采用基于密度泛函理论的第一性原理方法对ZnO(002)/β-Bi_2O_3(210)界面结构进行弛豫和电子结构计算.结果表明弛豫后,原子间的键长发生改变.界面区域差分电荷密度图和原子布居分析可得ZnO层片中Zn原子电荷缺失,β-Bi_2O_3层片中O原子电荷富集,ZnO层片向β-Bi_2O_3层片转移电子电荷23.61e.晶界结构的内建电场由ZnO层片指向β-Bi_2O_3层片,内建电场是ZnO电阻阀片具有非线性伏安特性的重要原因.界面附近态密度表明界面的结合主要依靠ZnO层片中Zn原子与β-Bi_2O_3层片中O原子相互作用.计算显示ZnO(002)/β-Bi_2O_3(210)界面结合较强,界面能约为-4.203 J/m~2.本文研究结果对于研制高性能非线性伏安特性氧化锌电阻片提供了机理解释和理论支持.     

Fe-Cr-Al合金氧化膜形成机理电子理论研究

通过自编软件建立了Fe-Cr-Al合金表面、氧化膜/基体界面模型,采用递归法计算了合金元素在Fe-Cr-Al合金表面、氧化膜/基体界面的环境敏感镶嵌能、亲和能、结合能、态密度等电子结构参数.从电子层次系统研究了Fe-Cr-Al合金氧化膜的形成机理、稀土元素和杂质硫对氧化膜形成过程及黏附性的影响机理.研究表明Fe-Cr-Al合金中Al的偏聚驱动力远大于Y,Cr.氧化初期氧从合金表面向合金内部扩散,合金内部Al向合金表面扩散,使合金形成富铝、氧表面层;氧与Al间的亲和力较大（亲和能低）,氧原子容易与Al结合生成Al₂O₃保护膜;合金中加入Y后,Y在合金表面偏聚,抑制Al向合金表面扩散,氧化膜的横向生长得到有效控制,从而避免氧化膜皱褶形貌的发生,提高氧化膜的黏附性;合金内部的S通过扩散汇集在基体/氧化膜界面,S使界面区原子的总能增高,总态密度降低,减小了界面的稳定性,进而削弱氧化膜与合金基体的结合力. 关键词： 电子结构 高温氧化 Fe-Cr-Al合金     

微合金化元素对Fe-Al界面结合的第一性原理研究

利用第一性原理中的DFT理论研究了Fe/Al界面的能量学和电子结构,讨论了替位型掺杂的元素Zn、Mn、Ni在Fe/Al界面处的作用.结果表明:元素Zn、Mn、Ni都会优先替换界面处的Fe原子,使得界面结合能增加,体系更稳定,有利于界面的结合;跨界面的Fe原子与Al原子之间的电荷布居、键长以及差分电荷密度图的计算表明:掺杂后有利于跨界面的Fe-Al间成键,从而加强了Al层与Fe基体的结合,且结合强度由强到弱依次为:掺Zn>掺Mn>掺Ni;与实验比较吻合.最后对掺杂Zn的增韧机理加以解释.     

Nb掺杂对TiO2/NiTi界面电子结构影响的第一性原理计算

采用基于密度泛函理论的第一性原理平面波超软赝势方法,计算了Nb掺杂对TiO₂/NiTi界面电子结构的影响.体系生成能的计算结果表明,4种TiO₂/NiTi界面结构中,NiTi中Ti原子和TiO₂中O原子相邻的界面,即Ti/O界面的生成能最大,结构最稳定.在Ti/O界面结构优化的基础上,态密度、电荷分布以及集居数的计算结果均表明：Nb原子取代界面上的Ti原子后,界面原子之间的结合力增强,且界面附近的基体和氧化层中原子之间的相互作用也增加,有利 关键词： NiTi金属间化合物 2/NiTi界面')" href="#">TiO₂/NiTi界面 电子结构 第一性原理计算     

硫在Fe(111)面吸附的密度泛函研究

采用基于密度泛函理论的第一性原理方法,系统研究了不同覆盖度下硫在Fe（111）表面的吸附构型和吸附特性,计算并分析了硫在Fe（111）表面的吸附能、电荷密度、分波态密度、电荷布局、电子局域化函数等数据. 研究结果表明：S在Fe（111）面的H位吸附最稳定,并且吸附能随着覆盖度的增加而增加. 另外,电子态密度、电子局域化函数和布局分析表明Fe、S之间呈较弱的共价键,这种作用力主要是Fe的3d轨道和S的2p轨道杂化所贡献,而随着覆盖度的增加,Fe、S之间的作用力逐渐减弱,这可能是由于S原子之间的排斥力减弱了Fe、S之间的作用. S在Fe（111）、Fe（110）和Fe（100）这三个晶面上吸附情况的对比分析发现,S与Fe（111）表面的相互作用最强,Fe（100）面次之,而Fe（110）面最弱.     

硫在Fe(111)面吸附的密度泛函研究

采用基于密度泛函理论的第一性原理方法,系统研究了不同覆盖度下硫在Fe(111)表面的吸附构型和吸附特性,计算并分析了硫在Fe(111)表面的吸附能、电荷密度、分波态密度、电荷布局、电子局域化函数等数据.研究结果表明:S在Fe(111)面的H位吸附最稳定,并且吸附能随着覆盖度的增加而增加.另外,电子态密度、电子局域化函数和布局分析表明Fe、S之间呈较弱的共价键,这种作用力主要是Fe的3d轨道和S的3p轨道杂化所贡献,而随着覆盖度的增加,Fe、S之间的作用力逐渐减弱,这可能是由于S原子之间的排斥力减弱了Fe、S之间的作用.S在Fe(111)、Fe(110)和Fe(100)这三个晶面上吸附情况的对比分析发现,S与Fe(111)表面的相互作用最强,Fe(100)面次之,而Fe(110)面最弱.     

Sulfur at nickel-alumina interfaces: Molecular orbital theory

An atom superposition and electron delocalization molecular orbital study has been made of surface atomic layer relaxations in Ni(110) and Ni(111), the binding of p(2 × 2)S to Ni(111), S on Ni(100), and the binding of A1₂O₃ to clean Ni(111) and p(2 × 2)S covered Ni(111). Surface Ni atom relaxations for three-layer thick cluster models are calculated to be close to the experimental results and S heights of 1.68 Å on Ni(111) and 1.40 Å on Ni(100) are also in close agreement with experimental determinations, which indicates cluster models are suitable for determining surface properties. Al³⁺ in the basal plane of Al₂O₃ are predicted to support a low-lying surface state band in the O2p---A13s3p band gap. These orbitals are found to participate in strong Al---Ni bonds and Al---S bonds of intermediate strength at the interfaces with Ni(111) and p(2 × 2) S-covered Ni(111). Should such bonds form, they are expected to be too few in number to lead to strong adhesion. The strongest Al₂O₃---Ni bonding is predicted to occur when the Ni surface is oxidized. In this case, though Ni---O bonds are relatively weak, their number is high. It is concluded from the structure models that are studied that the segregation of impurity S in Ni to the interface will markedly decrease the adhesion of protective Al₂O₃ films that grow on NiAl based alloys.     

空位缺陷和相变对冲击压缩下蓝宝石光学性质的影响

为了探究冲击压缩下蓝宝石光学性质的变化行为,本文采用第一性原理方法,在180 GPa的压力范围内计算了蓝宝石理想晶体和含空位点缺陷晶体的光学性质.吸收光谱数据表明,仅考虑压力和温度因素不能解释冲击消光实验的结果,而冲击诱导的氧离子空位点缺陷应该是导致该结果的一个重要原因.波长在532 nm处的折射率数据表明:1)蓝宝石的两个高压结构相变将导致其折射率明显上升;在Corundum和Rh_2O_3相区,其折射率将随冲击压力增大而降低;在CalrO_3相区,压力小于172 GPa时,其折射率随冲击压力增大而缓慢地降低,但172 GPa以上时折射率却随冲击压力增大而逐渐增大;2)空位点缺陷对折射率随冲击压力的变化规律有明显的影响.本文结果不仅有助于增强用空位点缺陷的物理机理来解释蓝宝石冲击透明性损伤现象的可靠性,而且对未来进一步的实验研究以及发展新型窗口材料有重要的参考作用.     

石墨烯在Al_2O_3(0001)表面生长的模拟研究

基于密度泛函理论的广义梯度近似法,对用化学气相沉积法在蓝宝石(α-Al_2O_3)(0001)表面上生长石墨烯进行理论研究.研究结果表明:CH_4在α-Al_2O_3(0001)表面上的分解是吸热过程,由CH_4完全分解出C需要较高能量及反应能垒,这些因素不利于C在衬底表面的存在.在α-Al_2O_3(0001)表面,石墨烯形核的活跃因子并不是通常认为的C原子,而是CH基团.通过CH基团在α-Al_2O_3(0001)表面上的迁移聚集首先形成能量较低的(CH)_x结构.模拟研究(CH)_x对揭示后续石墨烯的形核生长机理具有重要意义.     

Structural evolution of FexCo1−x/NM (NM=Ag, Cu, Al2O3) discontinuous multilayers by XAS

We discuss the specific features of the K-edge X-ray absorption spectroscopy (XAS) at the Fe and Co K-edges in Fe_xCo_1−x/NM discontinuous multilayers with NM=Ag, Cu, and Al₂O₃. Thermal treatments lead to the breakup of the layers forming a heterogeneous alloy with magnetic clusters of the FeCo embedded in a nonmagnetic (NM) matrix. Stabilization of the BCC phase of the FeCo alloy is directly evidenced by XAS. Differences among Fe and Co K-edge signatures indicate a strong dependence on the chemical nature of the absorbing atom for annealed samples. The amplitude of the extended X-ray absorption fine structure signal higher at the Co K-edge than at the Fe one reflect a smaller structural disorder in the Co environment. This behavior depends neither on the composition of the alloy nor on the NM material. In the case of Al₂O₃ a higher disorder around Fe atoms is observed also in the as-deposited sample. All these results indicate that the Fe segregates at the interface of the magnetic clusters/NM matrix after thermal annealing.     

不同散射机理对 Al2O3/InxGa1-xAs nMOSFET 反型沟道电子迁移率的影响

通过考虑体散射、界面电荷的库仑散射以及 Al₂O₃/In_xGa_1-xAs 界面粗糙散射等主要散射机理, 建立了以 Al₂O₃为栅介质In_xGa_1-xAs n 沟金属-氧化物-半导体场效应晶体管 (nMOSFETs) 反型沟道电子迁移率模型, 模拟结果与实验数据有好的符合. 利用该模型分析表明, 在低至中等有效电场下, 电子迁移率主要受界面电荷库仑散射的影响; 而在强场下, 电子迁移率则取决于界面粗糙度散射. 降低界面态密度, 减小 Al₂O₃/In_xGa_1-xAs 界面粗糙度, 适当提高In含量并控制沟道掺杂在合适值是提高 InGaAs nMOSFETs 反型沟道电子迁移率的主要途径. 关键词： InGaAs MOSFET 反型沟道电子迁移率 散射机理     

Surface termination, composition and reconstruction of Fe3O4(001) and γ-Fe2O3(001)

We address a current controversy concerning the nature of the surfaces of Fe₃O₄(001) and γ-Fe₂O₃(001) grown on MgO(001) by molecular beam epitaxy. Despite recent claims to the contrary, we show that γ-Fe₂O₃(001) unambiguously exhibits a (1×1) surface net, in contrast to Fe₃O₄(001), which assumes a R45 reconstruction. In addition, we present high-energy-resolution Fe 2p and O 1s core-level photoelectron spectra obtained at both normal and grazing emission for γ-Fe₂O₃(001) and Fe₃O₄(001). These spectra show that the Fe₃O₄(001) surface has a higher Fe(III)/Fe(II) ratio than the bulk, and that the asymmetry in the O 1s line shape for Fe₃O₄(001) is due to final state effects rather than the presence of a surface oxygen or hydroxyl species.     

虚晶近似法研究AlN-Al2O3固溶体系的力学性能和电子结构

基于密度泛函理论的第一性原理平面波赝势方法, 运用虚晶近似方法计算了AlN-Al₂O₃固溶区内尖晶石相氮氧化铝(Al₂₄O₂₄N₈, Al₂₃O₂₇N₅和Al₂₂O₃₀N₂)和α-Al₂O₃, AlN的力学性能和电子结构. 结果证明虚晶近似法应用到氮氧化铝结构计算中是可行的. 力学常数计算结果和弹性模量B, 剪切模量G, 杨氏模量E反映的材料硬度变化趋势与实验基本一致;Al₂O₃-AlN固 溶区内五种结构均为脆性性质且Al₂₃O₂₇N₅脆性最低, 硬度高、脆性低的特性反映了Al₂₃O₂₇N₅优异的抗弯强度性能. 五种结构满足力学结构上的稳定性, 立方尖晶石相氮氧化铝表现为弹性各向异性. 能带和态密度的计算分析表明这五种结构均为直接宽带隙结构. 在费米能级附近, 氮氧化铝结构中阴离子的2p态和阳离子的3s, 3p态发生了轨道杂化. 理论结果与实验数据基本符合, 为进一步研究提供了一定的理论方法和依据.     

The interaction of Cu and S2 with aluminum and alumina surfaces: a comparative study

The bonding interactions between Cu and Al are much stronger than those between Cu and Al₂O₃. Cu atoms supported on alumina show a narrow 3d band with a centroid shifted 0.35 eV with respect to that of the 3d band in bulk metallic Cu. In contrast, Cu atoms deposited on aluminum exhibit shifts of 1.3–1.6 eV in the centroid of the 3d band. Similar differences are observed when comparing the behavior of Ag and Pt overlayers on alumina and aluminum. The d band shifts on the oxide substrate are in the order of 0.3–0.4 eV, whereas on the metal substrate they vary from 0.8 to 2.0 eV. These trends are explained in terms of a simple model that takes into account changes in the energy of the Al(3s, 3p) bands when going from metallic aluminum to alumina. The sticking coefficient of S₂ on alumina surfaces is at least one order of magnitude smaller than on aluminum, a difference that also reflects variations in the position of the Al(3s,3p) bands. Submonolayer coverages of Cu do not produce significant changes in the electronic properties of Al₂O₃. In contrast, the deposition of small amounts of sulfur (0.1 ML) induces a substantial reduction (0.4–0.5 eV) in the binding energies of the O KVV, O 1s and Al 2p features of alumina. This is consistent with a transfer of electrons from alumina into the S atoms that produces a transformation similar to a change from n-type to p-type semiconductors. The reactivity of Cu/Al₂O₃ surfaces toward sulfur is much larger than that of pure Al₂O₃ surfaces. Cu clusters supported on alumina react with S₂ to form CuS_x compounds that decompose at temperatures between 850 and 1100 K.     

Growth and magnetism of Ni nanoparticles in Ni/Al2O3/Si or Si3N4 multilayers

We report on the fabrication of Ni/Al₂O₃/Si and textured Ni/Al₂O₃/Si₃N₄ multilayers containing Ni nanoparticles that exhibit significantly improved results. The secondary phases arising from thermal reaction between Ni and Si can be remarkably suppressed with increasing layers of Al₂O₃ and deposition of Ni/Al₂O₃ multilayers on Si₃N₄ substrates. Atomic force microscopy shows the formation of large as well as nanoclusters of Ni when grown on Si, whereas textured Ni nanoparticles are formed on Si₃N₄ substrates. The magnetization measurements on Ni/Al₂O₃/Si containing a single buffer layer of Al₂O₃ shows higher coercivity field with magnetic nanowire-like behavior, whereas with several Al₂O₃ alternate layers almost a superparamagnetic-like behavior is observed. However, significantly improved magnetic hysteresis was observed in textured Ni/Al₂O₃/Si₃N₄ multilayers due to preferred alignment of Ni nanocrystallites.     

Influence of the transparency of tunnel barriers in Nb/Al2O3/Al/Al2O3/Nb junctions on transport properties

The transparency of the tunnel barriers in double-barrier junctions influences the critical current density and the form of the current–voltage characteristics (IVC). Moreover, the barrier asymmetry is an important parameter, which has to be controlled in the technological process. We have performed a systematic study of the influence of the barrier transparency on critical current, I_C, and normal resistance, R_N, by preparing SIS and SINIS junctions under identical technological conditions and comparing their transport properties. We have fabricated Nb/Al₂O₃/Nb and Nb/Al₂O₃/Al/Al₂O₃/Nb devices with different current densities using a conventional fabrication process, varying pressure and oxidation time. The thickness of the Al middle electrode in all Nb/Al₂O₃/Al/Al₂O₃/Nb junctions was 6 nm. Patterning of the multilayers was done using conventional photolithography and the selective niobium etching process. The current density of SIS junctions was changed in the range from 0.5 to 10 kA/cm². At the same conditions the current density of SINIS devices revealed 1–100 A/cm² with non-hysteretic IVC and characteristic voltages, I_CR_N, of up to 200 μV. By comparing the experimental and theoretical temperature dependence of the I_CR_N product we estimated the barrier transparency and its asymmetry. The comparison shows a good agreement of experimental data with the theoretical model of tunneling through double-barrier structures in the dirty limit and provides the effective barrier transparency parameter γ_eff≈300. A theoretical framework is developed to study the influence of the barrier asymmetry on the current–phase relationship and it is proposed to determine the asymmetry parameter by measuring the critical current suppression as function of applied microwave power. The theoretical approach to determine the non-stationary properties of double-barrier junctions in the adiabatic regime is formulated and the results of calculations of the I–V characteristics are given in relevant limits. The existence and the magnitude of a current deficit are predicted as function of the barrier asymmetry.