过渡金属氮化物中单原子固溶和力学性能的第一性原理研究

基于密度泛函理论(DFT)的第一性原理,计算Si原子在Ti族和V族氮化物中以及B、C和Ge原子在TiN晶体中固溶的稳定结构,讨论置换型和间隙型固溶的低能量稳定结构与晶体间距的关系,研究金属氮化物和固溶原子固溶结构的力学性能.结果表明:Si原子在TiN、ZrN、HfN和TaN晶体中固溶以及Ge原子在TiN晶体中固溶情况为,单原子不进入对应过渡金属氮化物晶体中形成间隙固溶或置换固溶,随着晶体间距离变化单原子可以在晶体之间形成间隙固溶或置换固溶;Si原子在NbN以及B原子在TiN晶体中可以实现间隙固溶,而不能形成置换固溶;Si原子在VN和C原子在TiN晶体中固溶结构形式均为置换固溶.单原子固溶形成低能量置换型固溶体和间隙型固溶体的弹性常数、体模量和剪切模量均低于原过渡金属氮化物的对应值.     

立方KCaF_3电子、弹性和光学性质的第一性原理研究

基于密度泛函理论和赝势平面波近似法计算研究了立方钙钛矿KCaF_3的弹性、电子和光学性质.基态时,KCaF_3平衡晶格常数、体积弹性模量和实验及其他计算值一致.根据Hooke定律和Christoffel方程,研究了KCaF_3弹性常数Cij、体积弹性模量B、各向同性波速和弹性各向性异性因子随压力的变化关系.从电子能带理论出发,计算得到了KCaF_3电子能带、态密度和Milliken电荷布居数,并对其电子性质进行了详细分析.结果显示:立方钙钛矿KCaF_3为直接带隙绝缘体材料,其禁带宽度为6.22 e V;电荷主要从Ca和K原子向F原子转移;立方钙钛矿KCaF_3属于纯粹的共价型化合物.同时,本文还计算研究了KCaF_3的光学介电函数、吸收系数、复折射率、能量损失谱和反射系数等光学性质.     

高压下RhB的相变、弹性性质、电子结构及硬度的第一性原理计算

采用密度泛函理论中的赝势平面波方法系统地研究了高压下RhB的结构相变、弹性性质、电子结构和硬度.分析表明,RhB在25.3 GPa时从anti-NiAs结构相变到FeB结构,这两种结构的弹性常数、体弹模量、剪切模量、杨氏模量和弹性各向异性因子的外压力效应明显.电子态密度的计算结果显示,这两种结构是金属性的,且费米能级附近的峰随着压强的增大向两侧移动,赝能隙变宽,轨道杂化增强,共价性增强,非局域化更加明显.此外,硬度计算结果显示,anti-NiAs-RhB的金属性比较弱,有着较高的硬度,属于硬质材料.     

第一性原理研究Fe掺杂SnO2材料的光电性质

采用基于第一性原理的线性缀加平面波(FP-LAPW)方法,研究Fe掺杂SnO₂材料电子结构和光学性质,包括电子态密度、能带结构、介电函数和其他一些光学图谱. 研究结果表明,掺Fe后材料均属于直接跃迁半导体,且呈现半金属性;随掺杂浓度增加,费米能级进入价带,带隙逐渐减小,Fe原子之间耦合作用增强;通过掺杂能够在一定程度上改变成键性质,使其具有金属键性质. 光学谱线(吸收谱、消光系数等)与介电函数虚部谱线相对应,均发生蓝移,各峰值与电子跃迁吸收有关,从理论上指出光学性质和电子结构的内在联系. 关键词： 能带结构 态密度 光学性质 介电函数     

过渡金属与氮共掺杂ZnO电子结构和光学性质的第一性原理研究

采用基于密度泛函理论框架下的第一性原理平面波超软赝势方法,结合广义梯度近似(GGA)研究了过渡族金属(Mn,Fe,Co,Cu)与N共掺杂ZnO的能带结构、电子态密度分布、差分电荷密度和光学性质.计算表明Mn，Fe，Co与N共掺ZnO的光学性质与Mn，Fe，Co单掺杂相近，但是过渡族金属与N共掺杂有利于获得p型ZnO. 关键词： ZnO 第一性原理 电子结构 光学性质     

层数调控磷烯能带与光学性质的研究

近年来,黑磷作为兼具石墨烯和过渡金属硫化物之长的新型二维材料而倍受关注.本文基于密度泛函理论,研究了不同厚度黑磷的电子结构与光学性质.结果表明,黑磷的性质与其厚度密切相关,可通过厚度调整实现能带与光学性质的可调控性.层间相互作用导致费米能级附近价带和导带的劈裂,是造成黑磷带隙随层数减小的根本原因.黒磷的静态折射率和静态反射率的大小均随层数的增大有增大的趋势,并且各层黑磷的反射峰均位于紫外光波段.黑磷对光的吸收涵盖了可见光到紫外光区域,对光的损失范围小于4eV.本文基于能带图和分波态密度图,从电子跃迁的角度分析了黑磷各项光学性质的变化情况,旨在为黑磷的带隙及光学性质层数可调控性提供理论依据.     

二维黑磷的光学性质

黑磷是继石墨烯、过渡金属硫族化合物(TMDCs)之后又一个备受关注的二维材料.黑磷从单层到块材都是直接带隙半导体,且带隙从单层的1.7 eV一直随着层数的增加而减小,到块材则变为0.3 eV,涵盖了可见光到中红外波段,恰好填补了石墨烯和过渡金属硫族化合物的带隙在该波段的空白.同时,黑磷还具有很高的载流子迁移率、良好的调控性、面内各向异性等优异特性,很快便引起了人们广泛的研究兴趣.本论文主要介绍了当前有关二维黑磷光学性质方面的研究进展,包括黑磷的本征光学性质,如带间跃迁吸收、激子、光致发光、光学性质的稳定性;外界微扰,如应变、电场等对黑磷光学性质的影响;最后做了总结与展望.希望本文对黑磷光学性质研究的综述,能够引起对黑磷研究的更广泛兴趣.     

立方KCaF3电子、弹性和光学性质的第一性原理研究

基于密度泛函理论和赝势平面波近似法计算研究了立方钙钛矿KCaF3的弹性、电子和光学性质。基态时,KCaF3平衡晶格常数、体积弹性模量和其他计实验和算值一致。根据Hooke定律和Christoffel方程,研究了KCaF3弹性常数Cij、体积弹性模量B、各向同性波速和弹性各向性异性因子随压力的变化关系。从电子能带理论出发,计算得到了KCaF3电子能带、态密度和Milliken电荷布居数,并对其电子性质进行了详细分析。结果显示：立方钙钛矿KCaF3为直接带隙绝缘体材料,其禁带宽度为6.22eV;电荷主要从Ca和K原子向F原子转移;立方钙钛矿KCaF3属于纯粹的共价型化合物。同时,本文还计算研究了KCaF3的光学介电函数、吸收系数、复折射率、能量损失谱和反射系数等光学性质。     

过渡金属掺杂GaN的电子结构和光学性质理论研究

采用基于密度泛函理论的第一性原理平面波赝势法计算不同过渡金属（V, Cr, Mn, Fe, Co, Ni）掺杂GaN的电子结构及光学性质,分析掺杂对电子结构及光学性质的影响.结果表明,过渡金属掺杂在GaN的禁带中引入杂质能带,除掺Fe体系外其它掺杂体系都表现为半金属性.除掺Fe和Ni体系在低能区没有出现光吸收外,其它体系均在低能区杂质能级处出现光吸收.     

过渡金属Tc及其氮化物TcN，TcN$lt;sub$gt;2$lt;/sub$gt;，TcN$lt;sub$gt;3$lt;/sub$gt;与TcN$lt;sub$gt;4$lt;/sub$gt;低压缩性的第一性原理计算研究

采用基于密度泛函理论的第一性原理计算方法研究了Tc及其氮化物的弹性性质、电子结构、原子布局数等,并分析和计算了它的氮化物的理论硬度. 结果表明随着Tc中氮的掺入量的渐增,出现层状结构,它们的弹性模量并非单调增加,其中TcN的体弹模量最大而剪切模量最小;层状结构的TcN₃的剪切模量最大而体弹模量最小,TcN₄的理论计算硬度最大. 说明在Tc的氮化物中,其体弹模量与材料的晶体结构、平均每个原子上的电荷密度和材料的质量密度有关;化学键的共价性结构和氮元素的含量对理论计算硬度有正作用;而剪切模量的极大值则与其层状结构及体系中一定量的方向基本一致的N—N键相关. 关键词： 第一性原理 弹性性质 电子结构     

Al纳米线不同晶向力学行为和变形机制的模拟

采用分子动力学模拟计算方法,考察具有较高层错能的Al纳米线沿不同晶向的力学行为和变形机制。在相同计算条件下与具有较低层错能的Ni、Cu、Au和Ag等FCC金属纳米线进行比较。结果表明：在力学行为方面,Al纳米线的弹性模量呈现明显的结构各向异性,满足E_[111] > E_[110] > E_[100]的关系,这一关系在FCC金属纳米线中普遍成立;Al纳米线的屈服应力随晶向呈现σ_y[100] > σ_y[111] > σ_y[110]的关系,这一关系在具有较低层错能的FCC金属纳米线中不具有普遍性,这与体系中位错形成机制密切相关。根据拉伸变形过程微观结构的演变规律,阐明Al纳米线不同晶向的变形机制,并与具有较低层错能的Ni、Cu、Au和Ag等FCC金属纳米线的变形机制进行比较。结果表明,对于尺度较小的高层错能Al纳米线,Schmid因子和广义层错能均难以准确预测其变形机制。     

Reflectance difference spectroscopy during CdTe/ZnTe interface formation

We have investigated the first stages of epitaxial growth of CdTe on ZnTe and ZnTe on CdTe with reflectance difference (RD) spectroscopy. Spectroscopic RD data show strong optical anisotropy responses at the critical points of the bulk dielectric function at the E₀, E₁ and E₁+Δ₁ interband transitions of ZnTe and CdTe, respectively, which indicate that anisotropic in-plane strain occurs during epitaxial growth. Kinetic RD data taken at the E₁ transition of the respective material exhibit with an accuracy of 1 ML the onset of the formation of misfit dislocations for these material systems.     

Determination and analysis of the dispersive optical constants of the 5,5′,6,6′-tetraphenyl-2,2′-bi([1,3]dithiolo[4,5-b][1,4]dithiinylidene)–DDQ complex thin film

The synthesis and optical properties of the 5,5′,6,6′-tetraphenyl-2,2′-bi([1,3]dithiolo [4,5-b] [1,4]dithiinylidene)–2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) complex thin film were investigated by the optical characterization. The optical constants such as refractive index, extinction coefficient and absorption coefficient were determined using the transmittance T(λ) and reflectance R(λ) spectra and the refractive index dispersion was analyzed using single oscillator of Wemple–Didomenico model. The single oscillator energy E₀ and the dispersion energy E_d were calculated. The effect of temperature on refractive dispersion and optical band gap E_g is also discussed. As a result, the annealing temperatures have an important effect on refractive index of thin film.     

Influence of alkali metal superoxides on structure,electronic,and optical properties of Be_(12)O_(12) nanocage:Density functional theory study

The effect of alkali metal superoxides M_3O(M = Li,Na,K) on the electronic and optical properties of a Be_(12)O_(12) nanocage was studied by density functional theory(DFT) and time-dependent density functional theory(TD-DFT).The energy gaps(Eg) of all configurations were calculated.Generally,the adsorption of alkali metal superoxides on the Be_(12)O_(12) nanocage causes a decrease of Eg.Electric dipole moment μ,polarizability α,and static first hyperpolarizability β were calculated and it was shown that the adsorption of alkali metal superoxides on Be_(12)O_(12) increases its polarizability.It was found that the absorption of M_3 O on Be_(12)O_(12) nanocluster improves its nonlinear optical properties.The highest first hyperpolarizability(β≈ 214000 a.u.) is obtained in the K_3O–Be_(12)O_(12)nanocluster.The TD-DFT calculations were performed to investigate the origin of the first hyperpolarizabilities and it was shown that a higher first hyperpolarizability belongs to the structure that has a lower transition energy.     

β-PtO2: Phononic,thermodynamic, and elastic properties derived from first-principles calculations

β-PtO₂ is a useful transition metal dioxide, but its fundamental thermodynamic and elastic properties remain unexplored. Using first-principles calculations, we systematically studied the structure, phonon, thermodynamic and elastic properties of β-PtO₂. The lattice dynamics and structural stability of β-PtO₂ under pressure were studied using the phonon spectra and vibrational density of states. The vibrational frequencies of the optical modes of β-PtO₂ increase with elevating pressure; this result is comparable with the available experimental data. Then, the heat capacities and their pressure responses were determined based on the phonon calculations. The pressure dependence of the Debye temperature was studied, and the results were compared in two distinct aspects. The elastic moduli of β-PtO₂ were estimated through the Voigt–Reuss–Hill approximation. The bulk modulus of β-PtO₂ increases linearly with pressure, but the shear modulus is nearly independent of pressure. Our study revealed that the elastic stiffness coefficients C₄₄, C₅₅ and C₆₆ play a primary role in the slow variation of the shear modulus.     

A spectroscopic ellipsometric investigation of new critical points of Zn1−xMnxS epilayers

Zn_1−xMn_xS epilayers were grown on GaAs (1 0 0) substrates by hot-wall epitaxy. X-ray diffraction (XRD) patterns revealed that all the epilayers have a zincblende structure. The optical properties were investigated using spectroscopic ellipsometry at 300 K from 3.0 to 8.5 eV. The obtained data were analyzed for determining the critical points of pseudodielectric function spectra, (E) = ₁(E) + i₂(E), such as E₀, E₀ + Δ₀, and E₁, and three E₂ (Σ, Δ, Γ) structures at a lower Mn composition range. These critical points were determined by analytical line-shapes fitted to numerically calculated derivatives of their pseudodielectric functions. The observation of new peaks, as well as the shifting and broadening of the critical points of Zn_1−xMn_xS epilayers, were investigated as a function of Mn composition by ellipsometric measurements for the first time. The characteristics of the peaks changed with increasing Mn composition. In particular, four new peaks were observed between 4.0 and 8.0 eV for Zn_1−xMn_xS epilayers, and their characteristics were investigated in this study.     

High-pressure Raman study of osmium and rhenium up to 200 GPa and pressure dependent elastic shear modulus C44

High-pressure Raman scattering from hexagonal close-packed (HCP) metals Os and Re have been extended up to 200 GPa, and the pressure-dependent shear modulus C₄₄ has been deduced from the Raman-active mode E_2g, which is generated from the adjacent vibration of atoms in hexagonal planes, providing the valuable information about the elastic properties for HCP metals under high pressure. Combined with the available data of HCP metals from previous works, a further study indicates that the $C_{44}^\prime/C_{44}$ ratio would be close to a constant value, 0.01, with increasing atomic number of metals. The results obtained from high-pressure Raman scattering will allow us to probe the elastic anisotropy of the HCP metals at very high pressure.     

The thermodynamics of purely elastic scattering theories and conformal perturbation theory

We discuss the thermodynamic Bethe ansatz, and explain how it allows one to reduce the infinite-volume thermodynamics of a (1 + 1)-dimensional purely elastic scattering theory to the solution of a set of integral equations for the one-particle excitation energies. The free energy at zero chemical potential(s) and temperature T is related to the ground state energy E₀(R) of the theory on a cylinder of circumference R = 1/T. E₀(R) determines properties of the CFT describing the UV limit of the given massive theory. These include the central charge (which we investigated in earlier work), the scaling dimension d of the conformal field whose perturbation leads to the massive theory, the coefficients in the conformal perturbation theory (CPT) expansion of E₀(R) in powers of R^2−d, and the bulk term in the CPT calculation of the ground-state energy. We determine the bulk term analytically, and obtain numerically the first six coefficients in the expansion of E₀(R) for many purely elastic scattering theories, including the scaling limit of the T = T_c Ising model in a magnetic field. The perfect agreement with (more limited) direct CPT results provides further strong support for the identification of these theories as specific perturbed CFTs. We suggest that the singularities of E₀(R), the first of which is responsible for the finite radius of convergence of CPT, are square-root branch points and related to the zeros of the partition function of the corresponding lattice model.     

Diffusion of W on A W(211) plane

The diffusion of W on a (211) plane of a W field emitter has been re-examined by means of the fluctuation autocorrelation method. Diffusion along channels yielded E = 16.8 ± 0.5 kcal, D₀ = (3 ± 1) × 10⁻⁵ cm² s⁻¹. For diffusion across channels E =6.6 kcal, D₀ = 4 × 10⁻⁹cm² s⁻¹ at T < 752 K, and E = 24 kcal, D₀ = 5 × 10⁻⁴ cm² s⁻¹ at T > 752 K. The results for diffusion along channels yield E and D₀ values intermediate between recent results by Wang and Ehrlich [Surf. Sci. 206 (1988) 451] using field ion microscopy (E = 19 kcal, D₀ = 7.7 × 10⁻³ cm² s⁻¹) and Tringides and Gomer [J. Chem. Phys. 84 (1986) 4049], using the same method as the present work but a larger slit (E = 13.3 kcal, D₀ = 7 × 10⁻⁷ cm² s⁻¹). The results for cross channel diffus good agreement with those of Tringides and Gomer below 752 K, where these authors stopped. The new high temperature results suggest that the channel wall exchange mechanism postulated by Tringides and Gomer for cross channel diffusion at low T gives way to diffusion by climbing over the channel walls with higher E but also higher D₀ above 752 K. Possible reasons for the discrepancies between these three sets of results and the absence of cross channel diffusion in the work of Wang and Ehrlich are briefly discussed.