Magnetic coupling properties of Mn-doped AlN nanowires: First-principles calculations

Based on first-principles within the framework of the density functional theory, we have studied the magnetic coupling properties of Mn-doped AlN nanowires. By analyzing the results of different Mn-doped AlN nanowires, we found that for the passivated nanowire, ferromagnetic state is more stable, while for the unpassivated nanowire, the favorable state transits into anti-ferromagnetic state, which can be well explained by the band coupling model. The results indicate that the degree of surface passivation of dangling bonds is an important factor in the magnetic properties of doped nanowires.     

相变及空位缺陷对AlN在高压下光学性质的影响

采用基于密度泛函理论(DFT)的第一性原理方法, 计算了AlN理想晶体和含铝、氮空位点缺陷晶体在100 GPa压力范围内的光学性质. 波长在532 nm处的折射率计算结果表明：AlN从纤锌矿结构相转变为岩盐矿结构相将导致其折射率增加; 铝空位缺陷将引起AlN岩盐矿结构相的折射率增大, 而氮空位缺陷却导致其折射率降低. 能量损失谱计算数据指明：结构相变使得AlN能量损失谱蓝移、主峰峰值强度增强;铝和氮空位缺陷将导致AlN岩盐矿结构相的能量损失谱主峰进一步蓝移、峰值强度再次增强. 计算预测的结果将为进一步的实验探究提供理论参考.     

表面钝化效应对GaAs纳米线电子结构性质影响的第一性原理研究

纳米线表面存在大量的表面态,它们能够引起电子分布在纳米线表面,使得纳米线的电学性质对表面条件变得更加敏感,严重地制约器件的性能.表面钝化能够有效地移除纳米线的表面态,进而能够有效地优化器件的性能.采用基于密度泛函理论的第一性原理计算方法研究了表面钝化效应对GaAs纳米线电子结构性质的影响.考虑了不同的钝化材料,包括氢元素、氟元素、氯元素和溴元素.研究结果表明:具有小尺寸的GaAs裸纳米线的能带结构呈间接带隙特征,表面经过完全钝化后,转变为直接带隙特征;GaAs纳米线表面经过氢元素不同位置和不同比例钝化后,展示出不同的电学性质;表面钝化的物理机理是钝化原子与纳米线表面原子通过电荷补偿移除纳米线表面的电子态;与氢元素钝化相比,GaAs纳米线表面经过氟元素、氯元素和溴元素钝化后,带隙宽度较小,原因是氟元素、氯元素和溴元素在钝化过程中具有较小的电荷补偿能力,不能完全移除表面态.     

Anisotropic optical response of GaN and AlN nanowires

We present a theoretical study of the electronic structure and optical properties of free-standing GaN and AlN nanowires. We have implemented the empirical tight-binding method, with an orbital basis sp(3), that includes the spin-orbit interaction. The passivation of the dangling bonds at the free surfaces is also studied, together with the effects on the electronic structure of the nanowire. For both GaN and AlN nanowires, we have found a remarkable anisotropy of the optical absorption when the light-polarization changes, showing in the case of GaN a dependence on the nanowire size.     

First principles study of N-N split interstitial in GaN nanowires

Atomic and electronic properties of N-N split interstitial in GaN nanowires have been investigated using first principles calculations. The formation energy calculations show that the N-N interstitial favors substituting an N atom at the surface of the nanowires. The interstitial induces localized states in the band gap of GaN nanowires.     

First-principles studies on stabilities and electronic properties of AlN nanostructures

Under the generalized gradient approximation (GGA), the stabilities and electronic properties of semiconductor AlN nanostructures have been investigated by using the first-principles projector-augmented wave (PAW) potential within the density function theory (DFT) framework. The single-walled faceted AlNNTs present an obvious structural modification. The larger the diameter, the more stable the nanowire, and the wires without internal surfaces are more stable than the multiwalled tubes or the SWNT. Therefore, the large-size nanowires are easier to be synthesized than the corresponding multiwalled tubes or single-walled nanotube in experiment. The dangling bonds of surface atoms cause the “localized edge-induced states”. These two nanostructures C and F are still wide band gap semiconductors accompanied by a few surface states located in the band gap of bulk AlN and thus extremely suitable for application in flexible pulse wave sensors, nanomechanical resonators and light-emitting diodes.     

Influence of metallic coatings on the photoluminescence properties of ZnO nanowires

We report on low‐temperature photoluminescence studies of ZnO nanowires coated with thin metallic films. For all analyzed metals (Al, In, Au, Ni, Cu), we find an increased relative intensity of the green deep‐level emission. This is accompanied by a significant reduction of the relative intensity of the surface exciton band. The observed effects are most likely related to the formation of metal induced gap states in the surface region of the ZnO nanowires. A model for the band structure in the surface region of the metal‐coated nanowires is proposed that successfully explains the changes in the photoluminescence spectra after the coating process. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

六方氮化铝纳米线本征缺陷和氧杂质的光致发光谱研究

利用AlCl3和NaN3直接反应合成出六方结构氮化铝纳米线.变温光致发光谱显示,在可见光范围内有两个半高宽大约为5 nm的尖锐辐射峰,中心波长分别位于413 nm和422 nm处.同时,在近紫外区还有一个较宽的辐射带,随着温度升高,该辐射峰发生了明显的红移现象,其中心波长随温度线性变化.理论和实验分析表明,413 nm辐射与AlN本身性质无关,而422 nm辐射峰是与A1有关的两种本征缺陷所致.     

The electronic properties of SiCAlN quaternary compounds

We have investigated the properties of SiCAlN quaternary compounds composed of SiC and AlN polytypes by first-principle calculations. We find that their band gaps have a large tunability and are sensitive to the polytype structures. Their electronic properties vary from wide-band-gap semiconducting to metallic due to the complex charge transfer between the two constituents SiC and AlN. The formation energies are also calculated. These results show SiCAlN quaternary compounds have potential applications in the electronic devices that can be tuned over a large wavelength range.     

First principles study of the electronic properties of twinned SiC nanowires

The electronic properties of saturated and unsaturated twinned SiC nanowires grown along [111] direction and surrounded by {111} facets are investigated using first-principles calculations with density functional theory and generalized gradient approximation. All the nanowires considered, including saturated and unsaturated ones, exhibit semiconducting characteristics. The saturated nanowires have a direct band gap and the band gap decreases with increasing diameters of the nanowires. The hexagonal (2H) stacking inside the cubic (3C) stacking has no effect on electronic properties of the SiC nanowires. The highest occupied molecular orbitals and the lowest unoccupied molecular orbitals are distributed along the nanowire axis uniformly, which indicates that the twinned SiC nanowires are good candidates in realizing nano-optoelectronic devices.     

First principle study of nitrogen vacancy in aluminium nitride

In the framework of density functional theory, using the plane-wave pseudopotential method, the nitrogen vacancy ($V_{\rm N})$ in both wurtzite and zinc-blende AlN is studied by the supercell approach. The atom configuration, density of states, and formation energies of various charge states are calculated. Two defect states are introduced by the defect, which are a doubly occupied single state above the valance band maximum (VBM) and a singly occupied triple state below the conduction band minimum (CBM) for wurtzite AlN and above the CBM for zinc-blende AlN. So $V_{\rm N}$ acts as a deep donor in wurtzite AlN and a shallow donor in zinc-blende AlN. A thermodynamic transition level $E({3 + } \mathord{\left/ {\vphantom {{3 + } + }} \right. \kern-\nulldelimiterspace} + )$ with very low formation energy appears at 0.7 and 0.6eV above the VBM in wurtzite and zinc-blende structure respectively, which may have a wide shift to the low energy side if atoms surrounding the defect are not fully relaxed. Several other transition levels appear in the upper part of the bandgap. The number of these levels decreases with the structure relaxation. However, these levels are unimportant to AlN properties because of their high formation energy.     

The stability and electronic properties of wurtzite and zinc-blende ZnS nanowires

The stability and electronic properties of the pristine wurtzite (WZ) and zinc-blende (ZB) structural ZnS nanowires are investigated and compared by using first-principles approaches. It shows that the WZ-ZnS nanowire is more stable energetically than the ZB-ZnS nanowire. The two kinds of ZnS nanowires have different electronic properties due to both the quantum confinement effect and the surface effect. The band gaps of pristine WZ nanowires become larger than that of the corresponding bulk ZnS, while those of ZB nanowires are smaller. The electronic properties of the hydrogen-passivated WZ-ZnS and ZB-ZnS nanowires are further calculated. The underlying physical reason for their energetic and electronic structures is elucidated.     

First surface electronic structure of a wurtzite-type semiconductor the polar and nonpolar surfaces of ZnO

We report the first calculations of the surface electronic structure for a Wurtzite-type semiconductor, namely ZnO. The bulk electronic properties of the material are described by a realistic empirical tight binding Hamiltonian which we obtained by fitting a selfconsistent pseudopotential bulk band structure and experimental bulk XPS and UPS data. Using the scattering theoretical method, we have calculated the surface band structures and wavevector-integrated as well as wavevector-resolved layer densities of states for polar and nonpolar ZnO surfaces. In agreement with experiment, we find no surface states in the gap on clean ZnO surfaces. Within the projection of the bulk valence and conduction bands, however, distinct surface features occur. First, there are ionic O-2p and Zn-4s surface states which have predominantly resonance character. In addition, more covalent back bond and anti back bond surface states are found which are occupied and empty, respectively. We find very good agreement with recent EELS and UPS surface data.     

掺杂GaN/AlN超晶格第一性原理计算研究

第一性原理计算方法在解释实验现象和预测新材料结构及其性质上有着重要作用. 因此, 通过基于密度泛函理论的第一性原理的方法, 本文系统地研究了Mg和Si掺杂闪锌矿和纤锌矿两种晶体结构的GaN/AlN超晶格体系中的能量稳定性以及电学性质. 结果表明: 在势阱层(GaN 层)中, 掺杂原子在体系中的掺杂形成能不随掺杂位置的变化而发生变化, 在势垒层(AlN层)中也是类似的情况, 这表明对于掺杂原子来说, 替代势垒层(或势阱层)中的任意阳离子都是等同的; 然而, 相比势阱层和势垒层的掺杂形成能却有很大的不同, 并且势阱层的掺杂形成能远低于势垒层的掺杂形成能, 即掺杂元素(Mg_Ga, Mg_Al, Si_Ga和Si_Al)在势阱区域的形成能更低, 这表明杂质原子更易掺杂于结构的势阱层中. 此外, 闪锌矿更低的形成能表明: 闪锌矿结构的超晶格体系比纤锌矿结构的超晶格体系更易于实现掺杂; 其中, 闪锌矿结构中, 负的形成能表明: 当Mg原子掺入闪锌矿结构的势阱层中会自发引起缺陷. 由此, 制备以闪锌矿结构超晶格体系为基底的p型半导体超晶格比制备n型半导体超晶格需要的能量更低并且更为容易制备. 对于纤锌矿体系来说, 制备p型和n型半导体的难易程度基本相同. 电子态密度对掺杂体系的稳定性和电学性质进一步分析发现, 掺杂均使得体系的带隙减小, 掺杂前后仍然为第一类半导体. 综上所述, 本文内容为当前实验中关于纤锌矿结构难以实现p型掺杂问题提供了一种新的技术思路, 即可通过调控相结构实现其p型掺杂.     

Pressure-induced phase transition and electronic properties of AlN nanowires: an ab initio study

The structural stability of AlN nanowires have been analyzed in wurtzite (B4), zincblende (B3), rocksalt (B1) and CsCl (B2) type phases using density functional theory based ab initio approach. The total energy calculations have been performed in a self-consistent manner using local density approximation as exchange correlation functional. The analysis finds the B4 type phase as most stable amongst the other phases taken into consideration and observes the structural phase transition from B4?→?B3, B4?→?B1, B4?→?B2, B3?→?B1 and B3?→?B2 at 42.7, 76.54, 142, 30.4 and 108.9?GPa respectively. Lattice parameter, bulk modulus and pressure derivatives of AlN nanowires have also been calculated for all the stable phases. The electronic band structure analysis of AlN nanowires shows a semiconducting nature in its B4, B3 and B1 type phases, whereas the B2 type phase is found to be metallic.     

A simple method to synthesize worm-like AlN nanowires and its field emission studies

The worm-like AlN nanowires are fabricated by the plasma-enhanced chemical vapor deposition (PECVD) on Si substrates through using Al powder and N₂ as precursors, CaF₂ as fluxing medium, Au as catalyst, respectively. The as-grown worm-like AlN nanowires each have a polycrystalline and hexagonal wurtzite structure. Their diameters are about 300 nm, and the lengths are over 10 μm. The growth mechanism of worm-like AlN nanowires is discussed. Hydrogen plasma plays a very important role in forming the polycrystalline structure and rough surfaces of worm-like AlN nanowires. The worm-like AlN nanowires exhibit an excellent field-emission (FE) property with a low turn-on field of 4.5 V/μm at a current density of 0.01 mA/cm² and low threshold field of 9.9 V/μm at 1 mA/cm². The emission current densities of worm-like AlN nanowires each have a good stability. The enhanced FE properties of worm-like AlN nanowires may be due to their polycrystalline and rough structure with nanosize and high aspect ratio. The excellent FE properties of worm-like AlN nanowires can be explained by a grain boundary conduction mechanism. The results demonstrate that the worm-like AlN nanowires prepared by the proposed simple and the PECVD method possesses the potential applications in photoelectric and field-emission devices.     

Ab initio study of platinum induced reconstructions on Ge(001)-(1×2) surface with dimerization

We present first principle total energy calculation of Pt induced reconstructions on Ge(001)-(1×2) surface with dimerization. Study was undertaken using localized orbitals basis set DFT using SIESTA to compare pure Ge dimerized Ge(001)-(1×2) surface with 0.5 and 1.0 Pt covered dimerized Ge(001)-(1×2) surface with the possibility of homo (Ge-Ge and Pt-Pt) and hetro (Pt-Ge) dimers. From total energy calculation results we calculated dimer bond lengths, buckling angles and formation energy of dimers on Ge(001)-(1×2) surface. By calculating the formation energy of different configurations we find that Ge-Ge buckled dimerized surface has least (−1.23 eV/dimer) and Pt-Pt symmetric dimerized surface has largest (+0.09 eV/dimer) formation energy with respect to unreconstructed surface. We further calculated the electronic DOS and band structure of Ge dimerized as well as Pt dimerized surface to see the change in semiconducting behavior on dimerization. By comparing the DOS and electronic band structure of homo Ge dimerized surface, we found metallicity of Ge(001)-(1×2) surface results from dimer formation. Also by comparing the electronic band structure of homo Ge dimerized surface with unreconstructed surface we find that less number of bands crossing the Fermi level which is perhaps due to the saturation of one dangling bond per Ge surface atom. By introducing Pt at 0.5 and 1.0 coverage in place of Ge, except for homo Pt buckled dimerized surface having 1.0 coverage of Pt, we find in all other cases increase in number of bands are crossing the Fermi level, indicating strong metallic behavior of Ge(001)-(1×2) surface.     

B36团簇组装一维纳米线的密度泛函研究

采用密度泛函理论计算方法系统研究了B₃₆团簇组装一维纳米线的几何结构、电子结构及稳定性.发现两种不同构型的B₃₆团簇组装纳米线静态结构能量相同,且均为动力学稳定结构,但二者电子结构明显不同:分别呈现出半金属和小带隙半导体特征.对两类纳米线的H原子吸附显示:半金属纳米线转变为半导体,而半导体纳米线仍保持为半导体,但带隙明显增大.表明H原子吸附对于B₃₆团簇组装纳米线的电子结构具有明显的调控作用.     

Tuning electronic and magnetic properties of AlN nanosheets with hydrogen and fluorine: First-principles prediction

We performed first-principles calculations to study the electronic structures and magnetic properties of the two-dimensional AlN nanosheet decorated with hydrogen and fluorine. The results show that the band gap of AlN nanosheet can be tuned significantly, and they can be a direct or an indirect semiconductor when decorated with H or F atoms on AlN surface. Spin-polarized calculations show that semi-decorated AlN sheets with H or F atoms can present a half-metal or p-type ferromagnetic (FM) semiconductor with Curie temperatures above room temperature. More interestingly, when AlN nanosheet co-decorated with H and F on each side, they show anisotropic semiconducting characters with a band gap of 1.02 eV. Our studies demonstrate that the decoration III-V group semiconductor nanosheets with foreign atoms might be an efficient route to tune the electronic and magnetic properties in low-dimensional materials.