Vacancies in GaN bulk and nanowires: effect of self-interaction corrections

We investigate gallium and nitrogen vacancies in gallium nitride (GaN) bulk and nanowires using self-interaction corrected pseudopotentials (SIC). In particular, we examine the band structures to compare and contrast differences between the SIC results and standard density functional theory (DFT) results using a generalized gradient approximation (GGA) (Perdew et al 1996 Phys. Rev. Lett. 77 3865) functional. For pure nanowires, we observed similar trends in the bandgap behaviour, with the gap decreasing for increasing nanowire diameters (with larger bandgaps using SIC pseudopotentials). For gallium vacancies in bulk GaN and GaN nanowires, SIC results are similar to DFT-GGA results, albeit with larger bandgaps. Nitrogen vacancies in bulk GaN show similar defect-induced states near the conduction band, whilst a lower lying defect state is observed below the valence band for the DFT-GGA calculations and above the valence band for the SIC results. For nitrogen vacancies in GaN nanowires, similar defect states are observed near the conduction band, however, while the SIC calculations also show a defect state/s above the valence band, we were unable to locate this state for the DFT-GGA calculations (possibly because it is hybridized with edge states and buried below the valence band).     

闪锌矿相GaN热容和格林爱森参数

利用壳层模型分子动力学方法，在高温高压条件下对闪锌矿相GaN的压力体积关系、定压和定容热容及格林爱森参数进行了比较研究，其中Ga-Ga、Ga-N和N-N三组离子对间的相互作用通过极化势模型来描述，即出于对半导体材料GaN离子特性的考虑而分别给予Ga离子和N离子以两组不同大小的电荷．结果表明计算得到的环境条件下的热力学参数和最近的其他理论结果吻合，同第一性原理计算结果比较，定容热容在低温下的差别可以用来解释不同方法所采用的不同近似机制．最后在300?2000 K和0?40 GPa条件下，对闪锌矿相GaN的物理特性做了总结．     

Al2O3衬底无催化剂生长GaN纳米线及其光学性能

采用一种绿色的等离子增强化学气相沉积法,以Al2O3为衬底, Ga金属为镓源, N2为氮源,在不采用催化剂的情况下,成功制备获得了结晶质量良好的GaN纳米线.研究表明,生长温度可显著调控GaN纳米线的形貌,当反应温度为950℃时,生长出的GaN微米片为六边形;当反应温度为1000℃时,生长出了长度为10-20μm的超长GaN纳米线.随着反应时间增加, GaN纳米线的长度增加. GaN纳米线内部存在着压应力,应力大小为0.84 GPa.同时,也进一步讨论了GaN纳米线无催化剂生长机制. GaN纳米线光致发光结果显示, GaN纳米线缺陷较少,结晶质量良好,在360 nm处有一个较为尖锐的本征发光峰,可应用于紫外激光器等光电子器件.本研究结果将为新型光电器件低成本绿色制备提供一个可行的技术方案.     

Synthesis and field emission properties of GaN nanowires

Gallium nitride (GaN) nanowires grown on nickel-coated n-type Si (1 0 0) substrates have been synthesized using chemical vapor deposition (CVD), and the field emission properties of GaN nanowires have been studied. The results show that (1) the grown GaN nanowires, which have diameters in the range of 50-100 nm and lengths of several micrometers, are uniformly distributed on Si substrates. The characteristics of the grown GaN nanowires have been investigated using X-ray diffraction (XRD) and transmission electron microscopy (TEM), and through these investigations it was found that the GaN nanowires are of a good crystalline quality (2) When the emission current density is 100 μA/cm², the necessary electric field is an open electric field of around 9.1 V/μm (at room temperature). The field enhancement factor is ∼730. The field emission properties of GaN nanowires films are related both to the surface roughness and the density of the nanowires in the film.     

纳米晶粒团聚GaN纳米线A1(LO) Raman峰的非对称展宽

氮化镓(GaN)是一种直接带隙Ⅲ～Ⅴ族半导体化合物,具有较宽的禁带宽度(Eg=3.4eV),较高的热稳定性,以及抗辐照等特性[1-4],是制备近紫外和蓝光光电子器件、高速微电子器件的理想材料.制备低维纳米结构,研究其物理性质既是理解低维量子现象的要求,也是未来纳米电子器件发展的需要.近年来,很多小组已经通过不同的方法成功地制备出GaN纳米棒、纳米线等一系列一维材料.这些方法包括碳纳米管辅助的方法[5]、电弧放电的方法[6]、激光刻蚀的方法[7]、升华法[8]、高温分解法以及化学气相沉积(CVD)[9-15].其中CVD方法以其制备过程简单,制备材料晶…     

Synthesis of GaN nanowires by Tb catalysis

Rare earth metal seed Tb was employed as catalyst for the growth of GaN wires. GaN nanowires were synthesized successfully through ammoniating Ga₂O₃/Tb films sputtered on Si(1 1 1) substrates. The samples characterization by X-ray diffraction and Fourier transform infrared indicated that the nanowires are constituted of hexagonal wurtzite GaN. Scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy showed that the samples are single-crystal GaN nanowire structures. The growth mechanism of the GaN nanowires is discussed.     

未钝化和H钝化GaN纳米线的电子结构

用密度泛函理论研究直径为9.5Å,15.9Å和22.5Å,未钝化和H钝化GaN纳米线的能带和态密度.结果表明:未钝化和H钝化GaN纳米线的能隙都是直接带隙,未钝化GaN纳米线的禁带宽度随着直径的增加减小,但是变化不明显,H钝化GaN纳米线的禁带宽度随着直径增大也是减小的,但是减小的幅度比未钝化的大.未钝化GaN纳米线表面N原子的2p电子主要聚集在价带顶,表面Ga原子的4p电子主要聚集在导带底,这两种电子都具有很强的局域性,而且决定着能隙值;加H钝化可以消除表面原子产生的表面效应.     

Metal catalyst-assisted growth of GaN nanowires on graphene films for flexible photocatalyst applications

We report the growth of high-areal-density GaN nanowires on large-size graphene films using a nickel (Ni) catalyst-assisted vapor-liquid-solid (VLS) method. Before the nanowire growth, the graphene films were prepared on copper foils using hot-wall chemical vapor deposition and transferred onto SiO₂/Si substrates. Then, for catalyst-assisted VLS growth, Ni catalyst layers with thickness of a few nanometers were deposited on the graphene-coated substrates using a thermal evaporator. We investigated the effect of the Ni catalyst thickness on the formation of GaN nanowires. Furthermore, the structural and optical characteristics of GaN nanowires were investigated using X-ray diffraction, transmission electron microscopy, and photoluminescence spectroscopy. The GaN nanowires grown on graphene films were transferred onto polymer substrates using a simple lift-off method for applications as flexible photocatalysts. Photocatalysis activities of the GaN nanowires prepared on the flexible polymer substrates were investigated under bending conditions.     

Growth and characterization of high-quality GaN nanowires by ammonification technique

GaN nanowires were successfully synthesized at high quality and large yield on Si (1 1 1) substrate through ammoniating Ga₂O₃/BN films deposited by radio frequency (RF) magnetron sputtering system. X-ray diffraction (XRD), Fourier transformed infrared spectra (FTIR) and selected-area electron diffraction (SAED) confirm that the as-synthesized nanowires are of a hexagonal GaN with wurtzite structure. Scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) reveal that the nanowires have a straight and smooth curved structure with extremely uniform diameter of about 60 nm, which is helpful to the application of GaN nanowires. The present results demonstrate that the BN is a very important intermedium in the growth of GaN nanowires by this method.     

Synthesis of GaN nanowires on gold-coated SiC substrates by novel pulsed electron deposition technique

A two-step approach for macro-synthesis of GaN nanowires was developed in this study. GaN nanoparticles were firstly synthesized through a facile solid-state reaction using an organic reagent dicyandiamide (C₂N₄H₄) and Ga₂O₃ as precursors. Subsequently, single-crystalline wurtzite GaN nanowires were grown on gold-coated 6H-SiC substrates via novel pulsed electron deposition (PED) technique using the as-prepared GaN nanoparticles as target, which provides a new route employing nanoparticles as precursors to fabricate GaN nanowires. It is found that pulsed electron ablation induced Ga and N plasma directly towards the gold-coated substrate to initialize the vapor-liquid-solid (VLS) growth processes. The morphological and structural properties were investigated in detail and Raman scattering spectrum of these nanowires presented some new features.     

Preparation and characterization of carbon nanotubes encapsulated GaN nanowires

A novel two-step catalytic reaction is developed to synthesize gallium nitride nanowires encapsulated inside carbon nanotubes (GaN@CNT). The nanowires are prepared from the reaction of gallium metal and ammonium using metals or metal alloys as a catalyst. After the formation of the nanowires, carbon nanotubes are subsequently grown along the nanowires by chemical vapor deposition of methane. The structural and optical properties of pure GaN nanowires and GaN@CNT are characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy and Raman spectroscopy. The results show that GaN nanowires are indeed encapsulated inside carbon nanotubes. The field emission studies show that the turn-on field of GaN@CNT is higher than that of carbon nanotubes, but substantially lower than that of pure GaN nanowires. This work provides a wide route toward the preparation and applications of new one-dimensional semiconductor nanostructures.     

Synthesis and characterization of GaN nanowires by ammoniating Ga2O3/Cr thin films deposited on Si(1 1 1) substrates

GaN nanowires have been successfully synthesized on Si(1 1 1) substrates by magnetron sputtering through ammoniating Ga₂O₃/Cr thin films at 950 °C. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), FT-IR spectrophotometer, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TEM), and photoluminescence (PL) spectrum were carried out to characterize the microstructure, morphology, and optical properties of GaN samples. The results demonstrate that the nanowires are single-crystal GaN with hexagonal wurtzite structure and high-quality crystalline, have the size of 30-80 nm in diameter and several tens of microns in length with good emission properties. The growth direction of GaN nanowires is perpendicular to the fringe of (1 0 1) plane. The growth mechanism of GaN nanowires is also discussed in detail.     

化学气相沉积法制备GaN纳米结构设计性实验

在无催化剂辅助条件下,采用化学气相沉积法生长了GaN纳米线.通过调整衬底、NH3气流、生长时间等,实现了半导体GaN纳米线的生长以及形貌调控.用X射线衍射仪和扫描电子显微镜对产物的物相及形貌进行了表征.获得了合成GaN纳米线的优化条件.     

Synthesis of large-scale GaN nanowires by ammoniating Ga2O3 films on Co layer deposited on Si（111） substrates

A mass of GaN nanowires has been successfully synthesized on Si（111） substrates by magnetron sputtering through ammoniating Ga2O3/Co films at 950℃. X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscope and Fourier transformed infrared spectra are used to characterize the samples. The results demonstrate that the nanowires are of single-crystal GaN with a hexagonal wurtzite structure and possess relatively smooth surfaces. The growth mechanism of GaN nanowires is also discussed.     

Synthesis and characterization of GaN nanowires

In this work, GaN nanowires were fabricated on Si substrates coated with NiCl₂ thin films using chemical vapor deposition (CVD) method by evaporating Ga₂O₃ powder at 1100 °C in ammonia gas flow. X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscope (HRTEM) and photoluminescence (PL) spectrum are used to characterize the samples. The results demonstrate that the nanowires are single-crystal GaN with hexagonal wurtzite structure. The growth mechanism of GaN nanowires is also discussed.     

The origin of yellow band emission and cathodoluminescence of Au-catalyzed wurtzite GaN nanowires

GaN nanowires with large yield are directly synthesized by simply ammoniating the gallium oxide powders in the presence of ammonia gas at 1000 °C, under the assistance of Au nanocatalysts. The microstructure and crystallinity of as-synthesized GaN nanowires are well studied by using high-resolution transmission electron microscope (HRTEM) and some structural defects such as stacking faults are found in the GaN nano-crystal. Cathodoluminescence measurement shows that a strong near-band-edge (NBE) emission band centered at 384 nm and a broad yellow band in the range of 500–800 nm are observed. Finally, the growth mechanism and possible optical emission process of GaN nanowires are discussed.     

Ab initio study of [001] GaN nanowires

We present the results of a study of structural, electronic, and optical properties of the unpassivated and H-passivated GaN nanowires having diameters in the range of 3.29 to 18.33 Å grown along [001] direction by employing the first-principles pseudopotential method within density functional theory in the local density approximation. Two types of nanowires having hexagonal and triangular cross-sections have been investigated. The binding energy increases with the diameter of the nanowire because of a decrease in the relative number of the unsaturated surface bonds. The binding energies of the triangular cross-sectional nanowires are somewhat smaller than those of the hexagonal cross-sectional nanowires in accordance with the Wulff’s rule except the smallest diameter triangular cross-sectional nanowire, where the binding energy is comparable with the corresponding hexagonal cross-sectional nanowires. The band gap varies rapidly with the diameter of the nanowire in the case of the smaller diameter nanowires, and quite slowly for the larger diameter nanowires. After atomic relaxation, appreciable distortion occurs in the nanowires, where the chains of Ga- and N-atoms are curved in different directions. These distortions are reduced with the diameters of the nanowires. The optical absorption in the GaN nanowires is quite strong in the ultra-violet region but an appreciable absorption is also present in the visible region for the larger diameter nanowires. The present results indicate the possibility of engineering the properties of nanowires by manipulating their diameter and surface structure. The presently predicted smaller diameter GaN nanowire possessing the triangular cross-section should be observable in the experiments.     

The influence of growth temperatures on the characteristics of GaN nanowires

This paper presents the investigation of the properties of GaN nanowires synthesized from Ni-catalyzed chemical vapour deposition method under various growth temperatures. The influence of the growth temperatures on the morphological, structural and optical characteristics of the synthesized GaN nanowires was investigated in this work. Field-emission scanning electron microscopy images revealed that the 950 °C was the optimal growth temperature for synthesizing uniform, straight and smooth morphology of GaN nanowires. X-ray diffraction results demonstrated that the synthesized low dimensional GaN structures have the hexagonal wurtzite structure. Ultraviolet and blue emissions were detected from photoluminescence measurements. In addition, phonon replicas with the energy separation of 90 meV have been observed at the lower energy of the blue emission region in photoluminescence spectra.     

Near UV photoluminescence of Hg-doped GaN nanowires

Mass Hg-doped GaN nanowires with an average diameter of about 25 nm and lengths up to hundreds of micrometers are fabricated by chemical vapor reaction. The as-synthesized products have a single crystal phase and grow along the 0 0 1 direction. The growth of Hg-doped GaN nanowires is suggested for quasi vapor–solid mechanism (QVSM). In particular, for as large-scale GaN nanowires like films, a novel strong near ultraviolet PL spectrum appears with a doping Hg where the Hg-doped GaN nanowires are found to be responsible for the different characteristics; the PL mechanism is explained in detail.