Facet and in-plane crystallographic orientations of GaN nanowires grown on Si(111)

We have determined the in-plane orientation of GaN nanowires relative to the Si (111) substrate on which they were grown. We used x-ray diffraction pole figure measurements to evidence two types of crystallographic orientation, all the nanowires having [Formula: see text] lateral facets. The proportion of these two orientations was determined and shown to be influenced by the pre-deposition of Al(Ga)N intermediate layers. In the main orientation, the GaN basal [Formula: see text] directions are aligned with the [Formula: see text] directions. This orientation corresponds to an in-plane coincidence of GaN and Si lattices.     

Structural and optical properties of InGaN/GaN nanowire heterostructures grown by PA-MBE

The structural and optical properties of InGaN/GaN nanowire heterostructures grown by plasma-assisted molecular beam epitaxy have been studied using a combination of transmission electron microscopy, electron tomography and photoluminescence spectroscopy. It is found that, depending on In content, the strain relaxation of InGaN may be elastic or plastic. Elastic relaxation results in a pronounced radial In content gradient. Plastic relaxation is associated with the formation of misfit dislocations at the InGaN/GaN interface or with cracks in the InGaN nanowire section. In all cases, a GaN shell was formed around the InGaN core, which is assigned to differences in In and Ga diffusion mean free paths.     

Catalyst-free synthesis of well-aligned ZnO nanowires on In0.2Ga0.8N, GaN, and Al0.25Ga0.75N substrates

Well-aligned ZnO nanowires have been synthesized vertically on In0.2Ga0.8N, GaN, and Al0.25Ga0.75N substrates, using a catalyst-free carbon thermal-reduction vapor phase deposition method for the first time. The as-synthesized nanowires are single crystalline wurtzite structure, and have a growth direction of [0001]. Each nanowire has a smooth surface, and uniform diameter along the growth direction. The average diameter and length of these nanowires are 120-150 nm, and 3-10 )m, respectively. We suggest that the growth mechanism follow a self-catalyzing growth model. Excitonic emission peaked around 385 nm dominates the room-temperature photoluminescence spectra of these nanowires. The room-temperature photoluminescence and Raman scattering spectra show that these nanowires have good optical quality with very less structural defects.     

Optical properties and carrier dynamics of self-assembled GaN/Al(0.11)Ga(0.89)N quantum dots

GaN quantum dots were grown on an Al(0.11)Ga(0.89)N buffer layer by using flow rate modulation epitaxy. The Stranski-Krastanov growth mode was identified by an atomic force microscopy study. The thickness of the wetting layer is about 7.2 monolayers. The temperature dependent photoluminescence studies showed that at low temperature the localization energy, which accounts for de-trapping of excitons, decreases with the reducing dot size. The decrease in emission efficiency at high temperature is attributed to the activation of carriers from the GaN dot to the nitrogen vacancy (V(N)) state of the Al(0.11)Ga(0.89)N barrier layer. The activation energy decreases with reducing dot size.     

GaN nanowires: CVD synthesis and properties

The growth of GaN nanowires from Ga and NH₃ sources in the flow of Ar carrier gas using a chemical vapor deposition (CVD) system was systematically studied. The substrates used were Si(111) and Si(100). Fabricated nanowires were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). We investigated the influence of growth temperature, catalyst used, Ga amount, and the ratio of Ar and NH₃ flow rates on the morphology and properties of GaN nanowires. We found that the best results were obtained for a growth temperature of 950 °C. Optimal catalysts were Au and metallic Ni, while the use of nickel nitrate was found to lead to formation of SiO_x nanowire bunches in addition to GaN nanowires. For the optimal temperature and catalyst used, the influence of the Ga to N ratio on the nanowire growth was studied. It was found that different types of nanostructures are observed in relatively Ga-rich and in relatively N-rich conditions. Growth mechanisms of different types of nanowires, including the stacked-cone nanowires and the microscale structures formed by lateral growth under N-rich conditions, are discussed.     

Macro- and micro-strain in GaN nanowires on Si(111)

We analyze the strain state of GaN nanowire ensembles by x-ray diffraction. The nanowires are grown by molecular beam epitaxy on a Si(111) substrate in a self-organized manner. On a macroscopic scale, the nanowires are found to be free of strain. However, coalescence of the nanowires results in micro-strain with a magnitude from ± (0.015)% to ± (0.03)%. This micro-strain contributes to the linewidth observed in low-temperature photoluminescence spectra.     

An improved AFM cross-sectional method for piezoelectric nanostructures properties investigation: application to GaN nanowires

We present an improved atomic force microscopy (AFM) method to study the piezoelectric properties of nanostructures. An AFM tip is used to deform a free-standing piezoelectric nanowire. The deflection of the nanowire induces an electric potential via the piezoelectric effect, which is measured by the AFM coating tip. During the manipulation, the applied force, the forcing location and the nanowire's deflection are precisely known and under strict control. We show the measurements carried out on intrinsic GaN and n-doped GaN-AlN-GaN nanowires by using our method. The measured electric potential, as high as 200 mV for n-doped GaN-AlN-GaN nanowire and 150 mV for intrinsic GaN nanowire, have been obtained, these values are higher than theoretical calculations. Our investigation method is exceptionally useful to thoroughly examine and completely understand the piezoelectric phenomena of nanostructures. Our experimental observations intuitively reveal the great potential of piezoelectric nanostructures for converting mechanical energy into electricity. The piezoelectric properties of nanostructures, which are demonstrated in detail in this paper, represent a promising approach to fabricating cost-effective nano-generators and highly sensitive self-powered NEMS sensors.     

Spiral growth and formation of stacking faults and vacancy islands during molecular beam epitaxy of InN on GaN(0001)

The surface morphology and atomic structure of InN grown on the Ga-rich GaN(0001)-pseudo (1 × 1) structure is studied by scanning tunneling microscopy. Spirals are formed as a result of screw dislocations emerging at the surface to relieve the strain from the lattice mismatch. Two additional types of strain relaxation mechanisms are also found, both due to the incorporation of excess Ga atoms from the starting pseudo (1 × 1) surface into the growing films. For films below 8 nm where the Ga concentration is larger than 7%, the formation of stacking faults at the InN/GaN interface produces a triangular network on the surface. The density of the stacking faults is found to decrease with film thickness and with the gradual consumption of the Ga atoms, and the network is therefore no longer observable above a critical thickness that varies from 8 to 10 nm. Instead, vacancy islands, one atomic layer deep, are formed to relieve the stain near the surface region. These results provide atomic scale insights into the interplay between the surface morphology and strain relaxation during the epitaxial growth of highly lattice mismatched InN/GaN heterostructures.     

Growth mechanism and properties of InGaN insertions in GaN nanowires

We demonstrate the strong influence of strain on the morphology and In content of InGaN insertions in GaN nanowires, in agreement with theoretical predictions which establish that InGaN island nucleation on GaN nanowires may be energetically favorable, depending on In content and nanowire diameter. EDX analyses reveal In inhomogeneities between the successive dots but also along the growth direction within each dot, which is attributed to compositional pulling. Nanometer-resolved cathodoluminescence on single nanowires allowed us to probe the luminescence of single dots, revealing enhanced luminescence from the high In content top part with respect to the lower In content dot base.     

Controlled synthesis of AlN/GaN multiple quantum well nanowire structures and their optical properties

We report the controlled synthesis of AlN/GaN multi-quantum well (MQW) radial nanowire heterostructures by metal-organic chemical vapor deposition. The structure consists of a single-crystal GaN nanowire core and an epitaxially grown (AlN/GaN)(m) (m = 3, 13) MQW shell. Optical excitation of individual MQW nanowires yielded strong, blue-shifted photoluminescence in the range 340-360 nm, with respect to the GaN near band-edge emission at 368.8 nm. Cathodoluminescence analysis on the cross-sectional MQW nanowire samples showed that the blue-shifted ultraviolet luminescence originated from the GaN quantum wells, while the defect-associated yellow luminescence was emitted from the GaN core. Computational simulation provided a quantitative analysis of the mini-band energies in the AlN/GaN superlattices and suggested the observed blue-shifted emission corresponds to the interband transitions between the second subbands of GaN, as a result of quantum confinement and strain effect in these AlN/GaN MQW nanowire structures.     

Self-assembled GaN nanowires on diamond

We demonstrate the nucleation of self-assembled, epitaxial GaN nanowires (NWs) on (111) single-crystalline diamond without using a catalyst or buffer layer. The NWs show an excellent crystalline quality of the wurtzite crystal structure with m-plane faceting, a low defect density, and axial growth along the c-axis with N-face polarity, as shown by aberration corrected annular bright-field scanning transmission electron microscopy. X-ray diffraction confirms single domain growth with an in-plane epitaxial relationship of (10 ?10)(GaN) [parallel] (01 ?1)(Diamond) as well as some biaxial tensile strain induced by thermal expansion mismatch. In photoluminescence, a strong and sharp excitonic emission reveals excellent optical properties superior to state-of-the-art GaN NWs on silicon substrates. In combination with the high-quality diamond/NW interface, confirmed by high-resolution transmission electron microscopy measurements, these results underline the potential of p-type diamond/n-type nitride heterojunctions for efficient UV optoelectronic devices.     

Crystallographic tilt in GaN-on-Si (111) heterostructures grown by metal–organic chemical vapor deposition

We report on the studies of crystallographic tilt induced by miscut of the Si (111) substrate in GaN-on-Si (111) heterostructures grown by metal–organic chemical vapor deposition. By employing high-resolution X-ray diffraction, we found that the onset of crystallographic tilt occurred at the interface between the AlN nucleation layer and the Si (111) substrate. The orientation of the GaN overlayer always follows that of the AlN nucleation layer irrespective of its quality and miscut of the substrates. The resultant GaN [0002] is tilted toward GaN (11?20) and (10?10) atomic planes for the miscuts of Si (111) toward Si [1?10] and [11?2], respectively. In both cases, the misorientation of GaN (0002), i.e., the tilt of GaN [0002] from the surface normal direction, is in the same direction of the miscut of Si (111). The misorientation angle of the GaN epilayer is generally smaller than the miscut angle of the substrate. However, the crystallographic tilt, i.e., the angle formed between GaN [0002] and Si [111], is always much larger than the Nagai tilt. These observations are attributable to misfit dislocations that are anisotropically generated at the AlN/Si (111) interface. This mechanism is discussed based on recent microscopic observations of in-plane misfit dislocations at the interface near the atomic step edges.     

Novel method for site-controlled surface nanodot fabrication by ion beam synthesis

By using a Ga FIB system to spatially control the implantation of Ga into SiO(2) followed by vacuum annealing, we have fabricated self-assembled surface Ga nanodots with a high degree of control of nucleation location. The morphology of the Ga nanodots is closely related to Ga dose, showing a critical dose needed for nucleation that results in Ga nanodot formation just below the surface, while at higher doses Ga nanodots form on the surface as metallic Ga droplets. Possible applications include defining nucleation sites for subsequent growth, use as Ga source for GaN or GaAs quantum dots, or as catalyst for nanowire growth.     

Polarity determination by electron energy-loss spectroscopy: application to ultra-small III-nitride semiconductor nanocolumns

Channeling-enhanced electron energy-loss spectroscopy is applied to determine the polarity of ultra-small nitride semiconductor nanocolumns in transmission electron microscopy. The technique demonstrates some practical advantages in the nanostructure analysis, especially for feature sizes of less than 50 nm. We have studied GaN and (Al, Ga)N nanocolumns grown in a self-assembled way by molecular beam epitaxy directly on bare Si(111) substrates and on AlN buffer layers, respectively. The GaN nanocolumns on Si show an N polarity, while the (Al, Ga)N nanocolumns on an AlN buffer exhibit a Ga polarity. The different polarities of nanocolumns grown in a similar procedure are interpreted in terms of the specific interface bonding configurations. Our investigation contributes to the understanding of polarity control in III-nitride nanocolumn growth.     

硅基正六边形氮化镓纳米颗粒薄膜的制备,结构和形貌特性

本文通过在ZnO/Si(111)衬底上,利用JCK-500A型射频磁控溅射系统溅射氧化镓靶得到氧化镓薄膜.然后将硅基Ga2O3置于管武石英炉中,在850℃的氨化温度下氨化15min后,成功制备出GaN薄膜,该薄膜由正六边形的晶粒组成.X射线衍射(XRD)表明GaN具有六方纤锌矿结构,晶格常数为a=0.318nm和c=0.518nm.X射线光电子能谱(XPS)的测试确定了样品中Ga-N键的形成,并且Ga和N的化学计量比为1:1.用扫描电镜(SEM)和原子力显微镜(AFM)观察发现,样品表面非常光滑和平整.透射电镜(TEM)表明薄膜由正六边形晶粒组成.选区电子衍射(SAED)进一步验证了GaN薄膜的六方纤锌矿结构.最后,简单地讨论了其生长机制.     

Synthesis of GaN nanoparticles from NH4[Ga(OH)2CO3] under a flow of ammonia gas

In this investigation, we report the synthesis of gallium nitride (GaN) nanoparticles from ammonium-carbonato-dihydroxo-gallate (NH₄[Ga(OH)₂CO₃]) in the flow of NH₃ gas in a temperature range of 500-900 °C. The GaN nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR). The FTIR and XPS revealed that the conversion of NH₄[Ga(OH)₂CO₃] to GaN under a flow of ammonia proceeds stepwise via amorphous gallium oxynitrides (GaO_xN_y) intermediates. Nanosized GaN particles with an average diameter of approximately 20-40 nm were obtained. The results obtained demonstrate that the large-quantity nanosized GaN particles can be synthesized from NH₄[Ga(OH)₂CO₃] powders.     

Austrittsarbeitsanalyse von GaN basierten Lateral Polarity Strukturen durch Auger‐Elektronen‐Energie‐Messungen

Work Function Analysis of GaN‐based Lateral Polarity Structures by Auger Electron Energy Measurements Lateral polarity heterostructure (LPH) were grown with adjacent Ga‐ and N‐face domains in order to invert the polarity of the crystal within a periodicity of a few microns. In this study we focus on the analysis of these LPH by Auger electron spectroscopy (AES). Because of the relationship between the Auger electron energy and the Fermi level, AES is a suitable method to identify the domains of a lateral polarity heterostructure. In addition, we discuss the possibility of determining the work function difference of Ga‐ and N‐face GaN. This difference in the work function between Ga‐face and N‐face GaN is found to be 0.25 eV. This difference is caused by a surface band bending.     

Mutual passivation of electrically active and isovalent impurities

The alloy GaN(x) As(1-x) (with x typically less than 0.05) is a novel semiconductor that has many interesting electronic properties because of the nitrogen-induced dramatic modifications of the conduction band structure of the host material (GaAs). Here we demonstrate the existence of an entirely new effect in the GaN(x) As(1-x) alloy system in which the Si donor in the substitututional Ga site (Si(Ga)) and the isovalent atom N in the As sublattice (N(As)) passivate each other's electronic activity. This mutual passivation occurs in Si-doped GaN(x) As(1-x) through the formation of nearest-neighbour Si(Ga) -N(As) pairs and is thermally stable up to 950 degrees C. Consequently, Si doping in GaN(x) As(1-x) under equilibrium conditions results in a highly resistive GaN(x) As(1-x) layer with the fundamental bandgap governed by a net 'active' N, roughly equal to the total N content minus the Si concentration. Such mutual passivation is expected to be a general phenomenon for electrically active dopants and localized state impurities that can form nearest-neighbour pairs.     

High-Performance UV-Visible-NIR Broad Spectral Photodetectors Based on One-Dimensional In(2)Te(3) Nanostructures

For the first time, high quality In(2)Te(3) nanowires were synthesized via a chemical vapor deposition (CVD) method. The synthesized In(2)Te(3) nanowires are single crystals grown along the [132] direction with a uniform diameter of around 150 nm and an average length of tens of micrometers. Further, two kinds of photodetectors made by 1D In(2)Te(3) nanostructures synthesized by CVD and solvothermal (ST) methods respectively were fabricated. To our best knowledge, this is the first time photoresponse properties of In(2)Te(3) nanowire have been studied. The CVD grown nanowire device shows better performance than the ST device, which demonstrates a fast, reversible, and stable photoresponse and also a broad light detection range from 350 nm to 1090 nm, covering the UV-visible-NIR region. The excellent performance of the In(2)Te(3) nanowire photodetectors will enable significant advancements of the next-generation photodetection and photosensing applications.     

Growth of bulk GaN single crystals by flux method

The progresses on the growth of bulk GaN crystals by the flux method in our research group are reported in this review. The research work is mainly focused on the ternary system Li–Ga–N. The phase relations are constructed by the calculation of phase diagram (CALPHAD) technique based on the optimized thermodynamic data of the corresponding binary systems Li–N, Li–Ga and Ga–N. There exists a two-phase region of liquid+GaN at above 750 °C. The well-crystallized, transparent GaN plate-like crystals up to a size of 4 mm can be grown from the Li–Ga–N system under pressures of 1–2 N₂ atmospheres. The yield and quality of the GaN crystals depend on the composition of the starting materials, the growth temperature, the cooling rate, and the position of Li₃N in the crucible. Efforts are still needed to further enlarge the size of crystals.