Structural Properties of Doped GaN on Si(111) Studied by X-Ray Diffraction Techniques

X-ray diffraction (XRD) is a non-destructive technique which is widely used in material characterization, particularly to determine structure, crystalline quality and orientation of samples. Two representative samples are used in this work, these samples are sample I (Si-doped GaN/AlN/Si) nominally consisted of 284 nm AlN followed by 152 nm of Si-doped GaN, and sample II (Mg-doped GaN/AlN/Si), grown with 194 nm AlN followed by 136 nm of Mg-doped GaN. Both doped GaN films were investigated by high resolution X-ray diffraction (HRXRD) with rocking curve (RC) measurement around the symmetrical (0002) and asymmetrical (10 $\overline{1}$ 2) diffraction peaks. The phase analysis result revealed that monocrystalline GaN was obtained. The XRD pattern show sharp and well separated (000l) reflections of doped GaN and AlN indicating complete texture with GaN[0?0?0?2] ∥ AlN[0?0?0?2] ∥ Si[1?1?1]. From the HRXRD RC ω/2θ scans of (10 $\overline{1}$ 2) and (0002) plane, we determined both a and c lattice parameters of the doped GaN. The symmetrical and asymmetrical RC full width at half maximum (FWHM) of doped GaN were obtained.     

Fabrication and structure properties of GaN nanowires by ammoniating Ga2O3 films

The GaN nanowires were successfully synthesized on Si(111) substrates by ammoniating the Ga₂O₃/ZnO films at 900 °C. The structure and morphology of the as-prepared GaN nanowires were studied by X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), scanning electron microscopy (SEM) and field-emission transmission electron microscopy (FETEM). The results show that the single-crystal GaN nanowires have a hexagonal wurtzite structure with lengths of about several micrometers and diameters ranging from 30 nm to 120 nm, which are conducive to the application of nanodevices. Finally, the growth mechanism is also briefly discussed.     

X-ray absorption and Raman study of GaN films grown on different substrates by different techniques

Raman scattering and polarization-dependent synchrotron radiation X-ray absorption, in combination, have been employed to examine the residual stress of undoped GaN epitaxial layers grown on Si by molecular beam epitaxy and Si-doped n-type GaN layers grown on sapphire by metalorganic chemical vapor deposition. Values of the lattice constant of different GaN films can be deduced from the interatomic distances in the second coordination shell around Ga by polarization-dependent extended X-ray absorption fine structure analysis and the strain of the films can be obtained. This result is further confirmed by Raman scattering spectra in which the phonon modes show a significant shift between different GaN epitaxial layers with different growth conditions.     

Gallium nitride nanowires doped with magnesium

GaN nanowires doped with Mg have been synthesized on Si (111) substrate through ammoniating Ga₂O₃ films doped with Mg under flowing ammonia atmosphere. The Mg-doped GaN nanowires were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), high-resolution transmission electron microscopy (HRTEM) and photoluminescence (PL). The results demonstrate that the nanowires were single crystalline with hexagonal wurzite structure. The diameters of the nanowires ranged 20-30 nm and the lengths were about hundreds of micrometers. The intense PL peak at 359 nm showed a blueshift from the bulk band gap emission, attributed to Burstein-Moss effect. The growth mechanism of the crystalline GaN nanowires is discussed briefly.     

Synthesis of single-crystal GaN nanowires on Si(111) substrate by ammonification technology

GaN nanowires have been synthesized on Si(111) substrate through ammoniating Ga₂O₃/BN films under flowing ammonia atmosphere at the temperature of 900 °C. The as-synthesized GaN nanowires were characterized by X-ray diffraction (XRD), selected-area electron diffraction (SAED), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscope (SEM) and transmission electron microscope (TEM). The results demonstrated that the nanowires are hexagonal wurtzite GaN and possess a smooth surface with diameters ranging from 40 to 100 nm and lengths up to several tens of micrometers. The growth mechanism of crystalline GaN nanowires is discussed briefly.     

Fabrication of needle-shaped GaN nanowires by ammoniating Ga2O3 films on MgO layers deposited on Si (111) substrates

Needle-shaped GaN nanowires have been synthesized on Si (111) substrate through ammoniating Ga₂O₃/MgO films under flowing ammonia atmosphere at the temperature of 950 °C. The as-synthesized GaN nanowires were characterized by X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy, scanning electron microscope (SEM) and high-resolution transmission electron microscopy (HRTEM). The results demonstrate that these nanowires are hexagonal GaN and possess a smooth surface with an average diameter about 200 nm and a length ranging from 5 μm to 15 μm. In addition, the diameters of these nanowires diminish gradually. The growth mechanism of crystalline GaN nanowires is discussed briefly.     

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.     

Synthesis of GaN nanowires through Ga2O3 films' reaction with ammonia

GaN nanowires were synthesized by ammoniating Ga₂O₃ films on Ti layers deposited on Si (111) substrates at 950 °C. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transformed infrared spectroscopy (FTIR) and high-resolution transmission electron microscopy (HRTEM). The XRD, FTIR and HRTEM studies showed that these nanowires were hexagonal GaN single crystals. SEM observation demonstrated that these GaN nanorods with diameters ranging from 50 nm to 100 nm and lengths up to several micrometers intervene with each other on the substrate.     

Multi-quantum-well nanowire heterostructures for wavelength-controlled lasers

Rational design and synthesis of nanowires with increasingly complex structures can yield enhanced and/or novel electronic and photonic functions. For example, Ge/Si core/shell nanowires have exhibited substantially higher performance as field-effect transistors and low-temperature quantum devices compared with homogeneous materials, and nano-roughened Si nanowires were recently shown to have an unusually high thermoelectric figure of merit. Here, we report the first multi-quantum-well (MQW) core/shell nanowire heterostructures based on well-defined III-nitride materials that enable lasing over a broad range of wavelengths at room temperature. Transmission electron microscopy studies show that the triangular GaN nanowire cores enable epitaxial and dislocation-free growth of highly uniform (InGaN/GaN)n quantum wells with n=3, 13 and 26 and InGaN well thicknesses of 1-3 nm. Optical excitation of individual MQW nanowire structures yielded lasing with InGaN quantum-well composition-dependent emission from 365 to 494 nm, and threshold dependent on quantum well number, n. Our work demonstrates a new level of complexity in nanowire structures, which potentially can yield free-standing injection nanolasers.     

Diameter-dependent electromechanical properties of GaN nanowires

The diameter-dependent Young's modulus, E, and quality factor, Q, of GaN nanowires were measured using electromechanical resonance analysis in a transmission electron microscope. E is close to the theoretical bulk value ( approximately 300 GPa) for a large diameter nanowire (d=84 nm) but is significantly smaller for smaller diameters. At room temperature, Q is as high as 2,800 for d=84 nm, significantly greater than what is obtained from micromachined Si resonators of comparable surface-to-volume ratio. This implies significant advantages of smooth-surfaced GaN nanowire resonators for nanoelectromechanical system (NEMS) applications. Two closely spaced resonances are observed and attributed to the low-symmetry triangular cross section of the nanowires.     

Effect of the ammoniating time on microstructure and morphology of one-dimensional Mg-doped GaN nanowires catalysed with Au

Mg-doped GaN nanowires have been successfully synthesised on Si(1?1?1) substrates by magnetron sputtering through ammoniating Ga₂O₃/Au thin films, and the effect of ammoniating time on microstructure and morphology were analysed in detail. X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, high-resolution transmission electron microscopy and photoluminescence spectrum were carried out to characterise the microstructure, morphology and optical properties of the GaN samples. The results demonstrate that the nanowires after ammonification at 900°C for 15?min are single crystal GaN with a hexagonal wurtzite structure and high crystalline quality, having the size of 50–80?nm in diameter, more than 10 microns in length and good emission properties. The growth direction of this nanowire is parallel to [0?0?1] direction of hexagonal unit cell. Ammoniating time has a great impact on the microstructure, morphology and optical properties of the GaN nanowires.     

Mechanical elasticity of vapour-liquid-solid grown GaN nanowires

Mechanical elasticity of hexagonal wurtzite GaN nanowires with hexagonal cross sections grown through a vapour-liquid-solid (VLS) method was investigated using a three-point bending method with a digital-pulsed force mode (DPFM) atomic force microscope (AFM). In a diameter range of 57-135?nm, bending deflection and effective stiffness, or spring constant, profiles were recorded over the entire length of end-supported GaN nanowires and compared to the classic elastic beam models. Profiles reveal that the bending behaviour of the smallest nanowire (57.0?nm in diameter) is as a fixed beam, while larger nanowires (89.3-135.0?nm in diameter) all show simple-beam boundary conditions. Diameter dependence on the stiffness and elastic modulus are observed for these GaN nanowires. The GaN nanowire of 57.0?nm diameter displays the lowest stiffness (0.98?N?m(-1)) and the highest elastic modulus (400 ± 15?GPa). But with increasing diameter, elastic modulus decreases, while stiffness increases. Elastic moduli for most tested nanowires range from 218 to 317?GPa, which approaches or meets the literature values for bulk single crystal and GaN nanowires with triangular cross sections from other investigators. The present results together with further tests on plastic and fracture processes will provide fundamental information for the development of GaN nanowire devices.     

Synthesies and properties of Tb-doped GaN nanowires

The synthesis of Tb-doped GaN nanowires on Si (111) substrates through ammoniating Ga₂O₃ films doped with Tb was investigated. X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscope, high-resolution transmission electron microscopy and photoluminescence were used to characterize the composition, structure, morphology and optical properties of the products. The results show that the as-synthesized GaN nanowires doped with 3 at % Tb are of single-crystalline hexagonal wurtzite structure. The nanowires have diameters ranging from 30 to 50 nm and the lengths up to tens of micrometers. An f-f intra-atomic transition of rare earth at 545 nm corresponding to ⁵ D ₄–⁷ F ₅ of the Tb³⁺ and other two peaks related with doping are observed in PL spectrum, confirming the doping of Tb into GaN. The growth mechanism of GaN nanowires was discussed briefly.     

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.     

Selective area growth of GaN nanowires using metalorganic chemical vapor deposition on nano-patterned Si(111) formed by the etching of nano-sized Au droplets

We report on the selective area growth of GaN nanowires (NWs) on nano-patterned Si(111) substrates by metalorganic chemical vapor deposition. The nano-patterns were fabricated by the oxidation of Si followed by the etching process of Au nano-droplets. The size of formed nano-pattern on Si(111) substrate was corresponding to the size of Au nano-droplet, and the diameter of GaN NWs grown was similar to the diameter of fabricated nano-pattern. The interesting phenomenon of using the nano-patterned Si(111) substrates is the formation of very clear substrate surface even after the growth of GaN NWs. However, in the case of GaN NWs grown using Au nano-droplets, there was several nanoparticles including GaN bulk grains on the Si(111) substrates. The smooth surface morphology of nano-patterned Si(111) substrates was attributed to the presence of SiO₂ layer which prevents the formation of unnecessary GaN particles during the GaN NW growth. Therefore, we believe that nano-patterning method of Si(111) which was obtained by the oxidation of Si(111) substrate and subsequent Au etching process can be utilized to grow high-quality GaN NWs and its related nano-device applications.     

Influence of reaction time on growth of GaN nanowires fabricated by CVD method

GaN nanowires have been fabricated successfully on Si (111) substrates coated with NiCl₂ thin films by chemical vapor deposition method using Ga₂O₃ as raw material. The growth of GaN nanowires was investigated as a function of reaction times so as to study the influence of different durations on the components, microstructure, morphologies and optical properties of GaN samples in particular by X-ray diffraction, FT-IR spectrophotometer, scanning electron microscope, and photoluminescence. The results show that the samples after reaction are single crystal GaN with hexagonal wurtzite structure and high-quality crystalline after reaction at 1,100 °C for 60 min, which have good optical properties as revealed by PL spectra. Reaction time greatly influences the growth of GaN nanowires, that is, with the increase in reaction time, the crystalline quality of GaN nanowires is improved accordingly. The growth of the GaN nanowires follows the vapor–liquid-solid mechanism and Ni plays an important role as catalyst, which forms nucleation point in the growth of GaN nanowires.     

GaN纳米线材料的特性和制备技术

GaN是一种具有优越热稳定性和化学性质的宽禁带半导体材料，这种材料及相关器件可以工作在高温、高辐射等恶劣环境中，并可用于大功率微波器件．最近几年，由于GaN蓝光二极管的成功研制，使GaN成为了化合物半导体领域中最热门的研究课题．简要介绍了GaN纳米线材料的制备技术；综述了GaN纳米线材料的制备结果和特性．用CVD法研制的GaN纳米线的直径已经达到5～12nm，长度达到几百个微米．纳米线具有GaN的六方纤锌矿结构，其PL谱具有宽的发射峰，谱峰中心在420nm．GaN纳米线已经在肖特基二极管的研制中得到应用．     

Nucleation and growth of GaN nanowires on Si(111) performed by molecular beam epitaxy

GaN nanowires (NWs) have been grown on Si(111) substrates by plasma-assisted molecular beam epitaxy (PAMBE). The nucleation process of GaN-NWs has been investigated in terms of nucleation density and wire evolution with time for a given set of growth parameters. The wire density increases rapidly with time and then saturates. The growth period until the nucleation of new nanowires is terminated can be defined as the nucleation stage. Coalescence of closely spaced nanowires reduces the density for long deposition times. The average size of the well-nucleated NWs shows linear time dependence in the nucleation stage. High-resolution transmission electron microscopy measurements of alternating GaN and AlN layers give valuable information about the length and radial growth rates for GaN and AlN in NWs.     

Nitrogen-doped tungsten oxide nanowires: low-temperature synthesis on Si, and electrical, optical, and field-emission properties

Very dense and uniformly distributed nitrogen-doped tungsten oxide (WO(3)) nanowires were synthesized successfully on a 4-inch Si(100) wafer at low temperature. The nanowires were of lengths extending up to 5 mum and diameters ranging from 25 to 35 nm. The highest aspect ratio was estimated to be about 200. An emission peak at 470 nm was found by photoluminescence measurement at room temperature. The suggested growth mechanism of the nanowires is vapor-solid growth, in which gaseous ammonia plays a significant role to reduce the formation temperature. The approach has proved to be a reliable way to produce nitrogen-doped WO(3) nanowires on Si in large quantities. The direct fabrication of WO(3)-based nanodevices on Si has been demonstrated.     

Influence of substrates on the formation of the TiSi nanowire by atmosphere pressure chemical vapor deposition

TiSi nanowires were deposited on both Si(111) and glass substrates by using SiH4, TiCl4 and N2 as the Si, Ti precursors and diluted gas respectively through atmosphere pressure chemical vapor deposition (APCVD) method. Effects of the substrates on formation of the nanowires were investigated. The results show that the nanowires can be formed on both Si(111) and glass substrates at ratio of SiH4/TiCl4 of 4. However, the quantities of the TiSi nanowires that formed with glass substrate are less than that with Si(111) substrate. The nanowires formed with glass substrate has length of 2-3 microm and diameters of 15-25 nm while that is 4-5 microm and 25-35 nm respectively with Si(111) substrate. Great quantities of the titanium silicide nanowires with relative higher contents of the C54 TiSi2 crystalline phase underneath can be obtained through improving the deposition conditions.