Overgrowth of GaN on GaN nanowires produced by mask-less etching

We report on the generation of GaN nanowires (NWs) using mask-less reactive ion etching (RIE). The NWs are believed to be the result of a high etching rate in regions where a high dislocation density is present in the GaN films grown on sapphire substrates. We have studied the effect of defect densities in the original GaN films and its relation to the generation of these NWs. We show that defect reduction in the overgrown GaN is related to the presence of a network of embedded voids generated between these nanowires during the regrowth on the etched nanowires. We show that further reduction in dislocation density can be achieved by repeating the process of nanowire generation and overgrowth. Also we report on the residual strain and curvature in GaN after the first and second embedded voids approach (EVA).     

Low pressure MOVPE of GaN and GaInN/GaN heterostructures

GaN single layers and GaInN/GaN heterostructures have been grown by low pressure metalorganic vapor phase epitaxy on sapphire substrates. We found best growth conditions and the highest growth rate for GaN to be at about 1000°C, whereas the growth rate decreased for both, higher and lower temperatures. In contrast, GaInN with a significantly high In content could only be grown at lower temperatures around 700°C. Besides growth temperature and reactor pressure, the composition of the carrier gas was found to play an important role: the In incorporation rate is about doubled when reducing the hydrogen/nitrogen ratio. GaInN/GaN quantum wells show even higher In contents compared to bulk layers.     

Bulk ammonothermal GaN

In this work, results of structural characterization of high-quality ammonothermal GaN are presented. Besides expected low dislocation density (being of the order of 10³ cm⁻²) the most interesting feature seems perfect flatness of the crystal lattice of studied crystals. Regardless the size of crystals, lattice curvature radius exceeds 100 m, whereas better crystals reveal radius of several hundred meters and the best above 1000 m. Excellent crystallinity manifests in very narrow X-ray diffraction peaks of full-width at half-maximum (FWHM) values about 16 arcsec.     

Growth of freestanding GaN using pillar-epitaxial lateral overgrowth from GaN nanocolumns

Dislocation-free and strain-free GaN nanopillars, grown on Si by molecular beam epitaxy, were used as nanoseeds for a new form of epitaxial lateral overgrowth (ELO) by metalorganic vapour phase epitaxy (MOVPE) until full coalescence. Such overgrown GaN films are almost relaxed and were used as templates for producing thick GaN layers by halide vapour phase epitaxy (HVPE). The final GaN film is easily separated from the starting Si substrate. This is henceforth a new technology to produce freestanding GaN. The GaN crystal quality was assessed by transmission electron microscopy (TEM), photo- and cathodoluminescence (PL, CL). It was seen that the pillar-ELO is produced from a limited number of nanopillars. Some dislocations and basal stacking faults are formed during the coalescence. However, those that propagate parallel to the substrate do not replicate in the top layer and it is expected that the thickened material present a reduced defect density.     

Overgrowth of GaN on Be-doped coalesced GaN nanocolumn layer by rf-plasma-assisted molecular-beam epitaxy—Formation of high-quality GaN microcolumns

GaN crystals were overgrown on GaN nanocolumn platforms with a Be-doped coalesced layer by rf-plasma-assisted molecular-beam epitaxy (rf-MBE). The overgrown GaN included large micrometer-scale hexagonal columnar crystals. These microcrystals were named ‘microcolumns’ and showed high optical properties comparable to those of GaN bulk crystals grown by hydride vapor phase epitaxy (HVPE).     

Defect reduction of laterally regrown GaN on GaN/patterned sapphire substrates

Structural properties of GaN epilayers on wet-etched protruding and recess-patterned sapphire substrates (PSSs) have been investigated in detail using high-resolution double-crystal X-ray diffraction (DCXRD) and etch-pit density methods. The DCXRD results reveal various dislocation configurations on both types of PSSs. The etch pits of GaN on the recess PSS exhibit a regular distribution, i.e. less etch pits or threading dislocation density (TDD) onto the recess area than those onto the sapphire mesas. On the contrary, an irregular distribution is observed for the etch pits of GaN on the protruding PSS. A higher crystal quality of the GaN epilayer grown onto the recess PSS can be achieved as compared with that onto the protruding PSS. These data reflect that the GaN epilayer on the recess PSS could be a better template for the second epitaxial lateral overgrowth (ELOG) of GaN. As a result, the GaN epilayers after the ELOG process display the TDDs of around ∼10⁶ cm⁻².     

Theoretical approach to structural stability of GaN: How to grow cubic GaN

We investigated the growth conditions of cubic GaN (c-GaN) by ab initio-based approach which incorporates free energy of vapor phase. It is known that a c-GaN is a metastable phase and wurtzite GaN (h-GaN), which is a stable phase of GaN, is easily incorporated in the c-GaN crystal during growth. h-GaN is formed in the area grown on {1 1 1} faceted surface. In the present study, therefore, we studied the growth conditions of {1 1 1} facet formation in order to suppress h-GaN mixing. The results suggest that we can suppress the {1 1 1} facet formation, i.e., h-GaN mixing, by controlling the growth conditions such as temperature and gallium beam equivalent pressure.     

Investigation of GaN crystal quality on silicon substrates using GaN/AlN superlattice structures

The crystal quality of GaN thin film on silicon using GaN/AlN superlattice structures was investigated. The growth was carried out on Si(111) for GaN(0001) in a metal‐organic vapor phase epitaxy system. Various GaN/AlN superlattice intermediate layers have been designed to decrease the dislocation density. The results showed that the etch pit density could be greatly reduced by one order of magnitude. Cross‐sectional transmission electron microscopy (XTEM) study confirmed the efficiency of GaN/AlN superlattice in blocking threading dislocation propagation in GaN crystal. The design of nine period GaN/AlN (20nm/2nm) superlattice has been evidenced to be effective in reducing the dislocation density and improving the crystal quality. In addition, the dislocation bending in GaN/AlN interface and dislocation merging is investigated. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Metalorganic vapour phase epitaxy of GaN and GaInN/GaN heterostructures and quantum wells

This paper reviews the growth and some characteristics of group III-nitrides by metalorganic vapour phase epitaxy with a particular focus on GaInN layers and heterostructures. We discuss the problems encountered with the low In incorporation efficiency. This can be partly compensated by larger growth rates and higher nitrogen-hydrogen ratios in the carrier gas. However, the grown layers with larger In content show evidence of composition fluctuations and even surface roughening due to problems probably arising from the large lattice mismatch to GaN and from the miscibility gap predicted for essentially the whole composition range. This influences strongly the spectroscopic properties. Consequences on the functionality of optoelectronic devices are also shortly discussed.     

Homoepitaxy on bulk ammonothermal GaN

In this work results of extensive characterization of homoepitaxial layers grown on truly bulk ammonothermal gallium nitride (GaN) substrates are presented. The 2-μm-thick layers were deposited using metalorganic chemical vapor deposition. The photoluminescence (PL) and reflectance results show very intensive, perfectly resolved excitonic structure in range of band-edge emission of gallium nitride. This structure consists of both lines related to free excitons emission and very narrow lines (full-width at half-maximum (FWHM) value of the order of 0.3 meV) related with excitons bound to neutral acceptor and different neutral donors. In high excitation condition the biexciton emission was observed. The luminescence is uniform in the whole sample surface range. High PL homogeneity corresponds with structural and microscopic measurements performed on these layers. It proves that ammonothermal GaN substrates with perfect crystalline properties enable to grow excellent quality, strain-free homoepitaxial layers.     

Electrical properties of n-Type GaN

The electron mobility in GaN is calculated as function of the carrier and impurity concentrations. From a comparison of the theoretically calculated mobilities with electrical parameters measured experimentally it follows that native donor and acceptor concentrations of the same order of magnitude are present in undoped GaN.     

HRTEM investigation of high-reflectance AlN/GaN distributed Bragg-reflectors by inserting AlN/GaN superlattice

A high-quality AlN/GaN distributed Bragg-reflectors (DBR) was successfully grown on sapphire substrate by low-pressure metal-organic chemical vapor deposition using ultra-thin AlN/GaN superlattice insertion layers (SLILs). The reflectivity of AlN/GaN DBR with ultra-thin AlN/GaN SLIL was measured and achieved blue peak reflectivity of 99.4% at 462 nm. The effect of ultra-thin AlN/GaN superlattice insertion layer was examined in detail by transmission electron microscopy, and indicated that the crack of AlN/GaN DBR can be suppress by inserting AlN/GaN SLIL. For electronic properties, the turn on voltage is about 4.1 V and CW laser action of vertical-cavity surface-emitting laser (VCSEL) was achieved at a threshold injection current of 1.4 mA at 77 K, with an emission wavelength of 462 nm.     

非极性GaN薄膜及其衬底材料

本文分析了在不同衬底上生长无极性GaN薄膜的情况,这些衬底主要包括γ-LiAlO2、r面蓝宝石等.通常在蓝宝石上制备的GaN外延膜是沿c轴生长的,而c轴是GaN的极性轴,导致GaN基器件有源层量子阱中出现很强的内建电场,发光效率会因此降低,发展非极性面外延,有望克服这一物理现象,使发光效率提高.     

TEM investigations of GaN layers grown on silicon and sintered GaN nano‐ceramic substrates

GaN nano‐ceramics were analyzed using transmission electron microscopy (TEM), showing that these ceramics are characterized by highly disoriented grains of the linear size of 100–150 nm. These GaN ceramics were used as substrates for GaN epitaxy in standard MOVPE conditions. For the comparison, MOVPE GaN layers on silicon substrates were grown using similar conditions. It is shown that MOVPE growth of GaN layers is highly anisotropic for both cases. However, the disorientation of the highly mismatched GaN layer on silicon is different from that characterizing GaN layer deposited on the ceramic substrate. In the latter case the disorientation is much higher, and three dimensional in nature, causing creation of polycrystalline structure having large number of the dislocations. In the case of the GaN layer grown on the silicon substrate the principal disorientation is due to rotation around c‐axis, causing creation of mosaic structure of edge dislocations. Additionally, it is shown that the typical grain size in AlN nucleation layer on Si is smaller, of order of 20 nm. These two factors contribute to pronounced differences in later stage of the growth of GaN layer on the ceramic. Due to high growth anisotropy an appropriately thick GaN layer can, eventually, develop flat surfaces suitable for construction of optoelectronic and electronic structures. As shown by the TEM data, this can be achieved only at the cost of creation of the relatively large density of dislocations and stacking faults. The latter defects were not observed for the GaN growth on Si substrates. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Approach for dislocation free GaN epitaxy

The characteristics of confined epitaxial growth are investigated with the goal of determining the contributing effects of mask attributes (spacing, feature size) and growth conditions (V/III ratio, pressure, temperature) on the efficiency of the approach for dislocation density reduction of GaN. In addition to standard (secondary electron and atomic force) microscopy, electron channeling contrast imaging (ECCI) is employed to identify extended defects over large (tens of microns) areas. Using this method, it is illustrated that by confining the epitaxial growth, high quality GaN can be grown with dislocation densities approaching zero.     

High quality GaN grown by MOVPE

Several nitrogen precursors have been used for the growth of GaN in MOVPE, but so far the best results were obtained using NH₃, even though NH₃ does not produce a significant amount of active species at the growing interface. To produce active species from N₂ or NH₃, a remote plasma-enhanced chemical vapour deposition (RPECVD) process has been implemented. In addition, nitrogen metalorganic precursors, triethylamine and t-butylamine, were also used. To accurately control the critical parameters of the MOVPE of GaN, we have implemented a laser reflectometry equipment, which allows a real-time in situ monitoring of the different steps of the growth, i.e. nitridation of the substrate, nucleation, heat treatment, and deposition. Using an appropriate buffer layer, GaN grown on sapphire using NH₃ as nitrogen precursor, shows sharp low temperature photoluminescence lines (4 meV at 9 K), whereas other nitrogen precursors did not lead to comparable electronic quality.     

GaN微米片的制备及性能研究

通过采用化学气相沉积法(CVD),以金属Ga和NH3为原料,在Si (100)衬底和蓝宝石衬底上采用催化剂Ni合成了GaN微米片.利用X射线衍射仪(XRD)、场发射扫描电子显微镜(FESEM)、X-ray能谱仪(EDS)、光致发光谱(PL)和霍尔效应测试仪(HMS-3000)对样品进行表征.结果表明,生成的微米片为六方纤锌矿结构的GaN;样品在360 nm处有一近带边紫外发射峰,在676 nm处有一个因缺陷引起的弱的红光发射峰;不同衬底上产物GaN的电学性能有所不同.最后,对本实验所得的GaN微米片的形成机理进行了分析.     

Bulk GaN crystals grown by HVPE

We succeeded in preparing very thick c-plane bulk gallium nitride (GaN) crystals grown by hydride vapor phase epitaxy. Growth of the bulk GaN crystals was performed on templates with 3 μm GaN layer grown by metal organic chemical vapor deposition on (0 0 0 1) sapphire substrates. Colorless freestanding bulk GaN crystals were obtained through self-separation processes. The crystal's diameter and thickness were about 52 and 5.8 mm, respectively. No surface pits were observed within an area of 46 mm diameter of the bulk GaN crystal. The dislocation density decreased with growth direction (from N-face side to Ga-face side) and ranged from 5.1×10⁶ cm⁻² near the N-face surface to 1.2×10⁶ cm⁻² near the Ga-face. A major impurity was Si, and other impurities (O, C, Cl, H, Fe, Ni and Cr) were near or below the detection limits by SIMS measurements.