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)     

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.     

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.     

Cathodoluminescence study of the excitons localization in AlGaN/GaN and InGaN/GaN quantum wells grown on sapphire

Al_0.1Ga_0.9N(5 nm)/GaN(2 nm) and In_0.2Ga_0.8N/GaN quantum wells (QWs) grown on GaN/sapphire have been studied by cathodoluminescence (CL) spectroscopy and imaged using an experimental setup especially developed for scanning near-field CL microscopy, which combines a scanning force microscope and a scanning electron microscope. The CL spectra show the characteristic band edge emission peak of GaN at λ= 364 nm and the emission peaks related to the presence of QWs, at λ= 353 and 430 nm for the AlGaN/GaN and the InGaN/GaN samples, respectively. Monochromatic CL images reveal that the emission of the AlGaN/GaN and InGaN/GaN QWs is localized at the level of the grains observed by SFM. A cross sectional analysis of the InGaN/GaN sample gives insight into its growth and an estimation of the exciton diffusion length of about L=180 nm.     

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).     

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 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).     

Comparative analysis of characteristics of Si, Mg, and undoped GaN

We have grown undoped, Si- and Mg-doped GaN epilayers using metalorganic chemical vapor deposition. The grown samples have electron Hall mobilities (carrier concentrations) of 798 cm²/V s (7×10¹⁶ cm⁻³) for undoped GaN and 287 cm²/V s (2.2×10¹⁸ cm⁻³) for Si-doped GaN. Mg-doped GaN shows a high hole concentration of 8×10¹⁷ cm⁻³ and a low resistivity of 0.8 Ω cm. When compared with undoped GaN, Si and Mg dopings increase the threading dislocation density in GaN films by one order and two orders, respectively. Besides, it was observed that the Mg doping causes an additional biaxial compressive stress of 0.095 GPa compared with both undoped and Si-doped GaN layers, which is due to the incorporation of large amount of Mg atoms (4–5×10¹⁹ cm⁻³).     

N‐GaN column arrays on the vertical InGaN/GaN blue LEDs formed by maskless dry etching

The InGaN/GaN blue light emitting diodes (LED) structures have been grown on sapphire substrates with a hexagonal array of hemispherical patterns by low‐pressure metalorganic chemical vapor deposition. Vertical LED structures on Cu carriers are fabricated using electroplating and KrF laser lift‐off techniques. After removal of the patterned sapphire substrate, an inductively coupled plasma etching is carried out to expose the n‐GaN layer for n‐metal contact. It is observed that GaN columns are formed at the center of the concave hemispheres after dry etching processes. Cathodoluminescence and wet chemical etching investigations reveal that a high density of dislocations is found to be generated at these specific positions. The possible mechanism for these observations is attributed to the defect distribution and defect‐dependent selective etching of the GaN.     

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.     

宽周期掩膜法HVPE侧向外延自支撑GaN的研究

GaN膜在传统生长过程中主要通过异质外延获得,这往往会产生晶格失配和热失配,给GaN带来严重的位错和应力。目前降低位错最广泛的方法是使用侧向外延技术。在这项工作中,首先在蓝宝石基GaN衬底上沉积了一层SiO₂,并用光刻的方法将其制备成高掩膜宽度(窗口宽度20 μm/掩膜宽度280 μm)的宽周期掩膜,再通过氢化物气相外延(HVPE)侧向外延了厚度为325 μm的GaN厚膜,通过胶带可以将其进行剥离形成自支撑衬底。同时通过二维的Wulff结构图研究了GaN生长过程中晶面的变化趋势。宽周期掩膜法对于生长可剥离的低位错密度自支撑GaN有着重大意义。     

MOVPE homoepitaxy of high-quality GaN: Crystal growth and devices

Epitaxial growth on GaN bulk single crystal substrates sets new standards in GaN material quality. The outstanding properties provide insights into fundamental material parameters (e.g. lattice constants, exciton binding energies, etc.) with a precision not obtainable from heteroepitaxial growth on sapphire or SiC. With metalorganic vapor phase epitaxy (MOVPE) we realized unstrained GaN layers with dislocation densities about six orders of magnitude lower than in heteroepitaxy. By the use of dry etching techniques for surface preparation, an important improvement of crystal quality is achieved. Those layers reveal an exceptional optical quality as determined by a reduction of the low-temperature photoluminescence (PL) linewidth from 5 meV to 0.1 meV and a reduced X-ray diffraction (XRD) rocking curve width from 400 to 20 arcsec. As a consequence of the narrow PL linewidths, new features as, e. g. a fivefold fine structure of the donor-bound exciton line at 3.471 eV was detected. Additionally, all three free excitons as well as their excited states are visible in PL at 2 K.

Dry etching techniques for surface preparation allow morphologies of the layers suitable for device applications. We report on InGaN/GaN multi-quantum-well (MQW)_ structures as well as GaN pn- and InGaN/GaN double heterostructure light emitting diodes (LEDs) on GaN bulk single crystal substrates. Those LEDs are twice as bright as their counterparts grown on sapphire. In addition they reveal an improved high power characteristics, which is attributed to an enhanced crystal quality and an increased p-doping.     

Impedance spectroscopy analysis of AlGaN/GaN HFET structures

For HFET application a series of samples with 30 nm Al_xGa_1−xN (x=0.02–0.4) layers deposited at 1040°C onto optimised 2 μm thick undoped GaN buffers were fabricated. The Al_xGa_1−xN/GaN heterostructures were grown on c-plane sapphire in an atmospheric pressure, single wafer, vertical flow MOVPE system. Electrical properties of the Al_xGa_1−xN/GaN heterostructures and thick undoped GaN layers were evaluated by impedance spectroscopy method performed in the range of 80 Hz–10 MHz with an HP 4192A impedance meter using a mercury probe. The carrier concentration distribution through the layer thickness and the sheet carrier concentration were evaluated. A non-destructive, characterisation technique for verification of device heterostucture quality from the measured C–V and G–V versus frequency characteristics of the heterostructure is proposed.     

Thick GaN layers on sapphire with various buffer layers

Thick GaN layers deposited in HVPE system on composite substrates made on sapphire substrates in Metalorganic Vapour Phase Epitaxy (MOVPE) system have been investigated. The following substrates were used: (00.1) sapphire substrates with AlN, AlN/GaN and GaN thin layers. The crystallographic structure and the quality of the epitaxial thick GaN layers were determined. Comparison of the three types of thick layers was performed. Significant differences were observed. It was found that thick GaN deposited on the simplest MOVPE‐GaN/sapphire composite substrate has comparable structure's properties as the other, more complicated. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

InGaN/GaN微米阵列结构的生长及发光性能研究

采用金属有机化学气相外延技术,在图形化蓝宝石衬底上通过选区外延可控生长了三种不同形貌的InGaN/GaN微米阵列结构,阵列尺寸均为6 μm。其中,六方片状阵列结构以(0001)c面为主,高度为0.6 μm;六棱台状阵列结构包括一个(0001)c面和六个等效的(10-11)半极性面,高度为1.2 μm;六棱锥状阵列结构以(10-11)半极性面为主,高度为5 μm。采用微区光致发光光谱仪对InGaN/GaN微米阵列结构进行发光性能表征,结果表明不同形貌的InGaN/GaN微米阵列结构都可实现多波长发射;阴极荧光光谱结果表明六棱台状InGaN/GaN阵列结构不同晶面位置处发射的波长明显不同,这主要是由于表面迁移效应和横向气相扩散导致各个位置的In组分不同。InGaN/GaN微米阵列结构的成功制备对实现多彩发射和新型光电子器件设计具有重要意义。     

Vapor phase growth of GaN using GaN powder sources and thermogravimetric investigations of the evaporating behaviour of the source material

The growth of GaN from the vapor phase is a promising technique for producing both bulk GaN crystals and GaN layers. For establishing a growth method from the vapor phase the source material and reactor setup are of great importance. Highly pure and self synthesized GaN powder was chosen as source material. The evaporation behaviour of the GaN powder was studied by means of thermogravimetry (TG). A vertical growth reactor was set up according to the results of numerical simulations of the temperature distributions and flow patterns. Freely nucleated GaN platelets of some millimetres in length were grown. Furthermore, thin GaN layers were deposited directly on a sapphire substrate. This nucleation layer was successfully overgrown by low pressure solution growth. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

Zn掺杂Z形GaN纳米线的制备及表征

本文以氧化镓、氧化锌和氨气为原料,通过常压化学气相沉积法(APCVD)在Au/Si(100)衬底上成功生长出了Zn掺杂的"Z"形GaN纳米线。利用场发射扫描电镜(FESEM)、X-射线衍射仪(XRD)、透射电子显微镜(TEM)、光致发光谱(PL)等测试方法对样品的形貌、晶体结构及光学性质进行了表征。结果表明:在温度为950℃,氧化镓和氧化锌的质量比为8∶1的条件下,制备出的Zn掺杂Z形GaN单晶纳米线直径为70 nm、长度为数十个微米,生长机理遵循VLS机制。Zn元素的掺杂使GaN纳米线在420 nm处出现了光致发光峰,发光性能有所改善。     

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.     

Growth of undoped and Zn-doped GaN nanowires

Undoped and Zn-doped GaN nanowires were synthesized by chemical vapor deposition (CVD), and the effects of substrates, catalysts and precursors were studied. A high density of GaN nanowires was obtained. The diameter of GaN nanowires ranged from 20 nm to several hundreds of nm, and their length was about several tens of μm. The growth mechanism of GaN nanowires was discussed using a vapor–liquid–solid (VLS) model. Furthermore, room-temperature cathodoluminescence spectra of undoped and Zn-doped GaN nanowires showed emission peaks at 364 and 420 nm, respectively.