Influence of strain on growth mode and electro-optical properties of high-brightness InGaN-LEDs on SiC

We present a detailed study, on the influence of buffer strain on the MOVPE crystal growth mode in the QW active layer of high-brightness InGaN LEDs on SiC substrate. While highly strained buffers are related to InGaN QWs with homogeneous In-distribution, low In-concentration and reduced quantum efficiency, buffers with reduced strain are shown to induce InGaN-QW growth with a dot-like In-distribution, locally high In-concentration and good quantum efficiency. Using an optimised buffer technology, we developed extremely bright InGaN QW-LEDs with a brightness of more than 7 mW (at 460 nm and 20 mA) in a 5 mm radial lamp, good wavelength stability, low forward voltage, high ESD-stability and low ageing.     

In‐situ observation of InGaN quantum well decomposition during growth of laser diodes

The deterioration of the InGaN active region of laser diode structures emitting around 440 nm is observed in‐situ during epitaxial growth and analyzed ex‐situ by cathodoluminescence spectroscopy and transmission electron microscopy. The growth conditions of the p‐layers on top of the InGaN active region are found to affect the homogeneity of the InGaN material properties which can be monitored by the in‐situ reflectance signal at 950 nm. The deposition of the p‐layers at 950 °C results in the formation of metallic indium platelets as well as voids changing the refractive index of the active region and thus the reflectance. A reduction of the p‐layer deposition temperature by 30 °C prevents this undesirable decomposition.     

Theoretical stress calculations in polar,semipolar and nonpolar AlGaN/GaN heterostructures of different compositions

The new comprehensive model of the process for matching epitaxial layers to substrates, in dependence of theirs crystallographic orientation, was developed to allow a theoretical prediction of the strain and stress in thin AlGaN epitaxial layers with different composition grown on GaN template. The elements of the continuous anisotropic materials strength theory was applied to develop the model. It was observed that in AlGaN/GaN heterostructures the stress was greater than the upper limit of acceptable tensile stress even for a small Al content and also that the stress could greatly vary, in a value and a direction, depending on substrate crystallographic orientation and an Al content in AlGaN layer. The obtained results theoretically explained the commonly observed technological problems occurring during the growth of AlGaN layers even with a small Al content.     

Spatially resolved X‐ray diffraction as a tool for strain analysis in laterally modulated epitaxial structures

Spatially resolved X‐ray diffraction (SRXRD) is applied for micro‐imaging of strain in laterally modulated epitaxial structures. In GaAs layers grown by liquid phase epitaxial lateral overgrowth (ELO) on SiO₂‐masked GaAs substrates a downward tilt of ELO wings caused by their interaction with the mask is observed. The distribution of the tilt magnitude across the wings width is determined with μm‐scale spatial resolution. This allows measuring of the shape of the lattice planes in individual ELO stripes. If a large area of the sample is studied the X‐ray imaging provides precise information on the tilt of an individual wing and its distribution. In heteroepitaxial GaSb/GaAs ELO layers local mosaicity in the wing area is found. By the SRXRD the size of microblocks and their relative misorientation were analyzed. Finally, the SRXRD technique was applied to study distribution of localized strain in AlGaN epilayers grown by MOVPE on bulk GaN substrates with AlN mask. X‐ray mapping proves that by mask patterning strain in AlGaN layer can be easily engineered, which opens a way to produce thicker, crack‐free AlGaN layers with a higher Al content needed in GaN‐based laser diodes. All these examples show that high spatial and angular resolutions offered by SRXRD makes the technique a powerful tool to study local lattice distortions in semiconductor microstructures. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Suppression of phase separation in InGaN layers grown on lattice-matched ZnO substrates

Sapphire and SiC are typical substrates used for GaN growth. However, they are non-native substrates and result in highly defective materials. The use of ZnO substrates can result in perfect lattice-matched conditions for 22% indium InGaN layers, which have been found to suppress phase separation compared to the same growths on sapphire. InGaN layers were grown on standard (0 0 0 2) GaN template/sapphire and (0 0 0 1) ZnO substrates by metalorganic chemical vapor deposition. These two substrates exhibited two distinct states of strain relaxation, which have direct effects on phase separation. InGaN with 32% indium exhibited phase separation when grown on sapphire. Sapphire samples were compared with corresponding growths on ZnO, which showed no evidence of phase separation with indium content as high as 43%. Additional studies in Si-doping of InGaN films also strongly induced phase separation in the films on sapphire compared with those on ZnO. High-resolution transmission electron microscopy results showed perfectly matched crystals at the GaN buffer/ZnO interface. This implied that InGaN with high indium content may stay completely strained on a thin GaN buffer. This method of lattice matching InGaN on ZnO offers a new approach to grow efficient emitters.     

Selective area metal-organic vapor-phase epitaxy of InN,GaN and InGaN covering whole composition range

To investigate mask effects on InGaN selective area metal-organic vapor-phase epitaxy (SA-MOVPE), in-plane thickness profiles of InGaN were investigated with various indium contents covering between InN and GaN. A numerical simulation employing vapor-phase diffusion (VPD) model was also carried out for the quantitative analysis of VPD effect. At the growth temperatures of 650 and 700 °C, the indium content in the vapor phase and that in the solid phase exhibited almost linear relationship, suggesting that the growth of InGaN can be approximated as the superposition of the growth of InN and GaN. The effective vapor-phase diffusion length D/k_s of GaN was much smaller than InN. The profile of the InGaN growth rate in the selective area became more gradual as the solid indium content increased, and the trend seems to be the linear interpolation between the profiles of GaN and InN. However, as the indium content increases, deposition selectivity between mask and crystal surface become degenerated, and the VPD effect was almost canceled when the solid indium content exceeds 0.5. Although further improvement on the growth conditions is necessary to improve selectivity, basic information for the design of the SA-MOVPE of InGaN has been obtained, which will contribute to InGaN-based monolithically integrated multi-wavelength devices.     

Correlation of ordering formation and surface structure in (GaIn)P using modulated MOVPE

Modulated metalorganic vapour phase epitaxial growth (MOVPE) is used to clarify the role of the surface conditions on the ordering behaviour in ternary (GaIn)P layers. The alternating deposition of GaP and InP layers with individual thicknesses of up to one monolayer is successfully used for the growth of (GaIn)P bulk layers lattice matched to (100) GaAs substrates with various off-orientations. The layer quality and the degree of ordering are investigated using high-resolution X-ray diffraction (XRD), transmission electron microscopy (TEM), and photoluminescence spectroscopy (PL), respectively. The application of modulated growth conditions for the deposition of (GaIn)P bulk layers has a strong influence on the degree of ordering achieved in the intermediate growth temperature regime where the highest degree of ordering occurs under continuous MOVPE. Beside a new boundary structure observed in layers grown under modulated flux conditions, the successful growth of highly ordered (GaIn)P layers grown using the modulated MOVPE technique support the model that up to 2 monolayers of the (GaIn)P growth surface are involved in the ordering formation process.     

AlGaN epitaxial lateral overgrowth on Ti-evaporated GaN/sapphire substrate

AlGaN growth using epitaxial lateral overgrowth (ELO) by metalorganic chemical vapor deposition on striped Ti, evaporated GaN on sapphire, has been investigated. AlGaN/AlN films growth on GaN/AlGaN superlattices (SLs) structure on the Ti masks, with various SLs growth temperature (1030, 1060 and 1090 °C) were grown. With increasing the growth temperature, AlGaN surface became flat. The AlGaN film had a cathodoluminescence peak around 345 nm. However, in secondary ion mass spectrometry (SIMS) measurement, Ti signal was detected on the top of AlGaN surface when GaN/AlGaN SLs was grown on Ti striped masks. By inserting the AlN blocking layer on SLs, Ti diffusion was stopped at the AlN layer, and the AlGaN crystalline quality was improved.     

Growth monitoring by reflectance anisotropy spectroscopy in MOVPE reactors for device fabrication

Reflectance anisotropy spectroscopy (RAS) has proved its capability to study surface processes during metalorganic vapour phase epitaxy (MOVPE) growth of a variety of III–V compounds. However, these investigations up to now have been mostly restricted to specialized research reactors. Therefore, we studied the feasibility of in-situ monitoring by RAS during growth on two production-type MOVPE reactors: horizontal 2 inch single wafer reactor AIX 200 and Planetary Reactor™ AIX 2000 for 5 × 3 inch. The slight modifications of the reactors necessary to gain normal incidence optical access to the sample do not alter the properties of the grown materials. While in the horizontal reactor the strain-free optical window allows one to obtain well-resolved RAS spectra the signals in the multiwafer reactor are affected by the anisotropy of the ceiling plate. Even in this case RAS spectra can be extracted. First measurements on rotating samples in the horizontal reactor demonstrate the possibility to obtain RAS spectra by multitransient spectroscopy. As an application monitoring of the growth of p-type layers for the base of GaInP/GaAs hetero-bipolar-transistors (HBTs) is discussed. The linear electro-optic effect (LEO) gives information on doping type and doping level. Time-resolved transients at specific energies are used to study the impact of different switching schemes on the properties of the base-emitter interface.     

Growth of bulk InGaN films and quantum wells by atmospheric pressure metalorganic chemical vapour deposition

InGaN bulk layers and single quantum wells were grown on 1.4 to 2.4 μm thick GaN on sapphire films by atmospheric pressure metalorganic chemical vapour deposition (AP-MOCVD). The morphology of the epitaxial layers was strongly affected by the V/III ratio in the gas phase. The incorporation efficiency of indium was observed to increase with higher growth rates and decreasing temperature, but was independent of the V/III ratio in the investigated parameter range. In_0.16Ga_0.84N single quantum wells showed intense quantum well related luminescence at room temperature, with a full width at half maximum of 7.9 nm at a thickness of 50 Å. Single quantum wells embedded in InGaN of graded composition showed superior properties compared to quantum wells with In_0.04Ga_0.94N barriers of constant composition.     

Growth of gallium antimonide epitaxial layers on indium arsenide substrates

In the present work the possibility is demonstrated of growing gallium antimonide epitaxial layers on indium arsenide substrates using the liquid phase epitaxial (LPE) method. The influence is nivestigated of the growth conditions on the morphology of the surface and interface of the epitaxial structures InAs GaSb. The optimum technological regimes for growth of heterostructures in the system InAs GaSb are found.     

AlGaN双势垒结构对高In组分InGaN/GaN MQWs太阳能电池材料晶体质量和发光性能的影响

本文利用金属有机化合物化学气相沉积(MOCVD)技术在(001)面图形化蓝宝石衬底(PSS)上生长了一种含有AlGaN-InGaN/GaN MQWs (multiple quantum wells)-AlGaN双势垒结构的高In组分太阳能电池外延材料。高分辨率X射线衍射(HRXRD)和光致发光(PL)谱分析表明,与含有AlGaN电子阻挡层的低In组分的量子阱结构太阳能电池外延材料相比,该结构材料具有较小的半峰全宽(FWHM),计算表明:此结构材料的位错密度降低了一个数量级,达到10⁷ cm^-2;同时,有源区中的应变弛豫降低了51%;此外,此结构材料的发光强度增强了35%。研究结果表明含有AlGaN双势垒结构的外延材料可以减小有源区的位错密度,降低非辐射复合中心的数目,增大有源区有效光生载流子的数目,为制备高质量太阳能电池提供实验依据。     

In situ optical monitoring of AlGaN thickness and composition during MOVPE growth of AlGaN/GaN microwave HFETs

Real-time spectral reflectometry has been implemented to monitor the MOVPE growth of AlGaN/GaN microwave HFET structures. The aim is to monitor and control the thickness and composition of the thin AlGaN layer during growth. In order to extract useful information from the in situ spectra the optical constants of AlGaN as a function of alloy composition are required at the growth temperature (1050°C). As the first step to obtaining the high temperature optical constants, a room temperature spectroscopic ellipsometry study (energy range 1.65–4.95 eV) has been carried out on thin AlGaN films of various thickness (30 and 100 nm) and aluminium content (0.15 and 0.25). The multilayer model of each sample from the ellipsometry study is used to generate a reflectance spectrum which is compared with the in situ spectral reflectometry spectrum of the same sample acquired at room temperature to verify the technique. Further work is in progress to model the bandgap and optical constants of GaN and AlGaN at growth temperature.     

In situ reflectance difference spectroscopy of ZnSe-based semiconductor surfaces

We will give a brief report on applications of reflectance difference spectroscopy (RDS) for in situ growth monitoring during MOVPE. The experiments were made on GaAs(001) substrates using dimethylzinc-triethylamine, ditbutylselenide and as metalorganic precursors in a laminar flow reactor. We analyzed the influence of the in situ GaAs-substrate preparation on the optical response of the surface. The growth of ZnSe was investigated and compared to data obtained in an MBE process. Spectra at various stages of growth and time-dependent kinetic RDS records were measured during deposition and fitted with a three-layer growth model. Furthermore we utilized the surface sensitivity of the RDS technique to demonstrate surface kinetic processes during p-doping with tbutylamine.     

Control of the morphology of InGaN/GaN quantum wells grown by metalorganic chemical vapor deposition

Various techniques for morphological evolution of InGaN/GaN multiple quantum well (MQW) structures grown by metalorganic chemical vapor deposition have been evaluated. Atomic force microscopy, photoluminescence (PL) and X-ray diffraction measurements have been used for characterization. It is shown that inclusions, that are generated into the V-defects in the InGaN quantum wells (QW), can be removed by introducing a small amount of hydrogen during the growth of GaN barriers. This hydrogen treatment results in partial loss of indium from the QWs, but smooth surface morphology of the MQW structure and improved optical quality of InGaN wells are obtained. The density of the V-defects could be reduced by reducing the dislocation density of the underlying GaN buffer.     

Metalorganic vapor phase epitaxy and characterizations of nearly-lattice-matched AlInN alloys on GaN/sapphire templates and free-standing GaN substrates

The epitaxy optimization studies of high-quality n-type AlInN alloys with different indium contents grown on two types of substrates by metalorganic vapor phase epitaxy (MOVPE) were carried out. The effect of growth pressure and V/III molar ratio on growth rate, indium content, and surface morphology of these MOVPE-grown AlInN thin films were examined. The surface morphologies of the samples were characterized by scanning electron microscopy and atomic force microscopy. By varying the growth temperatures from 860 °C to 750 °C, the indium contents in AlInN alloys were increased from 0.37% up to 21.4% as determined by X-ray diffraction (XRD) measurements. The optimization studies on the growth conditions for achieving nearly-lattice-matched AlInN on GaN templates residing on sapphire and free-standing GaN substrates were performed, and the results were analyzed in a comparative way. Several applications of AlInN alloy for thermoelectric and light-emitting diodes are also discussed.     

Low-threshold strained multi-quantum well lasers fabricated by selective metalorganic vapor phase epitaxy without a semiconductor etching process

Strained InGaAsP multi-quantum well (MQW) buried hetero- (BH) laser diodes (LDs) on a p-InP substrate were fabricated by selective metalorganic vapor phase epitaxy (MOVPE). In the laser fabrication process, both the strained MQW active layer and current blocking structure were directly formed by selective MOVPE without a semiconductor etching process. This novel laser fabrication process produces extremely uniform device characteristics that are essential to the deployment of optical subscriber systems. Furthermore, important device design parameters (e.g. the active stripe shape or the leakage current path configuration) are precisely controlled by only the epitaxial growth steps. This highly controllable laser fabrication method results in a very low-threshold current with excellent uniformity (I_th = 1.78 ± 0.19 mA) for 20 consecutive LDs (L = 200 μm with 70%–90% coatings).     

Structural and optical properties of quaternary AlInGaN epilayers grown by MOCVD with various TMGa flows

AlInGaN quaternary epilayers have been grown with various TMGa flows by metalorganic chemical vapor deposition to investigate the influence of growth rate on the structural and optical properties. Triple-axis X-ray diffraction measurements show AlInGaN epilayers have good crystalline quality. Photoluminescence (PL) measurements show that the emission intensity of AlInGaN epilayers is twenty times stronger than that of AlGaN epilayer with comparable Al content. V-shaped pits are observed at the surface of AlInGaN epilayers by atomic force microscopy (AFM) and transmission electron microscopy (TEM). High growth rate leads to increased density and size of V-shaped pits, but crystalline quality is not degraded.     

Stress control by micropits density variation in strained AlGaN/GaN/SiN/AlN/Si(111) heterostructures

AlGaN/GaN heterostructures were deposited on Si utilizing in‐situ SiN masking layer as a mean to decrease stress present in the final heterostructures. Structures were grown under different V/III ratio using metalorganic vapour phase epitaxy (MOVPE). Additional approach was applied to obtain crack‐free heterostructures which was deposition of 15 nm low temperature AlN interlayer. Each of the heterostructure contained GaN layer of 2.4 μm total thickness. In‐situ SiN masking layer were obtained via introduction of SiH4 precursor into reactor under high temperature growth conditions for 100 s. In that manner, few monolayers of SixNx masking layer were deposited, which due to the partial coverage of AlN, played role of a mask leading to initial 3D growth mode enhancing longer coalescence of GaN buffer layer. To study surface morphology AFM images were observed. Three methods were used in order to obtain basal plane stress present in multilayer structures ‐ MicroRaman spectroscopy, XRD studies and optical profilometry. It was found that varying V/III precursors ratio during GaN layer growth characteristic for structures with the SiN mask approach formation of triangular micropits can be minimized. Outcomes for three different methods turned out to be coherent. It was found that certain amount of micropits on the surface can be advantageous lowering stress introduced during cooling after process to the AlGaN/GaN/SiN/AlN/Si(111) structure.     

Computational studies of the transient behavior of horizontal MOVPE reactors

Dynamic models of the mass transfer in horizontal reactors used for metalorganic vapor phase epitaxy (MOVPE) of compound semiconductors have been developed and used to study the duration of transients on the substrate during the growth of heterostructures. Dispersion of reactants during gas switching can be detrimental to the abruptness of the interfaces. A solution to this problem is the operation of MOVPE reactors at very high flow rates and low pressures, but this leads to low conversions of the expensive precursors. Our simulations indicate that critical Péclet numbers can be identified, beyond which no significant reduction in the duration of transients on the substrate occurs when increasing the gas velocity. The substrate always reached a new steady state much faster than the entire reactor. Symmetry of filling and purging with respect to transients was also observed. Performance diagrams connecting optimal operating conditions with reactor geometry have been constructed. Time-dependent models of the MOVPE process can help identify optimal operating conditions and reactor shapes leading to abrupt interfaces with maximum precursor utilization.