Transmission electron microscopy study of an AlN nucleation layer for the growth of GaN on a 7-degree off-oriented (0 0 1) Si substrate by metalorganic vapor phase epitaxy

We have investigated the morphology of the high-temperature-grown AlN nucleation layer and its role in the early stage of GaN growth, by means of transmission electron microscopy. The nitride was selectively grown on a 7-degree off-oriented (0 0 1) patterned Si substrate by metalorganic vapor phase epitaxy. AlN was deposited on the inclined unmasked (1 1 1) facet in the form of islands. The size of the islands varied along the slope, which is attributable to the diffusion of the growth species in the vapor phase. The GaN nucleation occurred at the region where rounded AlN islands formed densely. The threading dislocations were observed to generate in the GaN nucleated region.     

Growth of low defect density GaP layers on Si substrates within the critical thickness by optimized shutter sequence and post-growth annealing

We have developed a growth procedure for realizing a low defect density GaP layer on an Si substrate. The growth procedure consists of two parts. One is the post-growth annealing for the annihilation of stacking faults (SFs). We have investigated an annihilation mechanism with molecular beam epitaxy grown GaP layers. 1-monolayer-thick SFs typically generate from the GaP/Si interface in a non-annealed GaP layer. In a 700 °C annealed GaP layer, generation points of these SFs tend to shift toward the GaP surface. In a 730 °C annealed GaP layer, SFs density is effectively decreased. These results suggest that SFs are annihilated through the climb motion of two partial dislocations during the post-growth annealing. Another one is the optimized shutter sequence for migration enhanced epitaxy. We have revealed that it is effective for the suppression of both three-dimensional growth and melt-back etching to increase in a stepwise manner the number of supplied Ga atoms per cycle. As a result, the generation of threading dislocations and pits is remarkably suppressed. A root mean square surface roughness of 0.13 nm is obtained within the critical thickness. We have estimated etch pit density (EPD) to be ∼7×10⁵ cm⁻² with a GaPN/GaP/Si structure. To the best of our knowledge, this value is same as that of commercially available GaP substrates and is the lowest one in the EPD of GaP/Si heteroepitaxy.     

Revealing extended defects in HVPE-grown GaN

In this communication we will summarize the results of a complementary study of structural and chemical non-homogeneities that are present in thick HVPE-grown GaN layers. It will be shown that complex extended defects are formed during HVPE growth, and are clearly visible after photo-etching on both Ga-polar surface and on any non-polar cleavage or section planes. Large chemical (electrically active) defects, such as growth striations, overgrown or empty pits (pinholes) and clustered irregular inclusions, are accompanied by non-uniform distribution of crystallographic defects (dislocations). Possible reasons of formation of these complex structures are discussed. The nature of defects revealed by selective etching was subsequently confirmed using TEM, orthodox etching and compared with the CL method. The non-homogeneities were studied in GaN crystals grown in different laboratories showing markedly different morphological characteristics.     

Efficiency optimization of p-type doping in GaN:Mg layers grown by molecular-beam epitaxy

The Mg-doping efficiency in GaN layers grown by molecular-beam epitaxy has been studied as a function of the growth temperature, the growth rate, and the Mg beam flux. The Mg cell temperature window for efficient p-type doping is rather narrow, being limited by the GaN n-type background doping density (lower limit) and by the Mg surface coverage that, beyond a threshold, induces a layer polarity inversion (N-polarity), leading to a reduction of the Mg incorporation (upper limit). An increase of the growth temperature avoids this polarity inversion, but the Mg flux must be increased to compensate the strong desorption rate. Thus, a trade-off between both temperatures has to be reached. A reduction of the growth rate has a strong effect on the p-type doping level, yielding up to 7×10¹⁷ holes/cm³ for a total Mg concentration of 1×10¹⁹ cm⁻³. This high Mg concentration does not seem to generate Mg-related defects or deep traps.     

Controlling metal–insulator transition in the hetero-epitaxial VO2/TiO2 bilayer grown on Al2O3

Hetero-epitaxial VO₂/TiO₂ bilayers were synthesized on Al₂O₃ substrates by using pulsed laser deposition, and their physical properties with the changes of oxygen pressure and the substrate orientation were investigated. A metal–insulator transition of the VO₂ was observed only in a narrow oxygen pressure range of 5–20 mTorr. As the oxygen pressure increased, X-ray diffraction peak for the (2 0 0)VO₂ shifted to a lower 2θ position, while the metal–insulator transition temperature (T_MI) decreased by ∼7 K. On the other hand, T_MI was largely varied with substrate orientation. The (2 0 0)VO₂/TiO₂ on the c-plane sapphire showed the highest T_MI of about 350 K, while the (0 0 2)VO₂/TiO₂ on the m-plane sapphire displayed the lowest T_MI of about 310 K. The (1 0 1)VO₂/TiO₂ on the r-plane and the a-plane exhibited T_MI∼340 and 330 K, respectively. The observed variations of T_MI with the oxygen pressure and substrate orientation were presumably due to the change in oxygen content of the VO₂ layer and/or in lattice strain.     

Synthesis of AlN from Li3N and Al: Application to vapor phase epitaxy

We performed synthesis of AlN using Al and Li₃N. In this method, there are two problems that must be solved for obtaining single-phase AlN. One of them is suppression of Li₃AlN₂ formation and the other is precipitation of LiAl from the residual source materials during the cooling process. In the present work, we analyzed phase stability of products and found that AlN was stable at high temperatures and low Li–N/Al molar ratios. However, the products still contained LiAl and Al. Therefore, we examined the effectiveness of vapor phase epitaxy for separating AlN from the extra phase (LiAl and Al formed from residual source materials). From the experimental results, feasibility of vapor phase epitaxy was confirmed. That is, we can deposit only an AlN layer on a sapphire substrate by optimizing the growth conditions, i.e., temperature range above 1150 °C and Li–N/Al molar ratio less than 1.     

Selective etching of dislocations in GaN grown by low-pressure solution growth

This work presents an experimental study on the identification and quantification of different types of dislocations in GaN grown by low-pressure solution growth. A reliable defect selective etching procedure in a NaOH-KOH melt is developed and validated using transmission electron microscopy that permits to define groups of etch pits that belong each to dislocations with a specific Burgers vector. This way a comparably fast method is provided for determining the total, the specific dislocation densities and the type of dislocation in a statistically representative way. The results for the solution grown samples are compared to those obtained for MOCVD GaN.     

Growth of epitaxial TmFeCuO4 thin films by pulsed laser deposition

Epitaxial thin films of TmFeCuO₄ with a two-dimensional triangular lattice structure were successfully grown on yttria-stabilized-zirconia substrates by pulsed laser deposition and ex situ annealing in air. The films as-deposited below 500 °C showed no TmFeCuO₄ phase and the subsequent annealing resulted in the decomposition of film components. On the other hand, as-grown films deposited at 800 °C showed an amorphous nature. Thermal annealing converted the amorphous films into highly (0 0 1)-oriented epitaxial films. The results of scanning electron microscopic analysis suggest that the crystal growth process during thermal annealing is dominated by the regrowth of non-uniformly shaped islands to the distinct uniform islands of hexagonal base.     

Subtle interplay between polytypism and preferred growth direction alignment in GaN nanorods non-catalytically grown on Si(1 1 1) substrates by using hydride vapor phase epitaxy

GaN nanorods were grown on Si(1 1 1) substrates by using hydride vapor phase epitaxy, and the crystallographic characteristics associated with their preferred growth directions were investigated by utilizing synchrotron X-ray reciprocal space mapping in a grazing incidence geometry and scanning electron microscopy. Crystallographic analysis reveals that the nanorods containing both wurtzite and zinc blende phase tend to have narrower distribution of the preferred growth directions than those containing only wurtzite phase. This tendency is partly attributed to the subtle interplay between polytypism and the preferred growth directions of GaN nanorods.     

Self-assembled InAs quantum dots with two different matrix materials

The effects of matrix materials on the structural and optical properties of self-assembled InAs quantum dots (QDs) grown by a molecular beam epitaxy were investigated by atomic force microscopy, cross-sectional transmission electron microscopy (TEM), and photoluminescence (PL) spectroscopy. Cross-sectional TEM image indicated that the average lateral size and height of InAs QDs in a GaAs matrix on a GaAs substrate were 20.5 and 5.0 nm, respectively, which showed the PL peak position of 1.19 μm at room temperature. The average lateral size and height of InAs QDs buried in an InAlGaAs matrix on InP were 26.5 and 3.0 nm, respectively. The PL peak position for InP-based InAs QDs was around 1.55 μm at room temperature. If we only consider the size quantization effects, the difference in PL peak position between two QD systems with different matrices may be too large. The large difference in peak position can be mainly related to the QD size as well as the strain between the QDs and the matrix materials. The intermixing between the QDs and the matrix materials can partially change the In composition of QDs, resulting in the modification of the optical properties.     

Thermally induced stress in GaN layers with regard to film coalescence

Thermally induced plane stress in GaN layers of different thicknesses, grown by metalorganic vapour phase epitaxy on sapphire, is investigated. Thin layers, characterized by isolated grains, are found to be stress-free. With increasing layer thickness, however, grains start to coalesce and stress can build up when the samples are cooled down following growth. As soon as the coalescence process is completed and a compact film has been formed, a maximum stress level is reached which does not further increase for still thicker layers. Therefore, it is proposed that grain edges enable non-compact films to elastically relieve in-plane stress.     

(Ga, Gd, As) film growth on GaAs substrate by low-energy ion-beam deposit

(Ga, Gd, As) film was fabricated by the mass-analyzed dual ion-beam epitaxy system with the energy of 1000 eV at room temperature. There was no new peak found except GaAs substrate peaks (0 0 2) and (0 0 4) by X-ray diffraction. Rocking curves were measured for symmetric (0 0 4) reflections to further yield the lattice mismatch information by employing double-crystal X-ray diffraction. The element distributions vary so much due to the ion dose difference from AES depth profiles. The sample surface morphology indicates oxidizing layer roughness is also relative to the Gd ion dose, which leads to islandlike feature appearing on the high-dose sample. One sample shows ferromagnetic behavior at room temperature.     

Selective area epitaxy of InGaN quantum well triangular microrings with a single type of sidewall facets

Triangular microrings have been formed by selective area epitaxy of GaN and InGaN quantum wells (QWs) on patterned (0 0 0 1) AlN/sapphire. SiO₂ patterns consist of triangular ring openings oriented with edges parallel to two different orientations. InGaN QW microrings with each edge parallel to the 〈1 1? 0 0〉 direction have very rough sidewalls while microrings with each edge parallel to the 〈1 1 2¯ 0〉 direction exhibit well formed and smooth sidewalls as a result of the generation of a single type of {1 1? 0 1} facets on the inner and outer sidewalls. These {1 1? 0 1} facets demonstrate similar cathodoluminescence (CL) spectra that appear to be the superposition of two peaks at photon energies ∼2.5 eV (500 nm) and 2.7 eV (460 nm). Moreover, spatially matched striations are observed in the CL intensity images and surface morphologies of the {1 1? 0 1} sidewall facets. The observed striations are found to be related to subtle surface morphologies of the underlying GaN structures.     

Reduction of threading dislocations in migration enhanced epitaxy grown GaN with N-polarity by use of AlN multiple interlayer

High quality GaN layer was obtained by insertion of high temperature grown AlN multiple intermediate layers with migration enhanced epitaxy method by the RF-plasma assisted molecular beam epitaxy on (0 0 01) sapphire substrates. The propagating behaviors of dislocations were studied, using a transmission electron microscope. The results show that the edge dislocations were filtered at the AlN/GaN interfaces. The bending propagation of threading dislocations in GaN above AlN interlayers was confirmed. Thereby, further reduction of dislocations was achieved. Dislocation density being reduced, the drastic increase of electron mobility to 668 cm²/V s was obtained at the carrier density of 9.5×10¹⁶ cm⁻³ in Si doped GaN layer.     

Study of the metastable region in the growth of GaN using the Na flux method

It was revealed that the metastable region, in which liquid phase epitaxy (LPE) of GaN single crystals proceeds without the generation of polycrystals, expands with growth temperature in the Na flux method. The metastable region appears when LPE growth proceeds at temperatures above 1073 K, although generation of polycrystals inevitably occurs on a crucible at temperatures less than 1073 K. The highest growth rate of 14 μm/h in a small experimental setup was achieved at a temperature of 1163 K with a nitrogen pressure of 5.5 MPa due to complete suppression of the growth of polycrystals on a crucible, even though the supersaturation at this condition reached a fairly high level.Also, an LPE crystal with a flat surface could easily be obtained under high-temperature conditions.     

Epitaxial growth of tin oxide film on TiO2(1 1 0) using molecular beam epitaxy

Growth of tin oxide thin films using molecular beam epitaxy in a pyrolyzed nitrogen dioxide atmosphere on a titanium dioxide (1 1 0) substrate was investigated using X-ray photoelectron spectroscopy (XPS), electron diffraction, and atomic force microscopy (AFM). Properties of deposited films were studied for their dependence on substrate temperature and oxidation gas pressure. Analyses using XPS data revealed that tin atoms were fully oxidized to Sn⁴⁺ and SnO₂ films were grown epitaxially in deposition conditions of substrate temperatures of 627 K or higher and NO₂ pressure greater than 3×10⁻³ Pa. At a substrate temperature of 773 K, a smooth surface with atomic steps was visible in the SnO₂ films, but above or below this temperature, fine grains with crystal facets or porous structures appeared. At pressures of 8×10⁻⁴ to 3×10⁻⁴ Pa, the randomly oriented SnO phase was dominantly grown. Further decreasing the pressure, the Sn metal phase, which was epitaxially crystallized at less than 500 K, was also grown.     

Surface chemistry and transport effects in GaN hydride vapor phase epitaxy

A simple quasi-thermodynamic model of surface chemistry in GaN hydride vapor phase epitaxy (HVPE) is presented. The model is coupled with the detailed 3D simulations of species transport in a horizontal-tube reactor and validated by the comparison with the data on the GaN growth rate obtained by laser reflectometry. Parametric study of the growth rate as a function of temperature and species flow rates has been performed over a wide range of growth conditions. The important role of species transport in an HVPE reactor is demonstrated. In particular, a strong effect of the natural concentration convection resulting in the formation of recirculation zones and in a non-uniform vapor composition is revealed by modeling. The impact of these effects on the GaN growth rate and V/III ratio on the growth surface is discussed in detail.     

Step annealing effects on the structural and optical properties of InAs quantum dots grown on GaAs

The effects of multi-step rapid thermal annealing (RTA) for the self-assembled InAs quantum dots (QDs), which were grown by a molecular beam epitaxy (MBE), were investigated through photoluminescence (PL) and transmission electron microscopy (TEM). Postgrowth multi-step RTA was used to modify the structural and optical properties of the self-assembled InAs QDs. Postgrowth multi-step RTAs are as follows: one step (20 s at 750 °C); two step (20 s at 650 °C, 20 s at 750 °C); three step (30 s at 450 °C, 20 s at 650 °C, 20 s at 750 °C). It is found that significant narrowing of the luminescence linewidth (from 132 to 31 meV) from the InAs QDs occurs together with about 150 meV blueshift by two-step annealing, compared to as-grown InAs QDs. Observation of transmission electron microscopy (TEM) shows the existence of the dots under one- and two-step annealing but the disappearance of the dots by three-step annealing. Comparing with the samples under only one-step annealing, we demonstrate a significant enhancement of the interdiffusion in the dot layer under multi-step annealing.     

Properties of Ge-doped,high-quality bulk GaN crystals fabricated by hydride vapor phase epitaxy

We investigated the properties of Ge-doped, high-quality bulk GaN crystals with Ge concentrations up to 2.4×10¹⁹ cm⁻³. The Ge-doped crystals were fabricated by hydride vapor phase epitaxy with GeCl₄ as the dopant source. Cathodoluminescence imaging revealed no increase in the dislocation density at even the highest Ge concentration, with values as low as 3.4×10⁶ cm⁻². The carrier concentration, as determined by Hall measurement, was almost identical to the combined concentration of Ge and unintentionally incorporated Si. The electron mobilities were 260 and 146 cm² V⁻¹ s⁻¹ for n=3.3×10¹⁸ and 3.35×10¹⁹ cm⁻³, respectively; these values are markedly larger than those reported in the past for Ge-doped GaN thin films. The optical absorption coefficient was quite small below the band gap energy; it slightly increased with increase in Ge concentration. Thermal conductivity, estimated by the laser-flash method, was virtually independent of Ge concentration, maintaining an excellent value around 2.0 W cm⁻¹ K⁻¹. Thermal expansion coefficients along the a- and m-axes were approximately constant at 5.0×10⁻⁶ K⁻¹ in the measured doping concentration range.     

Investigation of characteristics of laterally overgrown GaN on striped sapphire substrates patterned by wet chemical etching

The new developed maskless lateral-epitaxial-overgrowth technique, in which the striped substrates are patterned by wet chemical etching, is systematically investigated using scanning electron microscopy, X-ray diffraction, and atomic force microscopy (AFM). Wing tilt is measured for the GaN films on patterned substrates with a range of “fill factor” (ratio of groove width to stripe period) and for the GaN in different growth time. It is found that changes in these parameters have a significant effect on the extent and distribution of wing tilt in the laterally overgrown regions relative to the GaN directly on the sapphire substrate. Increasing the thickness of GaN films is benefit to reduce wing tilt. The tilt is avoided in the GaN films with 4.5 μm thickness and fill factor for 0.46. The full-width at half-maximum of X-ray rocking curves of the asymmetric diffraction peaks and the image of AFM both show that the threading dislocations in the developed lateral epitaxial overgrowth of GaN films are reduced sharply. The GaN template could be used as an excellent substrate to fabricate high-performance optoelectronic devices.