Overgrowth Of GaN Research Articles

Geometrically Controlled Microscale Patterning and Epitaxial Lateral Overgrowth of Nitrogen-Polar GaN.

In this Letter, we report on a novel two-step epitaxial growth technique that enables a significant improvement of the crystal quality of nitrogen-polar GaN. The starting material is grown on 4° vicinal sapphire substrates by metal-organic vapor-phase epitaxy, with an initial high-temperature sapphire nitridation to control polarity. The material is then converted to a regular array of hexagonal pyramids by wet-etching in a KOH solution and subsequently regrown to coalesce the pyramids back into a smooth layer of improved crystal quality. The key points that enable this technique are the control of the array geometry, obtained by exploiting the anisotropic behavior of the wet-etch step, and the use of regrowth conditions that preserve the orientation of the pyramids' sidewalls. In contrast, growth conditions that cause an excessive expansion of the residual (0001̅) facets on the pyramids' tops cause the onset of a very rough surface morphology upon full coalescence. An X-ray diffraction study confirms the reduction of the threading dislocation density as the regrowth step develops. The analysis of the relative position of the 0002̅ GaN peak, with respect to the 0006 sapphire peak, reveals a macroscopic tilt of the pyramids, probably induced by the large off-axis substrate orientation. This tilt correlates very well with an anomalous broadening of the 0002̅ diffraction peaks at the beginning of the regrowth step.

Microstructural and spectroscopic analysis of epitaxial lateral overgrowth GaN via the self-decomposing hexagonal graphene mask

The use of two-dimensional material like graphene to alleviate lattice mismatch has been an effective way to realize high-quality GaN on heterogeneous substrates. The lack of hanging bonds on the graphene surface provides a new attempt for epitaxial lateral overgrowth (ELOG). In this study, a hexagonal graphene mask was used for the growth of GaN, the graphene mask disappeared during the GaN growth process, but GaN still maintained the ELOG mode, and the threading dislocation density was significantly reduced. Raman and PL spectra demonstrated the stress relaxation in ELOG GaN and showed a stress relaxation of 0.157 GPa at the interface between the substrate and ELOG GaN. This study demonstrates the feasibility and advantages of graphene masks for nitrides and extends the research on stress relaxation of ELOG GaN using a graphene mask.

Facet Control and Material Redistribution in GaN Growth on Three-Dimensional Structures

In this work, the influence of temperature and ammonia partial pressure on the GaN shell morphology grown on GaN microfin cores is investigated. We demonstrate that GaN overgrowth on 3D structures above a temperature of 1000 °C is determined by the competition between growth and decomposition that results in the redistribution of material between coexisting surfaces due to their different thermal stabilities. By studying the GaN shell growth under different reactor parameters, we show that decomposition processes, often disregarded during planar growth, strongly influence the vertical-to-lateral distribution of material during GaN growth on 3D structures. We observed that GaN shell growth on a-plane microfins at high temperatures and high ammonia fluxes results in an increase of the decomposition rate of the c-plane surfaces and thus, reduces the growth rate in the vertical direction. On the contrary, the lateral growth rate increases due to the diffusion of material from the less stable c-plane facet to the more stable a-plane facet where it reincorporates. Furthermore, under certain growth conditions, the decomposition of the c-plane outweighed the incorporation, reducing the height of the initial 3D structure during growth, while still gradually growing in the lateral direction, which resulted in the development of inclined facets. These findings highlight the high sensitivity of 3D structures to thermal decomposition processes and redistribution of material. Therefore, the understanding of these mechanisms and their interaction is required for controlling and optimizing growth on these architectures.

Growth of GaN Hexagonal Arrays on Partially Crystallized Sapphire Nanomembranes for Micro-Light-Emitting Diodes

100-nm-thick hexagonal fully and partially crystallized sapphire nanomembrane arrays were demonstrated as growth templates for hexagonal micro-sized GaN arrays for micro-light-emitting diodes (LEDs). By simply controlling the thermal treatment time for crystallization of the amorphous membrane, the partially crystallized nanomembrane which has both single- and polycrystalline alumina on the top surface was fabricated. The unique crystalline structures contributed to unique growth behavior which contains selective and lateral overgrowth of GaN, compared to that of GaN on fully crystallized sapphire nanomembranes, leading to superior structural and optical properties of GaN. Threading dislocation densities were reduced by 75% and 1.29 times higher integrated photoluminescence intensity was achieved compared to GaN on the fully crystallized sapphire nanomembranes. Stress in GaN was also fully relaxed due to the ultrathin membrane structure as a compliant substrate. The superior properties of GaN as well as the truncated inverted pyramid structure are expected to improve the performance of micro-LED devices. Hexagonal partially crystallized sapphire nanomembrane technology also provided advances in the fundamental study of epitaxial growth of GaN-based materials.

Polarity Inversion of Ga‐Polar GaN Surfaces by Exposing to Mg and NH3 in Metal–Organic Vapor Phase Epitaxy

AbstractA metal–organic vapor phase epitaxy process of polarity inversion (PI) from Ga‐ to N‐polar is reported by exposing the Ga‐polar surface simultaneously to Mg and ammonia flows. This process differs from the conventional Mg heavy‐doping technique by intentionally predepositing a Mg‐rich thin layer on the Ga‐polar surface for PI. A full PI with a smooth surface in the subsequent GaN overgrowth is achieved by an exposure process for 900 s at 700 °C. Atomic force microscopy and piezo‐force microscopy characterizations reveal that the polarity change undergoes simultaneously with pyramid formation after ≈15 nm thick GaN overgrowth. The electron dispersion spectroscopy mapping of Mg indicates high Mg concentrations at the regrowth interface and in the PI domain boundary. A Mg‐rich thin layer is believed to cover the surface after the exposure process and release Mg dopants in the subsequent growth, leading to a high Mg incorporation in the GaN overlayer and therefore inducing PI. P‐type conduction with a hole concentration of ≈2.7 × 1017 cm−3 is achieved in the N‐polar GaN overlayer. It is also demonstrated that such a PI technique can be employed in the growth of a hybrid polarity structured ultraviolet‐light‐emitting diode with a reversed N‐polar contact layer on a Ga‐polar main body.

Structural characterization of ELO-GaN film on mask-stripe patterned GaAs (0 0 1) substrate grown by metalorganic vapor phase epitaxy

GaN films were epitaxial laterally overgrown on the [110]-stripe-patterned GaAs (001) substrate by MOVPE. AlGaN intermediate layers and low-temperature GaN buffer layer were inserted in order to prevent structural defects. The epitaxial lateral overgrowth of GaN results in a trapezoidal shape with flat facets. Structural phases and defects distribution were studied by TEM. Selective-area diffraction pattern indicates the mixed phase of GaN and a high density of stacking faults at nucleation. However, with the deposition of dielectric SiNx masks, a lateral overgrowth resulted in nearly free of defects, and the cubic phase transformed into hexagonal despite a cubic template. Moreover, dark-field TEM images were used to demonstrate the structural phase transformation.

Hybrid density functional theory study on zinc blende GaN and diamond surfaces and interfaces: Effects of size, hydrogen passivation, and dipole corrections

GaN-diamond heterojunctions show promise in high electron mobility transistor applications. This prompts the need for accurate models of structural and electronic properties. We detail here a hybrid density functional theory study of zinc blende (ZB) GaN and diamond heterostructures using slab supercell models. The dependence of electronic properties on supercell size, pseudo-hydrogen passivation, and dipole corrections is detailed. The larger bulk modulus of diamond is shown to provide a templating structure for GaN to grow upon, where the large lattice mismatch is accounted for through the inclusion of a cationic Ga adlayer. Looking at both type I and II surfaces and interfaces of GaN shows the instability of zb GaN without an adlayer (type II), where increased size, pseudo-hydrogen passivation and dipole corrections do not remove the spurious interaction between the top and bottom layers in type II GaN. Layer dependent density of states, local potential differences, and charge density differences show that the type I interface (with a Ga adlayer) is stable with an adhesion energy of 0.704 eV/Å2 (4.346 J/m2); interestingly, the diamond charge density intercalates into the first layer of GaN, which was seen experimentally for wurtzite GaN grown over diamond. The type II interface is shown to be unstable which implies that, to form a stable, thin-film zb interface between GaN and diamond, the partial pressure of trimethylgallium must be controlled to ensure a Ga layer exists both on the top and bottom layer of the GaN thin film atop the diamond. We believe our results lead to a better understanding of the GaN/diamond multifaceted interface present in the GaN overgrowth on diamond heterojunction used in electronic device applications.

The role of Ga supersaturation on facet formation in the epitaxial lateral overgrowth of GaN

In this paper, facet formation of (0001) {112¯0} {112¯2} facets during epitaxial lateral overgrowth (ELO) of GaN is investigated for different Ga vapor supersaturations. The ELO was conducted via metalorganic chemical vapor deposition on patterned GaN/sapphire templates with SiO2 masks aligned along the ⟨11¯00⟩ direction of GaN. Scanning electron microscopy was used to characterize the cross section shapes of the ELO GaN islands. A correlation of supersaturation, facet formation, and the shape of the ELO GaN islands is found. It is shown that {112¯2} facets are favored under high Ga vapor supersaturation, while {112¯0} facets are favored under low Ga vapor supersaturation. A qualitative model based on Wulff construction and density functional theory calculation is proposed to illustrate the mechanism of the facet formation of the ELO GaN islands.

GaN nucleation on patterned sapphire substrate with different shapes for improved GaN overgrowth

GaN was grown on cone- and dome-patterned sapphire (CPSS and DPSS) at different nucleation times of 40, 80 and 160 s. The GaN was also grown on flat sapphire substrate (FSS) for comparison. The results showed that the GaN growth improved by increasing the nucleation time, except for the case of FSS. Compared to CPSS, DPSS led to better GaN growth. This was due to the geometry of the dome patterns, which had more slanted curvature than cone patterns. Hence, more nucleation was promoted on the trenches and this was desirable to improve the GaN overgrowth. With 160 s of nucleation, the GaN coalescence was better for the growth on DPSS than on CPSS. This resulted in an improved surface of the overgrown GaN layer and lower full-width at half-maximum of XRD (FWHM-XRD) peaks. Strain study showed that the GaN layers grown on DPSS exhibited larger residual in-plane strain than the layers on CPSS due to the achievement of better overgrown GaN. Nonetheless, the strain reduced with nucleation time due to further dislocations inclination. Generally, the GaN layers on FSS showed better crystalline quality than on CPSS and DPSS. However, the layers suffered from larger strain.

Integration of GaN and Diamond Using Epitaxial Lateral Overgrowth.

Growth of single-crystalline GaN on polycrystalline diamond is reported for the first time. The structure was achieved using a combined process including selective diamond growth on GaN/Si wafers using hot filament chemical vapor deposition (CVD) and epitaxial lateral overgrowth of GaN on the window region between then above the diamond stripes via metal organic CVD. Optimization of the growth was performed by varying the ammonia to trimethylgallium mole ratio (V/III), chamber pressure, and temperature in the range of 8000-1330, 40-200 Torr, and 975-1030 °C, respectively. A lower pressure, higher V/III ratio, higher temperature, and GaN window mask openings along [11̅00] resulted in enhanced lateral growth of GaN. Complete lateral coverage and coalescence of GaN were achieved over a [11̅00]-oriented 5 μm-wide GaN window between 5 μm diamond stripes when using V/III = 7880, P = 100 Torr, and T = 1030 °C. The crystalline quality of overgrown GaN was confirmed using cross-sectional scanning electron microscopy, high-resolution X-ray diffraction, micro-Raman spectroscopy, transmission electron microscopy, and selective-area electron diffraction.

Semi-polar (11–22) GaN epitaxial films with significantly reduced defect densities grown on m-plane sapphire using a sequence of two in situ SiNx interlayers

This letter reports an approach for growing semipolar (11–22) GaN films with significantly reduced defect densities on m-plane sapphire substrates by incorporating a sequence of two in situ SiNx layers. The first SiNx layer is deposited on an initial epitaxial GaN layer and acts as a nanomask for preventing the propagation of extended defects. The second SiNx layer is deposited just after subsequent epitaxial GaN overgrowth begins to form self-organized GaN islands, which encourages further GaN growth to initiate from the exposed island sidewalls while blocking the penetration of the remaining defects. X-ray rocking curve measurements show that our semipolar GaN films provide relatively low full width at half maximum values at 0.119° along both the [11–23] and [10–10] directions. Additionally, transmission electron microscopy analyses confirm that our semipolar GaN films provide a significantly reduced density of threading dislocations down to ∼6 × 108 cm−2, which is two orders of magnitude less than those of conventionally deposited films.

Overgrowth and characterization of (11-22) semi-polar GaN on (113) silicon with a two-step method

A two-step approach has been developed for the growth of semi-polar (11–22) GaN on patterned (113) silicon substrates, which effectively eliminates Ga melt-back etching at a high temperature, one of the most challenging issues. A (113) Si substrate is patterned into groove trenches by means of using a standard photolithography technique and then anisotropic chemical etching, forming (111) facets with an inclination angle of 58˚ with respect to c-axis in addition to the un-etched (113) facets. A thick AlN layer is subsequently epitaxially grown on the patterned silicon to cover all the facets ensuring to eliminate the melt-back, followed by selectively depositing SiO2 masks on the (113) facets only. Further GaN overgrowth is performed only on the exposed (111) facets, forming (11–22) semi-polar GaN with high crystal quality along the vertical direction. Stimulated emission at room temperature has been observed with a low threshold. Low-temperature photoluminescence measurements confirm a significant reduction in basal stacking faults density. This method provides a promising approach to effectively suppress the Ga melt-back etching issue, which is particularly important for Al(Ga)N growth on semi-polar GaN that requires a high growth temperature. The presented results are crucially important for developing monolithic on-chip integration of electronics and photonics on silicon.

Epitaxial lateral overgrowth of GaN on nano-cavity patterned sapphire substrates

The epitaxial lateral overgrowth of GaN by metal-organic chemical vapor deposition using a nano-cavity patterned sapphire substrate (NCPSS) was investigated. The NCPSS, with a hexagonal non-close-packed nano-cavity pattern on the sapphire substrate, was fabricated by polystyrene sphere coating and size reduction by reactive ion etching, followed by deposition of alumina and thermal oxidation. The coalescence of GaN on the NCPSS was achieved by the formation of relatively large GaN islands and enhanced lateral overgrowth of the GaN islands over several nano-cavity pattern areas. The threading dislocation density (TDD) measured by cathodoluminescence measurement was significantly reduced from 2.4 × 108 cm−2 to 6.9 × 107 cm−2 by using the NCPSS. A dislocation behavior that contributes to the reduction of TDD of the GaN layer was observed by transmission electron microscopy. Raman spectroscopy revealed that the compressive stress in the GaN layer was reduced by 21% due to the embedded nano-cavities. In addition, the diffuse reflectance of GaN on the NCPSS was enhanced by 54% ∼ 62%, which is attributed to the increased probability of light extraction through effective light scattering by nano-cavities.

Overgrowth and strain investigation of (11\u201320) non-polar GaN on patterned templates on sapphire

Non-polar (11–20) GaN with significantly improved crystal quality has been achieved by means of overgrowth on regularly arrayed micro-rod templates on sapphire in comparison with standard non-polar GaN grown without any patterning processes on sapphire. Our overgrown GaN shows massively reduced linewidth of X-ray rocking curves with typical values of 270 arcsec along the [0001] direction and 380 arcsec along the [1–100] direction, which are among the best reports. Detailed X-ray measurements have been performed in order to investigate strain relaxation and in-plane strain distribution. The study has been compared with the standard non-polar GaN grown without any patterning processes and an extra non-polar GaN sample overgrown on a standard stripe-patterned template. The standard non-polar GaN grown without involving any patterning processes typically exhibits highly anisotropic in-plane strain distribution, while the overgrown GaN on our regularly arrayed micro-rod templates shows a highly isotropic in-plane strain distribution. Between them is the overgrown non-polar GaN on the stripe-patterned template. The results presented demonstrate the major advantages of using our regularly arrayed micro-rod templates for the overgrowth of non-polar GaN, leading to both high crystal quality and isotropic in-plane strain distribution, which is important for the further growth of any device structures.

Heat Treatment of Carbonized Photoresist Mask with Ammonia for Epitaxial Lateral Overgrowth of a-plane GaN on R-plane Sapphire

Epitaxial (1120) a-plane GaN films were grown on a (1102) R-plane sapphire substrate with photoresist (PR) masks using metal organic chemical vapor deposition (MOCVD). The PR mask with striped patterns was prepared using an ex-situ lithography process, whereas carbonization and heat treatment of the PR mask were carried out using an in-situ MOCVD. The heat treatment of the PR mask was continuously conducted in ambient H2/NH3 mixture gas at 1140℃ after carbonization by the pyrolysis in ambient H2 at 1100℃. As the time of the heat treatment progressed, the striped patterns of the carbonized PR mask shrank. The heat treatment of the carbonized PR mask facilitated epitaxial lateral overgrowth (ELO) of a-plane GaN films without carbon contamination on the R-plane sapphire substrate. Thhe surface morphology of a-plane GaN films was investigated by scanning electron microscopy and atomic force microscopy. The structural characteristics of a-plane GaN films on an R-plane sapphire substrate were evaluated by ω-2θ high-resolution X-ray diffraction. The a-plane GaN films were characterized by X-ray photoelectron spectroscopy (XPS) to determine carbon contamination from carbonized PR masks in the GaN film bulk. After Ar+ ion etching, XPS spectra indicated that carbon contamination exists only in the surface region. Finally, the heat treatment of carbonized PR masks was used to grow high-quality a-plane GaN films without carbon contamination. This approach showed the promising potential of the ELO process by using a PR mask.

Defect analysis of the LED structure deposited on the sapphire substrate

Transmission electron microscope (TEM) and double-crystal X-ray diffraction (DCXRD) measurements have been performed to investigate dislocations of the whole structure of the LED layers deposited on both the conventional (unpatterned sapphire substrate, UPSS) and patterned sapphire substrates (PSS). TEM results show that there exists a dislocation-accumulated region near the substrate/GaN interface, where the dislocation density is much higher with the UPPS than that with the PSS. It indicates that the pattern on the substrate surface is able to block the formation and propagation of dislocations. Further analysis discloses that slope of the pattern is found to suppress the deposition of GaN, and thus to provide more spaces for the epitaxially lateral overgrowth (ELO) of high temperature GaN, which significantly reduces the number of the initial islands, and minimizes dislocation formation due to the island coalescence. V-defect incorporating the threading dislocation is detected in the InGaN/GaN multi-quantum wells (MQWs), and its propagation mechanism is determined as the decrease of the surface energy due to the incorporation of indium. In addition, temperature dependence of dislocation formation is further investigated. The results show that dislocation with the screw component decreases monotonously as temperature goes up. However, edge dislocation firstly drops, and then increases by temperature due to the enhanced thermal mismatch stress. It implies that an optimized range of the growth temperature can be obtained to improve quality of the LED layers.

Impact of N-plasma and Ga-irradiation on MoS2 layer in molecular beam epitaxy

Recent interest in two-dimensional materials has resulted in ultra-thin devices based on the transfer of transition metal dichalcogenides (TMDs) onto other TMDs or III-nitride materials. In this investigation, we realized p-type monolayer (ML) MoS2, and intrinsic GaN/p-type MoS2 heterojunction by the GaN overgrowth on ML-MoS2/c-sapphire using the plasma-assisted molecular beam epitaxy. A systematic nitrogen plasma (N2*) and gallium (Ga) irradiation studies are employed to understand the individual effect on the doping levels of ML-MoS2, which is evaluated by micro-Raman and high-resolution X-Ray photoelectron spectroscopy (HRXPS) measurements. With both methods, p-type doping was attained and was verified by softening and strengthening of characteristics phonon modes E2g1 and A1g from Raman spectroscopy. With adequate N2*-irradiation (3 min), respective shift of 1.79 cm−1 for A1g and 1.11 cm−1 for E2g1 are obtained while short term Ga-irradiated (30 s) exhibits the shift of 1.51 cm−1 for A1g and 0.93 cm−1 for E2g1. Moreover, in HRXPS valence band spectra analysis, the position of valence band maximum measured with respect to the Fermi level is determined to evaluate the type of doping levels in ML-MoS2. The observed values of valance band maximum are reduced to 0.5, and 0.2 eV from the intrinsic value of ≈1.0 eV for N2*- and Ga-irradiated MoS2 layers, which confirms the p-type doping of ML-MoS2. Further p-type doping is verified by Hall effect measurements. Thus, by GaN overgrowth, we attained the building block of intrinsic GaN/p-type MoS2 heterojunction. Through this work, we have provided the platform for the realization of dissimilar heterostructure via monolithic approach.

Orientation-controlled epitaxial lateral overgrowth of semipolar GaN on Si(001) with a directionally sputtered AlN buffer layer

We successfully grew semipolar (101̅3) and (101̅5) GaN films on Si(001) substrates employing metal-organic chemical vapor deposition (MOCVD) by inserting a directionally sputtered AlN (DS-AlN) buffer layer. To improve the crystal quality of the orientation-controlled semipolar (101̅3) and (101̅5) GaN films, a two-step epitaxial lateral overgrowth (ELO) process was performed with a striped mask. According to low-temperature cathodoluminescence (LT-CL) characterization, the ELO results in a coalesced morphology and a low defect density of <2.72×108cm−2 for both semipolar (101̅3) and (101̅5) GaN films. For comparing the properties of planar and ELO semipolar GaN, a rocking curve of x-ray diffraction (XRD) and low-temperature photoluminescence (LT-PL) spectra was measured. The crystal orientation of semipolar GaN films was confirmed using electron backscatter diffraction (EBSD).

Effect of curved graphene oxide in a GaN light-emitting-diode for improving heat dissipation with a patterned sapphire substrate

AbstactThis article reports on the development of a reduced graphene oxide (rGO)-embedded light-emitting diode (LED) on a patterned sapphire substrate (PSS), for improving heat dissipation and reducing threading dislocations. The prototype device fabrication involves the generation of scalable curved graphene oxide microscale patterns on a PSS, followed by thermal reduction and epitaxial lateral overgrowth of GaN in a metal–organic chemical vapor deposition system with a one-step process. Using the forward voltage method, the junction temperature Tj of the rGO-embedded LED was found to be reduced by about 17 °C from the ∼62 °C of the LED grown without the rGO buffer layer. Temperature-dependent light output power and chip surface temperature measurements were also performed and the results are discussed.

MOCVD growth of N-polar GaN on on-axis sapphire substrate: Impact of AlN nucleation layer on GaN surface hillock density

We report on the impact of growth conditions on surface hillock density of N-polar GaN grown on nominally on-axis (0001) sapphire substrate by metal organic chemical vapor deposition (MOCVD). Large reduction in hillock density was achieved by implementation of an optimized high temperature AlN nucleation layer and use of indium surfactant in GaN overgrowth. A reduction by more than a factor of five in hillock density from 1000 to 170 hillocks/cm−2 was achieved as a result. Crystal quality and surface morphology of the resultant GaN films were characterized by high resolution x-ray diffraction and atomic force microscopy and found to be relatively unaffected by the buffer conditions. It is also shown that the density of smaller surface features is unaffected by AlN buffer conditions.