Strain modulation of epitaxial h-BN on sapphire: the role of wrinkle formation for large-area two-dimensional materials.

Strain built-in electronic and optoelectronic devices can influence their properties and lifetime. This effect is particularly significant at the interface between two-dimensional materials and substrates. One such material is epitaxial hexagonal boron nitride (h-BN), which is grown at temperatures often exceeding 1000 °C. Due to the high growth temperature, h-BN based devices operating at room temperature can be strongly affected by strain generated during cooling due to the differences in lattice thermal expansion of h-BN and the substrate. Here, we present results of temperature-dependent Raman studies of the in-plane E2ghighphonon mode in the temperature range of 300-1100 K measured for h-BN grown by metalorganic vapor phase epitaxy. We observe a change, by an order of magnitude, in the rate of the temperature-induced frequency shift for temperatures below 900 K, indicating a strong reduction of the effective h-BN/substrate interaction. We attribute this behavior to the creation of h-BN wrinkles which results in strain relaxation. This interpretation is supported by the observation that no change of layer/substrate interaction and no wrinkles are observed for delaminated h-BN films transferred onto silicon. Our findings demonstrate that wrinkle formation is an inherent process for two-dimensional materials on foreign substrates that has to be understood to allow for the successful engineering of devices based on epitaxially grown van der Waals heterostructures.

Pulsed-Mode Metalorganic Vapor-Phase Epitaxy of GaN on Graphene-Coated c-Sapphire for Freestanding GaN Thin Films.

We report the growth of high-quality GaN epitaxial thin films on graphene-coated c-sapphire substrates using pulsed-mode metalorganic vapor-phase epitaxy, together with the fabrication of freestanding GaN films by simple mechanical exfoliation for transferable light-emitting diodes (LEDs). High-quality GaN films grown on the graphene-coated sapphire substrates were easily lifted off by using thermal release tape and transferred onto foreign substrates. Furthermore, we revealed that the pulsed operation of ammonia flow during GaN growth was a critical factor for the fabrication of high-quality freestanding GaN films. These films, exhibiting excellent single crystallinity, were utilized to fabricate transferable GaN LEDs by heteroepitaxially growing InxGa1-xN/GaN multiple quantum wells and a p-GaN layer on the GaN films, showing their potential application in advanced optoelectronic devices.

Nanotribological Characteristics of the Al Content of AlxGa1-xN Epitaxial Films.

The nanotribological properties of aluminum gallium nitride (AlxGa1-xN) epitaxial films grown on low-temperature-grown GaN/AlN/Si substrates were investigated using a nanoscratch system. It was confirmed that the Al compositions played an important role, which was directly influencing the strength of the bonding forces and the shear resistance. It was verified that the measured friction coefficient (µ) values of the AlxGa1-xN films from the Al compositions (where x = 0.065, 0.085, and 0.137) were in the range of 0.8, 0.5, and 0.3, respectively, for Fn = 2000 µN and 0.12, 0.9, and 0.7, respectively, for Fn = 4000 µN. The values of µ were found to decrease with the increases in the Al compositions. We concluded that the Al composition played an important role in the reconstruction of the crystallites, which induced the transition phenomenon of brittleness to ductility in the AlxGa1-xN system.

Lattice Strain Relaxation and Compositional Control in As-Rich GaAsP/(100)GaAs Heterostructures Grown by MOVPE.

The fabrication of high-efficiency GaAsP-based solar cells on GaAs wafers requires addressing structural issues arising from the materials lattice mismatch. We report on tensile strain relaxation and composition control of MOVPE-grown As-rich GaAs1-xPx/(100)GaAs heterostructures studied by double-crystal X-ray diffraction and field emission scanning electron microscopy. Thin (80-150 nm) GaAs1-xPx epilayers appear partially relaxed (within 1-12% of the initial misfit) through a network of misfit dislocations along the sample [011] and [011-] in plane directions. Values of the residual lattice strain as a function of epilayer thickness were compared with predictions from the equilibrium (Matthews-Blakeslee) and energy balance models. It is shown that the epilayers relax at a slower rate than expected based on the equilibrium model, an effect ascribed to the existence of an energy barrier to the nucleation of new dislocations. The study of GaAs1-xPx composition as a function of the V-group precursors ratio in the vapor during growth allowed for the determination of the As/P anion segregation coefficient. The latter agrees with values reported in the literature for P-rich alloys grown using the same precursor combination. P-incorporation into nearly pseudomorphic heterostructures turns out to be kinetically activated, with an activation energy EA = 1.41 ± 0.04 eV over the entire alloy compositional range.

Micro- and Nanostructure Analysis of Vapor-Phase-Grown AlN on Face-to-Face Annealed Sputtered AlN/Nanopatterned Sapphire Substrate Templates.

Micro- and nanostructures in vapor-phase-grown AlN on face-to-face annealed sputtered AlN (FFA Sp-AlN) templates formed on nanopatterned sapphire substrates (NPSS) were comprehensively analyzed using transmission electron microscopy. The comparison between metal-organic vapor-phase epitaxy-grown AlN/FFA Sp-AlN/hole-type NPSS (Sample MOH) and hydride vapor-phase epitaxy-grown AlN/FFA Sp-AlN/cone-type NPSS (Sample HVC) showed apparent differences in the morphology of dislocation propagation, presence of voids, shape of polarity inversion boundaries, and crystal structure on the slope region of NPSS. Notably, cross-sectional and plan-view observations revealed that the quality of FFA Sp-AlN significantly affects the threading dislocation density in the vapor-phase-grown layer. At the slope region of the AlN/NPSS interface, γ-AlON was observed in the MOH sample, while highly misaligned AlN grains were observed in the HVC sample. These characteristic crystal structures affect the occurrence of dislocations via different mechanisms in each sample. This study provides practical information for strategically controlling the micro- and nanostructures formed in AlN/NPSS structures for high-performance AlGaN-based deep-ultraviolet emitters. Supplementary Information: The online version contains supplementary material available at 10.1007/s11664-023-10348-3.

Growth of Ga0.70In0.30N/GaN Quantum-Wells on a ScAlMgO4 (0001) Substrate with an Ex-Situ Sputtered-AlN Buffer Layer.

This study attempted to improve the internal quantum efficiency (IQE) of 580 nm emitting Ga0.70In0.30N/GaN quantum-wells (QWs) through the replacement of a conventional c-sapphire substrate and an in-situ low-temperature GaN (LT-GaN) buffer layer with the ScAlMgO4 (0001) (SCAM) substrate and an ex-situ sputtered-AlN (sp-AlN) buffer layer, simultaneously. To this end, we initially tried to optimize the thickness of the sp-AlN buffer layer by investigating the properties/qualities of an undoped-GaN (u-GaN) template layer grown on the SCAM substrate with the sp-AlN buffer layer in terms of surface morphology, crystallographic orientation, and dislocation type/density. The experimental results showed that the crystallinity of the u-GaN layer grown on the SCAM substrate with the 30 nm thick sp-AlN buffer layer [GaN/sp-AlN(30 nm)/SCAM] was superior to that of the conventional u-GaN template layer grown on the c-sapphire substrate with an LT-GaN buffer layer (GaN/LT-GaN/FSS). Notably, the experimental results showed that the structural properties and crystallinity of GaN/sp-AlN(30 nm)/SCAM were considerably different from those of GaN/LT-GaN/FSS. Specifically, the edge-type dislocation density was approximately two orders of magnitude higher than the screw-/mixed-type dislocation density, i.e., the generation of screw-/mixed-type dislocation was suppressed through the replacement, unlike that of the GaN/LT-GaN/FSS. Next, to investigate the effect of replacement on the subsequent QW active layers, 580 nm emitting Ga0.70In0.30N/GaN QWs were grown on the u-GaN template layers. The IQEs of the samples were measured by means of temperature-dependent photoluminescence efficiency, and the results showed that the replacement improved the IQE at 300 K by approximately 1.8 times. We believe that the samples fabricated and described in the present study can provide a greater insight into future research directions for III-nitride light-emitting devices operating in yellow-red spectral regions.

Pre-trimethylindium Flow Treatment of GaInN/GaN Quantum Wells to Suppress Surface Defect Incorporation and Improve Efficiency.

This study aims to improve the emission efficiency of GaInN-based green light-emitting devices (LEDs) using the pre-trimethylindium (TMIn) flow treatment of a quantum well (QW) since we hypothesize that the pre-TMIn flow treatment is able to suppress the incorporation of surface defects (SDs) from the n-type GaN surface into the QWs. For this purpose, first, we investigate the effect of TMIn flow treatment on the SDs in n-type GaN samples by measuring time-resolved photoluminescence. The result of the investigation shows that the TMIn flow treatment effectively deactivated and/or neutralized the SDs from acting as the nonradiative recombination centers. Next, we prepare and investigate the GaInN-based green LEDs employing five pairs of multiple quantum wells (MQWs), in which the number of pre-TMIn treated QWs varies from zero to five. Through the analysis of prepared samples, we demonstrate that the pre-TMIn flow treatment of QWs works effectively in suppressing the SD incorporation into the MQWs, thereby improving the emission intensity.

Towards Efficient Electrically-Driven Deep UVC Lasing: Challenges and Opportunities.

The major issues confronting the performance of deep-UV (DUV) laser diodes (LDs) are reviewed along with the different approaches aimed at performance improvement. The impact of threading dislocations on the laser threshold current, limitations on heavy n- and p-doping in Al-rich AlGaN alloys, unavoidable electron leakage into the p-layers of (0001) LD structures, implementation of tunnel junctions, and non-uniform hole injection into multiple quantum wells in the active region are discussed. Special attention is paid to the current status of n- and p-type doping and threading dislocation density reduction, both being the factors largely determining the performance of DUV-LDs. It is shown that most of the above problems originate from intrinsic properties of the wide-bandgap AlGaN semiconductors, which emphasizes their fundamental role in the limitation of deep-UV LD performance. Among various remedies, novel promising technological and design approaches, such as high-temperature face-to-face annealing and distributed polarization doping, are discussed. Whenever possible, we provided a comparison between the growth capabilities of MOVPE and MBE techniques to fabricate DUV-LD structures.

Heteroepitaxial Growth of High Optical Quality, Wafer-Scale van der Waals Heterostrucutres.

Transition metal dichalcogenides (TMDs) are materials that can exhibit intriguing optical properties like a change of the bandgap from indirect to direct when being thinned down to a monolayer. Well-resolved narrow excitonic resonances can be observed for such monolayers although only for materials of sufficient crystalline quality and so far mostly available in the form of micrometer-sized flakes. A further significant improvement of optical and electrical properties can be achieved by transferring the TMD on hexagonal boron nitride (hBN). To exploit the full potential of TMDs in future applications, epitaxial techniques have to be developed that not only allow the growth of large-scale, high-quality TMD monolayers but also allow the growth to be performed directly on large-scale epitaxial hBN. In this work, we address this problem and demonstrate that MoSe2 of high optical quality can be directly grown on epitaxial hBN on an entire 2 in. wafer. We developed a combined growth theme for which hBN is first synthesized at high temperature by metal organic vapor phase epitaxy (MOVPE) and as a second step MoSe2 is deposited on top by molecular beam epitaxy (MBE) at much lower temperatures. We show that this structure exhibits excellent optical properties, manifested by narrow excitonic lines in the photoluminescence spectra. Moreover, the material is homogeneous on the area of the whole 2 in. wafer with only ±0.14 meV deviation of excitonic energy. Our mixed growth technique may guide the way for future large-scale production of high quality TMD/hBN heterostructures.

CH4 Adsorption Probability on GaN(0001) and (000-1) during Metalorganic Vapor Phase Epitaxy and Its Relationship to Carbon Contamination in the Films.

Suppression of carbon contamination in GaN films grown using metalorganic vapor phase epitaxy (MOVPE) is a crucial issue in its application to high power and high frequency electronic devices. To know how to reduce the C concentration in the films, a sequential analysis based on first principles calculations is performed. Thus, surface reconstruction and the adsorption of the CH4 produced by the decomposition of the Ga source, Ga(CH3)3, and its incorporation into the GaN sub-surface layers are investigated. In this sequential analysis, the dataset of the adsorption probability of CH4 on reconstructed surfaces is indispensable, as is the energy of the C impurity in the GaN sub-surface layers. The C adsorption probability is obtained based on steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic ensemble-based, non-phenomenological framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium. This framework is suitable especially when one studies the adsorption behavior of an impurity molecule because the conventional approach, the chemical potential control method, cannot be applied to a quantitative analysis for such a system. The proposed sequential model successfully explains the influence of the growth orientation, GaN(0001) and (000-1), on the incorporation of C into the film. This model can contribute to the suppression of the C contamination in GaN MOVPE.

Modeling the Non-Equilibrium Process of the Chemical Adsorption of Ammonia on GaN(0001) Reconstructed Surfaces Based on Steepest-Entropy-Ascent Quantum Thermodynamics.

Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and Nad-H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium where the state evolution is a combination of reversible and irreversible dynamics. SEAQT is an ideal choice to handle this problem on a first-principles basis since the chemical adsorption process starts from a highly non-equilibrium state. A result of the analysis shows that the probability of adsorption on 3Ga-H is significantly higher than that on Nad-H + Ga-H. Additionally, the growth temperature dependence of these adsorption probabilities and the temperature increase due to the heat of reaction is determined. The non-equilibrium thermodynamic modeling applied can lead to better control of the MOVPE process through the selection of preferable reconstructed surfaces. The modeling also demonstrates the efficacy of DFT-SEAQT coupling for determining detailed non-equilibrium process characteristics with a much smaller computational burden than would be entailed with mechanics-based, microscopic-mesoscopic approaches.

CdTe Nanowires by Au-Catalyzed Metalorganic Vapor Phase Epitaxy.

We report on the first Au-catalyzed growth of CdTe nanowires by metalorganic vapor phase epitaxy. The nanowires were obtained by a separate precursors flow process in which (i) di-isopropyl-telluride (iPr2Te) was first flowed through the reactor to ensure the formation of liquid Au-Te alloy droplets, and (ii) after purging with pure H2 to remove unreacted iPr2Te molecules from the vapor and the growth surface, (iii) dimethylcadmium (Me2Cd) was supplied to the vapor so that Cd atoms could enter the catalyst droplets, leading to nanowire self-assembly. CdTe nanowires were grown between 485 and 515 °C on (111)B-GaAs substrates, the latter preliminary deposited with a 2 µm thick (111)-oriented CdTe buffer layer onto which Au nanoparticles were provided. As-grown CdTe nanowires were vertical ([111]-aligned) straight segments of constant diameter and showed an Au-rich nanodroplet at their tips, the contact angle between the droplets and the nanowires being ∼130°. The nanowire axial growth rate appeared kinetics-limited with an activation energy ∼57 kcal/mol. However, the growth rate turned independent from the nanowire diameter. Present data are interpreted by a theoretical model explaining the nanowire growth through the diffusion transport of Te adatoms under the assumption that their growth occurs during the Me2Cd-flow process step. Low-temperature cathodoluminescence spectra recorded from single nanowires showed a well-resolved band-edge emission typical of zincblend CdTe along with a dominant band peaked at 1.539 eV.

Dense, Regular GaAs Nanowire Arrays by Catalyst-Free Vapor Phase Epitaxy for Light Harvesting.

Density dependent growth and optical properties of periodic arrays of GaAs nanowires (NWs) by fast selective area growth MOVPE are investigated. As the period of the arrays is decreased from 500 nm down to 100 nm, a volume growth enhancement by a factor of up to four compared with the growth of a planar layer is observed. This increase is explained as resulting from increased collection of precursors on the side walls of the nanowires due to the gas flow redistribution in the space between the NWs. Normal spectral reflectance of the arrays is strongly reduced compared with a flat substrate surface in all fabricated arrays. Electromagnetic modeling reveals that this reduction is caused by antireflective action of the nanowire arrays and nanowire-diameter dependent light absorption. Irrespective of the periodicity and diameter, Raman scattering and grazing angle X-ray diffraction show signal from zinc blende and wurtzite phases, the latter originating from stacking faults as observed by high resolution transmission electron microscopy. Raman spectra contain intense surface phonons peaks, whose intensity depends strongly on the nanowire diameters as a result of potential structural changes and as well as variations of optical field distribution in the nanowires.

Simultaneous Selective-Area and Vapor-Liquid-Solid Growth of InP Nanowire Arrays.

Selective-area epitaxy is highly successful in producing application-ready size-homogeneous arrays of III-V nanowires without the need to use metal catalysts. Previous works have demonstrated excellent control of nanowire properties but the growth mechanisms remain rather unclear. Herein, we report a detailed growth study revealing that fundamental growth mechanisms of pure wurtzite InP ⟨111⟩A nanowires can indeed differ significantly from the simple picture of a facet-limited selective-area growth process. A dual growth regime with and without metallic droplet is found to coexist under the same growth conditions for different diameter nanowires. Incubation times and highly nonmonotonous growth rate behaviors are revealed and explained within a dedicated kinetic model.

Lithography-Free Fabrication of Core-Shell GaAs Nanowire Tunnel Diodes.

GaAs core-shell p-n junction tunnel diodes were demonstrated by combining vapor-liquid-solid growth with gallium oxide deposition by atomic layer deposition for electrical isolation. The characterization of an ensemble of core-shell structures was enabled by the use of a tungsten probe in a scanning electron microscope without the need for lithographic processing. Radial tunneling transport was observed, exhibiting negative differential resistance behavior with peak-to-valley current ratios of up to 3.1. Peak current densities of up to 2.1 kA/cm(2) point the way to applications in core-shell photovoltaics and tunnel field effect transistors.