Metalorganic Vapor Phase Epitaxy Growth Research Articles

Lasing Characteristics of GaInAsP Laser Diodes on Directly Bonded InP/Si Substrates with a Gas out Channel

In this study, the lasing characteristics of GaInAsP laser diodes (LDs) grown on directly bonded InP/Si substrates with a gas out channel (GOC) structure are investigated. GOC InP/Si substrates are fabricated using hydrophilic direct bonding and metal–organic vapor phase epitaxy growth methods and subsequently their surface conditions, bonding strength, and lasing performance are examined. Herein, it is observed that the introduction of a GOC substantially reduces void formation and improves the threshold current density of the LDs. In the results, it is demonstrated that the performance of the GOC InP/Si substrates is comparable to that of InP substrates, highlighting their potential for use in high‐performance optical devices.

Review on ultrahigh growth rate GaAs solar cells by metalorganic vapor-phase epitaxy

The aim of this review paper is to summarize a decade of research focused on enhancing metalorganic vapor-phase epitaxy (MOVPE) growth rates of GaAs, driven by the imperative for most cost-effective and energy-efficient III–V compounds’ production. While MOVPE is renowned for producing high-quality devices, it has been constrained by production cost. For example, MOVPE was traditionally thought to have moderate growth rates that limit the throughput of the cost-intensive reactors. Recent research endeavors, however, have demonstrated ultrafast growth rates, exceeding 280 μm/h, with a remarkable group III precursor utilization efficiency of over 50%. It is worth noting that even with increased growth rates, the surface quality remains unaffected in terms of roughness and morphology. Nonetheless, optoelectronic properties, such as minority carrier lifetime, deteriorate for both p- and n-doped materials under constant growth conditions. This is attributed to an increase in the defect density of arsenic antisites, particularly EL2 and HM1 defects, as revealed by deep-level transient spectroscopy investigations. Some of these losses can be mitigated by optimizing growth conditions, such as elevating the temperature and reducing the V/III ratio. The latter not only restores some of the material quality but also increases the growth rate and reduces precursor consumption. Still, fully recovering the original reference lifetimes remains a challenge. Solar cell results indicate that structures with predominantly n-type absorbers are less affected by reduced minority carrier lifetimes. A remarkable 24.5% efficiency was achieved in a GaAs single-junction solar cell grown at 120 μm/h, representing less than 1 min of growth time for the absorber layers.

Size control of InP nanowires by in situ annealing and its application to the formation of InAsP quantum dots

We carried out in situ annealing of InP nanowires (NWs) in a metal-organic vapor phase epitaxial (MOVPE) growth reactor to control and reduce the tip size of InP NWs. InP NWs were grown by selective-area (SA) MOVPE on partially masked (111)A InP substrates, and annealing was successively applied in tertiarybutylphosphine (TBP) ambient. Initially, the InP NWs had a hexagonal cross-section with {112¯} facets vertical to the substrates; they became tapered, and the edges were rounded by annealing. By appropriately selecting the annealing temperature and initial NW diameter, the tip size of the NW was reduced and NWs with a tip size of 20 nm were successfully formed. Subsequently, a thin InAsP layer was grown on the annealed NWs and their photoluminescence was investigated at low temperatures. The characterization results indicated the formation of InAsP quantum dots (QDs) emitting in the telecom band. Our approach is useful for reducing the size of the NWs and for the controlled formation of InAsP QDs embedded in InP NWs in photonic devices compatible with telecom bands.

Defects in layered boron nitride grown by Metal Organic Vapor Phase Epitaxy: luminescence and positron annihilation studies

Defects in two-dimensional boron nitride (BN) are candidates for a manifold of applications, for example, as single-photon emitters or optically addressable spin defects. However, the topic has proven to be complex and despite extensive research efforts, knowledge on midgap defects and their signature in photoluminescence (PL) remains fragmentary. Mass production of high-quality layered BN by Metal Organic Vapor Phase Epitaxy (MOVPE) is possible and effective, thus understanding the conditions of formation and identifying defects that arise in the material grown by this method is extremely important. Here, we present an analysis of the influence of the MOVPE growth conditions of layered BN on the occurrence of specific structural defects. PL spectra in the visible range were analysed involving the Huang-Rhys theory implemented in the fitting procedure for polycrystalline samples grown under various conditions. Such an approach allowed us to separate bands from individual entities. Two bands at 1.57 eV and 2.6 eV with phonon replicas were observed. The three additional bands are characterized by a broad emission centered at 1.38 eV, 1.9 eV and 2.24 eV. Further properties, including an analysis of the surface morphology, the impact of annealing and laser bleaching on the PL spectra and Positron Annihilation Spectroscopy (PAS) were considered to draw conclusions about the nature of the examined defects. The PAS analysis correlated with the PL of the BN layers allows us to classify the studied samples in terms of the concentrations of boron vacancies and their complexes. Based on the obtained results, we propose that the rich family of PL bands observed in various sp2-BN layers is associated with different defect complexes build of boron vacancies (VB), boron antisite defects (BN), substitutional carbon defects (CB, CN) and their donor-acceptor pairs. The main value of this paper is the transfer of knowledge gained about defects and the corresponding luminescent bands to characterize high-quality continuous epitaxial sp2-BN layers. The presented results constitute an important step toward the deterministic manipulation of defect concentrations in two-dimensional boron nitride, which opens up new pathways for future optoelectronic device application.

Ab initio study for adsorption behavior on AlN(0001) surface with steps and kinks during metal-organic vapor-phase epitaxy

We present our systematic theoretical study by performing ab initio calculations to clarify the behavior of adsorption for constituent atoms such as Al and N on a vicinal AlN(0001) surface with step edges and kinks during metal-organic vapor-phase epitaxy (MOVPE). The calculations reveal that the surface reconstruction affects the adsorption of Al and N adatoms near the kinks and step edges. Furthermore, we find the incorporation of an Al adatom at the kink and that of N adatoms not only at the kink but also in the terrace regions. The calculated results give some insights for an atomic-scale understanding of the step-flow growth during the MOVPE growth of AlN.

Incorporation of indium into GaN layers in the context of MOVPE thermodynamics and growth – Ab initio studies

Indium incorporation on the GaN surface (0001) has been analyzed in the context of InGaN growth by Metal Organic Vapor Phase Epitaxy (MOVPE). To understand phenomena at the atomic level, calculations based on Density Functional Theory (DFT) and thermodynamic analysis of the surface processes have been performed. The considerations are limited to the terrace on GaN (0001) surface, covered fully by NH3/NH2 species. The ab initio results indicate that the adsorption energy strongly depends on the electronic properties of the surface. The adsorption energy varies from EadsDFT=-10.0eV for fully NH2 covered to EadsDFT=-3.0eV for mixed 0.69 NH2 + 0.31 NH3 covered surface. This change is related to Fermi level position moved from within valence band, across the bandgap, up to within conduction band. The shift in Fermi energy impacts the energy gained during adsorption due to electron occupation of surface states. Furthermore, a comprehensive thermodynamic analysis was conducted, revealing an additional, albeit smaller, contribution from the vibrational degrees of freedom to free energy. The combined effect of these factors leads to an increase in the equilibrium pressures of indium related to the increase in hydrogen pressure, which correlates with high coverage by ammonia molecules. The results demonstrate that the significant reduction in indium incorporation into InGaN layers during MOVPE growth under conditions of low hydrogen concentration in the vapor can be attributed to the influence of hydrogen on In adsorption processes.

From Layer-by-Layer Growth to Nanoridge Formation: Selective Area Epitaxy of GaAs by MOVPE.

Selective area epitaxy at the nanoscale enables fabrication of high-quality nanostructures in regular arrays with predefined geometry. Here, we investigate the growth mechanisms of GaAs nanoridges on GaAs (100) substrates in selective area trenches by metal-organic vapor-phase epitaxy (MOVPE). It is found that pre-growth annealing results in the formation of valley-like structures of GaAs with atomic terraces inside the trenches. MOVPE growth of GaAs nanoridges consists of three distinct stages. Filling the trench in the first stage exhibits a step-flow growth behavior. Once the structure grows above the mask surface, it enters the second stage of growth by forming {101} side facets as the (100) flat top facet progressively shrinks. In the third stage, the fully formed nanoridge begins to overgrow onto the mask with a significantly reduced growth rate. We develop a kinetic model that accurately describes the width-dependent evolution of the nanoridge morphology through all three stages. MOVPE growth of fully formed nanoridges takes only about 1 min, which is 60 times faster than in our set of molecular beam epitaxy (MBE) experiments reported recently, and with a more regular, triangular cross-sectional geometry defined solely by the {101} facets. In contrast to MBE, no material loss due to Ga adatom diffusion onto the mask surface is observed in MOVPE until the third stage of growth. These results are useful for the fabrication of GaAs nanoridges of different dimensions on the same substrate for various applications and can be extended to other material systems.

Al0.35Ga0.65As/InGaP heterojunction solar cell based on temperature-graded growth

The p-Al0.35Ga0.65As/n-InGaP heterojunction solar cells are promising competitors compared with conventional InGaP or AlGaAs solar cells as the heterogeneous combination can overcome the demerits of each material. However, InGaP has an optimized growth temperature much lower than that of AlGaAs in metal-organic vapor phase epitaxy (MOVPE) growth. Therefore, a challenge arises from oxygen contamination at the hetero-interface during temperature adjustment for obtaining MOVPE-grown high-quality p-AlGaAs/n-InGaP heterojunction. Here we report that a temperature-graded layer (TGL) of AlGaAs can solve the issue of growth temperature mismatch, and significantly improve the voltage performance of AlGaAs/InGaP solar cells. Absolute electroluminescence measurement and atomic force microscopy confirmed a smooth interface with less non-radiative recombination after TGL was applied. The temperature-graded growth is verified able to improve the AlGaAs/InGaP interface quality and provides a scalable method for AlGaAs-based heterogeneous growth.

MOVPE growth of AlN and AlGaN films on N-polar annealed and sputtered AlN templates

We performed metalorganic vapor phase epitaxy (MOVPE) growth of AlN (MOVPE-AlN) and AlGaN films on N-polar face-to-face annealed and sputtered AlN templates (N-polar FFA Sp-AlN) on sapphire substrates. The off-cut angle of the sapphire substrates was varied from 0.2° to 6.0°. The effects of the off-cut angle on the surface morphology and crystallinity of the N-polar MOVPE-AlN and AlGaN were elucidated. The results showed that the crystallinities of N-polar FFA Sp-AlN and MOVPE-AlN were independent of the off-cut angle. The threading dislocation density (TDD) was estimated to be approximately 5.0 × 108cm−2 by using values of the X-ray rocking curve full-width at half maximum. In comparison, the density of the hillocks on the MOVPE-AlN surfaces was suppressed, and the surface flatness was improved by increasing the off-cut angle of the sapphire substrate. The crystallinity of the AlGaN was improved by increasing the off-cut angle. Our results prove that N-polar AlN and AlGaN films with smooth surfaces and low TDDs could be achieved by MOVPE on N-polar FFA Sp-AlN with a large substrate off-cut angle of 6.0°.

Self-catalyzed GaP nanowire MOVPE growth on Si

Typically, vapour liquid solid (VLS)-grown nanowires via metal–organic vapour phase epitaxy (MOVPE) use gold as a liquid growth catalyst. However, incorporating gold as an impurity during growth is disadvantageous. Therefore, we introduce the self-catalyzed VLS growth of GaP nanowires on Si (111) substrates via MOVPE, utilizing (deposited) Ga droplets as seed particles. To understand and optimize the growth process, the influence of various growth parameters such as Ga precursor preflow, growth temperature, growth time and V/III ratio are studied. As main findings we show that nanowire growth without strong tapering is possible. By varying the V/III gas phase ratio the tapering of nanowires can be manipulated during growth via droplet consumption. In addition, nanowires with lengths up to 10 µm and an aspect ratio of around 20 are demonstrated, showing only slight tapering. High-resolution scanning transmission electron microscopy measurements prove the zincblende crystal structure of the GaP nanowires in horizontal and vertical ultramicrotomy cuts. In vertical cross sections, a high number of microtwin boundaries perpendicular to the growth direction are found.

Thermal stability of thin hexagonal boron nitride grown by MOVPE on epigraphene

Passivating graphene with a layer of hexagonal boron nitride (hBN) is known to protect it from environment effects that degrade its mobility. However, growth of high-quality BN on graphene is challenging because of the lack of surface dangling bonds. Here, we report the growth of thin BN films (down to 10 nm) on monolayer epigraphene grown on silicon carbide single-crystal substrates using metal–organic vapor phase epitaxy (MOVPE). The BN film has continuous coverage on the epigraphene surface, with smooth morphology. Particles consisting of layered BN are also observed on the surface with a higher density at the step edges. High-Resolution Scanning Transmission Electron Microscopy (HRSTEM) reveals high structural quality BN layers, with a clean and abrupt interface with graphene. The BN/epigraphene/SiC heterostructure is stable up to high temperature (1550 °C), and annealing improves its crystallinity. These results show that MOVPE growth technique has a potential for large-scale production of BN fully coated graphene and high-temperature applications.

In situ control of indium incorporation in (AlGa)1−xInxP layers

Metalorganic vapor phase epitaxy growth of red emitting laser structures based on (AlGa)1-xInxP (AlGaInP) compounds requires thorough control of In incorporation during growth of AlGaInP layers which heavily depends on growth parameters and reactor state. We established an in situ method to determine the In incorporation in AlGaInP layers during growth without any prior calibration based on ex situ characterization. This requires to model the lattice constants of substrate and growing layer and feed it with the in situ measured wafer temperature, growth rate and wafer curvature. The model makes use of the Stoney equation and Vegard’s law to calculate the In content of AlGaInP layers grown on GaAs substrates. Correlation of in situ results to ex situ results from X-ray diffraction confirmed the accuracy of our method. Our in situ method allowed us to study the influence of dopants on growth of AlGaInP layers. At high temperature Si doping from Si2H6 showed no influence on the In incorporation during growth, however, Zn doping from DMZn showed strong impact on In incorporation and growth rate. In particular, increasing the DMZn/III ratio during AlGaInP growth linearly decreases In incorporation and growth rate. Accordingly, the presence of Zn on the growth surface hinders In incorporation and causes enhanced In re-evaporation from the surface at high temperatures.

263 nm wavelength UV-C LED on face-to-face annealed sputter-deposited AlN with low screw- and mixed-type dislocation densities

Regarding deep-ultraviolet optical device applications, face-to-face annealed sputter-deposited AlN (FFA Sp-AlN) is a promising alternative to the conventional metalorganic vapor phase epitaxy (MOVPE)-prepared AlN templates on sapphire substrates. However, FFA Sp-AlN tends to exhibit AlGaN growth-related hillock generation and surface morphology deterioration. In this study, we optimized the sputter-deposition conditions for AlN and MOVPE growth conditions for AlGaN to respectively reduce hillock density and size. After confirming AlGaN surface-flattening, we fabricated 263 nm wavelength UV-C LEDs on the FFA Sp-AlN and achieved maximum external quantum efficiencies of approximately 4.9% and 8.0% without and with silicone encapsulation, respectively.

Improvement of structural quality of AlN layers grown on c-plane sapphire substrate by metal–organic vapor phase epitaxy using post-growth annealing with trimethylgallium

AlN layers were grown on a c-plane sapphire substrate by metal–organic vapor phase epitaxy (MOVPE) at 1350 °C. The structural quality of the grown AlN layers was drastically improved by post-growth annealing in mixed hydrogen, ammonia, and trimethylgallium ambiance at 1350 °C. As a first step, we grew the AlN layers exhibiting a double-domain structure with an in-plane rotation angle of ∼4°. Then, the domain structure was changed from double to single by the post-growth annealing. After 20 min post-growth annealing, the surface possessed an atomically flat step-and-terrace structure with a root-mean-square value of ∼0.11 nm measured across 5 × 5 µm2. The full-width at half maximum values for 0002 and 101̄4 AlN reflections using x-ray diffraction were as small as ∼75 and ∼280 arcsec, respectively. Since this work provides a simple continuous MOVPE growth procedure to improve the structural quality of AlN/sapphire, it is advantageous to the industrial fabrication of AlxGa1−xN-based ultraviolet light-emitters.

Effect of MOVPE growth conditions on AlN films on annealed sputtered AlN templates with nano-striped patterns

The metalorganic vapor phase epitaxial (MOVPE) growth of AlN films was performed on face-to-face annealed sputtered AlN templates (FFA Sp-AlN) having a nano-striped pattern with a period of 300 nm and depth of 120 nm. Then, the effect of MOVPE growth conditions on the crystallinity was elucidated. The faceted structure clearly changed with the growth temperature (Tg), following the same trend as the epitaxial lateral overgrowth of GaN film on micro-patterned GaN. High Tg levels enhanced the lateral growth, and thus with a high Tg of 1300 °C, the coalescence in the early growth stage resulted in AlN films with coalesced surfaces and a thickness of 1 µm. For the AlN film grown at a Tg of 1300 °C, the threading dislocation density (TDD) was estimated to be 6.0 × 108 cm−2. This value proved that coalesced AlN films on nano-patterned FFA Sp-AlN templates with low TDDs could be achieved with the appropriate MOVPE growth conditions. The compressive strain in the AlN film on nano-patterned FFA Sp-AlN was lower than that of the film grown on FFA Sp-AlN without a pattern.

Study of the Cross-Influence between III-V and IV Elements Deposited in the Same MOVPE Growth Chamber.

We have deposited Ge, SiGe, SiGeSn, AlAs, GaAs, InGaP and InGaAs based structures in the same metalorganic vapor phase epitaxy (MOVPE) growth chamber, in order to study the effect of the cross influence between groups IV and III-V elements on the growth rate, background doping and morphology. It is shown that by adopting an innovative design of the MOVPE growth chamber and proper growth condition, the IV elements growth rate penalization due to As “carry over” can be eliminated and the background doping level in both IV and III-V semiconductors can be drastically reduced. In the temperature range 748–888 K, Ge and SiGe morphologies do not degrade when the semiconductors are grown in a III-V-contaminated MOVPE growth chamber. Critical morphology aspects have been identified for SiGeSn and III-Vs, when the MOVPE deposition takes place, respectively, in a As or Sn-contaminated MOVPE growth chamber. III-Vs morphologies are influenced by substrate type and orientation. The results are promising in view of the monolithic integration of group-IV with III-V compounds in multi-junction solar cells.

Origin(s) of Anomalous Substrate Conduction in MOVPE-Grown GaN HEMTs on Highly Resistive Silicon.

The performance of transistors designed specifically for high-frequency applications is critically reliant upon the semi-insulating electrical properties of the substrate. The suspected formation of a conductive path for radio frequency (RF) signals in the highly resistive (HR) silicon substrate itself has been long held responsible for the suboptimal efficiency of as-grown GaN high electron mobility transistors (HEMTs) at higher operating frequencies. Here, we reveal that not one but two discrete channels distinguishable by their carrier type, spatial extent, and origin within the metal-organic vapor phase epitaxy (MOVPE) growth process participate in such parasitic substrate conduction. An n-type layer that forms first is uniformly distributed in the substrate, and it has a purely thermal origin. Alongside this, a p-type layer is localized on the substrate side of the AlN/Si interface and is induced by diffusion of group-III element of the metal-organic precursor. Fortunately, maintaining the sheet resistance of this p-type layer to high values (∼2000 Ω/□) seems feasible with particular durations of either organometallic precursor or ammonia gas predose of the Si surface, i.e., the intentional introduction of one chemical precursor just before nucleation. It is proposed that the mechanism behind the control actually relies on the formation of disordered AlSiN between the crystalline AlN nucleation layer and the crystalline silicon substrate.

Compensation in (2¯01) homoepitaxial β-Ga2O3 thin films grown by metalorganic vapor-phase epitaxy

Homoepitaxial growth of β-Ga2O3 using metalorganic vapor-phase epitaxy (MOVPE) on several different crystal orientations has previously been studied, but growth on the (2¯01) plane has remained comparatively unexplored. To investigate this, we grew Si-doped and unintentionally doped (UID) homoepitaxial layers simultaneously on Sn-doped (2¯01) and (010) substrates under conditions optimized for (010) growth. We report herein on results from current–voltage and capacitance–voltage (IV and CV) and deep level transient spectroscopy (DLTS) characterization of Schottky diodes fabricated on these samples. Devices on (010) display nearly ideal Schottky diode JV and CV behaviors while for (2¯01) evidence of complete depletion of >2 μm thickness, UID epilayers are observed. The (2¯01) UID diodes exhibited Mott–Gurney space charge-limited transport and were completely depleted even at zero bias. Doping (2¯01) samples heavily with Si was sufficient to overcome background compensation and reproduce near-ideal diode behavior. DLTS data from these doped devices show, in addition to typical negative majority-carrier transients, positive transients with a broad energy distribution, possibly indicating traps on structural defects or surface states. An etch pit analysis under SEM revealed intricate structures of the grown layers. Cross-sectional TEM characterization of a (2¯01) sample revealed a high density of structural defects within the epitaxial layer, likely stacking faults. Hypotheses for the origins of the compensation in (2¯01) β-Ga2O3 homoepitaxial MOVPE growth under (010) growth conditions are discussed; the most likely explanation is the presence of defect states introduced by the stacking faults visible under TEM.

High‐Quality AlN Template Prepared by Face‐to‐Face Annealing of Sputtered AlN on Sapphire

This study comprehensively investigates the properties of metalorganic vapor phase epitaxy (MOVPE)‐grown AlN films on high‐quality face‐to‐face annealed sputtered AlN (FFA Sp‐AlN) templates on sapphire substrates, which are highly important to control the surface morphology for various applications, such as UV light‐emitting diodes and laser diodes. The conditions of thermal cleaning and AlN growth by MOVPE are investigated to remove numerous small islands on as‐annealed FFA Sp‐AlN. Subsequent to thermal cleaning in H2 + NH3 at 1300 °C, MOVPE growth is performed with varying NH3 flow rate and growth temperature (Tg) under a constant pressure and group‐III flow rate. An atomically flat surface with an atomic step‐and‐terrace structure is obtained at a growth rate of ≈1.0 μm h−1 and a Tg of 1300 °C. Transmission electron microscopy images and secondary‐ion mass spectrometry reveal low dislocation densities and impurity concentrations. Finally, the effects of compressive strain in FFA Sp‐AlN on the lattice constant and curvature of the MOVPE‐grown AlN film on FFA Sp‐AlN are investigated. The compressive strain of the AlN film, which is carried over from FFA Sp‐AlN, can prevent crack formation but leads to a large wafer curvature after cooling down from the Tg.

Delta-doped β -Ga2O3 films with narrow FWHM grown by metalorganic vapor-phase epitaxy

We report on the low-temperature metalorganic vapor-phase epitaxy (MOVPE) growth of silicon delta-doped β-Ga2O3 films with a low full width at half maximum (FWHM). The as-grown films are characterized using secondary-ion mass spectroscopy, capacitance–voltage, and Hall techniques. Secondary ion mass spectroscopy measurements show that surface segregation is the chief cause of a large FWHM in MOVPE-grown films. The surface segregation coefficient (R) is observed to reduce with reduction in the growth temperature. Films grown at 600 °C show an electron concentration of 9.7 × 1012 cm−2 and a FWHM of 3.2 nm. High resolution scanning/transmission electron microscopy of the epitaxial film did not reveal any observable degradation in the crystal quality of the delta sheet and surrounding regions. Hall measurements of the delta-doped film on the Fe-doped substrate showed a sheet charge density of 6.1 × 1012 cm−2 and a carrier mobility of 83 cm2/V s. Realization of sharp delta doping profiles in MOVPE-grown β-Ga2O3 is promising for high performance device applications.