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Metal organic chemical vapor deposition (MOCVD) of group III nitrides on graphene heterostructures offers new opportunities for the development of flexible optoelectronic devices and for the stabilization of conceptually-new two-dimensional materials. However, the MOCVD of group III nitrides is regulated by an intricate interplay of gas-phase and surface reactions that are beyond the resolution of experimental techniques. We use density-functional ab initio molecular dynamics (AIMD) with van der Waals corrections to identify atomistic pathways and associated electronic mechanisms driving precursor/surface reactions during metal organic vapor phase epitaxy at elevated temperatures of aluminum nitride on graphene, considered here as model case study. The results presented provide plausible interpretations of atomistic and electronic processes responsible for delivery of Al, C adatoms, and C-Al, CHx, AlNH2 admolecules on pristine graphene via precursor/surface reactions. In addition, the simulations reveal C adatom permeation across defect-free graphene, as well as exchange of C monomers with graphene carbon atoms, for which we obtain rates of approximate to 0.3 THz at typical experimental temperatures (1500 K), and extract activation energies Eexca = 0.28 +/- 0.13 eV and attempt frequencies A(exc) = 2.1 (x1.7(+/- 1)) THz via Arrhenius linear regression. The results demonstrate that AIMD simulations enable understanding complex precursor/surface reaction mechanisms, and thus propose AIMD to become an indispensable routine prediction-tool toward more effective exploitation of chemical precursors and better control of MOCVD processes during synthesis of functional materials., Funding Agencies|Swedish Research Council (VR) through FLAG-ERA JTC project GRIFONE [VR 2015-06816, VR 2017-04071]; Olle Engkvist Foundation

Funding agencies: Swedish Research Council (VR); Linkoping Linnaeus Initiative for Novel Functional Materials (LiLi-NFM, VR); Swedish Governmental Agency for Innovation Systems (VINNOVA)Vid tiden för disputation förelåg publikationen som manuskript

We have studied the silicon donor behavior in intentionally silicon doped AlxGa1-xN (0.63≤x≤1) grown by hot-wall metal-organic chemical vapor deposition. Efficient silicon doping was obtained for lower Al contents whereas the conductivity drastically reduces for AlGaN layers with Al content in the range x~0.84-1. Degradation of the structural quality and compensation by residual O and C impurities were ruled out as possible explanations for the reduced conductivity. By combining frequency dependent capacitance-voltage and electron paramagnetic resonance measurements we show that the Si donors are electrically active and that the reduced conductivity can be explained by the increased activation energy caused by the sharp deepening of the Si DX– state.., Swedish Research Council (VR); VR Linkoping Linnaeus Initiative for Novel Functional Materials (LiLi-NFM); Swedish Energy Agency; Knut and Alice Wallenberg Foundation (KAW); Swedish Governmental Agency for Innovation Systems (VINNOVA)

The band structure and stability of XBi and XBi3 (X = B, Al, Ga, and In) single sheets are predicted using first-principles calculations. It is demonstrated that the band gap values of these new classes of two-dimensional (2D) materials depend on both the spin-orbit coupling (SOC) and type of group-III elements in these hetero-sheets. Thus, topological properties can be achieved, allowing for viable applications based on coherent spin transport at room temperature. The spin-orbit effects are proved to be essential to explain the tunability by group-III atoms. A clear effect of including SOC in the calculations is lifting the spin degeneracy of the bands at the Gamma point of the Brillouin zone. The nature of the band gaps, direct or indirect, is also tuned by SOC, and by the appropriate X element involved. It is observed that, in the case of XBi single sheets, band inversions naturally occur for GaBi and InBi, which exhibit band gap values around 172 meV. This indicates that these 2D materials are potential candidates for topological insulators. On the contrary, a similar type of band inversion, as obtained for the XBi, was not observed in the XBi3 band structure. In general, the calculations, taking into account SOC, reveal that some of these buckled sheets exhibit sizable gaps, making them suitable for applications in room-temperature spintronic devices., Funding Agencies|Swedish Research Council (VR) [348-2014-4249]; Linkoping Linnaeus Initiative for Novel Functionalized Materials (LiLi-NFM, VR); Swedish Foundation for Strategic Research (SSF) Synergy on Functional Carbides and Advanced Surface Engineering (FUNCASE) [RMA11-0029]; ConselhoNacional de DesenvolvimentoCientifico e Tecnologico (CNPq); Fundacao de Amparo a Pesquisa do Estado da Bahia (FAPESB); Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES)

Electron paramagnetic resonance studies of Si-doped AlxGa1−xN (0.79 ≤ x ≤ 1.0) reveal two Si negative-U (or DX) centers, which can be separately observed for x ≥ 0.84. We found that for the stable DX center, the energy |EDX| of the negatively charged state DX−, which is also considered as the donor activation energy, abruptly increases with Al content for x ∼ 0.83–1.0 approaching ∼240 meV in AlN, whereas EDX remains to be close to the neutral charge state Ed for the metastable DX center (∼11 meV below Ed in AlN).

This study presents analysis of the residual strain and related surface morphology of high-Al-content Al0.82Ga0.18N layers doped by silicon up to the level of 3×1019 cm-3, and delineates an interplay between thermodynamic and kinetic processes underlying the epitaxial growth of the layers. It particularly points to the development of certain facet structure (nanopipes) within the doped layers, which is apparent at the high Si doping levels. The formation of nanopipes is considered as a matter of consequence for the performance of the transport properties of the layers. It is anticipated to give rise to facets with SiN-related coverage, outcompeting the incorporation of Si at substitutional donor sites in the lattice of the Al0.82Ga0.18N layers. We do not find evidence for kinetic stabilization of preferential crystallographic facets when a dopant flow of bis(cyclopentadienyl)magnesium (Cp2Mg), instead of silane (SiH4), is implemented in the doping process.

Establishing n- and p- type conductivity via intentional doping in epitaxial layers is fundamental to any semiconductor material system and its relevant device applications. Process parameters such as temperature, precursor gas-flow-rates and pressure may all control intentional doping in metal-organic chemical vapour deposition (MOCVD) of semiconductor materials. The incorporation of impurities such as carbon and oxygen may also be affected by the same process parameters, and the concentration of these impurities has a direct impact on the electrical, optical and thermal properties of epitaxial layers, as has been observed in the MOCVD of technologically-important III-V semiconductor materials such as AlGaAs and GaN.

Issues of major relevance to the n-type conductivity of Al0.77Ga0.23N associated with Si and O incorporation, their shallow donor or deep donor level behavior, and carrier compensation are elucidated by allying (i) study of Si and O incorporation kinetics at high process temperature and low growth rate, and (ii) electron paramagnetic resonance measurements. The Al0.77Ga0.23N composition correlates to that Al content for which a drastic reduction of the conductivity of AlxGa1−xN is commonly reported. We note the incorporation of carbon, the role of which for the transport properties of AlxGa1−xN has not been widely discussed.

First-principles calculations, which also implement the nudged elastic band (NEB) code, are performed to investigate (i) the stability of the (C2H5)(3)B:NH3 adduct formed by the initial precursor molecules triethylborane (C2H5)(3)B and ammonia NH3 in the metal-chemical-vapor-deposition (MOCVD) of hexagonal BN, and (ii) the energy barrier to the first ethane elimination through consistent unimolecular, ammonia-assisted, and adduct-assisted reaction pathways. Comparison is done with the reference case of the (CH3)(3)Al:NH3 adduct, notoriously known for its high degree of stability and reactivity, which determines an overall severe parasitic gas-phase chemical reaction mechanism in the deposition of AlN., Funding Agencies|Swedish Foundation for International Cooperation in Research and Higher Education (STINT)|YR2009-7017|Linkoping Linnaeus Initiative on Novel Functionalized Materials (VR)||Swedish Governmental Agency for Innovation Systems (VINNOVA)||Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq)||Fundacao CAPES

We report on the cathodoluminescence (CL) of nominally undoped semi-insulating GaN layers grown by hot-wall metal-organic chemical vapor deposition (MOCVD) at a threefold increase of the growth rate limited by the TMGa flow. The growth kinetics is such, that C is the only background impurity in the layers with controllably increasing concentration from 5 x 10(16) to 6 x 10(17) cm(-3), while other background impurities, H. O and Si, are essentially at the SIMS detection levels. The hot-wall MOCVD is not an ordinary approach to GaN growth process and this study corroborates a more perceptive outlook on the C incorporation in GaN and any potential C-incorporation-mediated luminescence, including the observed here blue luminescence (BL) at similar to 417 nm, and the yellow luminescence (YL) with shifting peak position towards shorter wavelengths, similar to 555-543-525 nm.

A time-resolved micro-Raman technique was developed to probe the transient voltage in the GaN buffer layer of AlGaN/GaN heterostructure devices. The transient potential distribution under Ohmic contacts of devices behaved like a capacitance-resistance coupled network, with a decrease in amplitude and phase shift of the potential as a function of operating voltage frequency. This phenomenon was used to extract a value of 0.6 M Omega/square for sheet resistance of the AIN nucleation layer at the GaN/SiC interface from the characteristic RC value of the network. This demonstrates the effectiveness of this voltage probe technique as a non-invasive method of characterizing nucleation layers.

Capacitance-voltage [C(V)] measurements of metal-insulator-semiconductor-heterostructure capacitors are used to investigate the interface between silicon nitride passivation and AlGaN/AlN/GaN heterostructure material. AlGaN/AlN/GaN samples having different silicon nitride passivating layers, deposited using three different deposition techniques, are evaluated. Different interface state distributions result in large differences in the C(V) characteristics. A method to extract fixed charge as well as traps from the C(V) characteristics is presented. Rough estimates of the emission time constants of the traps can be extracted by careful analysis of the C(V) characteristics. The fixed charge is positive for all samples, with a density varying between 1.3 x 10(12) and 7.1 x 10(12) cm(-2). For the traps, the peak density of interface states is varying between 16 x 10(12) and 31 x 10(12) cm(-2) eV(-1) for the three samples. It is concluded that, of the deposition methods investigated in this report, the low pressure chemical vapor deposited silicon nitride passivation shows the most promising results with regards to low densities of interface states., Original Publication:M. Fagerlind, F. Allerstam, E.O. Sveinbjornsson, N. Rorsman, Anelia Kakanakova-Gueorguie, Anders Lundskog, Urban Forsberg and Erik Janzén, Investigation of the interface between silicon nitride passivations and AlGaN/AlN/GaN heterostructures by C(V) characterization of metal-insulator-semiconductor-heterostructure capacitors, 2010, Journal of Applied Physics, (108), 1, 014508.http://dx.doi.org/10.1063/1.3428442Copyright: American Institute of Physicshttp://www.aip.org

We report on the hot-wall MOCVD growth of Mg-doped AlxGa1-xN layers with an Al content as high as x similar to 0.85. After subjecting the layers to post-growth in-situ annealing in nitrogen in the growth reactor, a room temperature resistivity of 7 k Omega cm was obtained indicating an enhanced p-type conductivity compared to published data for AlxGa1-xN layers with a lower Al content of x similar to 0.70 and a room temperature resistivity of about 10 k Omega cm. It is believed that the enhanced p-type conductivity is a result of reduced compensation by native defects through growth conditions enabled by the distinct hot-wall MOCVD system.

The inherent advantages of the hot-wall metal organic chemical vapor deposition (MOCVD) reactor (low temperature gradients, less bowing of the wafer during growth, efficient precursor cracking) compared to a cold-wall reactor make it easier to obtain uniform growth. However, arcing may occur in the growth chamber during growth, which deteriorates the properties of the grown material. By inserting insulating pyrolytic BN (PBN) stripes in the growth chamber we have completely eliminated this problem. Using this novel approach we have grown highly uniform, advanced high electron mobility transistor (HEMT) structures on 4 semi-insulating (SI) SiC substrates with gas-foil rotation of the substrate. The nonuniformities of sheet resistance and epilayer thickness are typically less than 3% over the wafer. The room temperature hall mobility of the 2DEG is well above 2000 cm(2)/V s and the sheet resistance about 270 Omega/sqr., Original Publication: Urban Forsberg, Anders Lundskog, A Kakanakova-Georgieva, Rafal Ciechonski and Erik Janzén, Improved hot-wall MOCVD growth of highly uniform AlGaN/GaN/HEMT structures, 2009, JOURNAL OF CRYSTAL GROWTH, (311), 10, 3007-3010. http://dx.doi.org/10.1016/j.jcrysgro.2009.01.045 Copyright: Elsevier Science B.V., Amsterdam. http://www.elsevier.com

We demonstrated successful growth of AIN at a temperature of 1200 degrees C in a set of hot-wall MOCVD systems with the possibility of straightforward scaling up the process on larger wafer areas to meet the demand of device technologies. We outlined several aspects of the carefully optimized design and process parameters with relevance to achievement of a high overall growth rate (1 and up to 2 mu m/h), efficiency, and uniformity, which to a great extent depends on how consumption of growth-limiting species by gas-phase adduct formation can actively be prevented. Mixing of the precursors upstream from the deposition area facilitates uniform epitaxial growth, while the greater uniformity of substrate temperature inherent to the hot-wall reactor and rotation of the wafer are of fundamental importance for layer-growth uniformity. The AIN layer thickness can be controlled with an accuracy of +/- 1.3% on 2 in. wafers. The low-temperature cathodoluminescence spectrum of the AIN epitaxial material is strongly dominated by the intense near band-gap deep UV emission at about 208 nm.

Currently, up to 50% of the channel temperature in AlGaN/GaN electronic devices is due to the thermal-boundary resistance (TBR) associated with the nucleation layer (NL) needed between GaN and SiC substrates for high-quality heteroepitaxy. Using 3-D time-resolved Raman thermography, it is shown that modifying the NL used for GaN on SiC epitaxy from the metal-organic chemical vapor deposition (MOCVD)-grown standard AIN-NL to a hot-wall MOCVD-grown AIN-NL reduces NL TBR by 25%, resulting in similar to 10% reduction of the operating temperature of AlGaN/GaN HEMTs. Considering the exponential relationship between device lifetime and temperature, lower TBR NLs open new opportunities for improving the reliability of AlGaN/GaN devices.

AlxGa1-xN multiple quantum wells (MQW) were grown on AlN epilayer grown on 4H-SiC substrate. The growth was performed without interruption in a horizontal hot-wall MOCVD reactor using a mixture of hydrogen and nitrogen as carrier gases. The precursors were ammonia, trimethylaluminum and trimethylgallium. Results obtained from X-ray diffraction and infra-red reflectance were used to obtain the composition of the films when growing simple AlxGa1 xN layer. Visible reflectance was used to evaluate the thickness of the films. Finally the MQW parameters as thicknesses and composition variation were obtained by scanning transmission electron microscopy and demonstrated an agreement with the growth parameters used

AlGaN/AlN/GaN high electron mobility transistor heterostructures grown by metal-organic chemical vapor deposition have been studied by temperature dependent time-resolved photoluminescence. The AlGaN-related emission is found to be sensitive to the excitation power and to the built-in internal electric field. In addition, this emission shows a shift to higher energy with the reduction in the excitation density, which is rather unusual. Using a self-consistent calculation of the band potential profile, we suggest a recombination mechanism for the AlGaN-related emission involving electrons confined in the triangular AlGaN quantum well and holes weakly localized due to potential fluctuations., Original Publication:Galia Pozina, Carl Hemmingsson, Urban Forsberg, Anders Lundskog, Anelia Kakanakova-Gueorguie, Bo Monemar, Lars Hultman and Erik Janzén , Time-resolved photoluminescence properties of AlGaN/AlN/GaN high electron mobility transistor structures grown on 4H-SiC substrate, 2008, JOURNAL OF APPLIED PHYSICS, (104), 11, 113513.http://dx.doi.org/10.1063/1.3028687Copyright: American Institute of Physicshttp://www.aip.org

The metrological capability of the picosecond four-wave mixing (FWM) technique for evaluation of the photoelectrical properties of GaN heterostructures grown on sapphire, silicon carbide, and silicon substrates as well as of free-standing GaN films is demonstrated. Carrier recombination and transport features have been studied in a wide excitation, temperature, and dislocation density (from ∼1010 to 106 cm-2) range, exploring non-resonant refractive index modulation by a free carrier plasma. The studies allowed to establish the correlations between the dislocation density and the carrier lifetime, diffusion length, and stimulated emission threshold, to reveal a competition between the bimolecular and nonradiative recombination, and to verify the temperature dependence of bimolecular recombination coefficient in the 10-300 K temperature range. It was shown that the FWM technique is more advantageous than the time-resolved photoluminescence technique for determination of carrier lifetimes in high quality thick III-nitride layers. © 2006 Elsevier B.V. All rights reserved.

Direct impact of H2 and N2 diluents on the metal-organic-chemical-vapor-deposition gas-phase chemistry in M(CH3)3/NH3 (M = Al, Ga, In) systems is identified in the framework of Density Functional Theory in terms of cohesive energy differences. While both diluents destabilize model reaction species, i.e. adducts, transition states and chain complexes, the effect is particularly strong with respect to N2 in the Al(CH3)3/NH3 system, and can be a factor to restrain the expansion of chain complexes that deplete the gas-phase from precursors. Theoretical results are supported by experimental evidences of higher growth rate and superior optical properties of AlN grown in N2 vs. H2 diluent. © 2006 Elsevier B.V. All rights reserved.

The crystal structure and optical properties of thick (>100 nm) AlN layers grown by hot-wall metalorganic chemical vapor deposition are characterized by infrared spectroscopic ellipsometry, cathodoluminescence, and transmission electron microscopy. The choice of substrates among the available SiC wafer polytype modifications (4H/6H) and misorientations (on-/off-axis cut) is found to determine the AlN defect interaction, stress homogeneity, and luminescence. The growth of thick AlN layers benefits by performing the epitaxy on off-axis substrates because, due to stacking faults, the propagation of threading defects in AlN layers is stopped in a narrow interface region. © 2006 American Institute of Physics.