Wurtzite GaN Research Articles

Mechanistic study of β-Ga2O3 nitridation by RF nitrogen plasma for GaN heteroepitaxy

The transformation of 2¯01β-Ga2O3 to h-GaN under exposure to RF nitrogen plasma was monitored in situ by reflection high-energy electron diffraction. Analysis of the reaction kinetics reveals that the nitridation process is initiated by the formation of an oxynitride phase and proceeds via two-dimensional nucleation and growth of wurtzite GaN grains. X-ray photoelectron spectra suggest a Ga−(NxO1−x) type configuration dominates the surface early in the nitridation process. The surface restructuring is followed by a diffusion-fed phase transformation, which propagates the wurzite GaN structure into the substrate upon reaching 70% nitrogen anion site occupation, corresponding to the oxygen solubility in h-GaN. A direct correlation is observed between the nitridated film morphology and the epitaxial film crystallinity, demonstrating control of the residual strain, lateral coherence, and mosaicity in subsequent GaN epitaxy by the nitridation conditions. This study provides mechanistic details of the nitridation reaction of 2¯01β-Ga2O3 facilitating the optimization of the nitridation process toward improving GaN-2¯01β-Ga2O3 heterojunctions.

Transition-Metal-Related Quantum Emitters in Wurtzite AlN and GaN.

Transition-metal centers exhibit a paramagnetic ground state in wide-bandgap semiconductors and are promising for nanophotonics and quantum information processing. Specifically, there is a growing interest in discovering prominent paramagnetic spin defects that can be manipulated using optical methods. Here, we investigate the electronic structure and magneto-optical properties of Cr and Mn substitutional centers in wurtzite AlN and GaN. We use state-of-the-art hybrid density functional theory calculations to determine level structure, stability, optical signatures, and magnetic properties of these centers. The excitation energies are calculated using the constrained occupation approach and rigorously verified with the complete active space configuration interaction approach. Our simulations of the photoluminescence spectra indicate that in AlN and in GaN are responsible for the observed narrow quantum emission near 1.2 eV. We compute the zero-field splitting (ZFS) parameters and outline an optical spin polarization protocol for and . Our results demonstrate that these centers are promising candidates for spin qubits.

Control polarity of gallium nitride on Si (1 1 1) using atomic layer annealing and thermal atomic layer deposition

Ga-polar GaN thin films and N-polar GaN thin films were fabricated by using thermal ALD and plasma assisted ALA processes, respectively. The polarity of GaN wurtzite thin films was determined by cross-sectional STEM analysis of as-deposited films and top-view SEM images after KOH wet-etching. The crystallinity and grain size of thermal ALD GaN were drastically increased with the GaN ALA buffer layer. The ALA Ar plasma pulse in each ALD cycle decreased the oxygen and carbon impurity content and improved the crystallinity of GaN thin films by removing organic ligands. High purity GaN thin films were successfully deposited on oxide-free Si (111) substrate by using the ALA process with 100 ms of TDMAGa with push gas, 3 × 800 ms of N2H4, and 15 s of 25 W ALA plasma pulse with −25 V stage DC bias at 275 °C. The lowest FWHM value (0.59°), smooth surface morphology (RMS=1.0 nm), and 10–20 nm grain size of columnar GaN thin films were obtained by tuning process parameters.

Gallium Nitride Electrodeposition at Indium Tin Oxide and Fluorine Tin Oxide Electrodes in Ammonium Nitrate and Gallium Nitrate Aqueous Solution

The potential of gallium nitride thin films in semiconductor technology and devices has garnered interest. This study aims to develop an effective GaN electrodeposition technique that will function on both Earth and microgravity situations and may be applied to any kind of needed application, such as in photovoltaic devices. To determine the optimal electrodeposition conditions, e.g. applied potential, cyclic voltammetry (CV) was done on a boron-doped diamond electrode at 0.01 mV/s potential scan rate and at 0.8 V vs. Ag/AgCl (Saturated KCl) constant applied potential. In the CV study, a well-defined peak formed at -1.75 V vs. Ag/AgCl (Saturated KCl). To start examining all the features of the electrodeposition of a thin film on Indium Tin Oxide (ITO) and Fluorine Tin Oxide (FTO) Electrodes, chronoamperometry (CA) measurements were done at different time scales, ranging from 3600s to 14400s and at a constant applied potential of -1.7 V vs. Ag/AgCl (Saturated KCl). The characterization methods used to examine the materials' topography, elemental contrast, crystal structure, and electrodeposition weight percentages included scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive spectroscopy (EDS). Longer electrodeposition times produced the best grain formation, promoting dendritic structure at the electrode surface. Furthermore, the optimal weight electrodeposition percentage of Ga and N was 10% and 35 % at 3600s, respectively, although the electrodeposited electrode surface was heterogeneous. The surface topographies at 3600s showed less grains definition and dendritic structures. At higher electrodeposition times, e.g. 14400s, more grain definitions and dendritic structures were found. For the 3600s electrodeposition time, XRD peaks were found at 33o, 37o and 46o, which are characteristics of GaN wurtzite structure according to literature.

Influence of Xe+ and Ga+ milling species on the cathodoluminescence of wurtzite and zincblende GaN

III-nitride materials, such as GaN and its alloys, are essential for modern microelectronics and optoelectronics due to their unique properties. Focused ion beam (FIB) techniques play a crucial role in their prototyping and characterization at the micro- and nanoscale. However, conventional FIB milling with Ga ions presents challenges, including surface amorphization and point defect introduction, prompting the exploration of alternative ion sources. Xenon-based inductively coupled plasma or plasma FIB has emerged as a promising alternative, offering reduced damage and better sample property preservation. Despite extensive research on FIB-induced damage in GaN, systematic comparisons between Ga and Xe ion milling on the luminescence characteristics of GaN remain limited. This study aims to fill this gap by evaluating and comparing the extent of FIB-induced damage caused by Ga and Xe ions in wurtzite and zincblende GaN through cathodoluminescence measurements. Our findings indicate that Xe ion milling yields higher integrated intensities compared to Ga ion milling, attributed to shallower implantation depths and reduced lattice disorder. We also observe a decrease in integrated intensity with increasing ion beam acceleration voltage for both wurtzite and zincblende GaN layers. This study provides valuable insights into optimizing FIB-based sample preparation techniques for III-nitride materials, with implications for enhancing device performance and reliability.

Influence of excess silicon on polytype selection during metal-mediated epitaxy of GaN nanowires

We have examined the origins of polytype selection during metal-mediated molecular-beam epitaxy of GaN nanowires (NWs). High-angle annular dark-field scanning transmission electron microscopy reveals [111]-oriented zinc blende (ZB) NWs and [0001]-oriented wurtzite (WZ) NWs, with SixNy at the interface between individual NWs and the Si (001) substrate. Quantitative energy dispersive x-ray spectroscopy reveals a notably higher Si concentration of 7.0% ± 2.3% in zinc blende (ZB) NWs than 2.3% ± 1.2% in wurtzite (WZ) NWs. Meanwhile, density functional theory calculations show that incorporation of 8 at. % Si on the Ga sublattice inverts the difference in formation energies between WZ and ZB GaN, such that the ZB polytype of GaN is stabilized. This identification of Si and other ZB polytype stabilizers will enable the development of polytype heterostructures in a wide variety of WZ-preferring compounds.

Optical, Structural, and Synchrotron X-ray Absorption Studies for GaN Thin Films Grown on Si by Molecular Beam Epitaxy.

GaN on Si plays an important role in the integration and promotion of GaN-based wide-gap materials with Si-based integrated circuits (IC) technology. A series of GaN film materials were grown on Si (111) substrate using a unique plasma assistant molecular beam epitaxy (PA-MBE) technology and investigated using multiple characterization techniques of Nomarski microscopy (NM), high-resolution X-ray diffraction (HR-XRD), variable angular spectroscopic ellipsometry (VASE), Raman scattering, photoluminescence (PL), and synchrotron radiation (SR) near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. NM confirmed crack-free wurtzite (w-) GaN thin films in a large range of 180-1500 nm. XRD identified the w- single crystalline structure for these GaN films with the orientation along the c-axis in the normal growth direction. An optimized 700 °C growth temperature, plus other corresponding parameters, was obtained for the PA-MBE growth of GaN on Si, exhibiting strong PL emission, narrow/strong Raman phonon modes, XRD w-GaN peaks, and high crystalline perfection. VASE studies identified this set of MBE-grown GaN/Si as having very low Urbach energy of about 18 meV. UV (325 nm)-excited Raman spectra of GaN/Si samples exhibited the GaN E2(low) and E2(high) phonon modes clearly without Raman features from the Si substrate, overcoming the difficulties from visible (532 nm) Raman measurements with strong Si Raman features overwhelming the GaN signals. The combined UV excitation Raman-PL spectra revealed multiple LO phonons spread over the GaN fundamental band edge emission PL band due to the outgoing resonance effect. Calculation of the UV Raman spectra determined the carrier concentrations with excellent values. Angular-dependent NEXAFS on Ga K-edge revealed the significant anisotropy of the conduction band of w-GaN and identified the NEXAFS resonances corresponding to different final states in the hexagonal GaN films on Si. Comparative GaN material properties are investigated in depth.

Efficient Second‐Harmonic Generation with Weak Polarization Sensitivity in Gallium Nitride Metasurfaces via Bound States in the Continuum

AbstractBound states in the continuum (BICs) are widely exploited in all‐dielectric metasurfaces to significantly enhance the Q‐factor and second harmonic generation (SHG). However, a higher SHG conversion efficiency is overshadowed by the narrow transparency window of all‐dielectric materials and strict requirement of polarization‐matching. Herein, an augmented SHG assisted is demonstrated by symmetry‐protected quasi‐BICs from z‐cut wurtzite GaN metasurfaces, whose wide transparent range suppresses self‐absorption of second harmonic. Strong resonances emerge under both X‐ and Y‐polarized excitations, where the multipole characters of each eigenmode are quantitatively identified via decomposition simulations. The local field enhancement enabled by the extreme energy confinement of quasi‐BICs contributes to an efficient SHG, recording a conversion efficiency up to 2 × 10−7 at moderately low input peak intensity (≈1 GW cm−2), orders of magnitude larger than bulk GaN. With proper design, the overlapping X‐ and Y‐polarized resonances can support SHG from excitation with arbitrary polarizations. The alleviation of polarization‐matching remarkably enhances the SHG power by 66.2% under unpolarized illumination condition. The results of intense SHG reveal GaN as a promising candidate for high‐performance nanoscale nonlinear photonic devices. The weak polarization sensitivity of the designed structure will chart a novel course for the advancement of next‐generation efficient all‐dielectric metasurfaces.

ScN/GaN(11̅00): A New Platform for the Epitaxy of Twin-Free Metal-Semiconductor Heterostructures.

We study the molecular beam epitaxy of rock-salt ScN on the wurtzite GaN(11̅00) surface. To this end, ScN is grown on freestanding GaN(11̅00) substrates and self-assembled GaN nanowires exhibiting (11̅00) sidewalls. On both substrates, ScN crystallizes twin-free thanks to a specific epitaxial relationship, namely ScN(110)[001]∥GaN(11̅00)[0001], providing a congruent, low-symmetry interface. The 13.1% uniaxial lattice mismatch occurring in this orientation mostly relaxes within the first few monolayers of growth by forming a near-coincidence site lattice, where 7 GaN planes coincide with 8 ScN planes, leaving the ScN surface nearly free of extended defects. Overgrowth of the ScN with GaN leads to a kinetic stabilization of the zinc blende phase, that rapidly develops wurtzite inclusions nucleating on {111} nanofacets, commonly observed during zinc blende GaN growth. Our ScN/GaN(11̅00) platform opens a new route for the epitaxy of twin-free metal-semiconductor heterostructures including closely lattice-matched GaN, ScN, HfN, and ZrN compounds.

Weak effects of electron-phonon interactions on the lattice thermal conductivity of wurtzite GaN with high electron concentrations

Weak effects of electron-phonon interactions on the lattice thermal conductivity of wurtzite GaN with high electron concentrations

First-Principles Understanding on the Formation of Inversion Domain Boundaries of Wurtzite AlN, AlScN, and GaN

First-Principles Understanding on the Formation of Inversion Domain Boundaries of Wurtzite AlN, AlScN, and GaN

Enhancing sputtered GaN/Si film quality by adding AlGaN buffer layer in a continuous deposition process

In this work we demonstrate the achievement of significative improvements in the structural and morphological quality of wurtzite GaN films (approximately 250 nm thick) by introducing an initial growth step involving an AlGaN buffer layer on p-type Si (100) substrates through a continuous reactive sputtering process. We investigated the influence of using single and multiple AlxGa1-xN buffer layers with varying Al content (x ranging from 0.07 to 0.37) and different thicknesses (from 166 nm to 1 µm). The obtained samples underwent characterization through X-ray diffraction and scanning electron microscopy. The results reveal a slight increase in the c-axis preferred growth direction and grain sizes even with a single and thin (250 nm) Al0.07Ga0.93N buffer layer. Conversely, the use of a single Al0.37Ga0.63N buffer layer led to significant morphological changes and a remarkable improvement in the c-axis preferred orientation. The most favorable outcomes were observed with the implementation of a triple AlGaN buffer layer, featuring decreasing Al content from the substrate, indicating the attainment of a high-quality GaN top layer comparable to epitaxial GaN.

Molecular dynamics simulations and experimental studies on low-temperature growth of GaN

Growth mechanisms of (0001) wurtzite GaN films at low temperature are investigated by molecular dynamics simulations and experiments. The crystallization properties of GaN films deteriorate dramatically at low temperature due to the limited energy available for atomic surface migration and incorporation into the perfect lattice sites. In our simulation, growth interruption stage is periodically introduced and the as-deposited GaN films are treated with energy-carrying argon ions at this stage. The surface atoms located at the weak binding sites can acquire energy from the argon ions for secondary migration and incorporation into the perfect lattice sites. As a result, the crystallization properties of GaN films are significantly improved. GaN films are experimentally grown on sputtered AlN/sapphire substrates at 600 °C via inductively coupled plasma metal organic chemical vapor deposition along with periodic argon plasma treatment. The as-deposited film acquires energy from the plasma, leading to significant improvement of the crystalline properties. The surface morphology of the GaN film demonstrates a noticeable smoothing effect, with an evident increase in grain size from submicron to micron level. Additionally, GaN film with the optimized surface morphology exhibits high c-axis and in-plane orientations, and the full width half maximums of (002) and (102) x-ray diffraction rocking curves are 0.25° and 0.32°, respectively. These results provide effective guidance for the growth of GaN films at low temperature.

Surface Oxidation of GaN(0001) Simulated by Charge‐Transfer‐Type Molecular Dynamics

In this study, the oxidation of Ga–polar GaN(0001) surface simulated by using originally developed charge‐transfer‐type interatomic potential is reported on. The adjusted potential parameters reproduce the cohesive energies in the range of 0.3 eV atom−1 and atomic forces with correlation coefficient as high as 0.9, compared to the results of first‐principles calculations for more than 9000 structures associated with oxidation of GaN. The oxidation simulations reveal the formation of a periodic gallium oxide (GaOx) layer grown on GaN(0001) with O atoms replacing N atoms. The atomic distance between Ga–Ga in the GaOx layer along GaN[0001] direction is 3.05 Å, which is longer than wurtzite GaN (2.63 Å) and is quantitatively in agreement with the recent photoelectron holography measurement. The distances of the Ga atoms projected onto the GaN(11–20) plane are determined to be 3.19 Å for the GaOx layer and 2.79 Å for the interfacial GaN. These distances also align quantitatively with the scanning transmission electron microscopy imaging of the native oxide on GaN(0001). Further oxidation simulation in a larger model of 2304 atoms suggests the formation of the layered structure even in the subsequent layers away from the interface of GaN and gallium oxide.

Doping effect on electronic and magnetic properties of Ag-doped single-walled (6,0) GaN nanotubes: First-principles study

The electronic and magnetic properties of GaN wurtzite, un-doped, and Ag-doped single-walled (6,0) chiral GaN nanotubes (SWGaNNT) were investigated using Density Functional Theory and Local Spin Density Approximation methods within Hubbard U semiempirical correction (DFT-LSDA + U). In a consecutive DFT-LSDA + U electronic structure simulation, the effects of defects on the nature and origin of ferromagnetism (FM) are studied for an Ag-doped SWGaNNT system. For the Ag-doped GaN nanotube configurations, the energy gap decreases with increasing concentration of impurity. The total energy calculations for doped systems show the stability of the ferromagnetic phase. In the case of the Ag-doping GaN NT system, the wide energy gap is decreasing and the total magnetic moment of this system is ∼2.0 μB. From first-principles calculations, an Ag-doped GaN nanosystem can be made into a magnetic ferromagnetic material, and it is an important candidate for spintronics device applications.

Investigation of edge effect on wurtzite gallium nitride in nanoindentation using molecular dynamics simulation

In practical applications, block materials frequently experience edge collapse, yet our grasp of this phenomenon at the nanoscale remains limited. Understanding this is crucial, as nanoscale material behaviors can trigger intricate microscale effects that elude easy observation or comprehension at the macroscopic level. This work researched the edge effect of the wurtzite GaN with {0001} surface crystal orientation at different nanoindentation distances by molecular dynamics simulation. The results show that the GaN indentation edge effect is anisotropic. The atomic displacement directions prolonged [2–1–10], [–12–10], and [–1–120], which is hexagonal distributing, similar to the crystal structure. The dislocations are around the indenter and close to the upper surface, similar to the negative von Mises stress distributions. The closer the indenter is to the edge of the sample, the more atoms are extruded from the specimen edge, and the more serious the damage is to the edge generally. However, analysis of the mechanical response and phase transition shows that the damage to the edge can be weakened while the crystal structure is destroyed more severely at some specific locations of the indenter. This work reveals the evolution of GaN crystal structure under different nanoindentation distances and the mechanism of squeeze-out atoms from the edge at the atomic scale.

Size and pressure dependence lattice thermal conductivity of Wurtzite GaN nanowires

The size and pressure effect on lattice thermal conductivity (LTC) of Wurtzite GaN NWs with diameters of 97, 100, 126, and 160 nm in the temperature range (2–350) K fitted to those reported experimental data. The investigations were based on the Debye-Callaway model along with the Clapeyron and Murnaghan equations, for both longitudinal and transverse modes of phonons. by considering in the calculations, the nanosized dependence of melting temperature, lattice volume, Debye temperature, and group velocity. Nanosized melting temperature is used to calculate its related parameters of melting enthalpy, melting entropy, and surface energy. In this work, the nanosized dependence relation for the Gruneisen parameter gives values of 0.14475 for 160 nm and increases to 0.14535 for 97 nm. While its modification due to the applied pressure reduces its value. The relations are obtained for the nanosized dependence of surface roughness, Casimir length, dislocation concentration and lattice scattering factor, enabling this model to obtain LTC free from fitting parameters. The model was then applied successfully on 50 and 30 nm NWs diameter for this binary semiconductor.

The trigonal structure as a reference to access the spontaneous polarization of wurtzite crystals

The Berry-phase treatment of the spontaneous polarization defines this quantity as the polarization difference between the investigated system and an appropriate reference state. In the case of wurtzite crystals, the spontaneous polarization is usually referenced to the zinc blende structure. Here, we demonstrate that the closely-related trigonal structure can also be used as a reference to determine the spontaneous polarization of wurtzite materials. We compare the trigonal-based values for wurtzite nitrides XN (X = Al, Ga, In) and oxides YO (YBe, Zn) with the widely-known zinc blende results reported in the literature and find an excellent agreement. It is shown that the electronic contribution of polarization is greater than the ionic one. Furthermore, we reproduce the experimental value of the spontaneous polarization of wurtzite GaN reported by Lähnemann et al. [Phys. Rev. B 86, 081302(R) (2012)]. In order to do so, we calculate the spontaneous polarization for each type of basal stacking faults using periodic hexagonal supercells. This theoretical analysis leads to a value nearly identical to the experimental measurement.

A first-principles study of electronic and magnetic properties of 4d transition metals doped in Wurtzite GaN for spintronics applications.

We studied the electronic and magnetic properties of wurtzite GaN (w-GaN) doped with different concentrations of the 4d transition metal ions Nb, Mo, and Ru. We incorporated spin-polarized plane-wave density functional theory within an ultrasoft pseudopotential formalism. The 4d transition metals were doped at different geometrical sites to determine the geometry with the lowest total energy and the one that induced the largest magnetization. A spin-spin interaction study was performed to determine whether the doped compound was ferromagnetic or antiferromagnetic. The origin of magnetization in the transition metal-doped w-GaN compounds is due to the p-d hybridization of the nitrogen and 4d transition metals. From the bulk modulus results, we inferred that the structural integrity is preserved under compressive loads after doping w-GaN with these 4d transition metal ions. Our results indicate that these compounds can be used in spintronic applications.

Introduction of localized spin-state transitions in the optical absorption spectrum of Cr-doped GaN

Using a hybrid density functional, we study the electronic, magnetic, and neutral excitations of the paradigmatic Cr-doped GaN solid. Our results indicate that the $\ensuremath{\approx}1$% doped wurtzite GaN crystal retains the semiconducting nature of the host, associated with a magnetic moment of 3 ${\ensuremath{\mu}}_{B}$. As a consequence of Cr doping, additional hybridized bands are formed within the intrinsic band gap of GaN, leading to a considerable band gap narrowing by 1.4 eV and low-energy optical transitions. Our results indicate dark Cr $d\text{\ensuremath{-}}d$ transitions at very low energy (0.5--0.7 eV), followed by bright transitions in the visible energy range (1.8--2.2 eV). Characterization of the electron-hole pairs suggests that the latter originates from the internal transitions among hybridized ${\mathrm{Cr}}_{d}\text{--}{\mathrm{N}}_{p}$ states. With the existence of these additional optical features within the visible energy window, one can expect an enhancement to the photoelectric conversion efficiency of GaN upon Cr doping, in addition to applications in spintronics.