GaN Films Research Articles

Construction of Ag/Au bimetallic alloying nanoparticles on GaN films for high-performance SERS substrate, and modification of defect states

Construction of Ag/Au bimetallic alloying nanoparticles on GaN films for high-performance SERS substrate, and modification of defect states

Van der Waals epitaxial AlGaN/GaN growth on hexagonal BN via two-dimensional N-induced dislocation slip

We demonstrate the epitaxial growth of nitride heterojunction structures on two-dimensional materials. The growth behavior of Al atoms on hexagonal boron nitride (h-BN) involves preferential adsorption and diffusion along the N-top position, considerably improving AlN formation in the early stage of nucleation. Preferential N adsorption enables h-BN to provide a natural N surface for the substrate. Moreover, the natural N surface provided by h-BN can induce three-dimensional island-like order merging of the upper AlN layer, promoting dislocation slip annihilation. The dislocations annihilation depth of GaN films was shortened to 870 nm, resulting in an order of magnitude decrease in the density of screw dislocations to 5.50 × 107 cm−2 and considerable improvement in the performance of HEMT devices on SiC. Therefore, h-BN films can be used as two-dimensional insertion layers to obtain high-quality van der Waals epitaxial nitride films in GaN-based HEMT devices.

Epitaxial Growth of GaN Films on Chemical-Vapor-Deposited 2D MoS2 Layers by Plasma-Assisted Molecular Beam Epitaxy.

The van der Waals epitaxy of wafer-scale GaN on 2D MoS2 and the integration of GaN/MoS2 heterostructures were investigated in this report. GaN films have been successfully grown on 2D MoS2 layers using three different Ga fluxes via a plasma-assisted molecular beam epitaxy (PA-MBE) system. The substrate for the growth was a few-layer 2D MoS2 deposited on sapphire using chemical vapor deposition (CVD). Three different Ga fluxes were provided by the gallium source of the K-cell at temperatures of 825, 875, and 925 °C, respectively. After the growth, RHEED, HR-XRD, and TEM were conducted to study the crystal structure of GaN films. The surface morphology was obtained using FE-SEM and AFM. Chemical composition was confirmed by XPS and EDS. Raman and PL spectra were carried out to investigate the optical properties of GaN films. According to the characterizations of GaN films, the van der Waals epitaxial growth mechanism of GaN films changed from 3D to 2D with the increase in Ga flux, provided by higher temperatures of the K-cell. GaN films grown at 750 °C for 3 h with a K-cell temperature of 925 °C demonstrated the greatest crystal quality, chemical composition, and optical properties. The heterostructure of 3D GaN on 2D MoS2 was integrated successfully using the low-temperature PA-MBE technique, which could be applied to novel electronics and optoelectronics.

Heavy Ge Doping in GaN via Pulsed Sputtering to Tailor the Optical Bandgap Energy

The epitaxial growth of heavily Ge‐doped GaN films using pulsed sputtering deposition (PSD) on AlN (0001)/sapphire substrates is presented and the correlations among their structural, electrical, and optical properties are investigated. High‐quality Ge‐doped PSD‐GaN films are grown with electron concentrations of 0.33–4.4 × 1020 cm−3. Notably, cathode luminescence spectra reveal the absence of defect‐induced emissions associated with Ga vacancies (2.3–2.4 eV), consistent with the high electron mobilities of the films. As the electron concentration increases, the optical bandgap also increases. This correlation can be explained by combining the theoretical formulas for the Burstein–Moss shift and the bandgap renormalization effects. Remarkably, the optical bandgap reaches 3.84 eV at 4.4 × 1020 cm−3 carrier concentration, marking the highest value reported for the optical bandgap of GaN. These results indicate the potential of heavy Ge doping in GaN via PSD for applications in highly transparent conductive layers and tunneling junctions within GaN‐based optoelectronic devices.

Gallium nitride deposition via magnetron sputtering: Linking plasma-surface interactions and thin film crystalline features

Ga-atoms dynamic in an Ar/N2 magnetron sputtering discharge for GaN deposition is explored employing plasma diagnostic techniques such as optical emission spectroscopy and microwave interferometry. Through the assessment of gas temperature, electron temperature and density measured from the abovementioned diagnostics, we estimated both the flux and average energy of Ga-atoms impinging on the substrate. Emphasizing the working pressure as a pivotal factor, this study uncovers a correlation between the Ga-atoms flux, their average energy, and the growth rate and crystallinity of the GaN films extracted from ex-situ characterizations. Notably, the pressure value (6.6 Pa) at which both the growth rate and crystalline fraction are the greatest is also the condition at which both the flux and energy of Ga-atoms impinging on the target are maximal. The findings pave the way for improving the understanding and control of the complex interplay between plasma conditions and resulting film properties in the sputtering process.

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.

Quasi van der Waals Epitaxy of Single Crystalline GaN on Amorphous SiO2/Si(100) for Monolithic Optoelectronic Integration.

The realization of high quality (0001) GaN on Si(100) is paramount importance for the monolithic integration of Si-based integrated circuits and GaN-enabled optoelectronic devices. Nevertheless, thorny issues including large thermal mismatch and distinct crystal symmetries typically bring about uncontrollable polycrystalline GaN formation with considerable surface roughness on standard Si(100). Here a breakthrough of high-quality single-crystalline GaN film on polycrystalline SiO2/Si(100) is presented by quasi van der Waals epitaxy and fabricate the monolithically integrated photonic chips. The in-plane orientation of epilayer is aligned throughout a slip and rotation of high density AlN nuclei due to weak interfacial forces, while the out-of-plane orientation of GaN can be guided by multi-step growth on transfer-free graphene. For the first time, the monolithic integration of light-emitting diode (LED) and photodetector (PD) devices are accomplished on CMOS-compatible SiO2/Si(100). Remarkably, the self-powered PD affords a rapid response below 250µs under adjacent LED radiation, demonstrating the responsivity and detectivity of 2.01×105 A/W and 4.64×1013Jones, respectively. This work breaks a bottleneck of synthesizing large area single-crystal GaN on Si(100), which is anticipated to motivate the disruptive developments in Si-integrated optoelectronic devices.

Utilizing Island Growth in Superlattice Buffers for the Realization of Thick GaN‐on‐Si(111) PIN‐Structures for Power Electronics

In this study, the effect of implementing island growth in an AlN/Al0.1Ga0.9N superlattice on the structural properties of vertical GaN‐on‐Si(111) PIN‐structures is investigated. It is demonstrated by scanning electron microscopy (SEM) and atomic force microscopy (AFM) that islands are formed on‐top of V‐pits present in the AlN nucleation layer and that the island coalescence height can be controlled by the growth temperature. Defect selective etching analyses confirm a noteworthy reduction in the threading dislocation density (TDD), which diminishes from 1.2 × 109 cm−2 ± 7.5 × 107 cm−2 to 8.5 × 108 cm−2 ± 7.3 ×107 cm−2 as the island coalescence height increases from ≈160 nm to ≈450 nm, achieved by increasing the growth temperature. Cross‐sectional transmission electron microscopy (TEM) shows that island growth is particularly favorable for the reduction of a‐type dislocations. As a consequence of the significant reduction of a‐type dislocations in the buffer, stress relaxation during the GaN film growth is reduced, which is supported by in situ wafer curvature measurements and high‐resolution X‐ray diffraction (XRD). Owing to the optimized island growth conditions, thick and crack‐free GaN layers on Si(111) substrates are obtained with an absolute wafer bow of <50 μm.

Mg incorporation induced microstructural evolution of reactively sputtered GaN epitaxial films to Mg-doped GaN nanorods

Mg-doped GaN films/nanorods were grown epitaxially on c-sapphire by reactive co-sputtering of GaAs and Mg at different N2 percentages in Ar–N2 sputtering atmosphere. Energy dispersive x-ray spectroscopy revealed that the Mg incorporation increases with increase of Mg area coverage of GaAs target, but does not depend on N2 percentage. In comparison to undoped GaN films, Mg-doped GaN displayed substantial decrease of lateral conductivity and electron concentration with the initial incorporation of Mg, indicating p-type doping, but revealed insulating behaviour at larger Mg content. Morphological investigations by scanning electron microscopy have shown that the films grown with 2%–4% Mg area coverages displayed substantially improved columnar structure, compared to undoped GaN films, along with rough and voided surface features at lower N2 percentages. With increase of Mg area coverage to 6%, the growth of vertically aligned and well-separated nanorods, terminating with smooth hexagonal faces was observed in the range of 50%–75% N2 in sputtering atmosphere. High-resolution x-ray diffraction studies confirmed the epitaxial character of Mg-doped GaN films and nanorods, which displayed complete c-axis orientation of crystallites and a mosaic structure, aligned laterally with the c-sapphire lattice. The catalyst-free growth of self-assembled Mg-doped GaN nanorods is attributed to increase of surface energy anisotropy due to the incorporation of Mg. However, with further increase of Mg area coverage to 8%, the nanorods revealed lateral merger, suggesting enhanced radial growth at larger Mg content.

Heterogeneous integration of thick GaN and polycrystalline diamond at room temperature through dynamic plasma polishing and surface-activated bonding

Direct heterogeneous integration of GaN on diamond enhances device performance and reliability for high-power applications, while the implementation on thick GaN films and polycrystalline diamond (p-diamond) substrates remains challenging. In this study, the direct bonding between thick GaN films (∼370 μm) and p-diamond substrates was achieved. A dynamic plasma polishing (DPP) technique was adopted on the diamond to flatten surficial spikes from maximum 15 nm to 1.2 nm, obtaining a smooth surface with 0.29 nm Ra, achieving a robust GaN/diamond bonding with high bonding rate of ∼92% at room temperature combining the surface-activated bonding (SAB) method. The chemical status, thermal stress, and interfacial microstructures of GaN/diamond heterostructures were analyzed, revealing a residual stress of ∼200 MPa at the GaN/diamond interface, and the asymmetric increase of interfacial stress at rising temperature demonstrates the effectiveness of amorphous interlayer to release the stress.

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.

Realization of low specific-contact-resistance on N-polar GaN surfaces using heavily-Ge-doped n-type GaN films deposited by low-temperature reactive sputtering technique

We developed a low-temperature ohmic contact formation process for N-polar GaN surfaces. Specific-contact-resistances of 9.4 × 10−5 and 2.0 × 10−5 Ω cm2 were obtained using Ti/Al metal stacks on heavily-germanium-doped GaN films, which were deposited at 500 °C and 600 °C using a radical-assisted reactive sputtering method, respectively. The electrode sintering temperature was as low as 475 °C. Carrier concentrations for the 500 °C and 600 °C samples were 2.6 × 1020 and 1.8 × 1020 cm−3, respectively. These results suggest that this method is highly effective in reducing the contact resistance of GaN devices with low thermal budgets.

Threading dislocations reduction of GaN-on-Si by introducing AlN/3D-GaN with SiN interlayer for photodetectors

Gallium nitride-on-Silicon epitaxy technology has enabled a high level of large-scale GaN integrated manufacturing. However, the poor crystalline quality of GaN on Si substrates dramatically deteriorates device performance. This work demonstrates the application of a buffer layer structure of AlN/3D-GaN with a SiN interlayer to obtain GaN films with high crystalline quality on Si substrates. Transmission electron microscopy and X-ray diffraction reveal reductions in GaN dislocation density. The full width at half maximum values of the X-ray rocking curve for the GaN(0002) and (10–12) planes have decreased from 499 to 710 arcsec to 339 and 350 arcsec, respectively. Ultraviolet photodetectors based on the optimized GaN-on-Si substrates exhibit low dark currents (34 pA@10 V) and high responsivity (6.8 A/W@10 V). Our reported novel buffer architecture provides an important reference for improving the performance of other GaN-based optoelectronics and power electronic devices on Si substrates.

Improving Optical and Electrical Characteristics of GaN Films via 3D Island to 2D Growth Mode Transition Using Molecular Beam Epitaxy

Molecular beam epitaxy (MBE) is demonstrated as an excellent growth technique for growing a low-defect GaN channel layer, which is crucial for controlling vertical leakage current and improving breakdown voltage (BV) in GaN-based high-electron mobility transistors (HEMTs). The 3D islands to 2D growth mode transition approach was induced by modulating substrate growth temperature (Tsub), displaying an overall improvement in film quality. A comprehensive investigation was conducted into the effects of Tsub on surface morphologies, crystal quality, and the optical and electrical properties of GaN films. Optimal results were achieved with a strain-relaxed GaN film grown at 690 °C, exhibiting significantly improved surface characteristics (root-mean-square roughness, Rq = 0.3 nm) and impressively reduced edge dislocations. However, the film with the smoothest surface roughness, attributed to the effect of the Ga-rich condition, possessed a high surface pit density, negatively affecting optical and electrical properties. A reduction in defect-related yellow emission further confirmed the enhanced crystalline quality of MBE GaN films. The optimized GaN film demonstrated outstanding electrical properties with a BV of ~1450 V, surpassing that of MOCVD GaN (~1180 V). This research significantly contributes to the advancement of MBE GaN-based high electron mobility transistor (HEMT) applications by ensuring outstanding reliability.

Effects of gamma irradiation on non-polar GaN films deposited on sapphire using pulsed laser deposition

The GaN films/layers exposed to γ-radiations is known to harvest defects and vacancies in the crystals producing donor, acceptor and recombination centers within the bandgap. Therefore it is important to investigate and study the γ- ray irradiation effects on various physical and chemical properties of a material before any optoelectronic and/or electronic devices are being fabricated. To avoid Stark effect which is observed in most of the optoelectronic devices fabricated using GaN films grew along polar face, use of non-polar GaN films is suggested by researchers. To address such issues the article reports the investigations of physical and chemical properties of non-polar GaN films grown on polar substrate using pulsed laser deposition, which were exposed to the 60Co gamma rays varying dose values. Resistive nature against the impairment of the films caused by γ-rays observed herewith is highly encouraging, suggesting the use of non-polar GaN films as radiations harden material suitable for fabricating new generation γ-ray detectors. To our knowledge very limited information is available that report such investigations.

Electrical transport in epitaxially grown undoped and Si-doped degenerate GaN films

This study investigates the electrical transport properties of undoped and Si-doped, degenerate GaN heteroepitaxial films grown on sapphire by reactive rf sputtering of GaAs (and Si) in Ar-N2 mixture. The room temperature electrical measurements showed that the resistivity of undoped GaN film grown at 100% N2 was ∼2 × 105 Ω cm, which reduced to ∼1 Ω cm in Si-doped film, revealing the effect of Si doping. With decrease of N2 from 100% to 75%, the carrier concentration of Si-doped films increased from ∼7 × 1018 cm−3 to ∼2 × 1019 cm−3, but remained practically unchanged as N2 was decreased to 20%, which is explained by effects due to saturation of Si doping and increase of Ga interstitials as well as compensation by N interstitials and Ga vacancies. Undoped and Si-doped films grown below 20% N2 displayed similar carrier concentrations (∼1020 cm−3), due to dominance of Ga interstitials. Both undoped and Si-doped films were degenerate and displayed increase of mobility with carrier concentration and temperature, which was analyzed by the combined effect of ionized impurity and dislocation scattering, using compensation ratio as fitting parameter. At carrier concentrations ≲1019 cm−3, the mobility was governed by both ionized impurity and dislocation scattering, while at higher carrier concentrations, ionized impurity scattering was found to dominate, limited by compensation due to acceptors. In spite of the degenerate character, the films displayed a small decrease of carrier concentration with temperature, along with a nearly linear decrease of mobility, which are explained by a marginal increase of compensation ratio with decrease of temperature, taking into account the band edge fluctuation effects. These features of electrical transport have not been much explored for heteroepitaxial, n-type degenerate GaN films, possessing high density of dislocations and point defects.

In situ luminescence measurements of GaN/Al2O3 film under different energy proton irradiations

Ion beam-induced luminescence (IBIL) experiments were performed to investigate the in situ luminescence of GaN/Al2O3 at varying ion energies, which allowed for the measurement of defects at different depths within the material. The energies of H+ were set to 500 keV, 640 keV and 2 MeV, the Bragg peaks of which correspond to the GaN film, GaN/Al2O3 heterojunction and Al2O3 substrate, respectively. A photoluminescence measurement at 250 K was also performed for comparison, during which only near band edge (NBE) and yellow band luminescence in the GaN film were observed. The evolution of the luminescence of the NBE and yellow band in the GaN film was discussed, and both exhibited a decrease with the fluence of H+. Additionally, the luminescence of F centers, induced by oxygen vacancies, and Cr3+, resulting from the 2E →4A2 radiative transition in Al2O3, were measured using 2 MeV H+. The luminescence intensity of F centers increases gradually with the fluence of H+. The luminescence evolution of Cr3+ is consistent with a yellow band center, attributed to its weak intensity, and it is situated within the emission band of the yellow band in the GaN film. Our results show that IBIL measurement can effectively detect the luminescence behavior of multilayer films by adjusting the ion energy. Luminescence measurement can be excited by various techniques, but IBIL can satisfy in situ luminescence measurement, and multilayer structural materials of tens of micrometers can be measured through IBIL by adjusting the energy of the inducing ions. The evolution of defects at different layers with ion fluence can be obtained.

Self-powered dual-mode UV detector based on GaN/(BA)<sub>2</sub>PbI<sub>4</sub> heterojunction

As an important part of an intelligent photoelectric system, ultraviolet detector has been widely used in many fields in recent years. The research on self-powered heterojunction photodiode is particularly important. In this work, a dual-mode self-powered GaN/(BA)<sub>2</sub>PbI<sub>4</sub> heterojunction ultraviolet photodiode is prepared and discussed. The GaN film is deposited on sapphire by metal-organic chemical vapor deposition, and then the (BA)<sub>2</sub>PbI<sub>4</sub> film is spin-coated onto the surface of the GaN film to construct a planar heterojunction detector. The X-ray diffraction, energy-dispersive X-ray spectroscopy mapping and scanning electron microscope measurements are used to determine the quality of GaN and (BA)<sub>2</sub>PbI<sub>4</sub> thin films. When the film is illuminated by 365 nm light with a power density of 421 μW/cm<sup>2</sup> at 5 V bias, the responsiveness (<i>R</i>) and external quantum efficiency (EQE) are 60 mA/W and 20%, respectively. In self-powered mode, the rise time (<i>τ</i><sub>r</sub>) and decay time (<i>τ</i><sub>d</sub>) are 0.12 s and 0.13 s, respectively, illustrating the fast photogeneration process and recombination process for photo-excited electron-hole pairs. And, the <i>R</i> is 1.96×10<sup>–4</sup> mA/W, owing to the development of space charge region across the interface of GaN thin film and (BA)<sub>2</sub>PbI<sub>4</sub> thin film. The outcomes of this study unequivocally demonstrate the extensive potential and wide-ranging applicability of self-powered UV photodiodes based on the GaN/(BA)<sub>2</sub>PbI<sub>4</sub> heterojunction configuration. Moreover, this research presents a new concept that provides a novel avenue to the ongoing development of intelligent optoelectronic systems.

Effect of grain coalescence on dislocation and stress in GaN films grown on nanoscale patterned sapphire substrates

The effect of grain coalescence on the dislocation and stress in GaN films grown on nanoscale patterned sapphire substrates with low-temperature grown GaN and physical vapour deposition AlN nucleation layers is comparably investigated.

(Invited) The Use of Plasmas for Isotropic Atomic Layer Etching

Atomic layer etching (ALE) is set to be a vital part of the advanced semiconductor manufacturing toolbox, known for its precise control of the film thickness and minimal damage. These benefits are possible due to the sequential self-limiting half-cycles that are employed within an ALE process. Initially, ALE was underestimated due to low etch rates, but it is now experiencing a renaissance due to the requirements imposed by further downscaling.1 The ALE community is mostly divided into two groups: plasma anisotropic and thermal isotropic etching. 2 In this work, the focus is on exploring isotropic plasma ALE, which is a relatively unexplored direction. This approach involves using plasma radicals to modify and/or etch material isotropically, while minimizing the directional ion component of the plasma. Isotropic plasma ALE can offer several benefits over strictly thermal ALE, such as higher etch rates, lower operating temperatures, and the ability to etch more resistant materials.In this talk we will first address some of the different techniques employed for plasma isotropic ALE in the literature. Subsequently, we will discuss our own work, which has focused on two isotropic plasma ALE chemistries. The first involves alternating between plasma fluorination and ligand-exchange half-cycles, this ALE chemistry has been found to be effective for etching Al2O3, HfO2, AlN, and GaN films.3,4 Surface contaminants and roughness were found to be reduced post ALE, an aspect that is particularly important for AlN and GaN films that are used in quantum, power semiconductor and LED applications. The second approach involves using diketone (e.g. acetylacetone, hexafluoroacetylacetone) doses followed by either H2 or O2 plasma exposures for ALE of Al2O3 and ZnO.5 The diketone in this process acts to etch the surface, however due to competitive adsorption of different diketone orientations an etch inhibition layer forms. The plasma step is then utilized to clean the surface, removing the self-limiting inhibitor layer, enabling etching to continue in the next cycle. This ALE chemistry diverges from the typical modification/removal ALE cycle, where a modified layer if often observed on the material post ALE. In comparison the diketone ALE chemistry does not rely on modification of the surface making it an ideal process for surface cleaning. This approach provides improved selectivity over the plasma fluorination process and also enables smoothing.Plasma isotropic ALE is a growing part of the ALE community that can help accelerate the adoption of ALE in academia and industry. The potential benefits of ALE are only just beginning to be explored, and more processes are needed to etch the ever-increasing range of materials utilized in IC manufacturing. Kanarik, K. J., Tan, S. & Gottscho, R. A. Atomic Layer Etching: Rethinking the Art of Etch. J Phys Chem Lett 9, 4814–4821 (2018).George, S. M. Mechanisms of Thermal Atomic Layer Etching. Acc Chem Res 53, 1151–1160 (2020).Chittock, N. J. et al. Isotropic plasma atomic layer etching of Al2O3 using a fluorine containing plasma and Al(CH3)3. Appl Phys Lett 117, 162107 (2020).Wang, H., Hossain, A., Catherall, D. & Minnich, A. J. Isotropic plasma-thermal atomic layer etching of aluminum nitride using SF6 plasma and Al(CH3)3. 1–14 (2022) doi:arXiv.2209.00150.Mameli, A., Verheijen, M. A., Mackus, A. J. M., Kessels, W. M. M. & Roozeboom, F. Isotropic Atomic Layer Etching of ZnO Using Acetylacetone and O2 Plasma. ACS Appl Mater Interfaces 10, 38588–38595 (2018).