skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: γ -phase inclusions as common structural defects in alloyed β -(Al x Ga1− x )2O3 and doped β -Ga2O3 films
β-Ga2O3 is a promising ultra-wide bandgap semiconductor whose properties can be further enhanced by alloying with Al. Here, using atomic-resolution scanning transmission electron microscopy, we find the thermodynamically unstable γ-phase is a ubiquitous structural defect in both β-(AlxGa1−x)2O3 films and doped β-Ga2O3 films grown by molecular beam epitaxy. For undoped β-(AlxGa1−x)2O3 films, we observe γ-phase inclusions between nucleating islands of the β-phase at lower growth temperatures (∼500–600 °C). In doped β-Ga2O3, a thin layer of the γ-phase is observed on the surfaces of films grown with a wide range of n-type dopants and dopant concentrations. The thickness of the γ-phase layer was most strongly correlated with the growth temperature, peaking at about 600 °C. Ga interstitials are observed in the β-phase, especially near the interface with the γ-phase. By imaging the same region of the surface of a Sn-doped β-(AlxGa1−x)2O3 after ex situ heating up to 400 °C, a γ-phase region is observed to grow above the initial surface, accompanied by a decrease in Ga interstitials in the β-phase. This suggests that the diffusion of Ga interstitials toward the surface is likely the mechanism for growth of the surface γ-phase and more generally that the more-open γ-phase may offer diffusion pathways to be a kinetically favored and early forming phase in the growth of Ga2O3. However, more modeling and simulation of the γ-phase and the interstitials are needed to understand the energetics and kinetics, the impact on electronic properties, and how to control them.  more » « less
Award ID(s):
1719875
PAR ID:
10594712
Author(s) / Creator(s):
; ; ; ; ; ; ;
Publisher / Repository:
American Institute of Physics
Date Published:
Journal Name:
APL Materials
Volume:
9
Issue:
5
ISSN:
2166-532X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. This study investigates the electrical and structural properties of metal–oxide–semiconductor capacitors (MOSCAPs) with in situ metal-organic chemical vapor deposition-grown Al2O3 dielectrics deposited at varying temperatures on (010) β-Ga2O3 and β-(AlxGa1−x)2O3 films with different Al compositions. The Al2O3/β-Ga2O3 MOSCAPs exhibited a strong dependence of electrical properties on Al2O3 deposition temperature. At 900 °C, reduced voltage hysteresis (∼0.3 V) with improved reverse breakdown voltage (74.5 V) was observed, corresponding to breakdown fields of 5.01 MV/cm in Al2O3 and 4.11 MV/cm in β-Ga2O3 under reverse bias. In contrast, 650 °C deposition temperature resulted in higher voltage hysteresis (∼3.44 V) and lower reverse breakdown voltage (38.8 V) with breakdown fields of 3.69 and 2.87 MV/cm in Al2O3 and β-Ga2O3, respectively, but exhibited impressive forward breakdown field, increasing from 5.62 MV/cm at 900 °C to 7.25 MV/cm at 650 °C. High-resolution scanning transmission electron microscopy (STEM) revealed improved crystallinity and sharper interfaces at 900 °C, contributing to enhanced reverse breakdown performance. For Al2O3/β-(AlxGa1−x)2O3 MOSCAPs, increasing Al composition (x) from 5.5% to 9.2% reduced net carrier concentration and improved reverse breakdown field contributions from 2.55 to 2.90 MV/cm in β-(AlxGa1−x)2O3 and 2.41 to 3.13 MV/cm in Al2O3. The electric field in Al2O3 dielectric under forward bias breakdown also improved from 5.0 to 5.4 MV/cm as Al composition increased from 5.5% to 9.2%. The STEM imaging confirmed the compositional homogeneity and excellent stoichiometry of both Al2O3 and β-(AlxGa1−x)2O3 layers. These findings demonstrate the robust electrical performance, high breakdown fields, and excellent structural quality of Al2O3/β-Ga2O3 and Al2O3/β-(AlxGa1−x)2O3 MOSCAPs, highlighting their potential for high-power electronic applications. 
    more » « less
  2. We report the epitaxial growth of (010) β-(AlxGa1−x)2O3 using tritertiarybutylaluminum (TTBAl) as an aluminum gas precursor in a hybrid molecular beam epitaxy (h-MBE) system. In conventional MBE systems, a thermal effusion cell is typically used to supply Al. However, in an oxide MBE system, using a conventional Al effusion cell can cause difficulties due to the oxidation of the Al source during growth. This often requires breaking the vacuum frequently to reload Al. Our approach utilizes TTBAl, a gaseous Al source, via a h-MBE to circumvent the oxidation issues associated with traditional solid Al sources. We investigated the growth conditions of β-(AlxGa1−x)2O3, varying TTBAl supply and growth temperature. For this purpose, we utilized both elemental Ga and Ga-suboxide as Ga precursors. Controllable and repeatable growth of β-(AlxGa1−x)2O3 with Al compositions ranging from 1% to 25% was achieved. The impurity incorporation and crystal quality of the resulting β-(AlxGa1−x)2O3 films were also studied. Using TTBAl as a gaseous precursor in h-MBE has proven to maintain stable Al supply, enabling the controlled growth of high-quality β-(AlxGa1−x)2O3 films. 
    more » « less
  3. This study presents a comprehensive analysis of the etching effects on β-Ga2O3 using two methods: H2_N2 (a mixture of hydrogen and nitrogen) etching and triethylgallium (TEGa) in situ etching performed in a metal-organic chemical vapor deposition system. By employing a mix of H2 and N2 gases at varying chamber pressures and maintaining a constant etching temperature of 750 °C, we investigated the etching dynamics across three different β-Ga2O3 orientations: (010), (001), and (2¯01). Field emission scanning electron microscopy analysis showed that the etching behavior of β-Ga2O3 depends on the crystal orientation, with the (010) orientation showing notably uniform and smooth surfaces, indicating its suitability for vertical device applications. High-aspect-ratio β-Ga2O3 fin arrays were fabricated on (010) substrates using H2_N2 etching, yielding fin structures with widths of 2 μm and depths of 3.1 μm, along with smooth and well-defined sidewalls. The etching process achieved exceptionally high etch rates (>18 μm/h) with a strong dependence on pressure and sidewall orientation, revealing the trade-off between etch depth and surface smoothness. Separately, TEGa in situ etching was investigated as an alternative etching technique for both β-Ga2O3 and β-(AlxGa1−x)2O3 films. The results revealed that the (010) orientation exhibited relatively high etching rates while maintaining smoother sidewalls and top surfaces, making it favorable for device processing. In contrast, the (001) orientation showed strong resistance to TEGa etching. Furthermore, Al-incorporated β-(AlxGa1−x)2O3 films showed substantially lower etch rates compared to pure β-Ga2O3, suggesting their potential use as an effective etch-stop layer in advanced device fabrication. 
    more » « less
  4. Diffusion of native defects such as vacancies and their interactions with impurities are fundamental to semiconductor crystal growth, device processing, and design. However, the transient equilibration of native defects is difficult to directly measure. We used (AlxGa1−x)2O3/Ga2O3 superlattices (SLs) to detect and analyze transient diffusion of cation vacancies during annealing in O2 at 1000–1100 °C. Using a novel finite difference scheme for diffusion with time- and space-varying diffusion constants, we determined diffusion constants for Al, Fe, and cation vacancies, including the vacancy concentration dependence for Al. In the case of SLs grown on Sn-doped β-Ga2O3 (010) substrates, gradients observed in the extent of Al diffusion indicate a supersaturation of vacancies in the substrates that transiently diffuse through the SLs coupled strongly to Sn and thus slowed compared to undoped cases. In the case of SLs grown on (010) Fe-doped substrates, the Al diffusion is uniform through the SLs, indicating a depth-uniform concentration of vacancies. We find no evidence for the introduction of VGa from the free surface at rates sufficient to affect Al diffusion at at. % concentrations, establishing an upper bound on surface injection. In addition, we show that unintentional impurities in Sn-doped Ga2O3 such as Fe, Ni, Mn, Cu, and Li also diffuse toward the surface and accumulate. Many of these likely have fast interstitial diffusion modes capable of destabilizing devices, thus suggesting that impurities may require further reduction. This work provides a method to measure transients in diffusion-mediating native defects otherwise hidden in common processes such as ion implantation, etching, and film growth. 
    more » « less
  5. Crack formation limits the growth of (AlxGa1−x)2O3 epitaxial films on Ga2O3 substrates. We employ first-principles calculations to determine the brittle fracture toughness of such films for three growth orientations of the monoclinic structure: [100], [010], and [001]. Surface energies and elastic constants are computed for the end compounds—monoclinic Ga2O3 and Al2O3—and used to interpolate to (AlxGa1−x)2O3 alloys. The appropriate crack plane for each orientation is determined, and the corresponding critical thicknesses are calculated based on Griffith’s theory, which relies on the balance between elastic energy and surface energy. We obtain lower bounds for the critical thickness, which compare well with available experiments. We also perform an in-depth analysis of surface energies for both relaxed and unrelaxed surfaces, providing important insights into the factors that determine the relative stability of different surfaces. Our study provides physical insights into surface stability, crack planes, and the different degrees of crack formation in (AlxGa1−x)2O3 films for different growth orientations. 
    more » « less