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Abstract (Al_xGa_1–x)₂O₃ is an ultrawide‐bandgap semiconductor with a high critical electric field for next‐generation high‐power transistors and deep‐ultraviolet photodetectors. While (010)‐(Al_xGa_1–x)₂O₃ films have been studied, the recent availability of (100), (01)‐Ga₂O₃ substrates have developed interest in (100), (01)‐(Al_xGa_1–x)₂O₃ films. In this work, an investigation of microscopic and spectroscopic characteristics of (100), (01), (010)–(Al_xGa_1–x)₂O₃ films is conducted. A combination of scanning transmission electron microscopy, atom probe tomography (APT), and first‐principle calculations (DFT) is performed. The findings reveal consistent in‐plane chemical homogeneity in lower aluminum content (x = 0.2) films. However, higher aluminum content (x = 0.5), showed inhomogeneity in (100), (010)–(Al_xGa_1–x)₂O₃ films attributed to their spectroscopic properties. The study expanded APT's capabilities to determine Ga─O and Al─O bond lengths by mapping their ion‐pair separations in detector space. The change in ion‐pair separations is consistent with varying orientations, irrespective of aluminum content. DFT also demonstrated a similar trend, concluding that Ga─O and Al─O bonding energy has an inverse relationship with their bond length as crystallographic orientations vary. This systematic study of growth orientation dependence of (Al_xGa_1–x)₂O₃ films’ microscopic and spectroscopic properties will guide the development of new (100) and (01)‐(Al_xGa_1–x)₂O₃ along with existing (010)–(Al_xGa_1–x)₂O₃ films. 

Abstract The anisotropic dielectric functions (DF) of corundum structuredm-planeα-(Al_xGa_1−x)₂O₃thin films (up tox= 0.76) grown onm-plane sapphire substrate by metalorganic CVD have been investigated. IR and visible–UV spectroscopic ellipsometry yields the DFs, while X-ray diffraction revealed the lattice parameters (a,m,c), showing the samples are almost fully relaxed. Analysis of the IR DFs from 250 to 6000 cm⁻¹by a complex Lorentz oscillator model yields the anisotropic IR active phononsE_uandA_2uand the shift towards higher wavenumbers with increasing Al content. Analyzing the UV DFs from 0.5 to 6.6 eV we find the change in the dielectric limitsε_∞and the shift of the Γ-point transition energies with increasing Al content. This results in anisotropic bowing parameters forα-(Al_xGa_1−x)₂O₃ofb_⊥= 2.1 eV andb_∣∣= 1.7 eV. 

Growths of monoclinic (Al_xGa_1−x)₂O₃thin films up to 99% Al contents are demonstrated via metalorganic chemical vapor deposition (MOCVD) using trimethylgallium (TMGa) as the Ga precursor. The utilization of TMGa, rather than triethylgallium, enables a significant improvement of the growth rates (>2.5 μm h⁻¹) of β‐(Al_xGa_1−x)₂O₃thin films on (010), (100), and (01) β‐Ga₂O₃substrates. By systematically tuning the precursor molar flow rates, growth of coherently strained phase pure β‐(Al_xGa_1−x)₂O₃films is demonstrated by comprehensive material characterizations via high‐resolution X‐ray diffraction (XRD) and atomic‐resolution scanning transmission electron microscopy (STEM) imaging. Monoclinic (Al_xGa_1−x)₂O₃films with Al contents up to 99, 29, and 16% are achieved on (100), (010), and (01) β‐Ga₂O₃substrates, respectively. Beyond 29% of Al incorporation, the (010) (Al_xGa_1−x)₂O₃films exhibit β‐ to γ‐phase segregation. β‐(Al_xGa_1−x)₂O₃films grown on (01) β‐Ga₂O₃show local segregation of Al along (100) plane. Record‐high Al incorporations up to 99% in monoclinic (Al_xGa_1−x)₂O₃grown on (100) Ga₂O₃are confirmed from XRD, STEM, electron nanodiffraction, and X‐ray photoelectron spectroscopy measurements. These results indicate great promises of MOCVD development of β‐(Al_xGa_1−x)₂O₃films and heterostructures with high Al content and growth rates using TMGa for next‐generation high‐power and high‐frequency electronic devices. 

β-phase gallium oxide (Ga2O3) is an emerging ultrawide bandgap (UWBG) semiconductor with a bandgap energy of ∼ 4.8 eV and a predicted high critical electric field strength of ∼8 MV/cm, enabling promising applications in next generation high power electronics and deep ultraviolet optoelectronics. The advantages of Ga2O3 also stem from its availability of single crystal bulk native substrates synthesized from melt, and its well-controllable n-type doping from both bulk growth and thin film epitaxy. Among several thin film growth methods, metalorganic chemical vapor deposition (MOCVD) has been demonstrated as an enabling technology for developing high-quality epitaxy of Ga2O3 thin films, (AlxGa1−x)2O3 alloys, and heterostructures along various crystal orientations and with different phases. This tutorial summarizes the recent progresses in the epitaxial growth of β-Ga2O3 thin films via different growth methods, with a focus on the growth of Ga2O3 and its compositional alloys by MOCVD. The challenges for the epitaxial development of β-Ga2O3 are discussed, along with the opportunities of future works to enhance the state-of-the-art device performance based on this emerging UWBG semiconductor material system. 

In this Letter, the role of background carbon in metalorganic chemical vapor deposition (MOCVD) β-Ga2O3 growth using trimethylgallium (TMGa) as the Ga precursor was investigated. The quantitative C and H incorporations in MOCVD β-Ga2O3 thin films grown at different growth rates and temperatures were measured via quantitative secondary ion mass spectroscopy (SIMS). The SIMS results revealed both [C] and [H] increase as the TMGa molar flow rate/growth rate increases or growth temperature decreases. The intentional Si incorporation in MOCVD β-Ga2O3 thin films decreases as the growth rate increases or the growth temperature decreases. For films grown at relatively fast growth rates (GRs) (TMGa > 58 μmol/min, GR > 2.8 μm/h) or relatively low temperature (<950 °C), the [C] increases faster than that of the [H]. The experimental results from this study demonstrate the previously predicted theory—H can effectively passivate the compensation effect of C in n-type β-Ga2O3. The extracted net doping concentration from quantitative SIMS {[Si]-([C]-[H])} agrees well with the free carrier concentration measured from Hall measurement. The revealing of the role of C compensation in MOCVD β-Ga2O3 and the effect of H incorporation will provide guidance on designing material synthesis for targeted device applications. 

Phase pure β-(Al x Ga 1−x ) 2 O 3 thin films are grown on (001) oriented β-Ga 2 O 3 substrates via metalorganic chemical vapor deposition. By systematically tuning the precursor molar flow rates, the epitaxial growth of coherently strained β-(Al x Ga 1−x ) 2 O 3 films is demonstrated with up to 25% Al compositions as evaluated by high resolution x-ray diffraction. The asymmetrical reciprocal space mapping confirms the growth of coherent β-(Al x Ga 1−x ) 2 O 3 films (x < 25%) on (001) β-Ga 2 O 3 substrates. However, the alloy inhomogeneity with local segregation of Al along the ([Formula: see text]) plane is observed from atomic resolution STEM imaging, resulting in wavy and inhomogeneous interfaces in the β-(Al x Ga 1−x ) 2 O 3 /β-Ga 2 O 3 superlattice structure. Room temperature Raman spectra of β-(Al x Ga 1−x ) 2 O 3 films show similar characteristics peaks as the (001) β-Ga 2 O 3 substrate without obvious Raman shifts for films with different Al compositions. Atom probe tomography was used to investigate the atomic level structural chemistry with increasing Al content in the β-(Al x Ga 1−x ) 2 O 3 films. A monotonous increase in chemical heterogeneity is observed from the in-plane Al/Ga distributions, which was further confirmed via statistical frequency distribution analysis. Although the films exhibit alloy fluctuations, n-type doping demonstrates good electrical properties for films with various Al compositions. The determined valence and conduction band offsets at β-(Al x Ga 1−x ) 2 O 3 /β-Ga 2 O 3 heterojunctions using x-ray photoelectron spectroscopy reveal the formation of type-II (staggered) band alignment. 

Epitaxial growth of κ-phase Ga 2 O 3 thin films is investigated on c-plane sapphire, GaN- and AlN-on-sapphire, and (100) oriented yttria stabilized zirconia (YSZ) substrates via metalorganic chemical vapor deposition. The structural and surface morphological properties are investigated by comprehensive material characterization. Phase pure κ-Ga 2 O 3 films are successfully grown on GaN-, AlN-on-sapphire, and YSZ substrates through a systematical tuning of growth parameters including the precursor molar flow rates, chamber pressure, and growth temperature, whereas the growth on c-sapphire substrates leads to a mixture of β- and κ-polymorphs of Ga 2 O 3 under the investigated growth conditions. The influence of the crystalline structure, surface morphology, and roughness of κ-Ga 2 O 3 films grown on different substrates are investigated as a function of precursor flow rate. High-resolution scanning transmission electron microscopy imaging of κ-Ga 2 O 3 films reveals abrupt interfaces between the epitaxial film and the sapphire, GaN, and YSZ substrates. The growth of single crystal orthorhombic κ-Ga 2 O 3 films is confirmed by analyzing the scanning transmission electron microscopy nanodiffraction pattern. The chemical composition, surface stoichiometry, and bandgap energies of κ-Ga 2 O 3 thin films grown on different substrates are studied by high-resolution x-ray photoelectron spectroscopy (XPS) measurements. The type-II (staggered) band alignments at three interfaces between κ-Ga 2 O 3 and c-sapphire, AlN, and YSZ substrates are determined by XPS, with an exception of κ-Ga 2 O 3 /GaN interface, which shows type-I (straddling) band alignment. 

Metalorganic chemical vapor deposition (MOCVD) growths of β-Ga 2 O 3 on on-axis (100) Ga 2 O 3 substrates are comprehensively investigated. Key MOCVD growth parameters including growth temperature, pressure, group VI/III molar flow rate ratio, and carrier gas flow rate are mapped. The dependence of the growth conditions is correlated with surface morphology, growth rate, and electron transport properties of the MOCVD grown (100) β-Ga 2 O 3 thin films. Lower shroud gas (argon) flow is found to enhance the surface smoothness with higher room temperature (RT) electron Hall mobility. The growth rate of the films decreases but with an increase of electron mobility as the VI/III molar flow rate ratio increases. Although no significant variation on the surface morphologies is observed at different growth temperatures, the general trend of electron Hall mobilities are found to increase with increasing growth temperature. The growth rates reduce significantly with uniform surface morphologies as the chamber pressure increases. By tuning the silane flow rate, the controllable carrier concentration of (100) β-Ga 2 O 3 thin films between low-10 17  cm −3 and low-10 18  cm −3 was achieved. Under optimized growth condition, an (100) β-Ga 2 O 3 thin film with RMS roughness value of 1.64 nm and a RT mobility of 24 cm 2 /Vs at a carrier concentration of 7.0 × 10 17  cm −3 are demonstrated. The mobilities are primarily limited by the twin lamellae and stacking faults defects generated from the growth interface. Atomic resolution scanning transmission electron microscopy reveals the formation of twin boundary defects in the films, resulting in the degradation of crystalline quality. Results from this work provide fundamental understanding of the MOCVD epitaxy of (100) β-Ga 2 O 3 on on-axis Ga 2 O 3 substrates and the dependence of the material properties on growth conditions. The limitation of electron transport properties of the (100) β-Ga 2 O 3 thin films below 25 cm 2 /Vs is attributed to the formation of incoherent boundaries (twin lamellae) and stacking faults grown along the on-axis (100) crystal orientation.