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1. Al Composition Dependence of Band Offsets for SiO 2 on α-(Al x Ga 1−x ) 2 O 3

   https://doi.org/10.1149/2162-8777/ac39a8  

   Xia, Xinyi ; Fares, Chaker ; Ren, Fan ; Hassa, Anna ; von Wenckstern, Holger ; Grundmann, Marius ; Pearton, S. J. ( November 2021 , ECS Journal of Solid State Science and Technology)

   Valence band offsets for SiO 2 deposited by Atomic Layer Deposition on α -(Al x Ga 1-x ) 2 O 3 alloys with x = 0.26–0.74 were measured by X-ray Photoelectron Spectroscopy. The samples were grown with a continuous composition spread to enable investigations of the band alignment as a function of the alloy composition. From measurement of the core levels in the alloys, the bandgaps were determined to range from 5.8 eV (x = 0.26) to 7 eV (x = 0.74). These are consistent with previous measurements by transmission spectroscopy. The valence band offsets of SiO 2 with these alloys of different composition were, respectively, were −1.2 eV for x = 0.26, −0.2 eV for x = 0.42, 0.2 eV for x = 0.58 and 0.4 eV for x = 0.74. All of these band offsets are too low for most device applications. Given the bandgap of the SiO 2 was 8.7 eV, this led to conduction band offsets of 4.1 eV (x = 0.26) to 1.3 eV (x = 0.74). The band alignments were of the desired nested configuration for x > 0.5, but at lower Al contents the conduction band offsets were negative, with a staggered band alignment. This shows the challenge of finding appropriate dielectrics for this ultra-wide bandgap semiconductor system. 

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2. Annealing Effects on the Band Alignment of ALD SiO 2 on (In x Ga 1−x ) 2 O 3 for x = 0.25–0.74

   https://doi.org/10.1149/2162-8777/ab8364  

   Fares, Chaker ; Xian, Minghan ; Smith, David J. ; McCartney, M. R. ; Kneiß, Max ; von Wenckstern, Holger ; Grundmann, Marius ; Tadjer, Marko ; Ren, Fan ; Pearton, S. J. ( April 2020 , ECS Journal of Solid State Science and Technology)

   The band alignment of Atomic Layer Deposited SiO₂on (In_xGa_1−x)₂O₃at varying indium concentrations is reported before and after annealing at 450 °C and 600 °C to simulate potential processing steps during device fabrication and to determine the thermal stability of MOS structures in high-temperature applications. At all indium concentrations studied, the valence band offsets (VBO) showed a nearly constant decrease as a result of 450 °C annealing. The decrease in VBO was −0.35 eV for (In_0.25Ga_0.75)₂O₃, −0.45 eV for (In_0.42Ga_0.58)₂O₃, −0.40 eV for (In_0.60Ga_0.40)₂O₃, and −0.35 eV (In_0.74Ga_0.26)₂O₃for 450 °C annealing. After annealing at 600 °C, the band alignment remained stable, with <0.1 eV changes for all structures examined, compared to the offsets after the 450 °C anneal. The band offset shifts after annealing are likely due to changes in bonding at the heterointerface. Even after annealing up to 600 °C, the band alignment remains type I (nested gap) for all indium compositions of (In_xGa_1−x)₂O₃studied.

    

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3. In situ MOCVD growth and band offsets of Al 2 O 3 dielectric on β-Ga 2 O 3 and β-(Al x Ga 1−x ) 2 O 3 thin films

   https://doi.org/10.1063/5.0104433  

   Bhuiyan, A F ; Meng, Lingyu ; Huang, Hsien-Lien ; Hwang, Jinwoo ; Zhao, Hongping ( October 2022 , Journal of Applied Physics)

   The in situ metalorganic chemical vapor deposition (MOCVD) growth of Al 2 O 3 dielectrics on β-Ga 2 O 3 and β-(Al x Ga 1−x ) 2 O 3 films is investigated as a function of crystal orientations and Al compositions of β-(Al x Ga 1−x ) 2 O 3 films. The interface and film qualities of Al 2 O 3 dielectrics are evaluated by high-resolution x-ray diffraction and scanning transmission electron microscopy imaging, which indicate the growth of high-quality amorphous Al 2 O 3 dielectrics with abrupt interfaces on (010), (100), and [Formula: see text] oriented β-(Al x Ga 1−x ) 2 O 3 films. The surface stoichiometries of Al 2 O 3 deposited on all orientations of β-(Al x Ga 1−x ) 2 O 3 are found to be well maintained with a bandgap energy of 6.91 eV as evaluated by high-resolution x-ray photoelectron spectroscopy, which is consistent with the atomic layer deposited (ALD) Al 2 O 3 dielectrics. The evolution of band offsets at both in situ MOCVD and ex situ ALD deposited Al 2 O 3 /β-(Al x Ga 1−x ) 2 O 3 is determined as a function of Al composition, indicating the influence of the deposition method, orientation, and Al composition of β-(Al x Ga 1−x ) 2 O 3 films on resulting band alignments. Type II band alignments are determined at the MOCVD grown Al 2 O 3 /β-(Al x Ga 1−x ) 2 O 3 interfaces for the (010) and (100) orientations, whereas type I band alignments with relatively low conduction band offsets are observed along the [Formula: see text] orientation. The results from this study on MOCVD growth and band offsets of amorphous Al 2 O 3 deposited on differently oriented β-Ga 2 O 3 and β-(Al x Ga 1−x ) 2 O 3 films will potentially contribute to the design and fabrication of future high-performance β-Ga 2 O 3 and β-(Al x Ga 1−x ) 2 O 3 based transistors using MOCVD in situ deposited Al 2 O 3 as a gate dielectric. 

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4. Metalorganic chemical vapor deposition of β-(Al x Ga 1−x ) 2 O 3 thin films on (001) β-Ga 2 O 3 substrates

   https://doi.org/10.1063/5.0142746  

   Uddin Bhuiyan, A F ; Meng, Lingyu ; Huang, Hsien-Lien ; Sarker, Jith ; Chae, Chris ; Mazumder, Baishakhi ; Hwang, Jinwoo ; Zhao, Hongping ( April 2023 , APL Materials)

   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. 

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5. Anisotropic dielectric function, direction dependent bandgap energy, band order, and indirect to direct gap crossover in α -(Al x Ga 1−x ) 2 O 3 (0≤x≤1)

   https://doi.org/10.1063/5.0087602  

   Hilfiker, Matthew ; Kilic, Ufuk ; Stokey, Megan ; Jinno, Riena ; Cho, Yongjin ; Xing, Huili Grace ; Jena, Debdeep ; Korlacki, Rafał ; Schubert, Mathias ( August 2022 , Applied Physics Letters)

   Mueller matrix spectroscopic ellipsometry is applied to determine anisotropic optical properties for a set of single-crystal rhombohedral structure α-(Al x Ga 1− x ) 2 O 3 thin films (0 [Formula: see text] x [Formula: see text] 1). Samples are grown by plasma-assisted molecular beam epitaxy on m-plane sapphire. A critical-point model is used to render a spectroscopic model dielectric function tensor and to determine direct electronic band-to-band transition parameters, including the direction dependent two lowest-photon energy band-to-band transitions associated with the anisotropic bandgap. We obtain the composition dependence of the direction dependent two lowest band-to-band transitions with separate bandgap bowing parameters associated with the perpendicular ([Formula: see text] = 1.31 eV) and parallel ([Formula: see text] = 1.61 eV) electric field polarization to the lattice c direction. Our density functional theory calculations indicate a transition from indirect to direct characteristics between α-Ga 2 O 3 and α-Al 2 O 3 , respectively, and we identify a switch in band order where the lowest band-to-band transition occurs with polarization perpendicular to c in α-Ga 2 O 3 whereas for α-Al 2 O 3 the lowest transition occurs with polarization parallel to c. We estimate that the change in band order occurs at approximately 40% Al content. Additionally, the characteristic of the lowest energy critical point transition for polarization parallel to c changes from M 1 type in α-Ga 2 O 3 to M 0 type van Hove singularity in α-Al 2 O 3 . 

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