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1. Initial nucleation of metastable γ-Ga ₂ O ₃ during sub-millisecond thermal anneals of amorphous Ga ₂ O ₃

   https://doi.org/10.1063/5.0087093  

   Gann, Katie R.; Chang, Celesta S.; Chang, Ming-Chiang; Sutherland, Duncan R.; Connolly, Aine B.; Muller, David A.; van Dover, Robert B.; Thompson, Michael O. (August 2022, Applied Physics Letters)

   Beta-phase gallium oxide ([Formula: see text]-Ga 2 O 3 ) is a promising semiconductor for high frequency, high temperature, and high voltage applications. In addition to the [Formula: see text]-phase, numerous other polymorphs exist and understanding the competition between phases is critical to control practical devices. The phase formation sequence of Ga 2 O 3 , starting from amorphous thin films, was determined using lateral-gradient laser spike annealing at peak temperatures of 500–1400 °C on 400 μs to 10 ms timescales, with transformations characterized by optical microscopy, x-ray diffraction, and transmission electron microscopy (TEM). The resulting phase processing map showed the [Formula: see text]-phase, a defect-spinel structure, first nucleating under all annealing times for temperatures from 650 to 800 °C. The cross-sectional TEM at the onset of the [Formula: see text]-phase formation showed nucleation near the film center with no evidence of heterogeneous nucleation at the interfaces. For temperatures above 850 °C, the thermodynamically stable [Formula: see text]-phase was observed. For anneals of 1–4 ms and temperatures below 1200 °C, small randomly oriented grains were observed. Large grains were observed for anneals below 1 ms and above 1200 °C, with anneals above 4 ms and 1200 °C resulting in textured films. The formation of the [Formula: see text]-phase prior to [Formula: see text]-phase, coupled with the observed grain structure, suggests that the [Formula: see text]-phase is kinetically preferred during thermal annealing of amorphous films, with [Formula: see text]-phase subsequently forming by nucleation at higher temperatures. The low surface energy of the [Formula: see text]-phase implied by these results suggests an explanation for the widely observed [Formula: see text]-phase inclusions in [Formula: see text]-phase Ga 2 O 3 films grown by a variety of synthesis methods. 

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2. 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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3. Finally: The X-ray crystal structure of the illusive unsubstituted iron(III) phthalocyanine μ-oxo(1) dimer. DFT-predicted Mössbauer quadrupole splitting and antiferromagnetic coupling constants for X-ray geometry

   https://doi.org/10.1142/s1088424624500263  

   Nemykin, Victor N; Gerasimchuk, Nikolay N; Muldowney, Breanna E (May 2024, Journal of Porphyrins and Phthalocyanines)

   The molecular structure of the unsubstituted iron(III) phthalocyanine [Formula: see text]-oxo(1) dimer ((PcFe)₂O) was determined by single crystal X-ray diffraction. In agreement with the earlier speculations, the dimer has a bent (Fe-O-Fe angle is 152.4[Formula: see text]) structure. The interplay between the [Formula: see text]-[Formula: see text] interactions and steric hindrances caused by the isoindole units led to the observed staggering angle of [Formula: see text]24[Formula: see text] between two phthalocyanine ligands. The high-spin iron(III) centers are located significantly above the phthalocyanine N4 planes (0.57–0.58 Å). Several DFT exchange-correlation functionals were used to calculate the absolute value and sign of the Mössbauer quadrupole splitting and antiferromagnetic coupling constant for X-ray determined geometry of (PcFe)₂O. It was demonstrated that the hybrid functionals provide the correct sign of the electric field gradient and the magnitude of the antiferromagnetic coupling constant compared to the pure functionals. 

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4. Peculiarities of crystal structures and photophysical properties of Ga ^III /Ln ^III metallacrowns with a non-planar [12-MC-4] core

   https://doi.org/10.1039/c9qi01647c  

   Nguyen, Tu N.; Eliseeva, Svetlana V.; Chow, Chun Y.; Kampf, Jeff W.; Petoud, Stéphane; Pecoraro, Vincent L. (March 2020, Inorganic Chemistry Frontiers)

   A new series of gallium( iii )/lanthanide( iii ) metallacrown (MC) complexes ( Ln-1 ) was synthesized by the direct reaction of salicylhydroxamic acid (H 3 shi) with Ga III and Ln III nitrates in a CH 3 OH/pyridine mixture. X-ray single crystal analysis revealed two types of structures depending on whether the nitrate counterion coordinate or not to the Ln III : [LnGa 4 (shi) 4 (H 2 shi) 2 (py) 4 (NO 3 )](py) 2 (Ln = Gd III , Tb III , Dy III , Ho III ) and [LnGa 4 (shi) 4 (H 2 shi) 2 (py) 5 ](NO 3 )(py) (Ln = Er III , Tm III , Yb III ). The representative Tb-1 and Yb-1 MCs consist of a Tb/YbGa 4 core with four [Ga III –N–O] repeating units forming a non-planar ring that coordinates the central Ln III through the oxygen atoms of the four shi 3− groups. Two H 2 shi − groups bridge the Ln III to the Ga III ring ions. The Yb III in Yb-1 is eight-coordinated while the ligation of the nine-coordinated Tb III in Tb-1 is completed by one chelating nitrate ion. Ln-1 complexes in the solid state showed characteristic sharp f–f transitions in the visible (Tb, Dy) and near-infrared (Dy, Ho, Er, Yb) spectral ranges upon excitation into the ligand-centered electronic levels at 350 nm. Observed luminescence lifetimes and absolute quantum yields were collected and discussed. For Yb-1 , luminescence data were also acquired in CH 3 OH and CD 3 OD solutions and a more extensive analysis of photophysical properties was performed. This work demonstrates that while obtaining highly luminescent lanthanide( iii ) MCs via a direct synthesis is feasible, many factors such as molar absorptivities, triplet state energies, non-radiative deactivations through vibronic coupling with overtones of O–H, N–H, and C–H oscillators and crystal packing will strongly contribute to the luminescent properties and should be carefully considered. 

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5. Effect of electron–electron interaction on magnitude of quantum oscillations of dissipative resistance in magnetic fields

   https://doi.org/10.1063/5.0127286  

   Abedi, Sara; Vitkalov, Sergey; Bykov, A. A.; Bakarov, A. K. (December 2022, Journal of Applied Physics)

   Magneto-intersubband resistance oscillations (MISOs) of highly mobile 2D electrons in symmetric GaAs quantum wells with two populated subbands are studied in magnetic fields [Formula: see text] tilted from the normal to the 2D electron layer at different temperatures [Formula: see text]. The in-plane component ([Formula: see text]) of the field [Formula: see text] induces magnetic entanglement between subbands, leading to beating in oscillating density of states (DOS) and to MISO suppression. Model of the MISO suppression is proposed. Within the model, a comparison of MISO amplitude in the entangled and disentangled ([Formula: see text]) 2D systems yields both difference frequency of DOS oscillations, [Formula: see text], and strength of the electron–electron interaction, described by parameter [Formula: see text], in the 2D system. These properties are analyzed using two methods, yielding consistent but not identical results for both [Formula: see text] and [Formula: see text]. The analysis reveals an additional angular dependent factor of MISO suppression. The factor is related to spin splitting of quantum levels in magnetic fields. 

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