Among ultrawide bandgap semiconductors, beta-Ga2O3 is particularly promising for high power and frequency applications. For devices, n-type concentrations above 10^19 cm^-3 are required. Ge is a promising alternative n-type dopant with an ionic radius similar to Ga. Homoepitaxial 010 beta-Ga2O3 films were implanted with Ge to form 50 and 100 nm box concentration of 3*10^19 cm^-3 and 5*10^19 cm^-3, with damage ranging from 1.2 to 2.0 displacement per atom. For lower damage implants, optimized anneals in ultrahigh purity N2 at 950-1000 C for 5-10 minutes resulted in Rs of 600-700 omega/sqr, mobilities of 60-70 cm^2/Vs, and Ge activation of up to 40%. For higher damage implants, activation dropped to 23% with similar mobilities. Ge diffusion, measured by second ion mass spectrometry, showed formation of a Ge "clustering peak" with a concentration exceeding the initial implant following anneals in N2 or O2 at 950-1000 C. Beyond this peak, minimal Ge diffusion occurred for N2 anneals at 950 C, but at 1050 C non-Fickian diffusion extended to >200 nm. Electrical activation data suggests that clustered Ge is electrically inactive. To understand Ge clustering, several samples were characterized by synchrotron x-ray diffraction. Second-phase precipitates were observed in as-implanted samples which then fully dissoved after furnace annealing in N2 at 1050 C. Diffraction peaks suggest these implant-induced precipitates may be related to a high pressure Pa-3 phase of GeO2, and may evolve during anneals to explain the Ge clustering. Ultimately, we believe Ge clustering limits activation of implanted Ge at high concentrations.
We investigate the temperature dependence of the frequency and linewidth of the triply-degenerate T2g_{2g} zone-centered optical phonon in flux-grown ceria and hydrothermally-synthesized thoria single crystals from room temperature to 1273 K using Raman spectroscopy. Both crystals exhibit an expected increase in the phonon linewidth with temperature due to enhanced phonon-phonon scattering. However, ceria displays an anomalous linewidth reduction in the temperature range of 1023-1123 K. First-principles phonon linewidth calculations considering cubic and quartic phonon interactions within temperature-independent phonon dispersion fail to describe this anomaly. A parameterization of the temperature-dependent second order interatomic force constants based on previously reported phonon dispersion measured at room and high temperatures, predicts a deviation from the monotonic linewidth increase, albeit at temperatures lower than those observed experimentally for ceria. The qualitative agreement in the trend of temperature-dependent linewidth suggests that lattice anharmonicity-induced phonon renormalization plays a role in phonon lifetime. Specifically, a change in the overlap between softened acoustic and optical branches in the dispersion curve reduces the available phonon scattering phase space of the Raman active mode at the zone center, leading to an increased phonon lifetime within a narrow temperature interval. These findings provide new insights into higher-order anharmonic interactions in ceria and thoria, motivating further investigations into the role of anharmonicity-induced phonon renormalization on phonon lifetimes at high temperatures.
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