Herein, a study of photoluminescence (PL) of bulk β‐Ga2O3 crystals measured at different crystallographic directions is presented. The bulk β‐Ga2O3 crystals are grown using the optical floating zone method and cut to prepare three basic planes for optical investigations. The Ga2O3 emits PL from red (1.7 eV) to near UV (3.5 eV). The maximum is at about 3 eV. It is shown that the excitation of Ga2O3 depends on polarization: the lowest excitation energy 4.7 eV is observed for polarization along the b axis. The PL emission is clearly polarized, which can be used to build diodes emitting polarized light: polarized light‐emitting diodes. For example, the main emission from the (100) plane is polarized along [001] direction. Analysis of polarization and dynamics of PL shows that the main emission band is composed of a few spectrally overlapping luminescence bands. The bands are resolved thanks to different polarization and significantly different dynamics. The violet PL at about 3.0 eV has a lifetime τ = 0.6 μs and the blue PL at about 2.8 eV has τ of about 600 μs. Such long lifetimes are characteristic of deep centers, for example, the oxygen vacancy VO or the VGa–Gai–VGa defect.
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