AlxGa1−xN‐based quantum wells (QWs) are fabricated on AlN with macrosteps, which are formed by using vicinal sapphire and AlN (0001) substrates. The QWs on macrosteps (MS‐QWs) show photoluminescence lifetimes of nearly 2 ns at an emission wavelength of 242 nm at room temperature (RT). This is the longest lifetime so far reported for AlxGa1−xN‐based QWs emitting below 270 nm, indicating the suppression of nonradiative recombination, the dominant recombination process at RT. Compared with planar QWs without macrosteps, the emission internal quantum efficiency estimated by photoluminescence spectroscopy is improved approximately by two orders of magnitude under a weak excitation condition. Consequently, AlxGa1−xN‐based MS‐QWs are promising structures for highly efficient ultraviolet emitters.

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