Ge surfaces were etched by means of metal-assisted chemical etching (MaCE). The behavior of the MaCE reaction in diluted H2O2 was compared with that of a conventional etchant of HF/H2O2/H2O mixture (FPM). Herein we first report that a pyramidal structure on Ge (0 0 1) can be prepared by MaCE in dilute H2O2 solution, without the use of HF. Contrastingly, an octagonal trench structure was prepared by 4/5/1 FPM treatment of Ge (0 0 1) surface. This octagonal structure consisted of a square base, four large facets connected to the base, and other four small facets adjacent to the four large facets, which were considered to be (0 0 1), {1 10}, and {1 1 1}, respectively. The octagonal trench was formed as a result of the difference in etch rate of Ge depending on the orientation: {1 0 0} > {1 1 0} > {1 1 1}. Ge surfaces treated by MaCE exhibited improved solar cell efficiency due to their improved light absorption, which led to significant increases in the cells' short circuit current and fill factor. The results suggest that optimized MaCE procedures can be an effective method to improve the performance of Ge-based photovoltaic devices. (C) 2016 Elsevier B.V. All rights reserved.