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In this paper, a Monte Carlo model is used to investigate the impact ionization properties of AlxGa1-xAs with a high composition of Al (x ≥ 0.6). Two Geiger-mode avalanche photodiode (APD) structures using AlxGa1-xAs as the multiplication region are studied. Simulations show a strong link between the APD properties and the electric field profile. It was also found that Al9.6Ga0.4As APD structure has higher excess noise and more abrupt breakdown probability compared to Al0.8Ga0.2As.