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We experimentally investigate the nucleation behavior of metallic gallium droplets deposited on gallium arsenide substrates and calculate the critical cluster size for various growth conditions and substrate templating. We find that the critical cluster size for liquid Ga on GaAs is approximately six atoms. Deposition on substrates templated with arrays of holes does not result in significant ordering of the droplets at the array dimensions studied here, but does result in an apparent reduction of the critical cluster size due to heterogeneous nucleation.