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The anomalous behavior of impact ionization in dilute-nitride GaInNAs photodiodes with a range of nitrogen content below 4% is investigated. The ratio of hole- and electron-initiated ionization coefficients, k = β/α, is enhanced by a factor up to ∼4 with increasing nitrogen content. The absolute ionization coefficients are suppressed by up to two orders of magnitude at low electric fields in samples with 3% N. The narrow band gap, suppressed impact ionization, and increased breakdown voltage characteristics of GaInNAs make it a suitable material for use as part of a composite collector in GaAs-based heterojunction bipolar transistors.