Probing the photovoltaic external quantum efficiency (EQE) at photon energies well below the semiconductor bandgap is an important tool for achieving a better understanding of the contribution of trap and tail states involved in charge generation processes in photovoltaic devices, notably solar cells. In this work, we present an electrical and optical noise-reduced EQE apparatus achieving 100 dB dynamic range. We carefully identify and study several device- and EQE apparatus-related factors limiting the EQE measurement sensitivity. Minimizing these factors allows us to detect photocurrents smaller than a fA, corresponding to EQE signals as small as -100 dB. We use these ultra-sensitive EQE measurements to probe weak sub-bandgap absorption features in organic, inorganic and perovskite semiconductors. In this regard, we directly observe photocurrent-contributing sub-gab trap states in organic solar cells significantly lower in energy than the corresponding charge-transfer state.
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