Cs
2
AgBiBr
6
is a promising metal halide double
perovskite offering the possibility of efficient photovoltaic devices
based on lead-free materials. Here, we report on the evolution of
photoexcited charge carriers in Cs
2
AgBiBr
6
using
a combination of temperature-dependent photoluminescence, absorption
and optical pump–terahertz probe spectroscopy. We observe rapid
decays in terahertz photoconductivity transients that reveal an ultrafast,
barrier-free localization of free carriers on the time scale of 1.0
ps to an intrinsic small polaronic state. While the initially photogenerated
delocalized charge carriers show bandlike transport, the self-trapped,
small polaronic state exhibits temperature-activated mobilities, allowing
the mobilities of both to still exceed 1 cm
2
V
–1
s
–1
at room temperature. Self-trapped charge carriers
subsequently diffuse to color centers, causing broad emission that
is strongly red-shifted from a direct band edge whose band gap and
associated exciton binding energy shrink with increasing temperature
in a correlated manner. Overall, our observations suggest that strong
electron–phonon coupling in this material induces rapid charge-carrier
localization.
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