We in-situ observe the ultrafast dynamics of trapped carriers in organic methyl ammonium lead halide perovskite thin films by ultrafast photocurrent spectroscopy with a sub-25 picosecond time resolution. Upon ultrafast laser excitation, trapped carriers follow a phonon assisted tunneling mechanism and a hopping transport mechanism along ultra-shallow to shallow trap states ranging from 1.72–11.51 millielectronvolts and is demonstrated by time-dependent and independent activation energies. Using temperature as an energetic ruler, we map trap states with ultra-high energy resolution down to < 0.01 millielectronvolt. In addition to carrier mobility of ~4 cm2V−1s−1 and lifetime of ~1 nanosecond, we validate the above transport mechanisms by highlighting trap state dynamics, including trapping rates, de-trapping rates and trap properties, such as trap density, trap levels, and capture-cross sections. In this work we establish a foundation for trap dynamics in high defect-tolerant perovskites with ultra-fast temporal and ultra-high energetic resolution.

Carrier transport dynamics from sub-50 ps to ∼μs over five temporal decades in pentacene films was studied by transient photoconductivity. The behavior of the temperature independent photocurrent peak suggests that the photogenerated carriers exhibit pre-trapping transport in extended states upon pulsed laser excitation. From 300 ps to ∼30 ns, the carriers thermalize and fall into shallow band tail states, and multiple-trapping and release transport dominates. From ∼30 ns to ∼μs, the weak temperature dependence of power-law photocurrent decay and the linear relation of logarithmic photocurrent with T−1/4 suggest a variable range hopping transport in deep trap states.