With
solar conversion efficiencies surpassing 20%, organometallic perovskites
show tremendous promise for solar cell technology. Their high brightness
has also led to demonstrations of lasing and power-efficient electroluminescence.
Here we show that thin films of methylammonium lead iodide, prepared
by solution processing at temperatures not exceeding 100 °C,
exhibit a highly nonlinear intensity-dependent refractive index due
to changes in the free-carrier concentration and for femtosecond excitation
at higher intensities undergo saturation that can be attributed to
the Pauli blocking effect. Nonlinear refractive index and nonlinear
absorption coefficients were obtained by the Z-scan
technique, performed simultaneously in open- and closed-aperture configurations.
Both nanosecond- and femtosecond-pulsed lasers at multiple wavelengths
were used in order to distinguish between the mechanisms inducing
the nonlinearities. The magnitude and sign of the nonlinear refractive
index n
2 were determined. For resonant
excitation, free carrier generation is the dominant contribution to
the nonlinear refractive index, with a large nonlinear refractive
index of n
2 = 69 × 10–12 cm2/W being observed for resonant femtosecond pumping
and n
2 = 34.4 × 10–9 cm2/W for resonant nanosecond pumping. For nonresonant
femtosecond excitation, bound-charge-induced nonlinearity leads to n
2 = 36 × 10–12 cm2/W. These values are equivalent to the best reported metrics
for conventional semiconductors, suggesting that organometallic perovskites
are promising materials for optical switching and bistability applications.