Perovskite layer defects are a primary inhibiting factor
for their
optical nonlinearity, which restricts their use in nonlinear photonics
devices. Nevertheless, due to the variety of defect types, the passivation
and repair of these defects remain challenging. Herein, a novel bifunctional
passivation strategy was proposed, and the porphyrin with a donor–π–acceptor
structure was designed to bifunctionally repair perovskite defects
by linking different types of functional groups via acetylenic π-conjugated
linkage bridges on both sides, thus improving the nonlinear optical
(NLO) absorption properties of porphyrin–perovskite hybrid
materials. Research results indicate that the amino and carboxyl groups
of porphyrins endow the ability to bifunctionally passivate charged
defects via effective coordination interactions. The nonlinear absorption
properties of all porphyrin-passivated MAPbI3 films were
remarkably enhanced compared to that of the MAPbI3 film
across multiple wavelengths and temporal domains. Particularly, the Por3-passivated perovskite film (MAPbI
3
/Por3) exhibited optimized strongest NLO
performance, including reverse saturable absorption (RSA) under 800
nm femtosecond (fs) and 1064 nm nanosecond (ns) laser irradiations,
as well as saturable absorption (SA) with 515 and 532 nm ns laser
excitations. The value of the NLO absorption coefficient (β
= 266.23 cm GW–1) is 1 order of magnitude higher
than that of the pristine perovskite film (β = 12.93 cm GW–1), also outperforming other porphyrin-passivated perovskite
films and some reported materials. The bifunctional passivation mechanism
of porphyrin not only intensifies the perovskite’s photoinduced
ground-state dipole moment in the two-photon absorption (TPA) process
and the free carrier absorption ability to deepen the RSA properties
under 800 nm fs and 1064 nm ns lasers, respectively, but also enables
the improvement of SA responses under 515 nm fs and 532 nm ns lasers
by expediting the Pauli blocking effect of perovskite. Our study offers
a viable paradigm, which aims at exploiting high-performance NLO perovskite
materials across wide spectral regions and time scales.