Giant and Broadband Multiphoton Absorption Nonlinearities of a 2D Organometallic Perovskite Ferroelectric

Abstract

Multiphoton absorption (MPA) has been utilized for important technological applications. High‐order multiphoton harvesting (e.g., five‐photon absorption, 5PA) exhibits unique properties that could benefit biophotonics. Within this field, perovskite oxide ferroelectrics (e.g., BaTiO3) enable low‐order optical nonlinearities of 2PA/3PA processes. However, it is challenging to obtain efficient, high‐order 5PA effects. Herein, for the first time, giant and broadband MPA properties are presented in the 2D hybrid perovskite ferroelectric (IA)2(MA)2Pb3Br10 (1; IA = isoamylammonium and MA = methylammonium), where multiphoton‐excited optical nonlinearities related to different MPA mechanisms over a broadband range of 550–2400 nm are observed. Strikingly, its 5PA absorption cross‐section (σ5) reaches up to 1.2 × 10−132 cm10 s4 photon−4 (at 2400 nm), almost 10 orders larger than some state‐of‐the‐art organic molecules and a record‐high value among all known ferroelectrics. This unprecedented 5PA effect results from the quantum‐confined motif of inorganic trilayer sheets (wells) and organic cations (barriers) in 1. Moreover, its large ferroelectric polarization of 5 µC cm−2 could promote modulation of MPA effects under external electric fields. As far as it is known, this is the first report on giant, broadband high‐order MPA properties in ferroelectrics, which provides potential, novel electric‐ordered materials for next‐generation biophotonic applications.

Nonlinear Optical Thermometry—A Novel Temperature Sensing Strategy via Second Harmonic Generation (SHG) and Upconversion Luminescence in BaTiO3:Ho3+,Yb3+ Perovskite

“…Perovskite materials have unique features that make them promising candidates in various fields, such as solar cells, ferroelectric materials, solid‐state lasers, etc. [ 22–28 ] Titanate perovskites have received extensive attention, especially thanks to their splendid piezoelectric and emissive properties. [ 29,30 ] Barium titanate perovskite has a relatively low phonon energy (≈700 cm –1 ), favoring high UCL efficiency.…”

Two‐Dimensional Guanidine‐Based Hybrid Perovskites with Strong Dichroism for Multiwavelength Polarization‐Sensitive Detection

“…Organic-inorganic 2D hybrid perovskites have been used for various device applications, benefiting from their distinct virtues including structural adjustability, admirable stability and unique quantum-confined effects. [24][25][26][27][28][29][30][31][32][33] Despite deriving from the 3D prototypes, the 2D hybrid perovskites possess quite different structural lattices. The inorganic frameworks and organic layers stack alternately to constitute the quantum-confined structure, resulting in strong anisotropic characteristics including electric conductivity, carrier transport and linear optical dichroism.…”

2D Hybrid Halide Perovskites: Synthesis, Properties, and Applications

“…The 2DHPs also show multiphoton absorption (MPA) properties for potential technological applications due to the enhanced quantum and dielectric confinement effects. [ 108,176 ] In 2017, Liu et al reported a giant two‐photon absorption (TPA) in the 2DHP, , with the TPA coefficient of 211.5 cm MW −1 , about one order of magnitude larger than those of 3DHPs. [ 176 ] Interestingly, in 2020, Li et al reported a high‐order MPA, i.e., 5PA, in the 2DHP, (IA) 2 (MA) 2 Pb 3 Br 10 , with a cross section () value of 1.2 × 10 −132 cm 10 s 4 photon −4 (at 2400 nm).…”

“…[ 176 ] Interestingly, in 2020, Li et al reported a high‐order MPA, i.e., 5PA, in the 2DHP, (IA) 2 (MA) 2 Pb 3 Br 10 , with a cross section () value of 1.2 × 10 −132 cm 10 s 4 photon −4 (at 2400 nm). [ 108 ] The surprising 5PA effect is attributed to the quantum‐confined motif of inorganic wells and organic cations that serve as barriers, which provides opportunities for next‐generation biophotonic applications.…”

“…In a very recent work, Li et al reported a large ferroelectric polarization of 5 μC in (IA) 2 (MA) 2 Pb 3 Br 10 (IA = isoamylammonium) and found that such a large polarization could promote modulation of multiphoton absorption under external electric fields. [ 108 ] The enhanced multiphoton absorption properties in the ferroelectric 2DHP provides potential for next‐generation biophotonic applications.…”