The ultrafast polarization response to incident light and ensuing exciton/carrier generation are essential to outstanding optoelectronic properties of lead halide perovskites (LHPs). A large number of mechanistic studies in the LHP field to date have focused on contributions to polarizability from organic cations and the highly polarizable inorganic lattice. For a comprehensive understanding of the ultrafast polarization response, we must additionally account for the nearly instantaneous hyperpolarizability response to the propagating light field itself. While light propagation is pivotal to optoelectronics and photonics, little is known about this in LHPs in the vicinity of the bandgap where stimulated emission, polariton condensation, superfluorescence, and photon recycling may take place. Here we develop two-dimensional optical Kerr effect (2D-OKE) spectroscopy to energetically dissect broadband light propagation and dispersive nonlinear polarization responses in LHPs. In contrast to earlier interpretations, the below-bandgap OKE responses in both hybrid CH
3NH
3PbBr
3 and all-inorganic CsPbBr
3 perovskites are found to originate from strong hyperpolarizability and highly anisotropic dispersions. In both materials, the nonlinear mixing of anisotropically propagating light fields results in convoluted oscillatory polarization dynamics. Based on a four-wave mixing model, we quantitatively derive dispersion anisotropies, reproduce 2D-OKE frequency correlations, and establish polarization-dressed light propagation in single-crystal LHPs. Moreover, our findings highlight the importance of distinguishing the often-neglected anisotropic light propagation from underlying coherent quasiparticle responses in various forms of ultrafast spectroscopy.Understanding the ultrafast polarization response to light fields and the subsequent generation of charge carriers or excitons is key to establishing the photophysical mechanisms in the excellent optoelectronic material system of lead halide perovskites (LHPs) (
1). The two ionic polarization contributions by the reorientational motion of organic cations and the deformation of the inorganic cages have been discussed within dynamic screening models (
2–
4) and large polaron formation (
5), respectively and jointly, whereas the immediate electronic polarization response to the light field itself has been neglected so far. In many optoelectronic applications, nevertheless, not only charge carrier transport but also light propagation right below the bandgap is essential. In LHP nanowire lasers, the lasing modes are known to be redshifted from excitonic resonances due to efficient coupling to plasmon emission (
6). In LHP-based exciton–polariton devices, light–matter coupling redshifts the hybrid state on the lower polariton branch (
7). Propagation of subgap light is known to boost the efficiency of LHP photovoltaic cells and light-emitting devices by the so-called “photon recycling” (
8). Light propagation strongly influences the function of LHP photonic devices in general (
9,
10). A key feature of light propagation near the bandgap is its strong photon energy dependence, as is obvious from the classic Lorentzian model for the dielectric function near an optical resonance (
11). However, most photophysical experiments probing carrier/exciton formation, screening, scattering, and nonlinear optical responses employ ultrashort excitation pulses with inherently broad energy distribution and thus convoluted spectral responses. Here, we develop a Fourier-transform-based laser spectroscopy technique, two-dimensional optical Kerr effect (2D-OKE), to investigate light propagation and nonlinear polarization responses directly in the time domain with superior excitation energy resolution near the electronic bandgap.The third-order nonlinear electric polarization
serves as an in situ probe of a material’s polarizability and governs the ultrafast macroscopic response to an incident light field. This is employed in a variety of spectroscopies, such as (magneto-) OKE (
12,
13), coherent phonon spectroscopy (
14,
15), and four-wave mixing (FWM) in general (
11). Recently, OKE has been applied to LHP single crystals: Below the bandgap, the dominating nonoscillatory Kerr response of MAPbBr
3 (MA = CH
3NH
3) compared to its all-inorganic counterpart CsPbBr3 was previously attributed to the transient polarization anisotropy caused by liquidlike reorientation dynamics of organic cations (
2) and lattice disorder (
5). The exponentially decaying responses with above-gap excitations were discussed in relation to polaron formation in both materials (
5). Interestingly, for excitation energies close to the bandgap in CsPbBr
3 at room temperature, time-resolved OKE reveals complex oscillatory features. Such oscillatory transient birefringence signals are usually attributed to coherently excited collective modes, such as phonons (
15–
17) or magnons (
18,
19), but the strong dependence of the oscillatory frequency on pump-photon energy in OKE seems to contradict these origins in LHPs (
5). In this work, we unveil a unified source for the Kerr responses in single-crystal LHPs by tracing contributions from hyperpolarizability and the peculiar light propagation close to electronic transitions.
相似文献