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Zhou L, Wang YD, Kang JL et al. Observation of polaronic state assisted sub-bandgap saturable absorption. Opto-Electron Adv 8, 240312 (2025). doi: 10.29026/oea.2025.240312
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Article Open Access
Observation of polaronic state assisted sub-bandgap saturable absorption
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Abstract
In soft-lattice lead-halide perovskites, the polaronic effects involving stabilization of localized charge character by structural deformations and polarizations have an important effect on the properties of functional materials such as the band gap, which has attracted considerable investigations. However, the concept of polaron assisted nonlinear photonics remains largely unexplored, which has a wide range of applications from optoelectronics to telecommunications and quantum technologies. Here, we report the first observation of the polaronic state assisted saturable absorption through sub-bandgap excitation with a redshift exceeding 60 meV. By combining photoluminescence, transient absorption measurements and density functional theory calculations, we explicate that the anomalous nonlinear saturable absorption under sub-bandgap excitation is caused by the transient picosecond timescale polaronic state formed by strong carrier/exciton-phonon coupling effect. The bandgap fluctuation caused by polaron formation can be further tuned through exciton-phonon coupling of perovskites with different Young’s modulus. This suggests that we can design targeted soft lattice lead-halide perovskite with a specific structure to effectively manipulate exciton-phonon coupling and exciton-polaron formation. These findings profoundly expand our understanding of exciton-polaronic nonlinear optics physics and provide an ideal platform for developing actively tunable nonlinear photonics applications.-
Keywords:
- polaron /
- perovskite /
- soft lattice /
- nonlinear optics /
- saturable absorption
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References
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Zhou L, Wang YD, Kang JL et al. Observation of polaronic state assisted sub-bandgap saturable absorption. Opto-Electron Adv 8, 240312 (2025). doi: 10.29026/oea.2025.240312
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Figure 1.
Polaronic state assisted nonlinear saturable absorption (PSA_SA) picture in LHPs. (a) Schematic diagram of Z-scan. (b) Scheme of transformation from free excitons to exciton-polaron with lattice distortion by dynamic polaronic effect. (c) Schematic diagram of the effect of polaron formation on the band structure of materials, which will cause band energy fluctuations. (d) The valence band maximum (VBM) and conduction band minimum (CBM) at different temperature are extracted according to the molecular dynamics simulation calculation results. (e) The standard variations of the band energy for CBM and VBM at different temperatures. (f) Schematic of SA caused by single photon absorption under up-bandgap excitation in conventional semiconductors. (g) Schematic of PSA_SA under sub-bandgap excitation. CB and VB denote conduction band and valence band respectively.
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Figure 2.
Structural, linear and nonlinear optical characterizations of CsPbBr3. (a) Crystal structure of CsPbBr3 and associated lattice distortion, where green represents Cs atoms, gray represents Pb atoms, and purple represents Br atoms. (b) XRD pattern of the CsPbBr3 film and the standard card (ICSD-97851). (c) UV-vis absorption spectrum and Tauc plot of CsPbBr3. (d) Steady PL spectra of CsPbBr3 film. (e) The two-dimensional map of transmittance as a function of the scan distance and the excitation peak density under 530 nm laser pulse excitation and (f) the transmittance curves with 3 representative excitation intensities.
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Figure 3.
Z-scan and steady-state PL studies of polaronic state assisted nonlinear saturable absorption (PSA_SA). (a–c) The Z-scan results of CsPbBr3 under different excitation intensity at different wavelengths. The excitation wavelengths are (a) 515 nm (pump intensity: 2.07–4.25 GW/cm2), (b) 532 nm (pump intensity: 3.24–94.86 GW/cm2), and (c) 600 nm (pump intensity: 48.60–215.14 GW/cm2), respectively. From top to bottom, the light intensity increases in turn. (d) Power dependence of the PL intensity at different excitation wavelengths for CsPbBr3. (e) Wavelength dependence of slope (top) and nonlinear absorption coefficient β (bottom) for CsPbBr3. Error bars represent the standard error.
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Figure 4.
TA measurements confirming polaronic state assisted nonlinear saturable absorption (PSA_SA). (a–c) Representative pseudocolor TA spectrums at (a) 515 nm, (b) 530 nm and (c) 600 nm excitations, respectively. (d–f) Time-dependent photo-induced changes in absorption (ΔA) which is pumped by (d) 515 nm , (e) 530 nm and (f) 600 nm , respectively. (g–i) Exciton band bleach dynamics monitored at 519 nm for (g) 515 nm , (h) 530 nm, and (i) 600 nm excitations, respectively.
