Structurally Flexible 2D Spacer for Suppressing the Electron-Phonon Coupling Induced Non-Radiative Decay in Perovskite Solar Cells

doi:10.1007/s40820-024-01401-9

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Abstract

This study presents experimental evidence of the dependence of non-radiative recombination processes on the electron-phonon coupling of perovskite in perovskite solar cells (PSCs). Via A-site cation engineering, a weaker electron-phonon coupling in perovskite has been achieved by introducing the structurally soft cyclohexane methylamine (CMA⁺) cation, which could serve as a damper to alleviate the mechanical stress caused by lattice oscillations, compared to the rigid phenethyl methylamine (PEA⁺) analog. It demonstrates a significantly lower non-radiative recombination rate, even though the two types of bulky cations have similar chemical passivation effects on perovskite, which might be explained by the suppressed carrier capture process and improved lattice geometry relaxation. The resulting PSCs achieve an exceptional power conversion efficiency (PCE) of 25.5% with a record-high open-circuit voltage (V_OC) of 1.20 V for narrow bandgap perovskite (FAPbI₃). The established correlations between electron-phonon coupling and non-radiative decay provide design and screening criteria for more effective passivators for highly efficient PSCs approaching the Shockley-Queisser limit.

Key words： Electron-phonon coupling A-site cation engineering Non-radiative recombination

Received: 20 December 2023 Published: 24 April 2024

Corresponding Authors: Chang Liu, Ziyi Ge

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Ruikun Cao and Kexuan Sun have contributed equally to this work.

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	Ruikun Cao
	Kexuan Sun
	Chang Liu
	Yuhong Mao
	Wei Guo
	Ping Ouyang
	Yuanyuan Meng
	Ruijia Tian
	Lisha Xie
	Xujie Lü4
	Ziyi Ge

Cite this article:

Ruikun Cao,Kexuan Sun,Chang Liu, et al. Structurally Flexible 2D Spacer for Suppressing the Electron-Phonon Coupling Induced Non-Radiative Decay in Perovskite Solar Cells[J]. Nano-Micro Letters, 2024, 16(1): 178-.

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https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01401-9 OR https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/178

Fig. 1 a-c GIWAXS patterns of 3D, 3D/2D-CMAI, and 3D/2D-PEAI films. d-f TEM images of 3D, 3D/2D-CMAI, and 3D/2D-PEAI films. g-i GIXRD patterns at different tilting angles of 3D, 3D/2D-CMAI, and 3D/2D-PEAI films. j ToF-SIMS depth profile for the 2D treated perovskite film deposited on ITO substrate. k X-ray diffraction patterns of 3-13° with 3D, 3D/2D-CMAI, and 3D/2D-PEAI films. l Linear fit of 2θ-sin2 (ψ) for 3D, 3D/2D-CMAI, and 3D/2D-PEAI films

Fig. 2 a, b Theoretical energy band structure and density of states of (CMA)2FAPb2I7 and (PEA)2FAPb2I7. c Relative changes of lattice parameters of (CMA)2FAPb2I7 and (PEA)2FAPb2I7 with pressure change. d Relative changes of the Pb-I bond length of (CMA)2FAPb2I7 and (PEA)2FAPb2I7 with pressure change. e Variation of the Pb-I-Pb bond angle of (CMA)2FAPb2I7 and (PEA)2FAPb2I7 with pressure change. f Variation of the bandgap of (CMA)2FAPb2I7 and (PEA)2FAPb2I7 with pressure change. g Schematic diagram of bond length change and bond angle change between metal and halide. h Structural optimization models of (CMA)2FAPb2I7 and (PEA)2FAPb2I7 at 0 GPa and 1 GPa

Fig. 3 a-c PL spectra at selected pressures of pristine 3D, 3D/2D-CMAI, and 3D/2D-PEAI. d-f Absorption spectra at different pressures with 3D, 3D/2D-CMAI, and 3D/2D-PEAI. g Schematic diagram of DAC pressure device. h-i PL intensity and wavelength as a function of pressure

Fig. 4 a, b Pseudo-color maps of temperature-dependent PL spectra of 3D/2D-CMAI and 3D/2D-PEAI from 20 to 77 K. c Derived carrier-LO phonon coupling strength as a function of temperature ranging from 20 to 77 K for 3D/2D-CMAI and 3D/2D-PEAI (top), phonon energies derived from the peak fitting to the PL emission spectra for 3D/2D-CMAI and 3D/2D-PEAI (bottom). d, e PL emission spectra of 3D/2D-CMAI and 3D/2D-PEAI measured at 20 and 298 K. f Temperature dependence of PL emission spectral width (FWHM) of 3D/2D-CMAI and 3D/2D-PEAI from 77 to 300 K. g, h HCs at delay times from 0.3 to 15 ps. i Hot electron temperature decay for 3D/2D-CMAI and 3D/2D-PEAI films

Fig. 5 a J-V characteristics of optimized PSCs and the corresponding schematic illustrating of rigid PSCs (inset). b EQE spectra and the integrated current density. c Stabilized power output (SPO) at maximum power point tracking under working conditions with 100 mW cm−2 irradiation. d J-V characteristics of optimized f-PSCs and the corresponding schematic illustration of f-PSCs (inset). e, f Light intensity-dependent VOC and JSC. g, h Trap concentration estimated by dark J-V curves. i Electrochemical impedance spectroscopy of PSCs and the corresponding equivalent circuit model (inset). j Mechanical test of the f-PSCs based on bending radius of 5 mm. k Maximum power point tracking (MPPT) of 3D devices and 3D/2D-CMAI, 3D/2D-PEAI devices under 1 sun illumination in the N2 environment

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