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0 50151 - 50151

DOI: https://doi.org/10.6023/A26050151

Article

Mechanism of Modulating the Photovoltaic Properties of Two-Dimensional Perovskites via A-Site Cations

  • Jiadong Liu ,
  • Yanbo Liu ,
  • Zhaosheng Zhang
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  • College of Chemistry and Materials Science, Hebei University, Baoding 071002, China

Received date: 2026-05-06

  Online published: 2026-06-25

Supported by

National Natural Science Foundation of China (Grant No.22573026), the Hebei Natural Science Foundation (Grant No.B2024201051), and the Science Research Project of Hebei Education Department (Grant No.BJK2024094).

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Abstract

To elucidate the influence of A-site cations on the photovoltaic properties of two-dimensional Ruddlesden-Popper-type lead iodide perovskites, this work investigates (PA)2APb2I7 using first-principles calculations, where PA denotes n-pentylammonium cation ([CH3(CH2)4NH3]+, PA) and A denotes guanidinium ([C(NH2)3]+, Gua) or acetamidinium ([C2H3(NH2)2]+, Ace). The calculations were performed using the projector augmented-wave method and the Perdew-Burke-Ernzerhof exchange-correlation functional, and included geometry optimization, structural distortion analysis, electronic structure analysis, defect property calculations, and optical absorption analysis. The results show that the A-site organic cations mainly alter the local Pb-I framework structure through N-H···I hydrogen bonds, while contributing little to the band edge electronic states. In the Gua-based material, the Pb-I-Pb angle distortion is more pronounced, whereas the Ace-based material maintains a more linear in-plane Pb-I-Pb connection, which is beneficial for Pb/I orbital coupling within the inorganic layer. Both materials are direct band gap semiconductors. The valence band maximum is mainly derived from antibonding hybridization between I-5p and Pb-6s orbitals, while the conduction band minimum primarily originates from Pb-6p orbitals. Compared to Gua-based material, the Ace cation-regulated system exhibits a narrower band-gap, lower in-plane effective masses, and more pronounced band edge localization, which favors efficient carrier transport within the inorganic layer. In the Gua-based material, the Gua vacancy (VGua), Pb vacancy (VPb), and interstitial defects introduce deep transition levels, which may act as carrier trapping or recombination centers. In contrast, low-formation-energy defects in the Ace-based material generally show shallow-level characteristics. For the interstitial iodine defect (Ii), which appears as a deep-level defect in both systems, the Ace-based material shows a higher formation energy and migration barrier than the Gua-based material. Both materials exhibit strong absorption in the visible and near-ultraviolet regions, with absorption coefficients on the order of 105cm-1. The Ace-based material shows a red-shift absorption edge and reaches a maximum spectroscopic limited maximum efficiency (SLME) of 22.79%. In summary, A-site cation regulation alters the Pb-I framework connectivity and defect characteristics. Compared with the Gua-based material, the Ace-based material shows advantages in carrier transport, defect tolerance, and theoretical photovoltaic performance.

Key words： two-dimensional perovskite; first-principles; electronic structure; defect properties

Cite this article

Jiadong Liu , Yanbo Liu , Zhaosheng Zhang . Mechanism of Modulating the Photovoltaic Properties of Two-Dimensional Perovskites via A-Site Cations[J]. Acta Chimica Sinica, 0 : 50151 -50151 . DOI: 10.6023/A26050151

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