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

doi:10.6023/A26050151

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 (V_Gua), Pb vacancy (V_Pb), 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 (I_i), 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 10⁵ cm^－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-principle, electronic structure, defect property

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, 2026, 84(10): 1591-1600.

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Fig. & Tab. 10

Figure 1. Crystal structures of (PA)2APb2I7 (A=Gua, Ace) after optimization

	Lattice constant/nm			V/nm³	α=γ/(°)	β/(°)	d_Pb-I/nm
	a	b	c	V/nm³	α=γ/(°)	β/(°)	axial	equatorial	average
(PA)₂GuaPb₂I₇	4.124*	0.911*	0.898*	3.363*	90*	93.79*	0.321*	0.322*	0.321*
(PA)₂GuaPb₂I₇	3.986	0.909	0.844	3.059	90	91.09	0.318	0.317	0.318
(PA)₂AcePb₂I₇	4.159*	0.914*	0.895*	3.392*	90*	94.83*	0.323*	0.322*	0.322*
(PA)₂AcePb₂I₇	4.071	0.911	0.843	3.126	90	92.03	0.321	0.316	0.317

Table 1. Structural parameters of (PA)2APb2I7 (A=Gua, Ace) after optimization

	D	λ_oct	δ/nm	σ²
(PA)₂GuaPb₂I₇	0.015	1.019	0.011	62
(PA)₂AcePb₂I₇	0.018	1.013	0.057	41

Table 2. Distortion parameters of (PA)2APb2I7 (A=Gua, Ace)

	Bonds	ICOHP	Angles/(°)	d_N—H…I/nm
(PA)₂GuaPb₂I₇	H(12)—I(1)	－0.35	153.3	0.268
	H(10)—I(1)	－0.35	153.3	0.268
	H(2)—I(13)	－0.26	152.8	0.276
	H(18)—I(13)	－0.28	154.7	0.275
(PA)₂AcePb₂I₇	H(1)—I(25)	－0.41	152.2	0.263
	H(36)—I(25)	－0.39	151.0	0.265
	H(37)—I(13)	－0.24	155.8	0.283

Table 3. ICOHP, angles, and bond lengths of hydrogen bonds in (PA)2APb2I7 (A=Gua, Ace)

Figure 2. Hydrogen bonding sites in (PA)2APb2I7 (A=Gua, Ace): (a) (PA)2GuaPb2I7; (b) (PA)2AcePb2I7

Figure 3. Electronic structure properties of (PA)2APb2I7 (A=Gua, Ace): (a) PDOS of (PA)2GuaPb2I7; (b) band structure of (PA)2GuaPb2I7; (c) COHP of the axial bond Pb—I in (PA)2GuaPb2I7; (d) COHP of the equatorial bond Pb—I in (PA)2GuaPb2I7; (e) PDOS of (PA)2AcePb2I7; (f) band structure of (PA)2AcePb2I7; (g) COHP of the axial bond Pb—I in (PA)2AcePb2I7; (h) COHP of the equatorial bond Pb—I in (PA)2AcePb2I7 (The Fermi level is set at 0 eV)

Figure 4. Projected charge density along the x-axis (out-of-plane direction) for (PA)2APb2I7 (A=Gua, Ace): (a) CBM of (PA)2GuaPb2I7; (b) CBM of (PA)2AcePb2I7; (c) VBM of (PA)2GuaPb2I7; (d) VBM of (PA)2AcePb2I7

Figure 5. Transition energy levels and defect formation energies of intrinsic point defects in (PA)2APb2I7 (A=Gua, Ace): (a) vacancy defects in (PA)2GuaPb2I7; (b) interstitial defects in (PA)2GuaPb2I7; (c) vacancy defects in (PA)2AcePb2I7; (d) interstitial defects in (PA)2AcePb2I7

Figure 6. Defect migration barrier of (PA)2APb2I7 (A=Gua, Ace): (a) defect migration barrier of the Ii defect in (PA)2GuaPb2I7; (b) defect migration barrier of the Ii defect in (PA)2AcePb2I7; (c) migration pathway of Ii within the inorganic framework (x=0 and x=1 correspond to the initial and final states, respectively)

Figure 7. (PA)2APb2I7 (A=Gua, Ace): (a) optical absorption spectra and; (b) SLME

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