Formation of Lead Halide Perovskite Precursors in Solution: Insight from Electronic‐Structure Theory

Schier, Richard; Rodriguez, Alejandro Conesa; Valencia, Ana M.; Cocchi, Caterina

doi:10.1002/pssb.202100359

Cited by 6 publications

(33 citation statements)

References 72 publications

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“…The resulting complexes are all stable, as discussed in detail in Ref. [44], where the same level of theory adopted in this work was employed. DMSO as a solvent mostly stabilizes the complexes, leading to formation energies ranging from -0.6 eV in PbCl 2 to -0.8 eV in PbI 2 .…”

Section: Systemsmentioning

confidence: 93%

“…We construct the considered 18 systems assuming an axial geometry for the PbX 2 backbone (see SI, Fig. S1), which is known to be more stable than the equatorial arrangement [27,44]. Four identical solvent molecules are bound to the Pb atom such that the resulting system is overall in a charge-neutral state.…”

Section: Systemsmentioning

confidence: 99%

“…For further details on energetic and structural properties of these compounds, we refer interested readers to Ref. [44].…”

Section: Systemsmentioning

confidence: 99%

“…In the unoccupied region, the first three molecular orbitals are dominated by the hybridization between Pb and halogen p-states. In the solvated compounds, the chemical bond between the PbX 2 core and the solvent molecules [44] promotes charge delocalization to the latter (see Figs. S3 -S8 in the SI).…”

Section: A Electronic Propertiesmentioning

confidence: 99%

“…Atomistic simulations have recently provided important insight into the formation of LHP solution precursors and their stability in different environments [27,28,44] . However, there is still a lack of knowledge (i) on the electronic coupling between lead and the various halogen atoms; (ii) on the way these interactions affect the electronic structure of the materials;…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

First-principles analysis of the optical properties of lead halide perovskite solution precursors

Procida,

Schier,

Valencia

et al. 2021

Preprint

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Lead halide perovskites (LHPs) are promising materials for opto-electronics and photovoltaics, thanks to favorable characteristics and low manufacturing costs enabled by solution processing.In light of this, it is crucial to assess the impact of solvent-solute interactions on the electronic and optical properties of LHPs and of their solution precursors. In a first-principles work based on time-dependent density-functional theory coupled with the polarizable continuum model, we investigate the electronic and optical properties of a set of charge-neutral compounds with chemical formula, PbX 2 (Sol) 4 , where X=Cl, Br, and I, and Sol are the six common solvents. We find that single-particle energies and optical gaps depend on the halogen species as well as on the solvent molecules, which also affect the energy and the spatial distribution of the molecular orbitals, thereby impacting on the excitations. We clarify that dark states at the absorption onset are promoted by electron-withdrawing solvents, and we show the correlation between oscillator strength and HOMO→LUMO contribution to the excitations. Our results provide microscopic insight into the electronic and optical properties of LHP solution precursors, complementing ongoing experimental research on these systems and on their evolution to photovoltaic thin films.

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Section: Systemsmentioning

confidence: 93%

Section: Systemsmentioning

confidence: 99%

“…For further details on energetic and structural properties of these compounds, we refer interested readers to Ref. [44].…”

Section: Systemsmentioning

confidence: 99%

Section: A Electronic Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

First-principles analysis of the optical properties of lead halide perovskite solution precursors

Procida,

Schier,

Valencia

et al. 2021

Preprint

Self Cite

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Influence of Methylammonium Chloride on Wide‐Bandgap Halide Perovskites Films for Solar Cells

Guaita,

Szostak,

da Silva

et al. 2023

Adv Funct Materials

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Wide‐bandgap perovskites are of paramount importance as the photoactive layer of the top cell in high‐efficiency tandem solar cells. Comparably high Br contents are required to widen the perovskite bandgap. However, the increase in Br content causes heterogeneous halide distribution and photoinstability. Here, the positive effect of the additive methylammonium chloride (MACl) on the optical and electronic properties of Br‐rich perovskite, deposited using N‐methyl‐2‐pyrrolidone (NMP) as co‐solvent and the gas quenching method, is investigated. Simultaneous in situ grazing‐incidence wide‐angle X‐ray scattering and photoluminescence spectroscopy are used to track the evolution of the structural and optoelectronic properties of the perovskites with different amounts of Br and MACl during the spin‐coating and thermal annealing steps. The formation mechanism is elucidated in the presence of MACl. It is observed that chloride ions inhibit the intermediate phases, favoring the formation of a perovskite phase with higher crystallinity. Nano X‐ray fluorescence mapping recognizes Br‐richer and poorer nanometric domains, whose average sizes reduce for samples with MACl. In conclusion, it is demonstrated that adding MACl affects the formation of wide‐bandgap perovskites via destabilization of the intermediate phases and acts on the homogenization of the halide distribution, leading to improved solar cell performances.

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First‐Principle Characterization of Structural, Electronic, and Optical Properties of Tin‐Halide Monomers

Schütt,

Valencia,

Cocchi

2024

ChemPhysChem

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The growing interest in tin‐halide semiconductors for photovoltaic applications demands an in‐depth knowledge of the fundamental properties of their constituents, starting from the smallest monomers entering the initial stages of formation. In this first‐principles work based on time‐dependent density‐functional theory, we investigate the structural, electronic, and optical properties of tin‐halide molecules SnXn2‐n, with n=1,2,3,4 and X = Cl, Br, I, simulating these compounds in vacuo as well as in an implicit solvent. We find that structural properties are very sensitive to the halogen species while the charge distribution is also affected by stoichiometry. The ionicity of the Sn‐X bond is confirmed by the Bader charge analysis albeit charge displacement plots point to more complex metal‐halide coordination. Particular focus is posed on the neutral molecules SnX2, for which electronic and optical properties are discussed in detail. Band gaps and absorption onset decrease with increasing size of the halogen species, and despite general common features, each molecule displays peculiar optical signatures. Our results are elaborated in the context of experimental and theoretical literature, including the more widely studied lead‐halide analogs, aiming to contribute with microscopic insight to a better understanding of tin‐halide perovskites.

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Formation of Lead Halide Perovskite Precursors in Solution: Insight from Electronic‐Structure Theory

Abstract: The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/pssb.202100359.

Cited by 6 publications

References 72 publications

First-principles analysis of the optical properties of lead halide perovskite solution precursors

First-principles analysis of the optical properties of lead halide perovskite solution precursors

Influence of Methylammonium Chloride on Wide‐Bandgap Halide Perovskites Films for Solar Cells

First‐Principle Characterization of Structural, Electronic, and Optical Properties of Tin‐Halide Monomers

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