Connecting the solution chemistry of PbI<sub>2</sub> and MAI: a cyclodextrin-based supramolecular approach to the formation of hybrid halide perovskites

Masi, Sofia; Aiello, Federica; Listorti, Andrea; Balzano, Federica; Altamura, Davide; Giannini, Cinzia; Caliandro, Rocco; Barretta, Gloria Uccello; Rizzo, Aurora; Colella, Silvia

doi:10.1039/c7sc05095j

Cited by 59 publications

(58 citation statements)

References 47 publications

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“…[22,23,34] Accordingly, infiltrating nitrogen species into the perovskite layer is prospected as a convenient strategy for any kind of material since, besides the lattice recovery that can vary from sample to sample, [35] the need for surface stabilization is transversal to preserve the surface integrity. [22,23,34] Accordingly, infiltrating nitrogen species into the perovskite layer is prospected as a convenient strategy for any kind of material since, besides the lattice recovery that can vary from sample to sample, [35] the need for surface stabilization is transversal to preserve the surface integrity.…”

Section: Resultsmentioning

confidence: 99%

“…[22,23,34] Accordingly, infiltrating nitrogen species into the perovskite layer is prospected as a convenient strategy for any kind of material since, besides the lattice recovery that can vary from sample to sample, [35] the need for surface stabilization is transversal to preserve the surface integrity. [35] This phenomenon can be mitigated by the presence of nitrogen molecules in the surrounding. [25,36] In this view, a dynamic process of generation and annihilation of defects can be figured out which likely extends from the grain surface inward, for a certain extent (defective shell).…”

Section: Resultsmentioning

confidence: 99%

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Nitrogen Soaking Promotes Lattice Recovery in Polycrystalline Hybrid Perovskites

Alberti

Deretzis

Mannino

et al. 2019

Advanced Energy Materials

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wide dissemination, and high technological throughput. [8] As a unique event in the landscape of solar energy harvesting, perovskite solar cells have experienced an increment of their power conversion efficiency by ≈8% (from 13.4% to 23.7%) in the last 5 years. [9,10] This technology is expected to successfully contribute to the enormous challenge of future power supply from sustainable energy sources. However, the well-known structural instability of hybrid perovskites under working conditions limits a real market uptake of all the related technologies. Solutions to guarantee the durability of products are mandatory and can be numerous, if the problem is addressed from different perspectives.Within the possible approaches to stabilize the perovskite lattice and its behavior under illumination, recent efforts have focused on introducing various treatments, [11,12] molecules, or additives, [13][14][15][16][17][18][19] through different procedures. Nitrogen has been also exploited as inert species [20][21][22][23][24] but its role is still unfocused. The existing (direct or indirect) findings in the literature stimulate the idea of beneficially using N 2 molecules in technological solutions, if their role is persuasively afforded. [25] N 2 molecules are small, safe, and easy to apply.Related to the material stability, we emphasize that the plethora of perovskites produced in different laboratories, with preparation procedures changing from lab to lab and from time to time, ask for treatments that take care and, in a certain extent, reset the starting conditions in a convenient and reproducible manner. This is particularly needed for small grained perovskite layers, on one hand used to implement pinhole-free coverages, but, on the other hand, offering extended lattice discontinuities due to the high surface to volume ratio. In addition to morphology and environment, temperature-related effects are unavoidable during device operation. [24,26] A rationalization of the phenomena needs to embody heating and thermal cycles to preserve the material integrity and/or the structural reversibility versus temperature.In this framework, we argue that nitrogen species have an active role in the stabilization of all the exposed methylammonium lead iodide (MAPbI 3 ) surfaces via their action at grain shells. This conclusion is independent of the particular On the basis of experiment and theory, a general paradigm is drawn that reconsiders N 2 not simply being an inert species but rather an effective healing gas molecule if entering a methylammonium lead iodide (MAPbI 3 ) layer. Nitrogen is soaked into polycrystalline MAPbI 3 via a postdeposition mild thermal treatment under slightly overpressure conditions to promote its diffusion across the whole layer. A significant reduction of radiative recombination and a concurrent increase of light absorption, with a maximum benefit at 80 °C, are observed. Concomitantly, the current of holes drawn from the surfaces with nanometer resolution through a biased tip is raised by a factor of 3 un...

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Section: Resultsmentioning

confidence: 99%

“…[22,23,34] Accordingly, infiltrating nitrogen species into the perovskite layer is prospected as a convenient strategy for any kind of material since, besides the lattice recovery that can vary from sample to sample, [35] the need for surface stabilization is transversal to preserve the surface integrity. [35] This phenomenon can be mitigated by the presence of nitrogen molecules in the surrounding. [25,36] In this view, a dynamic process of generation and annihilation of defects can be figured out which likely extends from the grain surface inward, for a certain extent (defective shell).…”

Section: Resultsmentioning

confidence: 99%

Nitrogen Soaking Promotes Lattice Recovery in Polycrystalline Hybrid Perovskites

Alberti

Deretzis

Mannino

et al. 2019

Advanced Energy Materials

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“…chlorobenzene or toluene) and the treatment of precursors solution with additives, such as hexamethylphosphoramide 33 and 1,3-dimethyl-2-imidazolidinone, 34 as well as the use of solvent blends. 35 Various studies have been carried out on the solution chemistry of the perovskite precursors, 16,[36][37][38][39][40][41][42][43][44][45] Accordingly, in the present manuscript we investigate the chemistry of typical precursor solutions employed for LHPs synthesis by a combined experimental and computational approach.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Solution Chemistry of Lead Halide Perovskites Precursors

Radicchi

Mosconi

Elisei

et al. 2019

ACS Appl. Energy Mater.

105

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Identifying the composition of the solvated iodoplumbate complexes that are involved in the synthesis of perovskites in different solution environments is of great relevance in order to link the type and quantity of precursors to the final optoelectronic properties of the material. In this paper we clarify the nature of these species and the involved solution equilibria by combining experimental analysis and high-level theoretical calculations, focusing in particular on the DMSO and DMF solvents, largely employed in the perovskites synthesis. The specific molecular interactions between the iodoplumbate complexes, [PbIm] 2-m , and the solvent molecules, X, were analyzed by identifying the most thermodynamically stable structures in various solvent solutions and characterizing their optical properties trough DFT and TD-DFT calculations. A comparison with the experimental UV-Vis absorption spectra allows for the first time the definition of the number of iodide and solvent ligands bonded to the Pb 2+ ion and of the complex formation constants of the involved species.3

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“…However, luminescence intensity is also dependent on the native defects in the films, which are affected by the deposition conditions. Therefore, we performed comprehensive optimization of the film deposition conditions for (BA 0.5 PEA 0.5 ) 2 MAPb 2 Br 7 and BA 2 MAPb 2 Br 7 films, including the investigation of the factors that known to affect crystallization and/or optical quality, such as the effects of precursor purity, solvents and/or additives used, and the use of antisolvents . The details are given in Note S1 and Figures S6–S12 of the Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

Mixed Spacer Cation Stabilization of Blue‐Emitting n = 2 Ruddlesden–Popper Organic–Inorganic Halide Perovskite Films

Leung

Tam

Liu

et al. 2019

Advanced Optical Materials

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Ruddlesden–Popper halide perovskite (RPP) materials are of significant interest for light‐emitting devices since their emission wavelength can be controlled by tuning the number of layers n, resulting in improved spectral stability compared to mixed halide devices. However, RPP films typically contain phases with different n, and the low n phases tend to be unstable upon exposure to humidity, irradiation, and/or elevated temperature which hinders the achievement of pure blue emission from n = 2 films. In this work, two spacer cations are used to form an RPP film with mixed cation bilayer and high n = 2 phase purity, improved stability, and brighter light emission compared to a single spacer cation RPP. The stabilization of n = 2 phase is attributed to favorable formation energy, reduced strain, and reduced electron–phonon coupling compared to the RPP films with only one type of spacer cation. Using this approach, pure blue light‐emitting diodes (LEDs) with Commission Internationale de l'éclairage (CIE) coordinates of (0.156, 0.088) and excellent spectral stability are achieved.

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Connecting the solution chemistry of PbI₂ and MAI: a cyclodextrin-based supramolecular approach to the formation of hybrid halide perovskites

Abstract: Cyclodextrin macrocycles are able to modify and control the solvation equilibria of hybrid perovskite components in solution by establishing supramolecular interactions.

Cited by 59 publications

References 47 publications

Nitrogen Soaking Promotes Lattice Recovery in Polycrystalline Hybrid Perovskites

Nitrogen Soaking Promotes Lattice Recovery in Polycrystalline Hybrid Perovskites

Understanding the Solution Chemistry of Lead Halide Perovskites Precursors

Mixed Spacer Cation Stabilization of Blue‐Emitting n = 2 Ruddlesden–Popper Organic–Inorganic Halide Perovskite Films

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Connecting the solution chemistry of PbI2 and MAI: a cyclodextrin-based supramolecular approach to the formation of hybrid halide perovskites

Abstract: Cyclodextrin macrocycles are able to modify and control the solvation equilibria of hybrid perovskite components in solution by establishing supramolecular interactions.

Cited by 59 publications

References 47 publications

Nitrogen Soaking Promotes Lattice Recovery in Polycrystalline Hybrid Perovskites

Nitrogen Soaking Promotes Lattice Recovery in Polycrystalline Hybrid Perovskites

Understanding the Solution Chemistry of Lead Halide Perovskites Precursors

Mixed Spacer Cation Stabilization of Blue‐Emitting n = 2 Ruddlesden–Popper Organic–Inorganic Halide Perovskite Films

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Product

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Connecting the solution chemistry of PbI₂ and MAI: a cyclodextrin-based supramolecular approach to the formation of hybrid halide perovskites