Mechanosynthesis of pure phase mixed-cation MAxFA1−xPbI3hybrid perovskites: photovoltaic performance and electrochemical properties

Prochowicz, Daniel; Yadav, Pankaj; Saliba, Michael; Saski, Marcin; Zakeeruddin, Shaik M.; Lewiński, Janusz; Grätzel, Michaël

doi:10.1039/c7se00094d

Cited by 89 publications

(121 citation statements)

References 32 publications

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“…More importantly, films prepared from mechanochemically synthesized MAPI could be implemented in a single‐junction solar cell with a power conversion efficiency (PCE) on par to that prepared from the standard solution process and with lower hysteresis attributed to a lower surface defect density. A similar comparison was made with mixed MA‐FA films prepared by both methods, where the device prepared from MCS perovskites outperformed significantly the one made from standard solution process (PCEs of 14.98% and 10.97%, respectively), especially with a high short‐circuit current of 23.7 mA cm −2 . In a following paper, the authors were able to fabricate cesium chloride‐containing perovskites films by dissolving presynthesized perovskites in DMF and DMSO, whereas CsCl itself was found to be nonsoluble in the same solvents .…”

Section: Processing and Applications Of Mechanochemically Synthesizedmentioning

confidence: 71%

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Palazón

Ajjouri

Bolink

2019

Advanced Energy Materials

102

101

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Mechanochemical synthesis has recently emerged as a promising route for the synthesis of functional lead halide perovskites as well as other (lead‐free) metal halides. Mechanochemical synthesis presents several advantages with regards to more commonly used solution‐based processes such as an inherent lower toxicity by avoiding organic solvents and a finer control over stoichiometry of the final products. The ease of implementation, either through the use of a simple mortar and pestle or with an electrically powered ball‐mill, and low amount of side products make mechanochemical synthesis appealing for upscaling the production of halide perovskites. Due to the defect tolerance of lead halide perovskites, they are ideally suited to be prepared by this solvent‐free method. However, the implementation of these semiconductors in high‐efficiency optoelectronic devices requires the transformation of synthesized powder into smooth thin films where still some hurdles remain to be cleared.

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Section: Processing and Applications Of Mechanochemically Synthesizedmentioning

confidence: 71%

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Palazón

Ajjouri

Bolink

2019

Advanced Energy Materials

102

101

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“…27,29 However, so far it has been unclear whether their microscopic structure corresponds to that of thin films prepared by solution processing. In order to address this, we prepared a mechanochemical bulk sample of CsMAFA(Br,I) and compared it with a spin-coated CsMAFA(Br,I) thin film.…”

Section: Resultsmentioning

confidence: 99%

“…27,29 The thin film of CsMAFA was prepared according to the procedure described previously, except an uncoated glass substrate was used instead of FTO-coated glass. 16 Samples were packed into 3.2 mm rotors under inert dry nitrogen atmosphere.…”

Section: Experimental Sectionmentioning

confidence: 99%

Phase Segregation in Cs-, Rb- and K-Doped Mixed-Cation (MA)_x(FA)_1–xPbI₃ Hybrid Perovskites from Solid-State NMR

Kubicki¹,

Prochowicz

Hofstetter³

et al. 2017

J. Am. Chem. Soc.

340

439

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Hybrid (organic–inorganic) multication lead halide perovskites hold promise for a new generation of easily processable solar cells. Best performing compositions to date are multiple-cation solid alloys of formamidinium (FA), methylammonium (MA), cesium, and rubidium lead halides which provide power conversion efficiencies up to around 22%. Here, we elucidate the atomic-level nature of Cs and Rb incorporation into the perovskite lattice of FA-based materials. We use 133Cs, 87Rb, 39K, 13C, and 14N solid-state MAS NMR to probe microscopic composition of Cs-, Rb-, K-, MA-, and FA-containing phases in double-, triple-, and quadruple-cation lead halides in bulk and in a thin film. Contrary to previous reports, we have found no proof of Rb or K incorporation into the 3D perovskite lattice in these systems. We also show that the structure of bulk mechanochemical perovskites bears close resemblance to that of thin films, making them a good benchmark for structural studies. These findings provide fundamental understanding of previously reported excellent photovoltaic parameters in these systems and their superior stability.

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“…In addition, the spray reaction has been used to prepare FAPbI 3 and FA 0.9 Cs 0.1 PbI 3 films . Mechanochemical synthesis has also been applied for MA x FA 1− x PbI 3 , and the synthesized material has been used to prepare devices by a one‐step solution process …”

Section: Fabrication Methodology Of the Fa‐based Perovskitesmentioning

confidence: 99%

Formamidinium‐Based Lead Halide Perovskites: Structure, Properties, and Fabrication Methodologies

Liu

Waqas

et al. 2018

Small Methods

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Formamidinium (FA)‐based perovskites exhibit great potential for photovoltaics since they enable the achievement of power conversion efficiency (PCE) over 22%. The bandgap of FA‐based perovskite is lower than that of the methylammonium‐based one, while the larger ionic radius and dual‐ammonia group of FA ions restrain their movement in close‐packing [PbI6]4− cages, leading to improved stability. Here, the structure and properties of FAPbI3− and FA‐based mixed cation perovkites are discussed. In particular, the issues of polymorphism and stabilization of the desired low‐bandgap crystal phase of FAPbI3 are considered. FAPbI3 exhibits polymorphisms with a photovoltaically unfavorable δ‐phase that is stable at room temperature, and, thus, it is difficult to prepare continuous and compact FAPbI3 with the desired crystal structure, namely, the pure α‐phase. Hence, overcoming the limitations of phase transitions is the critical issue in obtaining high‐quality FA‐based perovskite films, which are a prerequisite for solar cells with high PCEs. Here, the focus is on the fabrication methods of FA‐based perovskite films, namely, additive engineering, intermolecular exchange, interfacial engineering, and chemical vapor deposition. A comprehensive overview of the fabrication methodology for the FA‐based perovskite films is provided to facilitate understanding of the underlying mechanisms.

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Mechanosynthesis of pure phase mixed-cation MA_xFA_1−xPbI₃hybrid perovskites: photovoltaic performance and electrochemical properties

Abstract: We report a facile mechanochemical route for the stabilization of a structurally stable α-FAPbI3perovskite by fine and controllable stoichiometry modification in mixed-cation (MA)x(FA)1−xPbI3perovskites.

Cited by 89 publications

References 32 publications

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Phase Segregation in Cs-, Rb- and K-Doped Mixed-Cation (MA)_x(FA)_1–xPbI₃ Hybrid Perovskites from Solid-State NMR

Formamidinium‐Based Lead Halide Perovskites: Structure, Properties, and Fabrication Methodologies

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Mechanosynthesis of pure phase mixed-cation MAxFA1−xPbI3hybrid perovskites: photovoltaic performance and electrochemical properties

Abstract: We report a facile mechanochemical route for the stabilization of a structurally stable α-FAPbI3perovskite by fine and controllable stoichiometry modification in mixed-cation (MA)x(FA)1−xPbI3perovskites.

Cited by 89 publications

References 32 publications

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Phase Segregation in Cs-, Rb- and K-Doped Mixed-Cation (MA)x(FA)1–xPbI3 Hybrid Perovskites from Solid-State NMR

Formamidinium‐Based Lead Halide Perovskites: Structure, Properties, and Fabrication Methodologies

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Mechanosynthesis of pure phase mixed-cation MA_xFA_1−xPbI₃hybrid perovskites: photovoltaic performance and electrochemical properties

Phase Segregation in Cs-, Rb- and K-Doped Mixed-Cation (MA)_x(FA)_1–xPbI₃ Hybrid Perovskites from Solid-State NMR