Crystal Structure of DMF-Intermediate Phases Uncovers the Link Between CH3NH3PbI3 Morphology and Precursor Stoichiometry

Petrov, Andrey A.; Sokolova, Iuliia P.; Belich, Nikolai A.; Peters, G. S.; Dorovatovskii, Pavel V.; Zubavichus, Yan V.; Khrustalev, Victor N.; Petrov, Andrey V.; Grätzel, Michaël; Goodilin, Eugene A.; Tarasov, Alexey B.

doi:10.1021/acs.jpcc.7b08468

Cited by 133 publications

(168 citation statements)

References 20 publications

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“…To confirm this, we show the 2D diffraction pattern as well as the converted diffraction pattern of the film during the spin‐coating process (i.e., before annealing) in Figures S1a, S2a,d, and S3a (Supporting Information). There is a slight difference in preferential orientation of our (MA) 2 (DMF) 2 Pb 3 I 8 phase compared to Petrov et al, but this is plausible given that P1 is a PbI 2 ‐rich precursor phase and that PbI 2 does show different orientations depending on whether it crystallizes rapidly or slowly . In addition, the 2D diffraction patterns of the P1 phase (Figure a) do show preferential orientation which would induce the integrated intensity in the 1D patterns to deviate from peak intensity distributions of reference or calculated patterns.…”

Section: Resultsmentioning

confidence: 59%

Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes

Song

Yuan

Mori

et al. 2019

Adv Funct Materials

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The exploration of the synthetic space of halide perovskites hinges on an enormous number of parameters requiring time-consuming experimentation to decouple and optimize. Here, the formation of the prototype material CH 3 NH 3 PbI 3 (MAPbI 3 ) is investigated at different time and length scales using multimodal in situ measurements to monitor the evolution of crystalline phases, morphology, and photoluminescence as a function of the lead precursors. Kinetically fast formation of crystalline precursor phases already during the spin-coat deposition is observed using lead iodide (PbI 2 ) or lead chloride (PbCl 2 ) routes. These precursor phases most likely template final MAPbI 3 film morphology. In particular, the emergence of the "needle-like" structure is shown to appear before film annealing. In situ photoluminescence measurements suggest nanoscale nucleation followed by rapid nuclei densification and growth. Using this multimodal in situ approach, different formation pathways can be identified either via precursor phases in the PbI 2 and PbCl 2 routes or direct perovskite formation from molecular building blocks as observed in the lead acetate (PbAc 2 ) route. Correlation of in situ results with photovoltaic device performance demonstrates the power of in situ multimodal techniques, paves the way to a fast screening of synthetic parameters, and ultimately leads to controlled synthetic procedures that yield high-efficiency devices.

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Section: Resultsmentioning

confidence: 59%

Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes

Song

Yuan

Mori

et al. 2019

Adv Funct Materials

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“…The equilibria between PbI 2 , PbI 3 − , and PbI 4 2− shift to higher coordinated plumbate species in the case of stoichiometric excess of MAI in the precursor solution, which could retard the fast crystallization of PbI 2 and improve the homogeneity of the perovskite thin films. Indeed, the presence of three different intermediate phases based on the ratios of MAI and PbI 2 have been confirmed . As shown in Figure c, both PbI 2 ‐rich (MA) 2 (DMF) 2 Pb 3 I 8 and stoichiometric (MA) 2 (DMF) 2 Pb 2 I 6 phases contain face‐sharing PbI 6 octahedral, which have a high anisotropy in the surface energy of growth, so that the resulting crystals tend to form needle‐like morphology.…”

Section: Controlling Precursor Solution Characteristics For Perovskitmentioning

confidence: 68%

Engineering Halide Perovskite Crystals through Precursor Chemistry

Binks

Cao

et al. 2019

Small

108

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The composition, crystallinity, morphology, and trap‐state density of halide perovskite thin films critically depend on the nature of the precursor solution. A fundamental understanding of the liquid‐to‐solid transformation mechanism is thus essential to the fabrication of high‐quality thin films of halide perovskite crystals for applications such as high‐performance photovoltaics and is the topic of this Review. The roles of additives on the evolution of coordination complex species in the precursor solutions and the resulting effect on perovskite crystallization are presented. The influence of colloid characteristics, DMF/DMSO‐free solutions and the degradation of precursor solutions on the formation of perovskite crystals are also discussed. Finally, the general formation mechanism of perovskite thin films from precursor solutions is summarized and some questions for further research are provided.

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“…[18][19][20][21][22][23] The structure of mixed halide precursors has not been clearly determined and their formation kinetics depend on the lead counterion in the precursor. 20,21,24,25 Furthermore, previous studies have established that the film formation is a kinetically trapped process, indicating that the reaction coordinates depend on the film processing route (e.g., drop casting, spin coating, blade coating). 20 While at first sight this introduces higher complexity, the rate dependency should rather be regarded as an additional knob that can be exploited to optimize film processing.…”

Section: Context and Scalementioning

confidence: 99%

Scalable Fabrication of Perovskite Solar Cells to Meet Climate Targets

Bruening

Dou

Simonaitis

et al. 2018

Joule

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HIGHLIGHTSOur cost model shows competitive perovskite PV requires high-throughput processingWe replace conventional annealing with rapid thermal processing without PCE lossThe combination of RTA and blade coating establishes a scalable processing routeIn situ XRD reveals a perovskite conversion mechanism and role of intermediates Bruening et al., Joule SUMMARYCost modeling shows that high-throughput processing of perovskite solar cells is required not only to compete with incumbent technologies in terms of levelized cost of energy, but more importantly, it is the major enabling factor facilitating sustainable growth rates of solar cell manufacturing capacity commensurate with global climate targets. We performed rapid thermal annealing at bladecoating speed to quickly deposit and convert perovskite thin films for scalable manufacturing of perovskite solar cells. In situ X-ray diffraction during film deposition and thermal conversion gave insight into the formation of crystalline intermediates, essential for high-quality films. Parameters were optimized based on the in situ study, allowing perovskite films to be annealed within 3 s with a champion power conversion efficiency of 16.8%. This opens up a clear pathway toward industrial-scale high-throughput manufacturing, which is required to fulfill the projected photovoltaic installation rates needed to reach climate goals.

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Crystal Structure of DMF-Intermediate Phases Uncovers the Link Between CH₃NH₃PbI₃ Morphology and Precursor Stoichiometry

Cited by 133 publications

References 20 publications

Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes

Revealing the Dynamics of Hybrid Metal Halide Perovskite Formation via Multimodal In Situ Probes

Engineering Halide Perovskite Crystals through Precursor Chemistry

Scalable Fabrication of Perovskite Solar Cells to Meet Climate Targets

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