Phase Stability and Diffusion in Lateral Heterostructures of Methyl Ammonium Lead Halide Perovskites

Kennard, Rhys M.; Dahlman, Clayton J.; Nakayama, Hidenori; DeCrescent, Ryan A.; Schuller, Jon A.; Seshadri, Ram; Mukherjee, Kunal; Chabinyc, Michael L.

doi:10.1021/acsami.9b06069

Cited by 35 publications

(34 citation statements)

References 67 publications

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“…Also, we distinguish between illuminated and nonilluminated samples because light enhances diffusion by providing energy to the system. Figure 3 indicates clearly that diffusion coefficients above 10 −9 cm 2 s −1 are obtained [50,59,[66][67][68]71,72] have a mixed I − , Br − formulation, ref. [58] is Br − based, and refs.…”

Section: Ch Nh H O Ch Nh H Omentioning

confidence: 91%

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Eppur si Muove: Proton Diffusion in Halide Perovskite Single Crystals

et al. 2020

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Halide perovskites, HaPs, can show remarkable to outstanding properties and photovoltaic (PV) devices in which they are the absorber can show excellent performances. [1-4] Apart from the PV results, also light-emission, radiation detection, and other electronics are explored. [5-8] During their relatively short history, numerous questions have arisen about the materials' properties and functions with many central ones still under discussion, such as the proposed idea of defect tolerance which awaits experimental evidence. At the same time, already several observables have been linked to fascinating phenomena, such as anharmonicity [9] and high entropy. [10] Ion migration in HaPs belongs to the latter class and has been widely discussed. Migrating ions modify conductivity and junction architecture with consequences for the overall efficiency of junction devices, such as solar cells. A wide consensus identifies halides, specifically I − and Br − , as the migrating ions, although, still without the gold standard experiment of isotope tracing. Remarkably, with some notable exceptions, there is no mention of contributions of protons to ion migration, although their absence in HaPs containing CH 3 NH 3 + (MA +) and HC(NH 2) 2 (FA +) (as the A cation in ABX 3) would be remarkable. In the past years of our research on dynamic effects in halide perovskites (self-healing and ion Ion diffusion affects the optoelectronic properties of halide-perovskites (HaPs). Until now, the fastest diffusion has been attributed to the movement of the halides, largely neglecting the contribution of protons, on the basis of computed density estimates. Here, the process of proton diffusion inside HaPs, following deuterium-hydrogen exchange and migration in MAPbI 3 , MAPbBr 3 , and FAPbBr 3 single crystals, is proven through D/H NMR quantification, Raman spectroscopy, and elastic recoil detection analysis, challenging the original assumption of halide-dominated diffusion. The results are confirmed by impedance spectroscopy, where MAPbBr 3-and CsPbBr 3-based solar cells respond at very different frequencies. Water plays a key role in allowing the migration of protons as deuteration is not detected in its absence. The water contribution is modeled to explain and forecast its effect as a function of its concentration in the perovskite structure. These findings are of great importance as they evidence how unexpected, waterdependent proton diffusion can be at the basis of the ≈7 orders of magnitude spread of diffusion (attributed to I − and Br −) coefficient values, reported in the literature. The reported enhancement of the optoelectronic properties of HaP when exposed to small amounts of water may be related to the finding.

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Section: Ch Nh H O Ch Nh H Omentioning

confidence: 91%

“…Samples from: refs. [50,59,66–68,71,72 ] have a mixed I − , Br − formulation, ref. [58 ] is Br − based, and refs.…”

Section: Figurementioning

confidence: 99%

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Eppur si Muove: Proton Diffusion in Halide Perovskite Single Crystals

et al. 2020

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“…The uncovered perovskite underwent anion exchange whereas the PMMA‐covered perovskite with their component remained, showing patterned PL in the NW heterojunction. This polymer mask‐assisted in situ conversion strategy was later used to fabricate lateral‐structured perovskite films [ 78 ] and CsPbI 3 –CsPbBr 3 heterojunction NW arrays on flexible substrates to construct self‐powered lateral photodetectors. [ 79 ] The anion exchange or metal–ion insertion reactions were also demonstrated for structure transformation in various lead‐free perovskite materials, e.g., from Cs 3 BiX 6 to Cs 3 Bi 2 X 9 (X = Cl,Br).…”

Section: Synthesis Methodsmentioning

confidence: 99%

Perovskite Nano‐Heterojunctions: Synthesis, Structures, Properties, Challenges, and Prospects

Wang

2020

Small Structures

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Scientific and industrial interest on perovskite semiconductor materials has grown rapidly in recent years. Through the efforts of researchers professionals in chemistry, physics, materials and electronics, etc., many records based on perovskites have been and are being refreshed. The brilliant performances emerge not only from the excellent properties of perovskite themselves, but also originate from the composite material systems of hybridizing perovskites with heteromaterials. Herein, first, the crystal and nanostructures of perovskite materials, semiconductor-based heterojunctions, and the categories of perovskite heterojunction are fundamentally introduced. Then, the state-of-the-art synthesis methods, size and structure control, electron structure-related physical properties, and applications of the perovskite-based nano-heterojunctions are comprehensively reviewed. Finally, perspectives on tackling challenges and developing trends are discussed.

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“…8 Phase engineering can also be used for fabrication of high-quality perovskitebased heterojunctions with potential applications in new functional devices. 9,10 Akriti, Davidson School of Chemical Engineering, Purdue University, USA Shuchen Zhang, Davidson School of Chemical Engineering, Purdue University, USA Letian Dou, Davidson School of Chemical Engineering and Birck Nanotechnology Center, Purdue University, USA; dou10@purdue.edu doi:10.1557/mrs.2020.281…”

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confidence: 99%