The pursuit of stability in halide perovskites: the monovalent cation and the key for surface and bulk self-healing

Ceratti, Davide-Raffaele; Cohen, Ayala V.; Tenne, Ron; Rakita, Yevgeny; Snarski, Lior; Jasti, Naga Prathibha; Cremonesi, Llorenç; Cohen, Reut; Weitman, Michal; Rosenhek‐Goldian, Irit; Kaplan‐Ashiri, Ifat; Bendikov, Tatyana; Kalchenko, Vyacheslav; Elbaum, Michael; Potenza, M. A. C.; Kronik, Leeor; Hodes, Gary

doi:10.1039/d1mh00006c

Cited by 36 publications

(69 citation statements)

References 84 publications

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“…[ 57 ] Because of this, the kinetic re‐formation of a damaged surface similar to the known phenomenon of Ostwald ripening takes place in short times, amending many of the defects that would be otherwise present on other, harder, semiconductor surfaces. Similar effects of self‐healing [ 52–56 ] were observed by Yadavalli et al. [ 57 ] which noted cracks formed in mechanically stretched thin films disappear over time once the tensile stress is removed.…”

Section: Effect Of Traps On Charge Transport In Mapbi3supporting

confidence: 75%

“…[57] Because of this, the kinetic re-formation of a damaged surface similar to the known phenomenon of Ostwald ripening takes place in short times, amending many of the defects that would be otherwise present on other, harder, semiconductor surfaces. Similar effects of self-healing [52][53][54][55][56] were observed by Yadavalli et al [57] which noted cracks formed in mechanically stretched thin films disappear over time once the tensile stress is removed. This effect is relevant when the surfaces are macro scopically smooth and have scratches below 1 µm as it is in our case, thanks to our accurate mechanical polishing procedure (see the Experimental Section).…”

Section: Free Hole Transport and Hole Trapssupporting

confidence: 60%

“…Our results demonstrate a suppressed interaction of defects and free carriers which explains the boost in stability and efficiency of singly crystal solar cells. [ 43–93 ] Further improvements in stability and conversion efficiency can be achieved by controlling shallow and deep defects, as demonstrated in this study. Special attention must be given to the collection of free electrons due to the lower electron diffusion length.…”

Section: Effect Of Defects On Optoelectronic Devices and Further Pathways Of Hybrid Perovskite Developmentmentioning

confidence: 86%

“…Classical semiconductors such as silicon show SRV over 1000 cm s −1 . [51] We relate slow surface recombination velocity-proportional to the concentration of defects on the surface-to the self-healing [52][53][54][55][56] nature of MAPI 3 . MAPbI 3 shows weak structural bonds (PbI) that can be considered to continuously brake and reform.…”

Section: Free Hole Transport and Hole Trapsmentioning

confidence: 99%

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Defects in Hybrid Perovskites: The Secret of Efficient Charge Transport

Musiienko

Ceratti

Pipek

et al. 2021

Adv Funct Materials

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The interaction of free carriers with defects and some critical defect properties are still unclear in methylammonium lead halide perovskites (MHPs). Here, a multi-method approach is used to quantify and characterize defects in single crystal MAPbI 3 , giving a cross-checked overview of their properties. Time of flight current waveform spectroscopy reveals the interaction of carriers with five shallow and deep defects. Photo-Hall and thermoelectric effect spectroscopy assess the defect density, cross-section, and relative (to the valence band) energy. The detailed reconstruction of free carrier relaxation through Monte Carlo simulation allows for quantifying the lifetime, mobility, and diffusion length of holes and electrons separately. Here, it is demonstrated that the dominant part of defects releases free carriers after trapping; this happens without non-radiative recombination with consequent positive effects on the photoconversion and charge transport properties. On the other hand, shallow traps decrease drift mobility sensibly. The results are the key for the optimization of the charge transport properties and defects in MHP and contribute to the research aiming to improve perovskite stability. This study paves the way for doping and defect control, enhancing the scalability of perovskite devices with large diffusion lengths and lifetimes.

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Section: Effect Of Traps On Charge Transport In Mapbi3supporting

confidence: 75%

Section: Free Hole Transport and Hole Trapssupporting

confidence: 60%

Section: Effect Of Defects On Optoelectronic Devices and Further Pathways Of Hybrid Perovskite Developmentmentioning

confidence: 86%

Section: Free Hole Transport and Hole Trapsmentioning

confidence: 99%

See 2 more Smart Citations

Defects in Hybrid Perovskites: The Secret of Efficient Charge Transport

Musiienko

Ceratti

Pipek

et al. 2021

Adv Funct Materials

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“…Needless to say, these properties are closely linked to the high material quality required in conventional (GaAs, Si) systems for high performance compared to polycrystalline halide perovskite, which exhibit a high degree of disorder yet work efficiently and are of high optoelectronic quality even when processed from solution. Moreover, low ion migration barriers [ 70 ] in halide perovskite allow efficient self‐healing mechanisms even at room temperatures that have been observed under light [ 71 ] and high energetic irradiation. [ 13 ]…”

Section: Comparing Radiation‐induced Damage In Iii–v On Ge 3j and Perovskite 2j Pvmentioning

confidence: 99%

Proton‐Radiation Tolerant All‐Perovskite Multijunction Solar Cells

Lang

Eperon

Frohna

et al. 2021

Advanced Energy Materials

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Radiation‐resistant but cost‐efficient, flexible, and ultralight solar sheets with high specific power (W g−1) are the “holy grail” of the new space revolution, powering private space exploration, low‐cost missions, and future habitats on Moon and Mars. Herein, this study investigates an all‐perovskite tandem photovoltaic (PV) technology that uses an ultrathin active layer (1.56 µm) but offers high power conversion efficiency, and discusses its potential for high‐specific‐power applications. This study demonstrates that all‐perovskite tandems possess a high tolerance to the harsh radiation environment in space. The tests under 68 MeV proton irradiation show negligible degradation (<6%) at a dose of 1013 p+ cm−2 where even commercially available radiation‐hardened space PV degrade >22%. Using high spatial resolution photoluminescence (PL) microscopy, it is revealed that defect clusters in GaAs are responsible for the degradation of current space‐PV. By contrast, negligible reduction in PL of the individual perovskite subcells even after the highest dose studied is observed. Studying the intensity‐dependent PL of bare low‐gap and high‐gap perovskite absorbers, it is shown that the VOC, fill factor, and efficiency potentials remain identically high after irradiation. Radiation damage of all‐perovskite tandems thus has a fundamentally different origin to traditional space PV.

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2D Pb‐Halide Perovskites Can Self‐Heal Photodamage Better than 3D Ones

Aharon

Ceratti

Jasti

et al. 2022

Adv Funct Materials

Self Cite

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Adding a 2D character to halide perovskite (HaP) active layers in ambientprotected cells can improve their stability drastically, which is not obvious from the hydrophobicity of the large cations that force the HaP into a 2D structure. Results of two-photon confocal microscopy are reported to study inherent photo-stability of 2D Pb iodide HaPs in the interior of single crystals. Compared to 3D HaP crystals, 2D ones have higher photo-stability and, under a few sun-equivalent conditions, self-heal efficiently after photo-damage. Using both photoluminescence (PL) intensities (as function of time after photo-damage) and spectra, self-healing dynamics of 2D HaP (C 4 H 9 NH 3 ) 2 PbI 4 , 2D/3D (C 4 H 9 NH 3 ) 2 (CH 3 NH 3 ) 2 Pb 3 I 10 and 3D MAPbI 3 are compared. Differences in response to photo-damage and selfhealing ability from different degrees of photo-damage are found between these HaPs. Based on the findings, a possible chemical mechanism for photo-damage and self-healing of the 2D HaPs is suggested: the layered lattice arrangement limits out-diffusion of degradation products, facilitating damage reversal, leading to better 2D HaP photo-stability and self-healing uniformity than for 2D/3D HaPs. One implication of the layered structures' resilience to photo-damage is transfer of their increased stability to devices made with them, such as photovoltaic solar cells and light-emitting diodes.

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The pursuit of stability in halide perovskites: the monovalent cation and the key for surface and bulk self-healing

Abstract: We find significant differences between degradation and healing at the surface or in the bulk for each of the different APbBr3 single crystals (A=CH3NH3+, methylammonium (MA); HC(NH2)2+, formamidinium (FA); and...

Cited by 36 publications

References 84 publications

Defects in Hybrid Perovskites: The Secret of Efficient Charge Transport

Defects in Hybrid Perovskites: The Secret of Efficient Charge Transport

Proton‐Radiation Tolerant All‐Perovskite Multijunction Solar Cells

2D Pb‐Halide Perovskites Can Self‐Heal Photodamage Better than 3D Ones

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