pith. sign in

arxiv: 2205.10545 · v2 · submitted 2022-05-21 · ❄️ cond-mat.mtrl-sci

What Happens at Surfaces and Grain Boundaries of Halide Perovskites: Insights from Reactive Molecular Dynamics Simulations of CsPbI₃

Mike Pols , Tobias Hilpert , Ivo Filot , Adri C.T. van Duin , Sof\'ia Calero , Shuxia Tao This is my paper

Pith reviewed 2026-05-24 11:59 UTC · model grok-4.3

classification ❄️ cond-mat.mtrl-sci
keywords halide perovskitesCsPbI3surface stabilitygrain boundariesmolecular dynamicsdegradation mechanismoctahedra geometryReaxFF
0
0 comments X

The pith

Reactive MD simulations show CsPbI3 surfaces degrade by shifting PbIx octahedra from corner- to edge- to face-sharing, driven by Pb dangling bonds.

A machine-rendered reading of the paper's core claim, the machinery that carries it, and where it could break.

Halide perovskite solar cells suffer from poor long-term stability partly because of degradation at surfaces and grain boundaries in real polycrystalline films. This work runs reactive force field molecular dynamics on CsPbI3 to map how different surface terminations and defects evolve over time. The simulations produce a clear stability ranking that lines up with which surfaces are seen in experiments, and they trace degradation to a progressive change in how PbIx octahedra share corners, edges, or faces. Two key triggers emerge: exposed Pb dangling bonds and the easy movement of iodine atoms that lack steric protection. The same simulations show that while extra point defects usually worsen stability, certain grain boundaries can improve it by adding steric hindrance.

Core claim

Our simulations establish a stability trend for a variety of surfaces, which correlates well with the occurrence of these surfaces in experiments. We find that a perovskite surface degrades by progressively changing the local geometry of PbIx octahedra from corner- to edge- to face-sharing. Importantly, we find that Pb dangling bonds and the lack of steric hindrance of I species are two crucial factors that induce degradation reactions. Finally, we show that the stability of these surfaces can be modulated by adjusting their atomistic details, either by creating additional point defects or merging them to form grain boundaries. While in general additional defects, particularly when clustered

What carries the argument

ReaxFF reactive molecular dynamics tracking the evolution of PbIx octahedra sharing geometry at surfaces, surface defects, and grain boundaries.

If this is right

  • Surfaces with fewer Pb dangling bonds and greater steric hindrance around I are more stable.
  • Degradation follows a repeatable sequence of octahedra geometry changes rather than random bond breaking.
  • Merging surfaces into certain grain boundaries can raise stability through added steric effects.
  • Clustered point defects generally accelerate degradation compared with isolated defects.
  • Stability trends from the simulations match which surfaces are observed experimentally.

Where Pith is reading between the lines

These are editorial extensions of the paper, not claims the author makes directly.

  • Surface engineering that targets Pb dangling bonds could extend operational lifetime without eliminating all defects.
  • Grain-boundary design rules derived here might transfer to other inorganic halide perovskites with similar octahedra networks.
  • Early-stage monitoring of octahedra coordination changes could serve as an experimental signature for impending surface failure.
  • The steric-hindrance mechanism suggests that bulky passivating molecules at surfaces may mimic the stabilizing effect of some grain boundaries.

Load-bearing premise

The ReaxFF reactive force field parameters accurately capture the bond-breaking and bond-forming events that drive surface degradation in CsPbI3 under the simulated conditions.

What would settle it

Direct experimental measurement of the predicted surface stability order or spectroscopic detection of edge- and face-sharing PbIx units appearing before bulk degradation in CsPbI3 films.

Figures

Figures reproduced from arXiv: 2205.10545 by Adri C.T. van Duin, Ivo Filot, Mike Pols, Shuxia Tao, Sof\'ia Calero, Tobias Hilpert.

Figure 1
Figure 1. Figure 1: Additional details of the surface models can be found in Supporting Note 1. [PITH_FULL_IMAGE:figures/full_fig_p005_1.png] view at source ↗
Figure 1
Figure 1. Figure 1: Structural models of the different surface orientations for orthorhombic CsPbI [PITH_FULL_IMAGE:figures/full_fig_p006_1.png] view at source ↗
Figure 2
Figure 2. Figure 2: Time-averaged values of the Pb-I-Pb valence angle ( [PITH_FULL_IMAGE:figures/full_fig_p007_2.png] view at source ↗
Figure 3
Figure 3. Figure 3: Degradation of a (110) orthorhombic perovskite surface at 600 K, with the Pb-rich [PITH_FULL_IMAGE:figures/full_fig_p010_3.png] view at source ↗
Figure 4
Figure 4. Figure 4: In the first step of the degradation process, an iodine Frenkel defect is formed in [PITH_FULL_IMAGE:figures/full_fig_p010_4.png] view at source ↗
Figure 4
Figure 4. Figure 4: Snapshots of the degradation of a Pb-rich (110) orthorhombic perovskite surface. [PITH_FULL_IMAGE:figures/full_fig_p012_4.png] view at source ↗
Figure 5
Figure 5. Figure 5: Snapshots of different point defects in CsPbI [PITH_FULL_IMAGE:figures/full_fig_p014_5.png] view at source ↗
Figure 6
Figure 6. Figure 6: Dynamical evolution of the CsPbI3 grain boundaries at 600 K after 200 ps from their initial structure. (a) 3Σ(112)(0.4, 0) grain boundary. (b) 5Σ(210)(0.4, 0) grain bound￾ary. (c) 3Σ(111)(0, 0) grain boundary. The blue areas highlight the grain boundaries in the structures. Note 8. Careful inspections point to a general mechanism in which the degradation is initi￾ated by the movement of iodine atoms near t… view at source ↗
Figure 7
Figure 7. Figure 7: Degradation of a 5Σ(210)(0.4, 0) grain boundary. (a-c) The degradation initiates at the grain boundary and (d-f) proceeds into the bulk of the perovskite. The blue areas in the figures highlight the grain boundary. 3 Conclusion In summary, using a ReaxFF force field, we study structural and thermal stability effects of surfaces and grain boundaries in the inorganic halide perovskite CsPbI3 . We show that s… view at source ↗
read the original abstract

The commercialization of perovskite solar cells is hindered by the poor long-term stability of the metal halide perovskite (MHP) light absorbing layer. Solution processing, the common fabrication method for MHPs, produces polycrystalline films with a wide variety of defects, such as point defects, surfaces, and grain boundaries. Although the optoelectronic effects of such defects have been widely studied, the evaluation of their impact on the long-term stability remains challenging. In particular, an understanding of the dynamics of degradation reactions at the atomistic scale is lacking. In this work, using reactive force field (ReaxFF) molecular dynamics simulations, we investigate the effects of defects, in the forms of surfaces, surface defects and grain boundaries, on the stability of the inorganic halide perovskite CsPbI$_{3}$. Our simulations establish a stability trend for a variety of surfaces, which correlates well with the occurrence of these surfaces in experiments. We find that a perovskite surface degrades by progressively changing the local geometry of PbI$_{\mathrm{x}}$ octahedra from corner- to edge- to face-sharing. Importantly, we find that Pb dangling bonds and the lack of steric hindrance of I species are two crucial factors that induce degradation reactions. Finally, we show that the stability of these surfaces can be modulated by adjusting their atomistic details, either by creating additional point defects or merging them to form grain boundaries. While in general additional defects, particularly when clustered, have a negative impact on the material stability, some grain boundaries have a stabilizing effect, primarily because of the additional steric hindrance.

Editorial analysis

A structured set of objections, weighed in public.

Desk editor's note, referee report, simulated authors' rebuttal, and a circularity audit. Tearing a paper down is the easy half of reading it; the pith above is the substance, this is the friction.

Referee Report

2 major / 2 minor

Summary. The manuscript uses reactive molecular dynamics simulations with a ReaxFF force field to investigate the stability of surfaces, surface defects, and grain boundaries in CsPbI3. It reports a stability ordering of surfaces that correlates with their experimental occurrence, a degradation mechanism in which PbIx octahedra progressively shift from corner- to edge- to face-sharing, the key roles of Pb dangling bonds and insufficient I steric hindrance in triggering reactions, and the finding that certain grain boundaries can stabilize the material while clustered point defects generally reduce stability.

Significance. If the underlying force field is reliable for the relevant bond rearrangements, the work supplies atomistic mechanistic detail on how common defects control long-term degradation in halide perovskites, an issue central to device lifetime. The explicit linkage of computed stability trends to independent experimental surface statistics is a positive feature.

major comments (2)
  1. [Methods] Methods section: The ReaxFF parameters for Pb-I-Cs interactions are adopted from earlier parametrizations without any new benchmarking or direct comparison to DFT (or experiment) for the surface-specific bond-breaking/forming events, relative stabilities of corner/edge/face-sharing PbIx configurations, or defect-induced energetics that underpin the reported stability ordering and degradation pathway. Because all mechanistic conclusions and the experimental correlation rest exclusively on these trajectories, the transferability assumption is load-bearing.
  2. [Results (stability trend)] Stability-trend results: No error bars, standard deviations from replicate trajectories, or convergence diagnostics are provided for the surface stability metrics or the ordering itself; without these, it is impossible to judge whether the claimed correlation with experimental surface occurrence is statistically robust.
minor comments (2)
  1. [Abstract] The abstract states that 'a variety of surfaces' were examined but does not enumerate them; an explicit list (with Miller indices) should appear in the abstract or early results section.
  2. [Throughout] Notation for the octahedra is inconsistent (PbI_x vs. PbIx vs. PbI$ x $); a single convention should be adopted throughout.

Simulated Author's Rebuttal

2 responses · 0 unresolved

We thank the referee for their constructive report and positive assessment of the work's significance. We address each major comment below, indicating planned revisions where appropriate.

read point-by-point responses

  1. Referee: [Methods] Methods section: The ReaxFF parameters for Pb-I-Cs interactions are adopted from earlier parametrizations without any new benchmarking or direct comparison to DFT (or experiment) for the surface-specific bond-breaking/forming events, relative stabilities of corner/edge/face-sharing PbIx configurations, or defect-induced energetics that underpin the reported stability ordering and degradation pathway. Because all mechanistic conclusions and the experimental correlation rest exclusively on these trajectories, the transferability assumption is load-bearing.

    Authors: We acknowledge that this manuscript adopts the ReaxFF parameters from our prior publications without performing additional DFT benchmarking specific to the surface and grain-boundary configurations studied here. Those earlier works validated the force field against DFT and experimental data for bulk CsPbI3 structural properties, Pb-I bond dissociation, and related reaction energetics. The degradation mechanisms observed (corner-to-edge-to-face sharing transitions) are consistent with known chemistry in halide perovskites. In revision we will expand the Methods section with a dedicated paragraph summarizing the prior validation metrics most relevant to bond rearrangement and surface stability, thereby making the transferability argument more explicit without new calculations. revision: partial

  2. Referee: [Results (stability trend)] Stability-trend results: No error bars, standard deviations from replicate trajectories, or convergence diagnostics are provided for the surface stability metrics or the ordering itself; without these, it is impossible to judge whether the claimed correlation with experimental surface occurrence is statistically robust.

    Authors: The stability ordering is based on the consistent observation, across independent trajectories, of whether and how rapidly each surface begins to reconstruct via the PbIx reconfiguration mechanism. Because the experimental comparison is itself qualitative (frequency of surface terminations reported in the literature), we did not compute numerical error bars on onset times. We agree that adding a statement on reproducibility would strengthen the presentation. In revision we will include a short paragraph noting that the same ordering and mechanism were recovered in multiple independent runs started from different initial velocities, and we will reference the supplementary trajectories that demonstrate this consistency. revision: partial

Circularity Check

0 steps flagged

No significant circularity; results are simulation outputs benchmarked externally

full rationale

The paper reports stability trends, degradation pathways, and defect effects extracted from ReaxFF MD trajectories on CsPbI3 surfaces and grain boundaries. These are direct outputs of applying an existing force-field model (developed in prior work) to the target system, then compared against independent experimental observations of surface occurrence. No equations, fitted parameters, or self-citations within this manuscript reduce the reported ordering, mechanism, or mechanistic factors to quantities defined or optimized inside the same study. The derivation chain is therefore self-contained against external benchmarks.

Axiom & Free-Parameter Ledger

1 free parameters · 1 axioms · 0 invented entities

The central claims rest on the transferability of an existing ReaxFF parameter set to CsPbI3 surface chemistry and on the assumption that nanosecond-scale MD trajectories capture the relevant degradation kinetics.

free parameters (1)
  • ReaxFF parameters for Pb-I-Cs interactions
    Fitted in prior literature; their accuracy for bond rearrangement at surfaces is a load-bearing input not re-derived here.
axioms (1)
  • domain assumption Classical reactive force-field MD sufficiently reproduces quantum-mechanical bond-breaking energetics at perovskite surfaces
    Invoked when interpreting octahedra reconfiguration as the degradation driver.

pith-pipeline@v0.9.0 · 5846 in / 1414 out tokens · 20069 ms · 2026-05-24T11:59:31.647195+00:00 · methodology

discussion (0)

Sign in with ORCID, Apple, or X to comment. Anyone can read and Pith papers without signing in.

Reference graph

Works this paper leans on

74 extracted references · 74 canonical work pages

  1. [1]

    Perovskite Solar Cell with an Efficient TiO2 Compact Film

    Ke, W.; Fang, G.; Wang, J.; Qin, P.; Tao, H.; Lei, H.; Liu, Q.; Dai, X.; Zhao, X. Perovskite Solar Cell with an Efficient TiO2 Compact Film. ACS Appl. Mater. Interfaces 2014, 6, 15959--15965

    work page 2014

  2. [2]

    Y.; Lee, J.-W.; Jung, H

    Kim, J. Y.; Lee, J.-W.; Jung, H. S.; Shin, H.; Park, N.-G. High-Efficiency Perovskite Solar Cells. Chem. Rev. 2020, 120, 7867--7918

    work page 2020

  3. [3]

    W.; Kim, S

    Van Le, Q.; Jang, H. W.; Kim, S. Y. Recent Advances Toward High-Efficiency Halide Perovskite Light-Emitting Diodes: Review and Perspective. Small Methods 2018, 2, 1700419

    work page 2018

  4. [4]

    Efficient Pure Blue Light-Emitting Diodes Based on CsPbBr3 Quantum-Confined Nanoplates

    Shen, W.; Yu, Y.; Zhang, W.; Chen, Y.; Zhang, J.; Yang, L.; Feng, J.; Cheng, G.; Liu, L.; Chen, S. Efficient Pure Blue Light-Emitting Diodes Based on CsPbBr3 Quantum-Confined Nanoplates. ACS Appl. Mater. Interfaces 2022, 14, 5682--5691

    work page 2022

  5. [5]

    Hybrid Halide Perovskite Solar Cell Precursors: Colloidal Chemistry and Coordination Engineering Behind Device Processing for High Efficiency

    Yan, K.; Long, M.; Zhang, T.; Wei, Z.; Chen, H.; Yang, S.; Xu, J. Hybrid Halide Perovskite Solar Cell Precursors: Colloidal Chemistry and Coordination Engineering Behind Device Processing for High Efficiency. J. Am. Chem. Soc. 2015, 137, 4460--4468

    work page 2015

  6. [6]

    K.; Moore, D

    Nayak, P. K.; Moore, D. T.; Wenger, B.; Nayak, S.; Haghighirad, A. A.; Fineberg, A.; Noel, N. K.; Reid, O. G.; Rumbles, G.; Kukura, P.; Vincent, K. A.; Snaith, H. J. Mechanism for Rapid Growth of Organic-Inorganic Halide Perovskite Crystals. Nat. Commun. 2016, 7, 13303

    work page 2016

  7. [7]

    P.; Wang, Z.; Rehman, W.; Pulvirenti, F.; Patel, J

    McMeekin, D. P.; Wang, Z.; Rehman, W.; Pulvirenti, F.; Patel, J. B.; Noel, N. K.; Johnston, M. B.; Marder, S. R.; Herz, L. M.; Snaith, H. J. Crystallization Kinetics and Morphology Control of Formamidinium-Cesium Mixed-Cation Lead Mixed-Halide Perovskite via Tunability of the Colloidal Precursor Solution. Adv. Mater. 2017, 29, 1607039

    work page 2017

  8. [8]

    A.; Hoell, A.; Wendt, R.; H \"a rk, E.; Dallmann, A.; Prause, A.; Pascual, J.; Unger, E.; Abate, A

    Flatken, M. A.; Hoell, A.; Wendt, R.; H \"a rk, E.; Dallmann, A.; Prause, A.; Pascual, J.; Unger, E.; Abate, A. Small-Angle Scattering to Reveal the Colloidal Nature of Halide Perovskite Precursor Solutions. J. Mater. Chem. A 2021, 9, 13477--13482

    work page 2021

  9. [9]

    M.; Petrozza, A

    Ball, J. M.; Petrozza, A. Defects in Perovskite-Halides and Their Effects in Solar Cells. Nat. Energy 2016, 1, 1--13

    work page 2016

  10. [10]

    K.; Liu, S

    Ono, L. K.; Liu, S. F.; Qi, Y. Reducing Detrimental Defects for High-Performance Metal Halide Perovskite Solar Cells. Angew. Chem. Int. Edit. 2020, 59, 6676--6698

    work page 2020

  11. [11]

    High Defect Tolerance in Lead Halide Perovskite CsPbBr3

    Kang, J.; Wang, L.-W. High Defect Tolerance in Lead Halide Perovskite CsPbBr3 . J. Phys. Chem. Lett. 2017, 8, 489--493

    work page 2017

  12. [12]

    A.; Zhao, J.; Prezhdo, O

    Chu, W.; Saidi, W. A.; Zhao, J.; Prezhdo, O. V. Soft Lattice and Defect Covalency Rationalize Tolerance of - CsPbI3 Perovskite Solar Cells to Native Defects. Angew. Chem. Int. Edit. 2020, 59, 6435--6441

    work page 2020

  13. [13]

    Intrinsic Defects in Primary Halide Perovskites: A First-Principles Study of the Thermodynamic Trends

    Xue, H.; Brocks, G.; Tao, S. Intrinsic Defects in Primary Halide Perovskites: A First-Principles Study of the Thermodynamic Trends. Phys. Rev. Mater. 2022, 6, 055402

    work page 2022

  14. [14]

    Termination Dependence of Tetragonal CH3NH3PbI3 Surfaces for Perovskite Solar Cells

    Haruyama, J.; Sodeyama, K.; Han, L.; Tateyama, Y. Termination Dependence of Tetragonal CH3NH3PbI3 Surfaces for Perovskite Solar Cells. J. Phys. Chem. Lett. 2014, 5, 2903--2909

    work page 2014

  15. [15]

    Surface Properties of CH3NH3PbI3 for Perovskite Solar Cells

    Haruyama, J.; Sodeyama, K.; Han, L.; Tateyama, Y. Surface Properties of CH3NH3PbI3 for Perovskite Solar Cells. Acc. Chem. Res. 2016, 49, 554--561

    work page 2016

  16. [16]

    Guo, Y.; Wang, Q.; Saidi, W. A. Structural Stabilities and Electronic Properties of High-Angle Grain Boundaries in Perovskite Cesium Lead Halides. J. Phys. Chem. C 2017, 121, 1715--1722

    work page 2017

  17. [17]

    Shan, W.; Saidi, W. A. Segregation of Native Defects to the Grain Boundaries in Methylammonium Lead Iodide Perovskite. J. Phys. Chem. Lett. 2017, 8, 5935--5942

    work page 2017

  18. [18]

    McKenna, K. P. Electronic Properties of \ 111\ Twin Boundaries in a Mixed-Ion Lead Halide Perovskite Solar Absorber. ACS Energy Lett. 2018, 3, 2663--2668

    work page 2018

  19. [19]

    U.; Jia, Y.; Gao, C.; Hao, M.; Pang, S.; Wang, P.; Lau, S

    Cai, S.; Dai, J.; Shao, Z.; Rothmann, M. U.; Jia, Y.; Gao, C.; Hao, M.; Pang, S.; Wang, P.; Lau, S. P.; Zhu, K.; Berry, J. J.; Herz, L. M.; Zeng, X. C.; Zhou, Y. Atomically Resolved Electrically Active Intragrain Interfaces in Perovskite Semiconductors. J. Am. Chem. Soc. 2022, 144, 1910--1920

    work page 2022

  20. [20]

    D.; Walsh, A

    Park, J.-S.; Calbo, J.; Jung, Y.-K.; Whalley, L. D.; Walsh, A. Accumulation of Deep Traps at Grain Boundaries in Halide Perovskites. ACS Energy Lett. 2019, 4, 1321--1327

    work page 2019

  21. [21]

    L.; Merdasa, A.; Abate, A

    Phung, N.; Al-Ashouri , A.; Meloni, S.; Mattoni, A.; Albrecht, S.; Unger, E. L.; Merdasa, A.; Abate, A. The Role of Grain Boundaries on Ionic Defect Migration in Metal Halide Perovskites. Adv. Energy Mater. 2020, 10, 1903735

    work page 2020

  22. [22]

    U.; Di Giacomo, F.; Matteocci, F.; Smith, J

    Di Girolamo, D.; Phung, N.; Kosasih, F. U.; Di Giacomo, F.; Matteocci, F.; Smith, J. A.; Flatken, M. A.; K \"o bler, H.; Turren Cruz, S. H.; Mattoni, A.; Cin \`a , L.; Rech, B.; Latini, A.; Divitini, G.; Ducati, C.; Di Carlo, A.; Dini, D.; Abate, A. Ion Migration-Induced Amorphization and Phase Segregation as a Degradation Mechanism in Planar Perovskite S...

    work page 2020

  23. [23]

    K.; Scheel, M

    Guo, R.; Han, D.; Chen, W.; Dai, L.; Ji, K.; Xiong, Q.; Li, S.; Reb, L. K.; Scheel, M. A.; Pratap, S.; Li, N.; Yin, S.; Xiao, T.; Liang, S.; Oechsle, A. L.; Weindl, C. L.; Schwartzkopf, M.; Ebert, H.; Gao, P.; Wang, K.; Yuan, M.; Greenham, N. C.; Stranks, S. D.; Roth, S. V.; Friend, R. H.; M \"u ller-Buschbaum , P. Degradation Mechanisms of Perovskite Sol...

    work page 2021

  24. [24]

    D.; Boyen, H.-G

    Conings, B.; Drijkoningen, J.; Gauquelin, N.; Babayigit, A.; D'Haen, J.; D'Olieslaeger, L.; Ethirajan, A.; Verbeeck, J.; Manca, J.; Mosconi, E.; Angelis, F. D.; Boyen, H.-G. Intrinsic Thermal Instability of Methylammonium Lead Trihalide Perovskite. Adv. Energy. Mater. 2015, 5, 1500477

    work page 2015

  25. [25]

    A.; Huang, Y.; Duan, X

    Fan, Z.; Xiao, H.; Wang, Y.; Zhao, Z.; Lin, Z.; Cheng, H.-C.; Lee, S.-J.; Wang, G.; Feng, Z.; Goddard, W. A.; Huang, Y.; Duan, X. Layer-by-Layer Degradation of Methylammonium Lead Tri-Iodide Perovskite Microplates. Joule 2017, 1, 548--562

    work page 2017

  26. [26]

    Comprehensive Understanding of Heat-Induced Degradation of Triple-Cation Mixed Halide Perovskite for a Robust Solar Cell

    Yang, J.; Liu, X.; Zhang, Y.; Zheng, X.; He, X.; Wang, H.; Yue, F.; Braun, S.; Chen, J.; Xu, J.; Li, Y.; Jin, Y.; Tang, J.; Duan, C.; Fahlman, M.; Bao, Q. Comprehensive Understanding of Heat-Induced Degradation of Triple-Cation Mixed Halide Perovskite for a Robust Solar Cell. Nano Energy 2018, 54, 218--226

    work page 2018

  27. [27]

    Pb Clustering and PbI2 Nanofragmentation During Methylammonium Lead Iodide Perovskite Degradation

    Alberti, A.; Bongiorno, C.; Smecca, E.; Deretzis, I.; La Magna, A.; Spinella, C. Pb Clustering and PbI2 Nanofragmentation During Methylammonium Lead Iodide Perovskite Degradation. Nat. Commun. 2019, 10, 2196

    work page 2019

  28. [28]

    Decisive Influence of Amorphous PbI_ 2-x on the Photodegradation of Halide Perovskites

    Lu, Y.; Hu, J.; Ge, Y.; Tian, B.; Zhang, Z.; Sui, M. Decisive Influence of Amorphous PbI_ 2-x on the Photodegradation of Halide Perovskites. J. Mater. Chem. A 2021, 9, 15059--15067

    work page 2021

  29. [29]

    Observation of Structural Phase Transitions and PbI2 Formation During the Degradation of Triple-Cation Double-Halide Perovskites

    Manekkathodi, A.; Marzouk, A.; Ponraj, J.; Belaidi, A.; Ashhab, S. Observation of Structural Phase Transitions and PbI2 Formation During the Degradation of Triple-Cation Double-Halide Perovskites. ACS Appl. Energy Mater. 2020, 3, 6302--6309

    work page 2020

  30. [30]

    M.; Grätzel, M.; Hagfeldt, A

    Lu, H.; Krishna, A.; Zakeeruddin, S. M.; Grätzel, M.; Hagfeldt, A. Compositional and Interface Engineering of Organic-Inorganic Lead Halide Perovskite Solar Cells. iScience 2020, 23, 101359

    work page 2020

  31. [31]

    K.-Y.; Wang, H.-L

    Yen, H.-J.; Liang, P.-W.; Chueh, C.-C.; Yang, Z.; Jen, A. K.-Y.; Wang, H.-L. Large Grained Perovskite Solar Cells Derived from Single-Crystal Perovskite Powders with Enhanced Ambient Stability. ACS Appl. Mater. Interfaces 2016, 8, 14513--14520

    work page 2016

  32. [32]

    M.; Steiner, U.; Gr \"a tzel, M.; Abate, A

    Seo, J.-Y.; Matsui, T.; Luo, J.; Correa-Baena , J.-P.; Giordano, F.; Saliba, M.; Schenk, K.; Ummadisingu, A.; Domanski, K.; Hadadian, M.; Hagfeldt, A.; Zakeeruddin, S. M.; Steiner, U.; Gr \"a tzel, M.; Abate, A. Ionic Liquid Control Crystal Growth to Enhance Planar Perovskite Solar Cells Efficiency. Adv. Energy Mater. 2016, 6, 1600767

    work page 2016

  33. [33]

    M.; Filot, I.; van Duin, A

    Pols, M.; Vicent-Luna, J. M.; Filot, I.; van Duin, A. C. T.; Tao, S. Atomistic Insights Into the Degradation of Inorganic Halide Perovskite CsPbI3 : A Reactive Force Field Molecular Dynamics Study. J. Phys. Chem. Lett. 2021, 12, 5519--5525

    work page 2021

  34. [34]

    van Duin , A. C. T.; Dasgupta, S.; Lorant, F.; Goddard, W. A. ReaxFF: A Reactive Force Field for Hydrocarbons. J. Phys. Chem. A 2001, 105, 9396--9409

    work page 2001

  35. [35]

    Chenoweth, K.; van Duin , A. C. T.; Persson, P.; Cheng, M.-J.; Oxgaard, J.; Goddard, W. A. Development and Application of a ReaxFF Reactive Force Field for Oxidative Dehydrogenation on Vanadium Oxide Catalysts. J. Phys. Chem. C 2008, 112, 14645--14654

    work page 2008

  36. [36]

    P.; Hong, S.; Islam, M

    Senftle, T. P.; Hong, S.; Islam, M. M.; Kylasa, S. B.; Zheng, Y.; Shin, Y. K.; Junkermeier, C.; Engel-Herbert , R.; Janik, M. J.; Aktulga, H. M.; Verstraelen, T.; Grama, A.; van Duin , A. C. T. The ReaxFF Reactive Force-Field : Development, Applications and Future Directions. npj Comput. Mater. 2016, 2, 1--14

    work page 2016

  37. [37]

    J.; Filip, M

    Sutton, R. J.; Filip, M. R.; Haghighirad, A. A.; Sakai, N.; Wenger, B.; Giustino, F.; Snaith, H. J. Cubic or Orthorhombic? Revealing the Crystal Structure of Metastable Black-Phase CsPbI3 by Theory and Experiment. ACS Energy Lett. 2018, 3, 1787--1794

    work page 2018

  38. [38]

    E.; Paternò, G

    Eperon, G. E.; Paternò, G. M.; Sutton, R. J.; Zampetti, A.; Haghighirad, A. A.; Cacialli, F.; Snaith, H. J. Inorganic Caesium Lead Iodide Perovskite Solar Cells. J. Mater. Chem. A 2015, 3, 19688--19695

    work page 2015

  39. [39]

    A.; Yi, H.; Wang, D.; Duan, L.; Xu, C.; Upama, M

    Haque, F.; Wright, M.; Mahmud, M. A.; Yi, H.; Wang, D.; Duan, L.; Xu, C.; Upama, M. B.; Uddin, A. Effects of Hydroiodic Acid Concentration on the Properties of CsPbI3 Perovskite Solar Cells. ACS Omega 2018, 3, 11937--11944

    work page 2018

  40. [40]

    Liu, T.; Zhang, J.; Qin, M.; Wu, X.; Li, F.; Lu, X.; Zhu, Z.; Jen, A. K.-Y. Modifying Surface Termination of CsPbI3 Grain Boundaries by 2D Perovskite Layer for Efficient and Stable Photovoltaics. Adv. Funct. Mater. 2021, 31, 2009515

    work page 2021

  41. [41]

    C.; Kanatzidis, M

    Marronnier, A.; Roma, G.; Boyer-Richard , S.; Pedesseau, L.; Jancu, J.-M.; Bonnassieux, Y.; Katan, C.; Stoumpos, C. C.; Kanatzidis, M. G.; Even, J. Anharmonicity and Disorder in the Black Phases of Cesium Lead Iodide Used for Stable Inorganic Perovskite Solar Cells. ACS Nano 2018, 12, 3477--3486

    work page 2018

  42. [42]

    T.; Liu, J.; Gaulding, E

    Zhao, Q.; Hazarika, A.; Schelhas, L. T.; Liu, J.; Gaulding, E. A.; Li, G.; Zhang, M.; Toney, M. F.; Sercel, P. C.; Luther, J. M. Size-Dependent Lattice Structure and Confinement Properties in CsPbI3 Perovskite Nanocrystals: Negative Surface Energy for Stabilization. ACS Energy Lett. 2020, 5, 238--247

    work page 2020

  43. [43]

    B.; Guo, S.; Abeykoon, A

    Straus, D. B.; Guo, S.; Abeykoon, A. M.; Cava, R. J. Understanding the Instability of the Halide Perovskite CsPbI3 through Temperature-Dependent Structural Analysis. Adv. Mater. 2020, 32, 2001069

    work page 2020

  44. [44]

    Enhancing Stability and Photostability of CsPbI3 by Reducing Its Dimensionality

    Shpatz Dayan, A.; Cohen, B.-E.; Aharon, S.; Tenailleau, C.; Wierzbowska, M.; Etgar, L. Enhancing Stability and Photostability of CsPbI3 by Reducing Its Dimensionality. Chem. Mater. 2018, 30, 8017--8024

    work page 2018

  45. [45]

    C.; Malliakas, C

    Stoumpos, C. C.; Malliakas, C. D.; Kanatzidis, M. G. Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties. Inorg. Chem. 2013, 52, 9019--9038

    work page 2013

  46. [46]

    Formation of Surface Defects Dominates Ion Migration in Lead-Halide Perovskites

    Meggiolaro, D.; Mosconi, E.; De Angelis, F. Formation of Surface Defects Dominates Ion Migration in Lead-Halide Perovskites . ACS Energy Lett. 2019, 4, 779--785

    work page 2019

  47. [47]

    G.; Huang, J.; Zhang, H.; Liu, P.; Yang, H.; Zhao, H

    Wang, Y.; Sumpter, B. G.; Huang, J.; Zhang, H.; Liu, P.; Yang, H.; Zhao, H. Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3 . J. Phys. Chem. C 2015, 119, 1136--1145

    work page 2015

  48. [48]

    Effect of Surface Intrinsic Defects on the Structural Stability and Electronic Properties of the All-Inorganic Halide Perovskite CsPbI3 (001) Film

    Long, L.; Cao, D.; Fei, J.; Wang, J.; Zhou, Y.; Jiang, Z.; Jiao, Z.; Shu, H. Effect of Surface Intrinsic Defects on the Structural Stability and Electronic Properties of the All-Inorganic Halide Perovskite CsPbI3 (001) Film. Chem. Phys. Lett. 2019, 734, 136719

    work page 2019

  49. [49]

    The Dominant Role of Surfaces in the Hysteretic Behavior of Hybrid Perovskites

    Caddeo, C.; Filippetti, A.; Mattoni, A. The Dominant Role of Surfaces in the Hysteretic Behavior of Hybrid Perovskites. Nano Energy 2020, 67, 104162

    work page 2020

  50. [50]

    Li, N.; Tao, S.; Chen, Y.; Niu, X.; Onwudinanti, C. K.; Hu, C.; Qiu, Z.; Xu, Z.; Zheng, G.; Wang, L.; Zhang, Y.; Li, L.; Liu, H.; Lun, Y.; Hong, J.; Wang, X.; Liu, Y.; Xie, H.; Gao, Y.; Bai, Y.; Yang, S.; Brocks, G.; Chen, Q.; Zhou, H. Cation and Anion Immobilization Through Chemical Bonding Enhancement with Fluorides for Stable Halide Perovskite Solar Ce...

    work page 2019

  51. [51]

    C.; Kanda, H.; Abuhelaiqa, M.; Shibayama, N.; Luo, W.; Li, M.; Tirani, F

    Gao, X.-X.; Ding, B.; Zhang, Y.; Zhang, S.; Turnell-Ritson , R. C.; Kanda, H.; Abuhelaiqa, M.; Shibayama, N.; Luo, W.; Li, M.; Tirani, F. F.; Scopelliti, R.; Kinge, S.; Z \"u ttel, A.; Zhu, D.; Zhang, B.; Feng, Y.; Fei, Z.; Nazeeruddin, M. K.; Dyson, P. J. Halide Exchange in the Passivation of Perovskite Solar Cells with Functionalized Ionic Liquids. Cell...

    work page 2022

  52. [52]

    J.; Agarwalla, A.; Kim, H.-S.; Prochowicz, D.; Borris \'e , X.; Bonn, M.; Bao, C.; Sun, X.; Zakeeruddin, S

    Xie, H.; Wang, Z.; Chen, Z.; Pereyra, C.; Pols, M.; Ga kowski, K.; Anaya, M.; Fu, S.; Jia, X.; Tang, P.; Kubicki, D. J.; Agarwalla, A.; Kim, H.-S.; Prochowicz, D.; Borris \'e , X.; Bonn, M.; Bao, C.; Sun, X.; Zakeeruddin, S. M.; Emsley, L.; Arbiol, J.; Gao, F.; Fu, F.; Wang, H. I.; Tielrooij, K.-J.; Stranks, S. D.; Tao, S.; Gr \"a tzel, M.; Hagfeldt, A.; ...

    work page 2021

  53. [53]

    Stable Perovskite Solar Cells with Bulk-Mixed Electron Transport Layer by Multifunctional Defect Passivation

    Ma, N.; Jiang, J.; Wang, G.; Wang, D.; Zhang, Y.; Wang, Y.; Wang, Y.; Ji, Y.; Wei, W.; Shen, L. Stable Perovskite Solar Cells with Bulk-Mixed Electron Transport Layer by Multifunctional Defect Passivation. ACS Appl. Mater. Interfaces 2021, 13, 44401--44408

    work page 2021

  54. [54]

    Phenylalkylammonium Passivation Enables Perovskite Light Emitting Diodes with Record High-Radiance Operational Lifetime: The Chain Length Matters

    Guo, Y.; Apergi, S.; Li, N.; Chen, M.; Yin, C.; Yuan, Z.; Gao, F.; Xie, F.; Brocks, G.; Tao, S.; Zhao, N. Phenylalkylammonium Passivation Enables Perovskite Light Emitting Diodes with Record High-Radiance Operational Lifetime: The Chain Length Matters. Nature Commun. 2021, 12, 644

    work page 2021

  55. [55]

    Efficient and Stable CsPbI3 Solar Cells via Regulating Lattice Distortion with Surface Organic Terminal Groups

    Wu, T.; Wang, Y.; Dai, Z.; Cui, D.; Wang, T.; Meng, X.; Bi, E.; Yang, X.; Han, L. Efficient and Stable CsPbI3 Solar Cells via Regulating Lattice Distortion with Surface Organic Terminal Groups. Adv. Mater. 2019, 31, 1900605

    work page 2019

  56. [56]

    J.; Girard, J.; Sorenson, B

    Foley, B. J.; Girard, J.; Sorenson, B. A.; Chen, A. Z.; Niezgoda, J. S.; Alpert, M. R.; Harper, A. F.; Smilgies, D.-M.; Clancy, P.; Saidi, W. A.; Choi, J. J. Controlling Nucleation, Growth, and Orientation of Metal Halide Perovskite Thin Films with Rationally Selected Additives. J. Mater. Chem. A 2016, 5, 113--123

    work page 2016

  57. [57]

    Controlled Growth of Large Grains in CH3NHPbI3 Perovskite Films Mediated by an Intermediate Liquid Phase Without an Antisolvent for Efficient Solar Cells

    Peter Amalathas, A.; Landov \'a , L.; H \'a jkov \'a , Z.; Hor \'a k, L.; Ledinsky, M.; Holovsk \'y , J. Controlled Growth of Large Grains in CH3NHPbI3 Perovskite Films Mediated by an Intermediate Liquid Phase Without an Antisolvent for Efficient Solar Cells. ACS Appl. Energy Mater. 2020, 3, 12484--12493

    work page 2020

  58. [58]

    A.; Syzgantseva, M

    Yang, Y.; Liu, C.; Syzgantseva, O. A.; Syzgantseva, M. A.; Ma, S.; Ding, Y.; Cai, M.; Liu, X.; Dai, S.; Nazeeruddin, M. K. Defect Suppression in Oriented 2D Perovskite Solar Cells with Efficiency over 18\ Crystallization Pathway. Adv. Energy Mater. 2021, 11, 2002966

    work page 2021

  59. [59]

    AMS 2021, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands , http://www.scm.com/

    work page 2021

  60. [60]

    Visualization and Analysis of Atomistic Simulation Data with OVITO - The Open Visualization Tool

    Stukowski, A. Visualization and Analysis of Atomistic Simulation Data with OVITO - The Open Visualization Tool. Modelling Simul. Mater. Sci. Eng. 2009, 18, 015012

    work page 2009

  61. [61]

    Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren , W. F.; DiNola, A.; Haak, J. R. Molecular Dynamics with Coupling to an External Bath. J. Chem. Phys. 1984, 81, 3684--3690

    work page 1984

  62. [62]

    J.; Klein, M

    Martyna, G. J.; Klein, M. L.; Tuckerman, M. Nos\'e Hoover Chains: The Canonical Ensemble via Continuous Dynamics. J. Chem. Phys. 1992, 97, 2635--2643

    work page 1992

  63. [63]

    J.; Tobias, D

    Martyna, G. J.; Tobias, D. J.; Klein, M. L. Constant Pressure Molecular Dynamics Algorithms. J. Chem. Phys. 1994, 101, 4177--4189

    work page 1994

  64. [64]

    Ab Initio Molecular-Dynamics Simulation of the Liquid-Metal--Amorphous-Semiconductor Transition in Germanium

    Kresse, G.; Hafner, J. Ab Initio Molecular-Dynamics Simulation of the Liquid-Metal--Amorphous-Semiconductor Transition in Germanium. Phys. Rev. B 1994, 49, 14251--14269

    work page 1994

  65. [65]

    Efficiency of Ab-Initio Total Energy Calculations for Metals and Semiconductors Using a Plane-Wave Basis Set

    Kresse, G.; Furthm \"u ller, J. Efficiency of Ab-Initio Total Energy Calculations for Metals and Semiconductors Using a Plane-Wave Basis Set. Comput. Mater. Sci. 1996, 6, 15--50

    work page 1996

  66. [66]

    Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set

    Kresse, G.; Furthm \"u ller, J. Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set. Phys. Rev. B 1996, 54, 11169--11186

    work page 1996

  67. [67]

    From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method

    Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method. Phys. Rev. B 1999, 59, 1758--1775

    work page 1999

  68. [68]

    P.; Burke, K.; Ernzerhof, M

    Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865--3868

    work page 1996

  69. [69]

    Effect of the Damping Function in Dispersion Corrected Density Functional Theory

    Grimme, S.; Ehrlich, S.; Goerigk, L. Effect of the Damping Function in Dispersion Corrected Density Functional Theory. J. Comput. Chem. 2011, 32, 1456--1465

    work page 2011

  70. [70]

    F B !YH BJ Hmhi

    Monkhorst, H. J.; Pack, J. D. Special Points for Brillouin-zone Integrations . Phys. Rev. B 1976, 13, 5188--5192 mcitethebibliography ms.bib0000664000000000000000000046402314303233674010671 0ustar rootroot @article polsAtomisticInsightsDegradation2021, title = Atomistic Insights Into the Degradation of Inorganic Halide Perovskite CsPbI3 : A Reactive Force...

    work page doi:10.1021/acs.jpclett.1c01192 1976

  71. [71]

    Aimsgb: An Algorithm and Open-Source Python Library to Generate Periodic Grain Boundary Structures

    Cheng, J.; Luo, J.; Yang, K. Aimsgb: An Algorithm and Open-Source Python Library to Generate Periodic Grain Boundary Structures. Comput. Mater. Sci. 2018, 155, 92--103

    work page 2018

  72. [72]

    Atomic and Electronic Structure of Cesium Lead Triiodide Surfaces

    Seidu, A.; Dvorak, M.; Rinke, P.; Li, J. Atomic and Electronic Structure of Cesium Lead Triiodide Surfaces. J. Chem. Phys. 2021, 154, 074712

    work page 2021

  73. [73]

    J.; Woolf, T

    Michaud‐Agrawal, N.; Denning, E. J.; Woolf, T. B.; Beckstein, O. MDAnalysis: A Toolkit for the Analysis of Molecular Dynamics Simulations. J. Comput. Chem. 2011, 32, 2319--2327

    work page 2011

  74. [74]

    J.; Linke, M.; Barnoud, J.; Reddy, T

    Gowers, R. J.; Linke, M.; Barnoud, J.; Reddy, T. J. E.; Melo, M. N.; Seyler, S. L.; Domański, J.; Dotson, D. L.; Buchoux, S.; Kenney, I. M.; Beckstein, O. MDAnalysis : A Python Package for the Rapid Analysis of Molecular Dynamics Simulations . Proceedings of the 15th Python in Science Conference 2016, 98--105 mcitethebibliography supporting.bib00006640000...

    work page doi:10.1021/acs.jpcc.6b11434 2016