[en] Polycrystalline perovskite solar cells show high power conversion efficiencies despite the presence of grain boundaries (GBs). The benign nature of GBs on the electronic properties and structural stability in metal-halide perovskites contradicts their propensity for point defect formation, a controversy that is far from being understood. In this work, we combine ab initio molecular dynamics and density functional theory calculations on the S5[130] GB of cesium lead iodide, CsPbI3, to shed light on the structural and
electronic properties of such GBs. Our results present the first evidence of structural healing of GBs driven by the facile migration of iodine ions, resulting in stabilized GB structures with reduced hole trap states and shallow electron trap states by strain-induced Pb–Pb dimers. Drift-diffusion simulations reveal that shallow electron trap states in GB mainly lower open-circuit voltage by enhanced non-radiative recombination. Finally, we observe the spontaneous formation of iodine Frenkel defects with reduced
formation energies compared to the perovskite bulk. Overall, our study reveals a controversy of GBs showing a moderate impact on the electronic properties by structural healing but a detrimental impact on the point defect densities, both being connected to the facile migration of iodine ions in GBs.
Disciplines :
Materials science & engineering
Author, co-author :
Kaiser, Waldemar; Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO) > Istituto CNR di Scienze e Tecnologie Chimiche “Giulio Natta” (CNR-SCITEC), Via Elce di Sotto 8, Perugiav 06123, Italy
Hussain, Kashif; Department of Electrical and Computer Engineering, Technical University of Munich, Hans-Piloty-Straße 1, 85748 Garching, Germany ; Department of Electrical Engineering, Sukkur IBA University, Sukkur 65200, Pakistan
Singh, Ajay ; University of Luxembourg > Faculty of Science, Technology and Medicine (FSTM) > Department of Physics and Materials Science (DPHYMS)
Alothman, Asma A.; Chemistry Department, College of Science, King Saud University, Riyadh 1451, Kingdom of Saudi Arabia
Meggiolaro, Daniele; Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO) > Istituto CNR di Scienze e Tecnologie Chimiche “Giulio Natta” (CNR-SCITEC), Via Elce di Sotto 8, Perugiav 06123, Italy
Gagliardi, Alessio; Department of Electrical and Computer Engineering, Technical University of Munich, Hans-Piloty-Straße 1, 85748 Garching, Germany
Mosconi, Edoardo; Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO) > Istituto CNR di Scienze e Tecnologie Chimiche “Giulio Natta” (CNR-SCITEC), Via Elce di Sotto 8, Perugiav 06123, Italy ; Chemistry Department, College of Science, King Saud University, Riyadh 1451, Kingdom of Saudi Arabia
De Angelis, Filippo; Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO) > Istituto CNR di Scienze e Tecnologie Chimiche “Giulio Natta” (CNR-SCITEC), Via Elce di Sotto 8, Perugiav 06123, Italy ; Department of Chemistry, Biology and Biotechnology, University of Perugia and UdR INSTM, Via Elce di Sotto 8, Perugia 06123, Italy
External co-authors :
yes
Language :
English
Title :
Defect Formation and Healing at Grain Boundaries in Lead-Halide Perovskites
Deutsche Forschungsgemeinschaft: Germany's Excellence Strategy/EXC 2089/1 – 390, TUM Innovation Network for Artificial Intelligence King Saud University Saudi Arabia: Distinguished Scientist Fellowship Program Ministero dell’Istruzione, dell’Universit` a e della Ricerca Italy Universit` a degli Studi di Perugia Italy Horizon 20220 Framework Programme European Union: LION-HEARTED/828984
Johnston M. B. Herz L. M. Hybrid Perovskites for Photovoltaics: Charge-Carrier Recombination, Diffusion, and Radiative Efficiencies Acc. Chem. Res. 2016 49 1 146 154 https://dx.doi.org/10.1021/acs.accounts.5b00411 10.1021/acs.accounts.5b00411 26653572
Stranks S. D. Eperon G. E. Grancini G. Menelaou C. Alcocer M. J. P. Leijtens T. Herz L. M. Petrozza A. Snaith H. J. Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber Science 2013 342 6156 341 344 https://dx.doi.org/10.1126/science.1243982 10.1126/science.1243982 24136964
Umari P. Mosconi E. De Angelis F. Relativistic GW Calculations on CH3NH3PbI3 and CH3NH3SnI3 Perovskites for Solar Cell Applications Sci. Rep. 2014 4 4467 https://dx.doi.org/10.1038/srep04467 10.1038/srep04467 24667758
Jeong J. Kim M. Seo J. Lu H. Ahlawat P. Mishra A. Yang Y. Hope M. A. Eickemeyer F. T. Kim M. Yoon Y. J. Choi I. W. Darwich B. P. Choi S. J. Jo Y. Lee J. H. Walker B. Zakeeruddin S. M. Emsley L. Rothlisberger U. Hagfeldt A. Kim D. S. Grätzel M. Kim J. Y. Pseudo-Halide Anion Engineering for α-FAPbI3 Perovskite Solar Cells Nature 2021 592 7854 381 385 https://dx.doi.org/10.1038/s41586-021-03406-5 10.1038/s41586-021-03406-5 33820983
Al-Ashouri A. Köhnen E. Li B. Magomedov A. Hempel H. Caprioglio P. Marquez J. A. Vliches A. B. M. Kasparavicius E. Smith J. A. Phung N. Menzel D. Grischek M. Kegelmann L. Skroblin D. Gollwitzer C. Malinauskas T. Marko J. Matic G. Rech B. Schlatmann R. Topic M. Korte L. Abate A. Stannowksi B. Neher D. Stolterfoht M. Unold T. Getautis V. Albrecht S. Monolithic Perovskite/Silicon Tandem Solar Cell with >29% Efficiency by Enhanced Hole Extraction Science 2020 370 1300 1309 10.1126/science.abd4016 33303611
Meggiolaro D. Motti S. G. Mosconi E. Barker A. J. Ball J. Andrea Riccardo Perini C. Deschler F. Petrozza A. De Angelis F. Iodine Chemistry Determines the Defect Tolerance of Lead-Halide Perovskites Energy Environ. Sci. 2018 11 3 702 713 https://dx.doi.org/10.1039/C8EE00124C 10.1039/C8EE00124C
Domanski K. Roose B. Matsui T. Saliba M. Turren-Cruz S.-H. Correa-Baena J.-P. Carmona C. R. Richardson G. Foster J. M. De Angelis F. Ball J. M. Petrozza A. Mine N. Nazeeruddin M. K. Tress W. Grätzel M. Steiner U. Hagfeldt A. Abate A. Migration of Cations Induces Reversible Performance Losses over Day/Night Cycling in Perovskite Solar Cells Energy Environ. Sci. 2017 10 2 604 613 https://dx.doi.org/10.1039/C6EE03352K 10.1039/C6EE03352K
Yaffe O. Guo Y. Tan L. Z. Egger D. A. Hull T. Stoumpos C. C. Zheng F. Heinz T. F. Kronik L. Kanatzidis M. G. Owen J. S. Rappe A. M. Pimenta M. A. Brus L. E. Local Polar Fluctuations in Lead Halide Perovskite Crystals Phys. Rev. Lett. 2017 118 13 136001 https://dx.doi.org/10.1103/PhysRevLett.118.136001 10.1103/PhysRevLett.118.136001 28409968
Quarti C. Mosconi E. De Angelis F. Interplay of Orientational Order and Electronic Structure in Methylammonium Lead Iodide: Implications for Solar Cell Operation Chem. Mater. 2014 26 22 6557 6569 https://dx.doi.org/10.1021/cm5032046 10.1021/cm5032046
Fan H. Huang J.-H. Chen L. Zhang Y. Wang Y. Gao C. Wang P. Zhou X. Jiang K.-J. Song Y. Methylamine-Assisted Secondary Grain Growth for CH3NH3PbI3 Perovskite Films with Large Grains and a Highly Preferred Orientation J. Mater. Chem. A 2021 9 12 7625 7630 https://dx.doi.org/10.1039/D0TA11916D 10.1039/D0TA11916D
Phung N. Abate A. The Impact of Nano- and Microstructure on the Stability of Perovskite Solar Cells Small 2018 14 46 e1802573 https://dx.doi.org/10.1002/smll.201802573 10.1002/smll.201802573 30295009
Conings B. Drijkoningen J. Gauquelin N. Babayigit A. D'Haen J. D'Olieslaeger L. Ethirajan A. Verbeeck J. Manca J. Mosconi E. De Angelis F. Boyen H.-G. Intrinsic Thermal Instability of Methylammonium Lead Trihalide Perovskite Adv. Energy Mater. 2015 5 15 1500477 https://dx.doi.org/10.1002/aenm.201500477 10.1002/aenm.201500477
Akbulatov A. F. Tsarev S. A. Elshobaki M. Luchkin S. Y. Zhidkov I. S. Kurmaev E. Z. Aldoshin S. M. Stevenson K. J. Troshin P. A. Comparative Intrinsic Thermal and Photochemical Stability of Sn(II) Complex Halides as Next-Generation Materials for Lead-Free Perovskite Solar Cells J. Phys. Chem. C 2019 123 44 26862 26869 https://dx.doi.org/10.1021/acs.jpcc.9b09200 10.1021/acs.jpcc.9b09200
Kaiser W. Ricciarelli D. Mosconi E. Alothman A. A. Ambrosio F. De Angelis F. Stability of Tin- versus Lead-Halide Perovskites: Ab Initio Molecular Dynamics Simulations of Perovskite/Water Interfaces J. Phys. Chem. Lett. 2022 13 10 2321 2329 https://dx.doi.org/10.1021/acs.jpclett.2c00273 10.1021/acs.jpclett.2c00273 35245058
Heo S. Seo G. Lee Y. Lee D. Seol M. Lee J. Park J.-B. Kim K. Yun D.-J. Kim Y. S. Shin J. K. Ahn T. K. Nazeeruddin M. K. Deep Level Trapped Defect Analysis in CH3NH3PbI3 Perovskite Solar Cells by Deep Level Transient Spectroscopy Energy Environ. Sci. 2017 10 5 1128 1133 https://dx.doi.org/10.1039/C7EE00303J 10.1039/C7EE00303J
Chu W. Saidi W. A. Zhao J. Prezhdo O. V. Soft Lattice and Defect Covalency Rationalize Tolerance of β-CsPbI3 Perovskite Solar Cells to Native Defects Angew. Chem., Int. Ed. 2020 59 16 6435 6441 https://dx.doi.org/10.1002/anie.201915702 10.1002/anie.201915702 31958363
Chu W. Zheng Q. Prezhdo O. V. Zhao J. Saidi W. A. Low-Frequency Lattice Phonons in Halide Perovskites Explain High Defect Tolerance toward Electron-Hole Recombination Sci. Adv. 2020 6 7 eaaw7453 https://dx.doi.org/10.1126/sciadv.aaw7453 10.1126/sciadv.aaw7453 32110721
Sherkar T. S. Momblona C. Gil-Escrig L. Ávila J. Sessolo M. Bolink H. J. Koster L. J. A. Recombination in Perovskite Solar Cells: Significance of Grain Boundaries, Interface Traps, and Defect Ions ACS Energy Lett. 2017 2 5 1214 1222 https://dx.doi.org/10.1021/acsenergylett.7b00236 10.1021/acsenergylett.7b00236 28540366
Castro-Méndez A.-F. Hidalgo J. Correa-Baena J.-P. The Role of Grain Boundaries in Perovskite Solar Cells Adv. Energy Mater. 2019 9 38 1901489 https://dx.doi.org/10.1002/aenm.201901489 10.1002/aenm.201901489
Correa-Baena J.-P. Anaya M. Lozano G. Tress W. Domanski K. Saliba M. Matsui T. Jacobsson T. J. Calvo M. E. Abate A. Grätzel M. Míguez H. Hagfeldt A. Unbroken Perovskite: Interplay of Morphology, Electro-optical Properties, and Ionic Movement Adv. Mater. 2016 28 25 5031 5037 https://dx.doi.org/10.1002/adma.201600624 10.1002/adma.201600624 27122472
Shao Y. Fang Y. Li T. Wang Q. Dong Q. Deng Y. Yuan Y. Wei H. Wang M. Gruverman A. Shield J. Huang J. Grain Boundary Dominated Ion Migration in Polycrystalline Organic-Inorganic Halide Perovskite Films Energy Environ. Sci. 2016 9 5 1752 1759 https://dx.doi.org/10.1039/C6EE00413J 10.1039/C6EE00413J
Azpiroz J. M. Mosconi E. Bisquert J. De Angelis F. Defect Migration in Methylammonium Lead Iodide and its Role in Perovskite Solar Cell Operation Energy Environ. Sci. 2015 8 7 2118 2127 https://dx.doi.org/10.1039/C5EE01265A 10.1039/C5EE01265A
Eames C. Frost J. M. Barnes P. R. F. O'Regan B. C. Walsh A. Islam M. S. Ionic Transport in Hybrid Lead Iodide Perovskite Solar Cells Nat. Commun. 2015 6 7497 https://dx.doi.org/10.1038/ncomms8497 10.1038/ncomms8497 26105623
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 20 1903735 https://dx.doi.org/10.1002/aenm.201903735 10.1002/aenm.201903735
Mattoni A. Meloni S. Defect Dynamics in MAPbI3 Polycrystalline Films: The Trapping Effect of Grain Boundaries Helv. Chim. Acta 2020 103 9 e2000110 https://dx.doi.org/10.1002/hlca.202000110 10.1002/hlca.202000110
Leijtens T. Eperon G. E. Barker A. J. Grancini G. Zhang W. Ball J. M. Kandada A. R. S. Snaith H. J. Petrozza A. Carrier Trapping and Recombination: The Role of Defect Physics in Enhancing the Open Circuit Voltage of Metal Halide Perovskite Solar Cells Energy Environ. Sci. 2016 9 11 3472 3481 https://dx.doi.org/10.1039/C6EE01729K 10.1039/C6EE01729K
Kosar S. Winchester A. J. Doherty T. A. S. Macpherson S. Petoukhoff C. E. Frohna K. Anaya M. Chan N. S. Madéo J. Man M. K. L. Stranks S. D. Dani K. M. Unraveling the Varied Nature and Roles of Defects in Hybrid Halide Perovskites with Time-Resolved Photoemission Electron Microscopy Energy Environ. Sci. 2021 14 6320 6328 https://dx.doi.org/10.1039/D1EE02055B 10.1039/D1EE02055B 35003331
deQuilettes D. W. Vorpahl S. M. Stranks S. D. Nagaoka H. Eperon G. E. Ziffer M. E. Snaith H. J. Ginger D. S. Impact of Microstructure on Local Carrier Lifetime in Perovskite Solar Cells Science 2015 348 6235 683 686 https://dx.doi.org/10.1126/science.aaa5333 10.1126/science.aaa5333 25931446
Doherty T. A. S. Winchester A. J. Macpherson S. Johnstone D. N. Pareek V. Tennyson E. M. Kosar S. Kosasih F. U. Anaya M. Abdi-Jalebi M. Andaji-Garmaroudi Z. Wong E. L. Madéo J. Chiang Y.-H. Park J.-S. Jung Y.-K. Petoukhoff C. E. Divitini G. Man M. K. L. Ducati C. Walsh A. Midgley P. A. Dani K. M. Stranks S. D. Performance-Limiting Nanoscale Trap Clusters at Grain Junctions in Halide Perovskites Nature 2020 580 7803 360 366 https://dx.doi.org/10.1038/s41586-020-2184-1 10.1038/s41586-020-2184-1 32296189
Jariwala S. Sun H. Adhyaksa G. W. Lof A. Muscarella L. A. Ehrler B. Garnett E. C. Ginger D. S. Local Crystal Misorientation Influences Non-radiative Recombination in Halide Perovskites Joule 2019 3 12 3048 3060 https://dx.doi.org/10.1016/j.joule.2019.09.001 10.1016/j.joule.2019.09.001
Sun Q. Fassl P. Becker-Koch D. Bausch A. Rivkin B. Bai S. Hopkinson P. E. Snaith H. J. Vaynzof Y. Role of Microstructure in Oxygen Induced Photodegradation of Methylammonium Lead Triiodide Perovskite Films Adv. Energy Mater. 2017 7 20 1700977 https://dx.doi.org/10.1002/aenm.201700977 10.1002/aenm.201700977
Wang Q. Chen B. Liu Y. Deng Y. Bai Y. Dong Q. Huang J. Scaling Behavior of Moisture-Induced Grain Degradation in Polycrystalline Hybrid Perovskite Thin Films Energy Environ. Sci. 2017 10 2 516 522 https://dx.doi.org/10.1039/C6EE02941H 10.1039/C6EE02941H
Wang C. Song Z. Zhao D. Awni R. A. Li C. Shrestha N. Chen C. Yin X. Li D. Ellingson R. J. Zhao X. Li X. Yan Y. Improving Performance and Stability of Planar Perovskite Solar Cells through Grain Boundary Passivation with Block Copolymers Sol. RRL 2019 3 9 1900078 https://dx.doi.org/10.1002/solr.201900078 10.1002/solr.201900078
Qiao L. Fang W.-H. Long R. Prezhdo O. V. Atomic Model for Alkali Metal Passivation of Point Defects at Perovskite Grain Boundaries ACS Energy Lett. 2020 5 12 3813 3820 https://dx.doi.org/10.1021/acsenergylett.0c02136 10.1021/acsenergylett.0c02136
Liu D. Luo D. Iqbal A. N. Orr K. W. P. Doherty T. A. S. Lu Z.-H. Stranks S. D. Zhang W. Strain Analysis and Engineering in Halide Perovskite Photovoltaics Nat. Mater. 2021 20 10 1337 1346 https://dx.doi.org/10.1038/s41563-021-01097-x 10.1038/s41563-021-01097-x 34531574
Park J.-S. Walsh A. Modeling Grain Boundaries in Polycrystalline Halide Perovskite Solar Cells Annu. Rev. Condens. Matter Phys. 2021 12 1 95 109 https://dx.doi.org/10.1146/annurev-conmatphys-042020-025347 10.1146/annurev-conmatphys-042020-025347
Rothmann M. U. Kim J. S. Borchert J. Lohmann K. B. O’Leary C. M. Sheader A. A. Clark L. Snaith H. J. Johnston M. B. Nellist P. D. Herz L. M. Atomic-Scale Microstructure of Metal Halide Perovskite Science 2020 370 6516 eabb5940 https://dx.doi.org/10.1126/science.abb5940 10.1126/science.abb5940 33122356
Yang D. Ming W. Shi H. Zhang L. Du M.-H. Fast Diffusion of Native Defects and Impurities in Perovskite Solar Cell Material CH3NH3PbI3 Chem. Mater. 2016 28 12 4349 4357 https://dx.doi.org/10.1021/acs.chemmater.6b01348 10.1021/acs.chemmater.6b01348
Meggiolaro D. Mosconi E. De Angelis F. Formation of Surface Defects Dominates Ion Migration in Lead-Halide Perovskites ACS Energy Lett. 2019 4 3 779 785 https://dx.doi.org/10.1021/acsenergylett.9b00247 10.1021/acsenergylett.9b00247
Long R. Liu J. Prezhdo O. V. Unravelling the Effects of Grain Boundary and Chemical Doping on Electron-Hole Recombination in CH3NH3PbI3 Perovskite by Time-Domain Atomistic Simulation J. Am. Chem. Soc. 2016 138 11 3884 3890 https://dx.doi.org/10.1021/jacs.6b00645 10.1021/jacs.6b00645 26930494
Wang Y. Fang W.-H. Long R. Prezhdo O. V. Symmetry Breaking at MAPbI3 Perovskite Grain Boundaries Suppresses Charge Recombination: Time-Domain ab Initio Analysis J. Phys. Chem. Lett. 2019 10 7 1617 1623 https://dx.doi.org/10.1021/acs.jpclett.9b00763 10.1021/acs.jpclett.9b00763 30892907
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 3 1715 1722 https://dx.doi.org/10.1021/acs.jpcc.6b11434 10.1021/acs.jpcc.6b11434
Shan W. Saidi W. A. Segregation of Native Defects to the Grain Boundaries in Methylammonium Lead Iodide Perovskite J. Phys. Chem. Lett. 2017 8 23 5935 5942 https://dx.doi.org/10.1021/acs.jpclett.7b02727 10.1021/acs.jpclett.7b02727 29160076
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 6 1321 1327 https://dx.doi.org/10.1021/acsenergylett.9b00840 10.1021/acsenergylett.9b00840
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 4 3477 3486 https://dx.doi.org/10.1021/acsnano.8b00267 10.1021/acsnano.8b00267 29565559
Mosconi E. De Angelis F. Mobile Ions in Organohalide Perovskites: Interplay of Electronic Structure and Dynamics ACS Energy Lett. 2016 1 1 182 188 https://dx.doi.org/10.1021/acsenergylett.6b00108 10.1021/acsenergylett.6b00108
Kaiser W. Carignano M. Alothman A. A. Mosconi E. Kachmar A. Goddard W. A. De Angelis F. First-Principles Molecular Dynamics in Metal-Halide Perovskites: Contrasting Generalized Gradient Approximation and Hybrid Functionals J. Phys. Chem. Lett. 2021 12 49 11886 11893 https://dx.doi.org/10.1021/acs.jpclett.1c03428 10.1021/acs.jpclett.1c03428 34875174
Car R. Parrinello M. Unified Approach for Molecular Dynamics and Density-Functional Theory Phys. Rev. Lett. 1985 55 2471 2474 https://dx.doi.org/10.1103/PhysRevLett.55.2471 10.1103/PhysRevLett.55.2471 10032153
Tuckerman M. E. Ab Initio Molecular Dynamics: Basic Concepts, Current Trends and Novel Applications J. Phys.: Condens. Matter 2002 14 50 R1297 R1355 https://dx.doi.org/10.1088/0953-8984/14/50/202 10.1088/0953-8984/14/50/202
Giannozzi P. Baroni S. Bonini N. Calandra M. Car R. Cavazzoni C. Ceresoli D. Chiarotti G. L. Cococcioni M. Dabo I. Dal Corso A. Gironcoli S. d. Fabris S. Fratesi G. Gebauer R. Gerstmann U. Gougoussis C. Kokalj A. Lazzeri M. Martin-Samos L. Marzari N. Mauri F. Mazzarello R. Paolini S. Pasquarello A. Paulatto L. Sbraccia C. Scandolo S. Sclauzero G. Seitsonen A. P. Smogunov A. Umari P. Wentzcovitch R. M. QUANTUM ESPRESSO: A Modular and Open-Source Software Project for Quantum Simulations of Materials J. Phys.: Condens. Matter 2009 21 39 395502 https://dx.doi.org/10.1088/0953-8984/21/39/395502 10.1088/0953-8984/21/39/395502 21832390
Perdew J. P. Burke K. Ernzerhof M. Generalized Gradient Approximation Made Simple Phys. Rev. Lett. 1996 77 18 3865 3868 https://dx.doi.org/10.1103/PhysRevLett.77.3865 10.1103/PhysRevLett.77.3865 10062328
Ratanaphan S. Yoon Y. Rohrer G. S. The Five Parameter Grain Boundary Character Distribution of Polycrystalline Silicon J. Mater. Sci. 2014 49 14 4938 4945 https://dx.doi.org/10.1007/s10853-014-8195-2 10.1007/s10853-014-8195-2
Park J.-S. Kang J. Yang J.-H. Metzger W. Wei S.-H. Stability and Electronic Structure of the Low-Σ Grain Boundaries in CdTe: A Density Functional Study New J. Phys. 2015 17 1 13027 https://dx.doi.org/10.1088/1367-2630/17/1/013027 10.1088/1367-2630/17/1/013027
Dawson J. A. Canepa P. Famprikis T. Masquelier C. Islam M. S. Atomic-Scale Influence of Grain Boundaries on Li-Ion Conduction in Solid Electrolytes for All-Solid-State Batteries J. Am. Chem. Soc. 2018 140 1 362 368 https://dx.doi.org/10.1021/jacs.7b10593 10.1021/jacs.7b10593 29224340
Kühne T. D. Iannuzzi M. Ben M. D. Rybkin V. V. Seewald P. Stein F. Laino T. Khaliullin R. Z. Schütt O. Schiffmann F. Golze D. Wilhelm J. Chulkov S. Bani-Hashemian M. H. Weber V. Borstnik U. Taillefumier M. Jakobovits A. S. Lazzaro A. Pabst H. Müller T. Schade R. Guidon M. Andermatt S. Holmberg N. Schenter G. K. Hehn A. Bussy A. Belleflamme F. Tabacchi G. Glöβ A. Lass M. Bethune I. Mundy C. J. Plessl C. Watkins M. VandeVondele J. Krack M. Hutter J. CP2K: An Electronic Structure and Molecular Dynamics Software Package - Quickstep: Efficient and Accurate Electronic Structure Calculations J. Chem. Phys. 2020 152 19 194103 https://dx.doi.org/10.1063/5.0007045 10.1063/5.0007045 33687235
Goedecker S. Teter M. Hutter J. Separable Dual-Space Gaussian Pseudopotentials Phys. Rev. B: Condens. Matter Mater. Phys. 1996 54 3 1703 1710 10.1103/PhysRevB.54.1703 9986014
VandeVondele J. Hutter J. Gaussian Basis Sets for Accurate Calculations on Molecular Systems in Gas and Condensed Phases J. Chem. Phys. 2007 127 11 114105 https://dx.doi.org/10.1063/1.2770708 10.1063/1.2770708 17887826
Guidon M. Hutter J. VandeVondele J. Auxiliary Density Matrix Methods for Hartree-Fock Exchange Calculations J. Chem. Theory Comput. 2010 6 8 2348 2364 https://dx.doi.org/10.1021/ct1002225 10.1021/ct1002225 26613491
Kaiser W. Mosconi E. Alothman A. A. Meggiolaro D. Gagliardi A. De Angelis F. Halide-Driven Formation of Lead Halide Perovskites: Insight from Ab Initio Molecular Dynamics Simulations Mater. Adv. 2021 2 3915 3926 https://dx.doi.org/10.1039/D1MA00371B 10.1039/D1MA00371B
Ahlawat P. Dar M. I. Piaggi P. Grätzel M. Parrinello M. Rothlisberger U. Atomistic Mechanism of the Nucleation of Methylammonium Lead Iodide Perovskite from Solution Chem. Mater. 2020 32 1 529 536 https://dx.doi.org/10.1021/acs.chemmater.9b04259 10.1021/acs.chemmater.9b04259
Caddeo C. Filippetti A. Mattoni A. The Dominant Role of Surfaces in the Hysteretic Behavior of Hybrid Perovskites Nano Energy 2020 67 104162 https://dx.doi.org/10.1016/j.nanoen.2019.104162 10.1016/j.nanoen.2019.104162
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 23 5519 5525 https://dx.doi.org/10.1021/acs.jpclett.1c01192 10.1021/acs.jpclett.1c01192 34096726
Meggiolaro D. De Angelis F. First-Principles Modeling of Defects in Lead Halide Perovskites: Best Practices and Open Issues ACS Energy Lett. 2018 3 9 2206 2222 https://dx.doi.org/10.1021/acsenergylett.8b01212 10.1021/acsenergylett.8b01212
Roose B. Ummadisingu A. Correa-Baena J.-P. Saliba M. Hagfeldt A. Graetzel M. Steiner U. Abate A. Spontaneous Crystal Coalescence Enables Highly Efficient Perovskite Solar Cells Nano Energy 2017 39 24 29 https://dx.doi.org/10.1016/j.nanoen.2017.06.037 10.1016/j.nanoen.2017.06.037
deQuilettes D. W. Zhang W. Burlakov V. M. Graham D. J. Leijtens T. Osherov A. Bulović V. Snaith H. J. Ginger D. S. Stranks S. D. Photo-Induced Halide Redistribution in Organic-Inorganic Perovskite Films Nat. Commun. 2016 7 11683 https://dx.doi.org/10.1038/ncomms11683 10.1038/ncomms11683 27216703
Mosconi E. Meggiolaro D. Snaith H. J. Stranks S. D. De Angelis F. Light-Induced Annihilation of Frenkel Defects in Organo-Lead Halide Perovskites Energy Environ. Sci. 2016 9 10 3180 3187 https://dx.doi.org/10.1039/C6EE01504B 10.1039/C6EE01504B
Galisteo-López J. F. Calvo M. E. Míguez H. Spatially Resolved Analysis of Defect Annihilation and Recovery Dynamics in Metal Halide Perovskite Single Crystals ACS Appl. Energy Mater. 2019 2 10 6967 6972 https://dx.doi.org/10.1021/acsaem.9b01335 10.1021/acsaem.9b01335
Yang B. Brown C. C. Huang J. Collins L. Sang X. Unocic R. R. Jesse S. Kalinin S. V. Belianinov A. Jakowski J. Geohegan D. B. Sumpter B. G. Xiao K. Ovchinnikova O. S. Enhancing Ion Migration in Grain Boundaries of Hybrid Organic-Inorganic Perovskites by Chlorine Adv. Funct. Mater. 2017 27 26 1700749 10.1002/adfm.201700749
McGovern L. Koschany I. Grimaldi G. Muscarella L. A. Ehrler B. Grain Size Influences Activation Energy and Migration Pathways in MAPbBr3 Perovskite Solar Cells J. Phys. Chem. Lett. 2021 12 9 2423 2428 https://dx.doi.org/10.1021/acs.jpclett.1c00205 10.1021/acs.jpclett.1c00205 33661008
Shi Y. Prezhdo O. V. Zhao J. Saidi W. A. Iodine and Sulfur Vacancy Cooperation Promotes Ultrafast Charge Extraction at MAPbI3/MoS2 Interface ACS Energy Lett. 2020 5 5 1346 1354 https://dx.doi.org/10.1021/acsenergylett.0c00485 10.1021/acsenergylett.0c00485
Evarestov R. A. Senocrate A. Kotomin E. A. Maier J. First-Principles Calculations of Iodine-Related Point Defects in CsPbI3 Phys. Chem. Chem. Phys. 2019 21 15 7841 7846 https://dx.doi.org/10.1039/c9cp00414a 10.1039/C9CP00414A 30933210
Hassan Y. Park J. H. Crawford M. L. Sadhanala A. Lee J. Sadighian J. C. Mosconi E. Shivanna R. Radicchi E. Jeong M. Yang C. Choi H. Park S. H. Song M. H. De Angelis F. Wong C. Y. Friend R. H. Lee B. R. Snaith H. J. Ligand-Engineered Bandgap Stability in Mixed-Halide Perovskite LEDs Nature 2021 591 7848 72 77 https://dx.doi.org/10.1038/s41586-021-03217-8 10.1038/s41586-021-03217-8 33658694
Tan S. Yavuz I. Weber M. H. Huang T. Chen C.-H. Wang R. Wang H.-C. Ko J. H. Nuryyeva S. Xue J. Zhao Y. Wei K.-H. Lee J.-W. Yang Y. Shallow Iodine Defects Accelerate the Degradation of α-Phase Formamidinium Perovskite Joule 2020 4 11 2426 2442 https://dx.doi.org/10.1016/j.joule.2020.08.016 10.1016/j.joule.2020.08.016
Yang B. Suo J. Mosconi E. Ricciarelli D. Tress W. De Angelis F. Kim H.-S. Hagfeldt A. Outstanding Passivation Effect by a Mixed-Salt Interlayer with Internal Interactions in Perovskite Solar Cells ACS Energy Lett. 2020 5 10 3159 3167 https://dx.doi.org/10.1021/acsenergylett.0c01664 10.1021/acsenergylett.0c01664
Yang S. Chen S. Mosconi E. Fang Y. Xiao X. Wang C. Zhou Y. Zhao J. Gao Y. De Angelis F. Huang J. Stabilizing Halide Perovskite Surfaces for Solar Cell Operation with Wide-Bandgap Lead Oxysalts Science 2019 365 473 478 10.1126/science.aax3294 31371610
Jiang Q. Zhao Y. Zhang X. Yang X. Chen Y. Chu Z. Ye Q. Li X. Yin Z. You J. Surface Passivation of Perovskite Film for Efficient Solar Cells Nat. Photonics 2019 13 7 460 466 https://dx.doi.org/10.1038/s41566-019-0398-2 10.1038/s41566-019-0398-2
Xu Y. Zhu L. Shi J. Lv S. Xu X. Xiao J. Dong J. Wu H. Luo Y. Li D. Meng Q. Efficient Hybrid Mesoscopic Solar Cells with Morphology-Controlled CH3NH3PbI3−xClx Derived from Two-Step Spin Coating Method ACS Appl. Mater. Interfaces 2015 7 4 2242 2248 https://dx.doi.org/10.1021/am5057807 10.1021/am5057807 25587643
Amat A. Mosconi E. Ronca E. Quarti C. Umari P. Nazeeruddin M. K. Grätzel M. De Angelis F. Cation-Induced Band-Gap Tuning in Organohalide Perovskites: Interplay of Spin-Orbit Coupling and Octahedra Tilting Nano Lett. 2014 14 6 3608 3616 https://dx.doi.org/10.1021/nl5012992 10.1021/nl5012992 24797342
Even J. Pedesseau L. Jancu J.-M. Katan C. Importance of Spin-Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications J. Phys. Chem. Lett. 2013 4 17 2999 3005 https://dx.doi.org/10.1021/jz401532q 10.1021/jz401532q
Trots D. M. Myagkota S. V. High-Temperature Structural Evolution of Caesium and Rubidium Triiodoplumbates J. Phys. Chem. Solids 2008 69 10 2520 2526 https://dx.doi.org/10.1016/j.jpcs.2008.05.007 10.1016/j.jpcs.2008.05.007
Uratani H. Yamashita K. Charge Carrier Trapping at Surface Defects of Perovskite Solar Cell Absorbers: A First-Principles Study J. Phys. Chem. Lett. 2017 8 4 742 746 https://dx.doi.org/10.1021/acs.jpclett.7b00055 10.1021/acs.jpclett.7b00055 28129504
Kim J. Chung C.-H. Hong K.-H. Understanding of the Formation of Shallow Level Defects from the Intrinsic Defects of Lead Tri-Halide Perovskites Phys. Chem. Chem. Phys. 2016 18 39 27143 27147 https://dx.doi.org/10.1039/c6cp02886a 10.1039/C6CP02886A 27711400
Tong C.-J. Li L. Liu L.-M. Prezhdo O. V. Synergy between Ion Migration and Charge Carrier Recombination in Metal-Halide Perovskites J. Am. Chem. Soc. 2020 142 6 3060 3068 https://dx.doi.org/10.1021/jacs.9b12391 10.1021/jacs.9b12391 31965789
Leijtens T. Stranks S. D. Eperon G. E. Lindblad R. Johansson E. M. J. McPherson I. J. Rensmo H. Ball J. M. Lee M. M. Snaith H. J. Electronic Properties of Meso-Superstructured and Planar Organometal Halide Perovskite Films: Charge Trapping, Photodoping, and Carrier Mobility ACS Nano 2014 8 7 7147 7155 https://dx.doi.org/10.1021/nn502115k 10.1021/nn502115k 24949826
Shao S. Abdu-Aguye M. Sherkar T. S. Fang H.-H. Adjokatse S. Brink ten G. Kooi B. J. Koster L. J. A. Loi M. A. The Effect of the Microstructure on Trap-Assisted Recombination and Light Soaking Phenomenon in Hybrid Perovskite Solar Cells Adv. Funct. Mater. 2016 26 44 8094 8102 https://dx.doi.org/10.1002/adfm.201602519 10.1002/adfm.201602519
Park J.-S. Stabilization and Self-Passivation of Grain Boundaries in Halide Perovskite by Rigid Body Translation J. Phys. Chem. Lett. 2022 13 20 4628 4633 https://dx.doi.org/10.1021/acs.jpclett.2c01123 10.1021/acs.jpclett.2c01123 35587377
Zhao W. Yao Z. Yu F. Yang D. Liu S. F. Alkali Metal Doping for Improved CH3NH3PbI3 Perovskite Solar Cells Adv. Sci. 2018 5 2 1700131 https://dx.doi.org/10.1002/advs.201700131 10.1002/advs.201700131 29610718
Qiao L. Fang W.-H. Long R. Dual Passivation of Point Defects at Perovskite Grain Boundaries with Ammonium Salts Greatly Inhibits Nonradiative Charge Recombination J. Phys. Chem. Lett. 2022 13 4 954 961 https://dx.doi.org/10.1021/acs.jpclett.1c04038 10.1021/acs.jpclett.1c04038 35060385
Wang Y. He J. Yang Y. Zhang Z. Long R. Chlorine Passivation of Grain Boundary Suppresses Electron-Hole Recombination in CsPbBr3 Perovskite by Nonadiabatic Molecular Dynamics Simulation ACS Appl. Energy Mater. 2019 2 5 3419 3426 https://dx.doi.org/10.1021/acsaem.9b00220 10.1021/acsaem.9b00220
Guo Y. Sato W. Shoyama K. Nakamura E. Sulfamic Acid-Catalyzed Lead Perovskite Formation for Solar Cell Fabrication on Glass or Plastic Substrates J. Am. Chem. Soc. 2016 138 16 5410 5416 https://dx.doi.org/10.1021/jacs.6b02130 10.1021/jacs.6b02130 27054265
Niu T. Lu J. Munir R. Li J. Barrit D. Zhang X. Hu H. Yang Z. Amassian A. Zhao K. Liu S. F. Stable High-Performance Perovskite Solar Cells via Grain Boundary Passivation Adv. Mater. 2018 30 16 e1706576 https://dx.doi.org/10.1002/adma.201706576 10.1002/adma.201706576 29527750
Gagliardi A. Abate A. Mesoporous Electron-Selective Contacts Enhance the Tolerance to Interfacial Ion Accumulation in Perovskite Solar Cells ACS Energy Lett. 2018 3 163 169 10.1021/acsenergylett.7b01101