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1. Ligand Driven Control and F‐Doping of Surface Characteristics in FASnI3 Lead‐Free Perovskites: Relation Between Molecular Dipoles, Surface Dipoles, Work Function Shifts, and Surface Strain

Author: Pooja Basera, Boubacar Traore, Pingping Jiang, Laurent Pedesseau, Mikaël Kepenekian, Jacky Even, and Claudine Katan
Subjects: interface, Pb‐free perovskites, surface, work function, Physics, QC1-999, Technology
Abstract: Abstract The performance and operational stability of perovskite‐based devices heavily rely on the interfacial properties between the photoactive perovskite layer and charge transport layers. Understanding the theoretical relationship between surface/interface dipoles and surface energetics is crucial for scientific understanding and practical applications. In this study, a method is applied that bridges classical electromagnetism and modern atomistic approaches. The impact of dipolar ligand molecules functionalizing the FASnI3 perovskite surface is investigated, with inspection of the interplay between surface dipole, charge transfer, and local strain effect, and corresponding shifts in the valence level. The results reveal that the contribution of individual molecular entities to surface dipoles and electric susceptibilities follows an essentially additive behavior. The influence of F doping usually used to mitigate Sn oxidation in Sn‐based layer for photovoltaic applications, is also discussed. Furthermore, the findings are compared with predictions from classical approaches employing a capacitor model that links the induced vacuum level shift and the molecular dipole moment. The insights gained from the study provide theoretical guidelines for fine‐tuning the work functions of materials, thus enabling effective interfacial engineering in this class of semiconductors.
Published: 2024
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2. Universal scaling laws for charge-carrier interactions with quantum confinement in lead-halide perovskites

Author: Philippe Tamarat, Elise Prin, Yullia Berezovska, Anastasiia Moskalenko, Thi Phuc Tan Nguyen, Chenghui Xia, Lei Hou, Jean-Baptiste Trebbia, Marios Zacharias, Laurent Pedesseau, Claudine Katan, Maryna I. Bodnarchuk, Maksym V. Kovalenko, Jacky Even, and Brahim Lounis
Subjects: Science
Abstract: Knowledge of fundamental properties of lead halide perovskites is crucial for their technological development. Here, authors perform magneto-optical spectroscopy, develop universal scaling laws and offer a predictive picture for interaction energies within photo-generated charge-carrier complexes.
Published: 2023
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3. Pb-free halide perovskites for solar cells, light-emitting diodes, and photocatalysts

Author: Pingping Jiang, Debdipto Acharya, George Volonakis, Marios Zacharias, Mikaël Kepenekian, Laurent Pedesseau, Claudine Katan, and Jacky Even
Subjects: Biotechnology, TP248.13-248.65, Physics, QC1-999
Abstract: Metal halide perovskites have recently emerged as one of the most promising classes of semiconductors for various applications, especially in the field of optoelectronics. Lead-based halide perovskite materials, virtually unexploited for decades, have become prominent candidates due to their unique and intrinsic physicochemical and optical properties. Current challenges faced by the scientific community to capitalize on the properties of Pb-based perovskites are mainly associated with environmental concerns due to the toxicity of Pb and their poor stability. Under this context, over recent years, a number of new Pb-free halide perovskite (and perovskite-like) semiconductor classes have been introduced. This Perspective reviews recent developments in Pb-free halide perovskites, which specifically target their application in solar cells, light-emitting devices, and photocatalysts. Each type of Pb-free material is paired with a specific optoelectronic application, and the latest record performances are reported. Although these materials do not yet exhibit as attractive intrinsic optoelectronic properties as the Pb-based halide perovskites, their potential as alternatives for well-suited applications is discussed.
Published: 2022
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4. Author Correction: Universal scaling laws for charge-carrier interactions with quantum confinement in lead-halide perovskites

Author: Philippe Tamarat, Elise Prin, Yuliia Berezovska, Anastasiia Moskalenko, Thi Phuc Tan Nguyen, Chenghui Xia, Lei Hou, Jean-Baptiste Trebbia, Marios Zacharias, Laurent Pedesseau, Claudine Katan, Maryna I. Bodnarchuk, Maksym V. Kovalenko, Jacky Even, and Brahim Lounis
Subjects: Science
Published: 2023
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5. The importance of relativistic effects on two-photon absorption spectra in metal halide perovskites

Author: Zimu Wei, Dengyang Guo, Jos Thieme, Claudine Katan, Valentina M. Caselli, Jacky Even, and Tom J. Savenije
Subjects: Science
Abstract: Metal halide perovskites possess interesting properties but their sub-bandgap absorption remains largely unexplored. Here Wei et al. employ two-photon absorption spectroscopy with time-resolved microwave conductivity technique to confirm the existence of strong spin-orbit coupling effect.
Published: 2019
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6. A 3D Lead Iodide Hybrid Based on a 2D Perovskite Subnetwork

Author: Maroua Ben Haj Salah, Justine Tessier, Nicolas Mercier, Magali Allain, Antonin Leblanc, Xiaoyang Che, Claudine Katan, and Mikael Kepenekian
Subjects: 3D network, halide perovskite, electronic structure, lead iodide hybrid, Crystallography, QD901-999
Abstract: Lead halide perovskites have emerged as promising materials for various optoelectronic applications. For photovoltaics, the reference compound is the 3D perovskite (MA)PbI3 (MA+ = methylammonium). However, this material suffers from instabilities towards humidity or light. This makes the search of new stable 3D lead halide materials very relevant. A strategy is the use of intermediate size cations instead of MA, which are not suitable to form the 3D ABX3 perovskites or 2D perovskites. Here, we report on a novel 3D metal halide hybrid material based on the intermediate size cation hydroxypropylammonium (HPA+), (HPA)6(MA)Pb5I17. We will see that extending the carbon chain length from two CH2 units (in the hydroxylethylammonium cation, HEA+) to three (HPA+) precludes the formation of a perovskite network as found in the lead and iodide deficient perovskite (HEA,MA)1+xPbxI3−x. In (HPA)6(MA)Pb5I17 the 3D lead halide network results from a 2D perovskite subnetworks linked by a PbI6 octahedra sharing its faces. DFT calculations confirm the direct band gap and reveal the peculiar band structure of this 3D network. On one hand the valence band has a 1D nature involving the p orbitals of the halide. On the other, the conduction band possesses a clear 2D character involving hybridization between the p orbitals of the metal and the halide.
Published: 2021
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7. Fine Structure of Excitons in Vacancy-Ordered Halide Double Perovskites

Author: Bruno Cucco, Claudine Katan, Jacky Even, Mikaël Kepenekian, George Volonakis, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), he research leading to these results has received funding from the Chaire deRecherche Rennes Metropole and the European Union’s Horizon 2020 program, through a FETOpen research and innovation action under the grant agreement No 862656 (DROP-IT). This workwas granted access to the HPC resources of TGCC under the allocations 2020-A0100911434 and2021-A0110907682 made by GENCI. We acknowledge PRACE for awarding us access to theARCHER2, United Kingdom., and European Project: 862656,DROPIT
Subjects: [PHYS]Physics [physics], Condensed Matter - Materials Science, General Chemical Engineering, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Biomedical Engineering, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, [CHIM]Chemical Sciences, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry
Abstract: International audience; Vacancy-ordered halide double perovskites (VODPs) have been widely explored throughout the past few years as promising lead-free alternatives for optoelectronic applications. Yet, the atomic-scale mechanisms that underlie their optical properties remain elusive. In this work, a thorough investigation of the excitonic properties of key members within the VODP family is presented. We employ state-of-the-art ab initio calculations and unveil critical details regarding the role of electron–hole interactions in the electronic and optical properties of VODPs. The materials family is sampled by picking prototypes based on the electronic configuration of the tetravalent metal at the center of the octahedron. Hence, groups with a valence comprised of s, p, and d closed shells are represented by the known materials Cs2SnX6, Cs2TeX6, and Cs2ZrX6 (with X = Br, I), respectively. The electronic structure is investigated within the G0W0 many-body Green’s function method, while the Bethe–Salpeter equation is solved to account for electron–hole interactions that play a crucial role in the optical properties of the family. A detailed symmetry analysis unravels the fine structure of excitons for all compounds. The exciton binding energy, excitonic wavefunctions, and the dark–bright splitting are also reported for each material. It is shown that these quantities can be tuned over a wide range, from Wannier- to Frenkel-type excitons, through for example substitutional engineering. In particular, Te-based materials, which share the electronic valency of corner-sharing Pb halide perovskites, are predicted to have exciton binding energies of above 1 eV and a dark–bright splitting of the excitons reaching over 100 meV. Our findings provide a fundamental understanding of the optical properties of the entire family of VODP materials and highlight how these are not, in fact, suitable Pb-free alternatives to traditional halide perovskites.
Published: 2022
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8. Synthesis and Characterization of (FA)3(HEA)2Pb3I11: A Rare Example of <1 1 0>-Oriented Multilayered Halide Perovskites

Author: Maroua Ben Haj Salah, Nicolas Mercier, Magali Allain, Antonin Leblanc, Jens Dittmer, Chiara Botta, Claudio Quarti, and Claudine Katan
Subjects: General Chemical Engineering, Materials Chemistry, General Chemistry
Published: 2022
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9. Many-body Correlations and Exciton Complexes in CsPbBr3 Quantum Dots

Author: Chenglian Zhu, Tan Nguyen, Simon C. Boehme, Anastasiia Moskalenko, Dmitry N. Dirin, Maryna I. Bodnarchuk, Claudine Katan, Jacky Even, Gabriele Rainò, Maksym V. Kovalenko, Department of Chemistry and Applied Biosciences [ETH Zürich] (D-CHAB), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Swiss Federal Laboratories for Materials Science and Technology [Dübendorf] (EMPA), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), This project was funded by the European Union’s Horizon 2020 program, through a FET Open research and innovation action under the grant agreement No 899141 (PoLLoC). J.E. acknowledges financial support from the Institute Universitaire de France. C.Z, M.I.B. and G.R. acknowledge funding from the Swiss National Science Foundation (Grant No. 200021_192308, \'Q-Light -Engineered Quantum Light Sources with Nanocrystal Assemblies\'). The project was also partially supported by the Air Force Office of Scientific Research and the Office of Naval Research under award number FA8655-21-1-7013and by the Swiss National Science Foundation (Grant No. 188404, \'Novel inorganic light emitters: synthesis, spectroscopy and applications\')., European Project: 899141,PoLLoC, Swiss Federal Institute of Technology (ETHZ), Gouvernement suisse, EMPA Advanced Materials Processing, and Swiss Federal Laboratories for Materials Science and Technology [Thun] (EMPA)
Subjects: [PHYS]Physics [physics], polaron, Mechanical Engineering, quantum correlations, effective mass calculations, binding energies in exciton complexes, configuration interaction methods, single quantum dot spectroscopy, CsPbBr 3 quantum dots, polarons, Mechanics of Materials, k.p effective mass calculations, [CHIM]Chemical Sciences, General Materials Science, CsPbBr3 QDs
Abstract: All-inorganic lead-halide perovskite (LHP) (CsPbX3, X = Cl, Br, I) quantum dots (QDs) have emerged as a competitive platform for classical light-emitting devices (in the weak light–matter interaction regime, e.g., LEDs and laser), as well as for devices exploiting strong light–matter interaction at room temperature. Many-body interactions and quantum correlations among photogenerated exciton complexes play an essential role, for example, by determining the laser threshold, the overall brightness of LEDs, and the single-photon purity in quantum light sources. Here, by combining cryogenic single-QD photoluminescence spectroscopy with configuration-interaction (CI) calculations, the size-dependent trion and biexciton binding energies are addressed. Trion binding energies increase from 7 to 17 meV for QD sizes decreasing from 30 to 9 nm, while the biexciton binding energies increase from 15 to 30 meV, respectively. CI calculations quantitatively corroborate the experimental results and suggest that the effective dielectric constant for biexcitons slightly deviates from the one of the single excitons, potentially as a result of coupling to the lattice in the multiexciton regime. The findings here provide a deep insight into the multiexciton properties in all-inorganic LHP QDs, essential for classical and quantum optoelectronic devices., Advanced Materials, 35 (9), ISSN:0935-9648, ISSN:1521-4095
Published: 2023
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10. Design and Synthesis of a 4‑Nitrobromobenzene Derivative Bearing an Ethylene Glycol Tetraacetic Acid Unit for a New Generation of Caged Calcium Compounds with Two-Photon Absorption Properties in the Near-IR Region and Their Application in Vivo

Author: Satish Jakkampudi, Manabu Abe, Naomitsu Komori, Ryukichi Takagi, Ko Furukawa, Claudine Katan, Wakako Sawada, Noriko Takahashi, and Haruo Kasai
Subjects: Chemistry, QD1-999
Published: 2016
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11. Light-activated photocurrent degradation and self-healing in perovskite solar cells

Author: Wanyi Nie, Jean-Christophe Blancon, Amanda J. Neukirch, Kannatassen Appavoo, Hsinhan Tsai, Manish Chhowalla, Muhammad A. Alam, Matthew Y. Sfeir, Claudine Katan, Jacky Even, Sergei Tretiak, Jared J. Crochet, Gautam Gupta, and Aditya D. Mohite
Subjects: Science
Abstract: Organometallic perovskite solar cells exhibit good efficiency but their photostability is still relatively poorly understood and controlled. Here the authors show that photo-degradation arises from the formation of light-activated meta-stable trap states, is reversible, and can be frozen at 0 °C.
Published: 2016
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12. Ultrafast relaxation of lattice distortion in 2D perovskites

Author: Hao Zhang, Wenbin Li, Joseph Essman, Claudio Quarti, Isaac Metcalf, Wei-Yi Chiang, Siraj Sidhik, Jin Hou, Austin Fehr, Andrew Attar, Ming-Fu Lin, Alexander Britz, Xiaozhe Shen, Stephan Link, Xijie Wang, Uwe Bergmann, Mercouri Kanatzidis, Claudine Katan, Jacky Even, Jean-Christophe Blancon, Aditya Mohite
Published: 2023
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13. Interstitial Nature of Mn2+ Doping in 2D Perovskites

Author: Andrew J. Torma, Wenbin Li, Hao Zhang, Qing Tu, Vladislav V. Klepov, Michael C. Brennan, Christopher L. McCleese, Matthew D. Krzyaniak, Michael R. Wasielewski, Claudine Katan, Jacky Even, Martin V. Holt, Tod A. Grusenmeyer, Jie Jiang, Ruth Pachter, Mercouri G. Kanatzidis, Jean-Christophe Blancon, Aditya D. Mohite, Rice University [Houston], Texas A&M University [College Station], Northwestern University [Evanston], Air Force Research Laboratory (AFRL), United States Air Force (USAF), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Argonne National Laboratory [Lemont] (ANL), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), FA8650-16-D-5402-0001, Air Force Research Laboratory, Army Research Office, DE-FG02-99ER14999, Basic Energy Sciences, Texas A and M Engineering Experiment Station, Texas A and M University, Institut Universitaire de France, 20-587, National Science Foundation, and Triads for Transformation, Texas A and M University
Subjects: [PHYS]Physics [physics], crystal structure, strain mapping, General Engineering, General Physics and Astronomy, doping, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, nano X-ray diffraction, 01 natural sciences, transition metals, 0104 chemical sciences, Condensed Matter::Materials Science, halide perovskites, [CHIM]Chemical Sciences, Condensed Matter::Strongly Correlated Electrons, General Materials Science, 0210 nano-technology, density functional theory, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; Halide perovskites doped with magnetic impurities (such as the transition metals Mn2+, Co2+, Ni2+) are being explored for a wide range of applications beyond photovoltaics, such as spintronic devices, stable light-emitting diodes, single-photon emitters, and magneto-optical devices. However, despite several recent studies, there is no consensus on whether the doped magnetic ions will predominantly replace the octahedral B-site metal via substitution or reside at interstitial defect sites. Here, by performing correlated nanoscale X-ray microscopy, spatially and temporally resolved photoluminescence measurements, and magnetic force microscopy on the inorganic 2D perovskite Cs2PbI2Cl2, we show that doping Mn2+ into the structure results in a lattice expansion. The observed lattice expansion contrasts with the predicted contraction expected to arise from the B-site metal substitution, thus implying that Mn2+ does not replace the Pb2+ sites. Photoluminescence and electron paramagnetic resonance measurements confirm the presence of Mn2+ in the lattice, while correlated nano-XRD and X-ray fluorescence track the local strain and chemical composition. Density functional theory calculations predict that Mn2+ atoms reside at the interstitial sites between two octahedra in the triangle formed by one Cl– and two I– atoms, which results in a locally expanded structure. These measurements show the fate of the transition metal dopants, the local structure, and optical emission when they are doped at dilute concentrations into a wide band gap semiconductor.
Published: 2021
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14. Silver‐Bismuth Halide Double Salts for Lead‐free Photovoltaics: Insights From Symmetry‐Based Modeling

Author: Bruno Cucco, Laurent Pedesseau, Claudine Katan, Jacky Even, Mikaël Kepenekian, George Volonakis, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA), The research leading to these results has received funding from the Chaire de Recherche Rennes Metropole project. This work was granted access to the HPC resources of TGCC under the allocations 2020-A0100911434 and 2021-A0110907682 made by GENCI. The authors acknowledge PRACE for awarding us access to the ARCHER2, United Kingdom., and European Project: 862656,DROPIT
Subjects: Energy Engineering and Power Technology, [CHIM.MATE]Chemical Sciences/Material chemistry, Electrical and Electronic Engineering, Atomic and Molecular Physics, and Optics, Electronic, Optical and Magnetic Materials
Abstract: International audience; Ag/Bi halide double salts, also called rudorffites, constitute a promising path to achieve low-cost, high-efficiency lead-free optoelectronic devices, in particular solar cells. These materials present tunable gaps within the visible range, high short-circuit currents, and interesting efficiencies in outdoor and indoor devices. Herein, a combination of symmetry analysis and first-principles calculations is used to explore the structural, electronic, and optical properties of prototypical rudorffites solar cell absorbers AgBiI4 and Ag3BiI6. The challenges to model those ternary materials are first established. It is shown that Ag/Bi double salts cannot be modeled as random alloys. Second, a Wyckoff position splitting method is developed leading to the generation of model structures, which are unique for each compound, and agrees with experimental structural data. These structures are used to establish the optoelectronic properties of AgBiI4 and Ag3BiI6. Finally, the ideal photovoltaic performance of the materials is predicted through the spectral limited maximum efficiency approach. It is shown that AgBiI4 presents a slightly higher potential for solar cell applications, and the realized devices are mostly limited by the low open-circuit voltage. The structural models developed here can help unveiling complex properties of the materials and explore substitutional engineering within halide double salts.
Published: 2022
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15. Influence of surface termination on the structural and electronic properties at the Pb-free perovskite/charge transport material interfaces

Author: Pingping JIANG, Boubacar TRAORE, Mikael KEPENEKIAN, George VOLONAKIS, Claudine KATAN, Laurent PEDESSEAU, Jacky EVEN, Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and European Project: 862656,DROP-IT
Subjects: [PHYS]Physics [physics], [CHIM]Chemical Sciences
Abstract: International audience; To cope with the toxicity of Pb-based perovskites and achieve smaller electronic band gaps, replacing Pb with Sn has gained growing attention recently 1,2. Importantly, the low-bandgap Pb-Sn alloyed perovskite allows the building of all-perovskite tandem solar cells that shall overcome the performances of single-junction perovskite cells 3,4. In fact, of all possible means to improve perovskite film quality and suppress nonradiative recombination in optoelectronic devices for a high photo conversion efficiency purpose, the surface and interface functionalizations after the assembly with charge transport layer (CTL) are one of the most critical parameters 5,6. In view of the sophisticated chemical and physical properties of Sn-based perovskites, theoretical calculations based on density functional theory (DFT) provide a useful insight into the interplay between absorbers and CTLs. Here, FASnI3 is chosen as a benchmark material. We thoroughly investigate the influence of its surface termination on structural and electronic properties when interfacing with organic C60 (100) and inorganic SnO2 (100) and (110), including the intermediate work function calculations on the free-standing slabs. Based on the theoretical methology developed in our team7, we have evidenced the proportionality between work function shifts and surface dipoles, making the optimization of interfacial charge transport possible by surface dipole tuning. Our findings on the charge transport properties of the two targeted CTLs, contribute to analyzepromising alternatives as CTLs for Pb-free perovskites thanks tosurface and interface engineering.
Published: 2022

16. Many-body physics of emission from excitonic complexes in cesium lead halide perovskite quantum dots

Author: Tan NGUYEN, Chenglian ZHU, Simon BOEHME, Anastasiia MOSKALENKO, Dmitry DIRIN, Maryna BODNARCHUK, Gabriele RAINO, Maksym KOVALENKO, Claudine KATAN, Jacky EVEN, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry and Applied Biosciences [ETH Zürich] (D-CHAB), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Laboratory for Thin Films and Photovoltaics, Empa, Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), and European Project: 899141,PoLLoC
Subjects: [PHYS]Physics [physics], [CHIM]Chemical Sciences
Abstract: International audience; In the current context of rising popularity of perovskites as excellent materials for optoelectronics, inorganic lead halide perovskite (CsPbX3, X=Cl, Br, I) quantum dots constitute a promising platform for light emitting devices thanks to their emission spectra having extensive coverage of frequencies with narrow band as well as their photoluminescence (PL) quantum yield approaching 100%. Understanding light-matter coupling and the various many-body effects is at the core of realizing the full potential of perovskite quantum dots as both classical and quantum light sources. Many-body interaction is notably important not only for single-exciton PL but also for the emission energies of trion and biexciton systems. For this purpose, we utilize the Configuration Interaction (CI) approach to study the binding energies of these multiexcitonic complexes. Corroborating the experimental findings from single-dot spectroscopy, our calculations quantitatively reproduce the measured redshifts of the trion and biexciton relative to the single exciton emission from CsPbX3 quantum dots [6]. Additionally, the same theoretical method can also be employed to explain the sub-nanosecond exciton radiative lifetime in these fascinating materials.
Published: 2022

17. Bismuth/Silver-Based Two-Dimensional Iodide Double and One-Dimensional Bi Perovskites: Interplay between Structural and Electronic Dimensions

Author: Linda Li, Mercouri G. Kanatzidis, Jacky Even, Mikael Kepenekian, Peijun Guo, Constantinos C. Stoumpos, Claudine Katan, Boubacar Traoré, Xiaotong Li, Northwestern University [Evanston], Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Yale University [New Haven], University of Crete [Heraklion] (UOC), For DFT calculations, the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2019-A0080911434, 2020-A0080911434 and 2020-A0090907682 made by GENCI. M. K. acknowledges support from Region Bretagne through Boost'ERC LaHPerOS project. J.E acknowledges the financial support from the Institut Universitaire de France., Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: 2D iodide double perovskite, Materials science, optical property, General Chemical Engineering, Iodide, Halide, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Bismuth, chemistry.chemical_compound, symbols.namesake, Materials Chemistry, electronic dimension, Electronic band structure, Perovskite (structure), chemistry.chemical_classification, 1D Bi perovskite, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, chemistry, Octahedron, symbols, Pyridinium, 0210 nano-technology, Raman spectroscopy
Abstract: International audience; New structures with favorable band structure and optical properties are of broad interest to the halide perovskite community. Recently, lead-free two-dimensional (2D) double perovskites have emerged as dimensionally reduced counterparts of their 3D analogues. Besides the structural diversity provided by the organic cation, the achievement of 2D lead-free iodide double perovskites has attached researchers to explore more structures in this new material family. Here, we report the synthesis and structures of a series of 2D iodide double perovskites based on cyclic diammonium cations (aminomethyl)piperidinium (AMP) and (aminomethyl)pyridinium (AMPY), (4AMP)2AgBiI8 and (3AMPY)2AgBiI8, and compare them with 1D structures with Bi only (x-AMP)BiI5 and (x-AMPY)BiI5 (x = 3 and 4). The crystallographic structures of the double perovskite phases are highly distorted, because of the inability of Ag to form regular octahedral coordination with iodine. The experimental bandgaps of the double perovskite phases are surprisingly similar ((4AMP)2AgBiI8) or even larger ((3AMPY)2AgBiI8) than in the 1D structures with the same cations ((4AMP)BiI5 and (3AMPY)BiI5). DFT calculations suggest that the effective electronic dimensionality of the double perovskites is on par or lower than that of 1D structures. The reduced electronic dimension of the 2D compounds originates from the weak electronic coupling between the corner-sharing Ag and Bi octahedra. The band structures for the 1D compounds are dispersive in the chain direction, suggesting that their electronic and structural dimensions are similar. Low frequency Raman spectra exhibit distinct peaks at room temperature for all compounds reported here, suggesting rigid lattices
Published: 2021
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18. Influence of Chemical Engineering, Photodoping and Lattice Distortions on the Optoelectronic Properties of Multilayered Perovskites

Author: jacky even, claudine katan, wenbin li, hao zhang, boubacar traoré, claudio quarti, siraj sidhik, nicolas mercier, wei li, mercouri kanatzidis, jean-christophe blancon, aditya mohite, alia Skorokhod, Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Rice University [Houston], Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Mons (UMons), Université d'Angers (UA), Nankai University (NKU), Northwestern University [Evanston], ANR-18-CE05-0026,MORELESS,Cellules solaires perovskite plus stables et à teneur réduite en plomb.(2018), and European Project: PeroCUBE
Subjects: [PHYS]Physics [physics], [CHIM]Chemical Sciences
Abstract: International audience; The presentation will give an insight into new results on the interplay between structural, interfacial and optoelectronic properties in 2D multilayered halide perovskites, either in Ruddlesden Popper (RP) or Dion Jacobson (DJ) structure. We will see that the funneling of electronic carriers to the 2D crystal edges, important for ionization of electron-hole pairs in 2D RP phases, is also at work in bromide perovskites. Continuous and ultrafast photodoping will be further discussed, demonstrating their strong impact on the structural and carrier transport properties of DJ perovskites. It will also be illustrated how chemical engineering allows tuning the optoelectronic properties of 2D perovskites. Finally, we will introduce a DFT-based semi-empirical methodology to simulate band alignments, interface or surface dipoles and dielectric mismatches in 2D multilayered perovskites.
Published: 2022
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19. Diazine-based thermally activated delayed fluorescence chromophores

Author: Sylvain Achelle, Maxime Hodée, Julien Massue, Arnaud Fihey, Claudine Katan, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), and KATAN, Claudine
Subjects: Pyrimidine, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Process Chemistry and Technology, General Chemical Engineering, Push-Pull, TD-DFT, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Pyrazine, Thermally Activated Delayed Fluorescence, Diazine
Abstract: International audience; Diazines are electron deficient six-membered aromatic rings heterocycles which have successfully been employed in the design of a wide range of push-pull chromophores for various applications in the field of organic electronics and optoelectronics. For instance, some have been specifically designed to be inserted in the electroluminescent emission layer of organic light emitting diodes (OLED). OLED technology has continuously evolved and is currently used in industry for display and lighting purposes, offering many advantages including low turn-on voltage and power consumption. In the prospect to further reduce energy waste, a third generation of OLED based on thermally activated delayed fluorescence (TADF), which allows harvesting both triplet and singlet excitons, attracts increasing attention from the scientific community. In this review, we provide a comprehensive overview of the present status of diazine-based dyes developed for TADF. The pyrimidine core is by far the most used and has demonstrated deep blue, blue or sky-blue and green emission when combined with carbazole, acridan and phenoxazine fragments, respectively. Further design of TADF emitters is desirable to afford red OLED and both the pyrazine and pyridazine cores have been scarcely explored.
Published: 2022
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20. Reaching ultimate perovskite quantum dot optical properties with a new synthetic approach

Author: Tan NGUYEN, Quinten AKKERMAN, Simon BOEHME, Gabriele RAINO, Claudine KATAN, Jacky EVEN, Maksym KOVALENKO, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), European Project: 899141,PoLLoC, Nguyen, Thi Phuc Tan, and Polariton logic - PoLLoC - 899141 - INCOMING
Subjects: [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], [PHYS.COND.CM-MS] Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci]
Abstract: International audience; A new synthetic method for colloidal perovskite nanocrystals has been designed, which offers slow thermodynamic control [1] instead of conventional kinetic growth [2]. The reaction time is increased up to 30 minutes while a wide size range of nanoparticles, some even reaching the strong confinement regime, is obtained with high level control of size and shape [1]. The synthesized quantum dots (QDs) turn out to have a spheroidal shape on average with remarkably well-separated higher absorption peaks. For the first time, this allows for a direct comparison between theory and experimental data related to the transitions beyond the lowest absorption line. Using empirical modelling with second-order many body perturbation theory, we are able to predict the energy positions as well as the oscillator strength of not only the lowest 1s-1s exciton but also of the higher excitonic transitions [3]. The calculated values are in fair agreement with the experimental data. Besides, by taking into consideration the spherical and cuboidal confining potentials, our theory offers an explanation for the well-defined higher transitions inthe spheroidal QDs compared to cuboidal ones obtaining from more standard synthetic approaches [4]. The accuracy of the theoretical methods will be also critically discussed
Published: 2022

21. Organic Cation Alloying on Intralayer A and Interlayer A’ sites in 2D Hybrid Dion–Jacobson Lead Bromide Perovskites (A’)(A)Pb2Br7

Author: Constantinos C. Stoumpos, Peijun Guo, Ioannis Spanopoulos, Mercouri G. Kanatzidis, Claudine Katan, Richard D. Schaller, MikaÃ«l Kepenekian, Lingling Mao, Yihui He, Jacky Even, Ram Seshadri, Northwestern University [Evanston], Argonne National Laboratory [Lemont] (ANL), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), University of California [Santa Barbara] (UCSB), University of California, University of Crete [Heraklion] (UOC), SC0012541, Basic Energy Sciences, DE-AC02-06CH11357, U.S. Department of Energy, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), University of California [Santa Barbara] (UC Santa Barbara), and University of California (UC)
Subjects: [PHYS]Physics [physics], Photoluminescence, Band gap, Chemistry, Halide, General Chemistry, Crystal structure, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, symbols.namesake, Crystallography, Colloid and Surface Chemistry, Formamidinium, Lattice (order), symbols, [CHIM]Chemical Sciences, Density functional theory, Raman spectroscopy
Abstract: International audience; Hybrid layered halide perovskites have achieved impressive performance in optoelectronics. New structural types in the two-dimensional (2D) halide system such as the Dion-Jacobson phases have attracted wide research attention due to the short interlayer distance and unique layer orientation that facilitate better charge-transport and higher stability in optoelectronic devices. Here, we report the first solid solution series incorporating both A and A’ cations in the 2D Jacobson-Dion family, with the general formula (A’)(A)Pb2Br7 ((A’ = 3-(aminomethyl)piperidinium (3AMP) and 4-(aminomethyl)piperidinium) (4AMP); A= methylammonium (MA) and formamidinium (FA)). Mixing the spacing A’ cations and perovskitizer A cations generates the new (3AMP)a(4AMP)1-a(FA)b(MA)1-bPb2Br7 perovskites. The crystallographically refined crystal structures using single-crystal X-ray diffraction data re-veal that the distortion of the inorganic framework is heavily influenced by the degree of A’ and A alloying. A rising fraction of 4AMP in the structure, decreases the Pb-Br-Pb angles, making the framework more distorted. On the contrary, higher FA fractions increase the Pb-Br-Pb angles. This structural evolution fine tunes the optical properties where the larger the Pb-Br-Pb angle, the narrower the band gap. The photoluminescence emission energy mirrors this trend. Raman spectroscopy reveals a highly dynamical lattice similar to MAPbBr3 and consistent with the local distortion environment of the [Pb2Br7] framework. Density Functional Theory (DFT) calculations of the electronic structures reveal the same trend as the experimental results where (3AMP)(FA)Pb2Br7 has the smallest band gap while (4AMP)(MA)Pb2Br7 has the largest band gap. The structural effects from solely the organic cati-ons in the 2D system highlight the importance of understanding the high sensitivity of the optoelectronic properties on the struc-tural tuning in this broad class of materials.
Published: 2020
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22. Cation Engineering in Two-Dimensional Ruddlesden–Popper Lead Iodide Perovskites with Mixed Large A-Site Cations in the Cages

Author: Claudine Katan, Elad Harel, Ioannis Spanopoulos, Yongping Fu, Xiaotong Li, Xinyi Jiang, Jacky Even, Boubacar Traore, Mercouri G. Kanatzidis, Northwestern University [Evanston], Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), University of Crete [Heraklion] (UOC), Michigan State University System, W. M. Keck Foundation, Institut Universitaire de France, DMR-1838507, Division of Materials Research, International Institute for Nanotechnology, Northwestern University, State of Illinois, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Band gap, Iodide, Halide, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Crystallography, A-site, Colloid and Surface Chemistry, chemistry, Octahedron, Goldschmidt tolerance factor, Structural deformation, Perovskite (structure)
Abstract: International audience; The Goldschmidt tolerance factor in halide perovskites limits the number of cations that can enter their cages without destabilizing their overall structure. Here we have explored the limits of this geometric factor and found that the ethylammonium (EA) cations which lie outside the tolerance factor range can still enter the cages of the 2D halide perovskites by stretching them. The new perovskites allow us to study how these large cations occupying the perovskite cages affect the structural, optical, and electronic properties. We report a series of cation engineered 2D Ruddlesden-Popper lead iodide perovskites (BA)2(EAxMA1-x)2Pb3I10 (x = 0-1, BA is n-butylammonium, MA is methylammonium) by incorporating large EA cation in the cage. Analysis of the single-crystal structures reveals that the incorporation of EA in the cage significantly stretches Pb-I bonds, expands the cage, and induces a large octahedral distortion in the inorganic framework. Spectroscopic and theoretical studies show that such structural deformation leads to a blue-shifted bandgap, sub-bandgap trap states with wider energetic distribution, and stronger photoluminescence quenching. These results enrich the family of 2D perovskites and provide new insights for understanding the structure-property relationship in perovskite materials.
Published: 2020
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23. Tolerance Factor for Stabilizing 3D Hybrid Halide Perovskitoids Using Linear Diammonium Cations

Author: Xiaotong Li, Mikaël Kepenekian, Linda Li, Hao Dong, Constantinos C. Stoumpos, Ram Seshadri, Claudine Katan, Peijun Guo, Jacky Even, Mercouri G. Kanatzidis, Northwestern University [Evanston], Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Yale University [New Haven], University of Crete [Heraklion] (UOC), University of California [Los Angeles] (UCLA), University of California (UC), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), and At Northwestern University this work is mainly supported by the Department of Energy, Office of Science, Basic Energy Sciences, under Grant No. SC0012541 (synthesis, structure, and physical property characterization). For DFT calculations, the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2020-A0090907682 made by GENCI. M.K. acknowledges support from Region Bretagne through the Boost’ERC LaHPerOS project. J.E. acknowledges the financial support from the Institut Universitaire de France. Work at Yale is supported by the Yale University Lab Setup Fund.
Subjects: Colloid and Surface Chemistry, Chemical structure, Cations, Electrical conductivity, [CHIM]Chemical Sciences, Perovskites, General Chemistry, Biochemistry, Crystals, Catalysis
Abstract: International audience; Three-dimensional (3D) halide perovskites have attracted enormous research interest, but the choice of the A-site cations is limited by the Goldschmidt tolerance factor. In order to accommodate cations that lie outside the acceptable range of the tolerance factor, low-dimensional structures usually form. To maintain the favorable 3D connection, the links among the metal-halide octahedra need to be rearranged to fit the large cations. This can result in a departure from the proper corner-sharing perovskite architectures and lead to distinctly different perovskitoid motifs with edge- and face-sharing. In this work, we report four new 3D bromide perovskitoids incorporating linear organic diammonium cations, A’Pb(2)Br(6) (A’ is a +2 cation). We propose a rule that can guide the further expansion of this class of compounds, analogous to the notion of Goldschmidt tolerance factor widely adopted for 3D AMX(3) perovskites. The fundamental building blocks in A’Pb(2)Br(6) consist of two edge-shared octahedra, which are then connected by corner-sharing to form a 3D network. Different compounds adopt different structural motifs, which can be transformed from one to another by symmetry operations. Electronic structure calculations suggest that they are direct bandgap semiconductors, with relatively large band dispersions created by octahedra connected by corner-sharing. They exhibit similar electronic band structures and dynamic lattice characteristics to the regular 3D AMX(3) perovskites. Structures with smaller Pb-Br-Pb angles and larger octahedra distortion exhibit broad photoluminescence at room temperature. The emerging structure-property relationships in these 3D perovskitoids set the foundation for designing and investigating these compounds for a variety of optoelectronic applications.
Published: 2022
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24. Expanding the Cage of 2D Bromide Perovskites by Large A-Site Cations

Author: Xiaotong Li, Shelby A. Cuthriell, Ashanti Bergonzoni, Hao Dong, Boubacar Traoré, Constantinos C. Stoumpos, Peijun Guo, Jacky Even, Claudine Katan, Richard D. Schaller, Mercouri G. Kanatzidis, Northwestern University [Evanston], Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Yale University [New Haven], Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Crete [Heraklion] (UOC), Argonne National Laboratory [Lemont] (ANL), A.B. acknowledges support from Region Bretagne through the PERFOTON project. This work was granted access to the HPC resources of [TGCC/CINES/IDRIS] under the allocations 2021-A0100911434 and 2021-A0110907682 made by GENCI. J.E. acknowledges financial support from the Institut Universitaire de France., and European Project: PeroCUBE
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, General Chemical Engineering, Materials Chemistry, General Chemistry
Abstract: International audience; Two-dimensional (2D) halide perovskites have outstanding optoelectronic properties, and they feature a variety of organic cation spacers and cage A-site cations that can be incorporated into their structures. It has recently been reported that the Goldschmidt tolerance factor can be relaxed and expanded in iodide 2D perovskites. Bromide 2D perovskites, whose multilayer structures and optical properties are much less studied, provide a great platform for studying structure–property relationships for 2D perovskites with large A-site cations. Herein, we report the synthesis and structure of three new 2D bromide perovskites─(BA)2(MHy)2Pb3Br10 (BA, butylammonium; MHy, methylhydrazinium), (BA)2(EA)2Pb3Br10 (EA is ethylammonium), and (BA)2(DMA)Pb2Br7 (DMA is dimethylammonium). We compared them with other 2D perovskites with different A-site cations but with the same spacer and layer thickness. Single-crystal structures show that the Pb–Br bonds are elongated to accommodate the large A-site cations. Additionally, the octahedra in (BA)2(MHy)2Pb3Br10 and (BA)2(EA)2Pb3Br10 are highly distorted, and their different stacking patterns of the inner and outer layers lead to the formation of the n = 3 phases. Density functional theory calculations show that 2D perovskites with larger A-site cations (e.g., DMA, MHy, and EA) have smaller band dispersions and larger effective masses than those with Cs+ and MA. (BA)2(MHy)2Pb3Br10 also exhibits one of the largest Rashba splittings in the literature. Structures with large cage cations also exhibit high band gaps within the same n number and short photoluminescence (PL) lifetimes. Temperature- and power-dependent PL measurements reveal that the broad shoulder in the PL peak originates from the trap states.
Published: 2022
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25. Non-Equilibrium Lattice Dynamics in Photo-Excited Two-Dimensional Perovskites

Author: Shelby A. Cuthriell, Shobhana Panuganti, Craig C. Laing, Michael A. Quintero, Burak Guzelturk, Nuri Yazdani, Boubacar Traore, Alexandra Brumberg, Christos D. Malliakas, Aaron M. Lindenberg, Vanessa Wood, Claudine Katan, Jacky Even, Xiaoyi Zhang, Mercouri G. Kanatzidis, Richard D. Schaller
Published: 2022
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26. Band gap, effective masses, and energy level alignment of 2D and 3D halide perovskites and heterostructures using DFT-1/2

Author: Boubacar Traore, Jacky Even, Laurent Pedesseau, Mikaël Képénekian, Claudine Katan, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA), J.E. acknowledges financial support from the Institute Universitaire de France., and European Project: PeroCUBE
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Physics and Astronomy (miscellaneous), General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry
Abstract: The work was granted access to the HPC resources of [TGCC/CINES/IDRIS] under the allocations 2020-A0100911434 and 2020-A0090907682 made by GENCI.; International audience; We revisit the Slater half-occupation technique within the DFT-1/2 method to provide improved accuracy of 2D and 3D halide perovskites band gaps at a moderate computational cost. We propose an electron removal scheme from the halide states that drastically improve the predicted band gaps of 2D compounds. Concurrently, we compute the effective masses of the considered structures and show that DFT-1/2 describes them with a nice degree of accuracy when compared to available experimental data. Moreover, we assess the suitability of DFT-1/2 to compute the energy level alignments of this family of compounds. We compare the results in light of those we predict using the hybrid functional HSE06 and the many body perturbation theory within the $G0W0$ approximation. We discuss the limitations of our refined DFT-1/2 scheme, which tends to overestimate the downshift of the absolute valence energy levels of the layered perovskite systems. We anticipate that our results would be useful to initiate benchmark studies and investigate large systems such as heterostructures for which other approaches may be out of reach.
Published: 2022
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27. Taming the nucleation and growth kinetics of lead halide perovskite quantum dots

Author: Maksym Kovalenko, Quinten Akkerman, Tan Nguyen, Simon Boehme, Federico Montanarella, Dmitry Dirin, Philipp Wechsler, Finn Beiglböck, Rolf Erni, Claudine Katan, and Jacky Even
Abstract: Colloidal lead halide perovskite (LHP) nanocrystals (NCs, with bright and spectrally narrow photoluminescence (PL) tunable over the entire visible spectral range, are the latest generation of semiconductor quantum dots (QDs) of immense interest as classical and quantum light sources. LHP NCs form by sub-second fast and hence hard-to-control ionic metathesis reactions, which severely limits the access to size-uniform and shape-regular NCs in the sub-10 nm range. We posit that a synthesis path comprising an intricate equilibrium between the precursor (PbBr2) and the Cs[PbBr3] solute for the QD nucleation may circumvent this challenge. Here, we report a room-temperature synthesis of monodisperse, isolable spheroidal CsPbBr3 QDs, size-tunable in the 3-13 nm range. The kinetics of both nucleation and therefrom temporally separated growth are drastically slowed down by the formation of transient Cs[PbBr3], resulting in total reaction times of up to 30 minutes. The methodology is then extended to FAPbBr3 (FA = formamidinium) and MAPbBr3 (MA = methylammonium), allowing for thorough experimental comparison and modeling of their physical properties under intermediate quantum confinement. In particular, QDs of all these compositions exhibit up to four excitonic transitions in their linear absorption spectra and we demonstrate that the size-dependent confinement energy for all transitions is independent of the A-site cation.
Published: 2022
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28. A 3D Lead Iodide Hybrid Based on a 2D Perovskite Subnetwork

Author: Kepenekian, Maroua Ben Haj Salah, Justine Tessier, Nicolas Mercier, Magali Allain, Antonin Leblanc, Xiaoyang Che, Claudine Katan, and Mikael
Subjects: 3D network, halide perovskite, electronic structure, lead iodide hybrid
Abstract: Lead halide perovskites have emerged as promising materials for various optoelectronic applications. For photovoltaics, the reference compound is the 3D perovskite (MA)PbI3 (MA+ = methylammonium). However, this material suffers from instabilities towards humidity or light. This makes the search of new stable 3D lead halide materials very relevant. A strategy is the use of intermediate size cations instead of MA, which are not suitable to form the 3D ABX3 perovskites or 2D perovskites. Here, we report on a novel 3D metal halide hybrid material based on the intermediate size cation hydroxypropylammonium (HPA+), (HPA)6(MA)Pb5I17. We will see that extending the carbon chain length from two CH2 units (in the hydroxylethylammonium cation, HEA+) to three (HPA+) precludes the formation of a perovskite network as found in the lead and iodide deficient perovskite (HEA,MA)1+xPbxI3−x. In (HPA)6(MA)Pb5I17 the 3D lead halide network results from a 2D perovskite subnetworks linked by a PbI6 octahedra sharing its faces. DFT calculations confirm the direct band gap and reveal the peculiar band structure of this 3D network. On one hand the valence band has a 1D nature involving the p orbitals of the halide. On the other, the conduction band possesses a clear 2D character involving hybridization between the p orbitals of the metal and the halide.
Published: 2021
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29. Tetrazine molecules as an efficient electronic diversion channel in 2D organic-inorganic perovskites

Author: Jean-Sébastien Lauret, Gaëlle Trippé-Allard, Claudio Quarti, Laurent Galmiche, Jacky Even, Ferdinand Lédée, Damien Garrot, Pierre Audebert, Jérôme Marrot, Claudine Katan, Emmanuelle Deleporte, Laboratoire Lumière, Matière et Interfaces (LuMIn), CentraleSupélec-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Ecole Normale Supérieure Paris-Saclay (ENS Paris Saclay), Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM), École normale supérieure - Cachan (ENS Cachan)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Nano Optique et Spectroscopy (NOOS), CentraleSupélec-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Ecole Normale Supérieure Paris-Saclay (ENS Paris Saclay)-CentraleSupélec-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Ecole Normale Supérieure Paris-Saclay (ENS Paris Saclay), Groupe d'Etude de la Matière Condensée (GEMAC), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Université de Mons (UMons), J.E and J.S.L acknowledges the financial support from the Institut Universitaire de France. Computational investigations were conducted thanks to HPC resources provided by [TGCC/CINES/IDRIS] under the allocation 2020-A0010907682 made by GENCI., ANR-18-CE05-0026,MORELESS,Cellules solaires perovskite plus stables et à teneur réduite en plomb.(2018), ANR-18-CE24-0016,EMIPERO,Dispositifs émetteurs de lumière, pompés électriquement, à base de pérovskites hybrides(2018), European Project: 687008,H2020,H2020-FETOPEN-2014-2015-RIA,GOTSolar(2016), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), and Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)
Subjects: Materials science, 02 engineering and technology, Electronic structure, 010402 general chemistry, 01 natural sciences, 7. Clean energy, DFT, Electron transfer, Tetrazine, chemistry.chemical_compound, halide perovskites, Molecule, Moiety, General Materials Science, Electrical and Electronic Engineering, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], HOMO/LUMO, Perovskite (structure), energy transfer, Process Chemistry and Technology, band alignement, Heterojunction, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Mechanics of Materials, Chemical physics, tetrazine, 0210 nano-technology
Abstract: International audience; Taking advantage of an innovative design concept for layered halide perovskites with active chromophores acting as organic spacers, we present here the synthesis of two novel two-dimensional (2D) hybrid organic-inorganic halide perovskites incorporating for the first time 100% of a photoactive tetrazine derivative as organic component. Namely, the use of a heterocyclic ring containing a nitrogen proportion imparts a unique electronic structure to the organic component, with lowest energy optical absorption in the blue. The present compound, a tetrazine, presents several resonances between the organic and inorganic components, both in terms of single particle electronic levels and exciton states, providing the ideal playground to discuss charge and energy transfer mechanisms at the organic/inorganic interface. Photophysical studies along with hybrid Time-Dependent DFT simulations demonstrate partial energy transfer and rationalise the suppressed emission from the perovskite frame in terms of different energy-transfer diversion channels, potentially involving both singlet and triplet states of the organic spacer. Periodic DFT simulations also support the feasibility of electron transfers from the conduction band of the inorganic component to the LUMO of the spacer as potential quenching mechanism, suggesting the coexistence and competition of charge and energy transfer mechanisms in these heterostructure. Our work proves the feasibility of inserting photoactive small rings in a 2D perovskite structure, meanwhile providing a robust frame to rationalize the electronic interactions between the semiconducting inorganic layer and organic chromophores, with the prospects of optimizing the organic moiety according to the envisaged application.
Published: 2021
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30. Light-activated interlayer contraction in two-dimensional perovskites for high-efficiency solar cells

Author: Mercouri G. Kanatzidis, Boubacar Traore, Yafei Wang, Hao Zhang, Jean-Christophe Blancon, Joseph Strzalka, Justin M. Hoffman, Aditya D. Mohite, Wenbin Li, Joseph Essman, Claudine Katan, Ioannis Spanopoulos, Jared Crochet, Jacky Even, Austin Fehr, Jin Hou, Muhammad A. Alam, Siraj Sidhik, Reza Asadpour, Esther H. R. Tsai, Rice University [Houston], Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Purdue University [West Lafayette], Northwestern University [Evanston], Los Alamos National Laboratory (LANL), Brookhaven National Laboratory [Upton, NY] (BNL), U.S. Department of Energy [Washington] (DOE)-UT-Battelle, LLC-Stony Brook University [SUNY] (SBU), State University of New York (SUNY)-State University of New York (SUNY), Argonne National Laboratory [Lemont] (ANL), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), UT-Battelle, LLC-Stony Brook University [SUNY] (SBU), State University of New York (SUNY)-State University of New York (SUNY)-U.S. Department of Energy [Washington] (DOE), NSF 20-587, National Science Foundation, N00014-20-1-2725, United States Department of Defense | United States Navy | ONR | Office of Naval Research Global, DE-SC0012704, U.S. Department of Energy, N00014-20-1-2725, United States Department of Defense | United States Navy | Office of Naval Research, and U.S. Department of Defense
Subjects: [PHYS]Physics [physics], Electron mobility, Materials science, Superlattice, Photovoltaic system, Biomedical Engineering, Bioengineering, 02 engineering and technology, Conductivity, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 7. Clean energy, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, X-ray photoelectron spectroscopy, Chemical physics, [CHIM]Chemical Sciences, General Materials Science, Electrical and Electronic Engineering, 0210 nano-technology, Dispersion (chemistry), Perovskite (structure), Voltage
Abstract: Understanding and tailoring the physical behaviour of halide perovskites under practical environments is critical for designing efficient and durable optoelectronic devices. Here, we report that continuous light illumination leads to >1% contraction in the out-of-plane direction in two-dimensional hybrid perovskites, which is reversible and strongly dependent on the specific superlattice packing. X-ray photoelectron spectroscopy measurements show that constant light illumination results in the accumulation of positive charges in the terminal iodine atoms, thereby enhancing the bonding character of inter-slab I–I interactions across the organic barrier and activating out-of-plane contraction. Correlated charge transport, structural and photovoltaic measurements confirm that the onset of the light-induced contraction is synchronized to a threefold increase in carrier mobility and conductivity, which is consistent with an increase in the electronic band dispersion predicted by first-principles calculations. Flux-dependent space-charge-limited current measurement reveals that light-induced interlayer contraction activates interlayer charge transport. The enhanced charge transport boosts the photovoltaic efficiency of two-dimensional perovskite solar cells up to 18.3% by increasing the device’s fill factor and open-circuit voltage. Light-induced contraction in the out-of-plane direction in two-dimensional (2D) hybrid perovskites enables the realization of high-efficiency 2D perovskite solar cells.
Published: 2021
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31. Electronic structure and stability of Cs2TiX6 and Cs2ZrX6 (X = Br, I) vacancy ordered double perovskites

Author: Jacky Even, B. Cucco, Claudine Katan, Laurent Pedesseau, George Volonakis, Gaëlle Bouder, Mikael Kepenekian, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), The research leading to these results has received funding from the Chaire de Recherche Rennes Metropole project. This work was granted access to the HPC resources of TGCC under the allocations 2020-A0100911434 and 2020-A0090907682 made by GENCI. We acknowledge PRACE for awarding us access to the ARCHER2, United Kingdom., European Project: 862656,DROPIT, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), and Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)
Subjects: Materials science, Physics and Astronomy (miscellaneous), Phonon, Band gap, Optoelectronic Materials and Devices, FOS: Physical sciences, 02 engineering and technology, Electronic structure, 010402 general chemistry, 01 natural sciences, Stability (probability), Vacancy defect, [CHIM]Chemical Sciences, [PHYS]Physics [physics], Condensed Matter - Materials Science, Materials Science (cond-mat.mtrl-sci), 021001 nanoscience & nanotechnology, electronic structure, 0104 chemical sciences, solar cell, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemical physics, Charge carrier, Chemical stability, Electron configuration, lead free, 0210 nano-technology
Abstract: Vacancy ordered halide perovskites have been extensively investigated as promising lead-free alternatives to halide perovskites for various opto-electronic applications. Among these, Cs2TiBr6 has been reported as a stable absorber with interesting electronic and optical properties, such as a bandgap in the visible, and long carrier diffusion lengths. Yet, a thorough theoretical analysis of the exhibited properties is still missing in order to further assess its application potential from a material's design point of view. In this Letter, we perform a detailed analysis for the established Ti-based compounds and investigate the less-known materials based on Zr. We discuss in detail their electronic properties and band symmetries, highlight the similarity between the materials in terms of properties, and reveal limits for tuning electronic and optical properties within this family of vacancy ordered double perovskites that share the same electron configuration. We also show the challenges to compute accurate and meaningful quasi-particle corrections at the GW level. Furthermore, we address their chemical stability against different decomposition reaction pathways, identifying stable regions for the formation of all materials, while probing their mechanical stability employing phonon calculations. We predict that Cs2ZrI6, a material practically unexplored to date, shall exhibit a quasi-direct electronic bandgap well within the visible range, the smallest charge carrier effective masses within the Cs2BX6 (B = Ti, Zr; X = Br, I) compounds, and a good chemical stability. The research leading to these results has received funding from the Chaire de Recherche Rennes Metropole project and from the European Union's Horizon 2020 program through a FET Open research and innovation action under Grant Agreement No. 862656 (DROP-IT). This work was granted access to the HPC resources of TGCC under Allocation Nos. 2020-A0100911434 and 2020-A0090907682 made by GENCI. We acknowledge PRACE for awarding us access to the ARCHER2, United Kingdom.
Published: 2021
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32. From Zero- to One-Dimensional, Opportunities and Caveats of Hybrid Iodobismuthates for Optoelectronic Applications

Author: Claudine Katan, Nicolas Mercier, Matthieu Manceau, Mikael Kepenekian, Magali Allain, Alla Skorokhod, MOLTECH-Anjou, Université d'Angers (UA)-Centre National de la Recherche Scientifique (CNRS), Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Laboratoire Innovation pour les Technologies des Energies Nouvelles et les Nano matériaux [Université Hassan 1er - Settat] (LITEN), Université Hassan 1er [Settat], Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Centre National de la Recherche Scientifique (CNRS), At ISCR and MOLTECH-Anjou, the work was mainly supported by the Agence Nationale pour la Recherche (MORELESS project). For DFT calculations, this work was granted access to the HPC resources of TGCC/CINES/IDRIS under Allocation 2020-A0090907682 made by GENCI. ISCR has benefited from the support of European Union’s Horizon 2020 research and innovation Programme under the grant agreement no. 862656., ANR-18-CE05-0026,MORELESS,Cellules solaires perovskite plus stables et à teneur réduite en plomb.(2018), European Project: 862656,DROPIT, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: chemistry.chemical_classification, Zero (complex analysis), 02 engineering and technology, Electron acceptor, electronic structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, Dication, solar cell, Inorganic Chemistry, chemistry, Chemical physics, [CHIM]Chemical Sciences, lead free, Physical and Theoretical Chemistry, 0210 nano-technology, Hybrid material, Optoelectronic Applications
Abstract: The association of the electron acceptor 4,4’-amino-bipyridinium (AmV2+) dication and BiI3 in an acidic solution affords three organic−inorganic hybrid materials, (AmV)3(BiI6)2 (1), (AmV)2(Bi4I16) (2), and (AmV)BiI5 (3), whose structures are based on isolated BiI63− and Bi4I164− anion clusters in 1 and 2, respectively, and on a one-dimensional (1D) chain of trans-connected corner-sharing octahedra in 3. In contrast with known methylviologen-based hybrids, these compounds are more soluble in polar solvents, allowing thin film formation by spin-coating. (AmV)BiI5 exhibits a broad absorption band in the visible region leading to an optical bandgap of 1.54 eV and shows a PV effect as demonstrated by a significant open-circuit voltage close to 500 mV. The electronic structure of the three compounds has been investigated using first-principles calculations based on density functional theory (DFT). Unexpectedly, despite the trans-connected corner-shared octahedra, for (AmV)BiI5, the valence state shows no coupling along the wire direction, leading to a high effective mass for holes, while in contrast, the strong coupling between Bi 6px orbitals in the same direction at the conduction band minimum suggests excellent electron transport properties. This contributes to the low current output leading to the low efficiency of perovskite solar cells based on (AmV)BiI5. Further insight is provided for trans- and cis-MI5 1D model structures (M = Bi or Pb) based on DFT investigations.
Published: 2021
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33. Insight into the exciton fine structure, the role of phonons and depolarization effects in halide perovskite nanocrystals

Author: Guido Roma, Philippe Tamarat, Claudine Katan, Maryna I. Bodnarchuk, Maksym V. Kovalenko, Brahim Lounis, philipe bourges, Jacky Even, Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Photonique, Numérique et Nanosciences (LP2N), Université de Bordeaux (UB)-Institut d'Optique Graduate School (IOGS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Service de recherches de métallurgie physique (SRMP), Département des Matériaux pour le Nucléaire (DMN), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratory for Thin Films and Photovoltaics, Empa, Institute of Inorganic Chemistry, ETH Zürich, European Project: 899141,PoLLoC, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: [PHYS]Physics [physics], Condensed Matter::Materials Science, Materials science, Nanocrystal, Phonon, Chemical physics, Exciton, Physics::Atomic and Molecular Clusters, Halide, [CHIM]Chemical Sciences, Depolarization, Perovskite (structure)
Abstract: International audience; Halide perovskite nanocrystals have been introduced in 2015 as a promising route to efficient light emitting devices, and more recently as potential single photon emitters. Their radiative recombinations are governed by excitons, but the bright or dark character of the ground state is debated.
Published: 2021
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34. Influence of surface termination on electronic configurations at FASnI3/C60 interfaces

Author: Pingping Jiang, Claudine Katan, Laurent Pedesseau, Mikael Kepenekian, Jacky Even, George Volonakis, Boubacar Traore, Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), European Project: 862656,DROPIT, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Surface (mathematics), [PHYS]Physics [physics], Materials science, [CHIM]Chemical Sciences, Electron configuration, 7. Clean energy, Molecular physics
Abstract: International audience; Ever since organic-inorganic halide perovskites have been employed in electronics and optoelectronics, their unique and excellent photophysical and electrical properties have guaranteed their versatile applications in solar cells, LEDs, lasers, photodetectors and beyond . Sn-based perovskites along with their surface and interface functionalization after assembling with charge transport layers (CTLs) are considered promising ways to achieve a win-win between environmental friendliness and cell performance.
Published: 2021
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35. New results on the interplay between structural and optoelectronic properties of multilayered perovskites

Author: Wei Li, Claudine Katan, Mercouri G. Kanatzidis, Siraj Sidhik, Jacky Even, Jean-Christophe Blancon, Aditya D. Mohite, weibin li, Hao Zhang, Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Rice University [Houston], Nankai University (NKU), Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Northwestern University [Evanston], Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: [PHYS]Physics [physics], Materials science, business.industry, Optoelectronics, [CHIM]Chemical Sciences, business
Abstract: International audience; The presentation will give an insight into the interplay between structural and optoelectronic properties in 2D multilayered halide perovskites, either in Ruddlesden Popper or Dion Jacobson structure.
Published: 2021
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36. m -Phenylenediammonium as a New Spacer for Dion–Jacobson Two-Dimensional Perovskites

Author: Shengzhong Liu, Yalan Zhang, Boubacar Traoré, Xiaotong Li, Claudine Katan, Yu Han, Kui Zhao, Mercouri G. Kanatzidis, Lili Gao, Junjie Fang, Jacky Even, Shaanxi Normal University (SNNU), Northwestern University [Evanston], Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), J.E. acknowledges the financial support fromthe Institut Universitaire de France. The calculation work wasgranted access to the HPC resources of [TGCC/CINES/IDRIS] under the allocation 2020-A0080911434 made byGENCI., European Project: PeroCUBE, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), and Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)
Subjects: business.industry, Chemistry, Band gap, Stacking, Halide, 02 engineering and technology, General Chemistry, Crystal structure, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Crystallography, Colloid and Surface Chemistry, Semiconductor, [CHIM.CRIS]Chemical Sciences/Cristallography, Density functional theory, 0210 nano-technology, Dispersion (chemistry), business, Perovskite (structure)
Abstract: International audience; Two-dimensional (2D) halide perovskites have several distinct structural classes and exhibit great tunability, stability, and high potential for photovoltaic applications. Here, we report a new series of hybrid 2D perovskites in the Dion–Jacobson (DJ) class based on aromatic m-phenylenediammonium (mPDA) dications. The crystal structures of the DJ perovskite materials (mPDA)MAn–1PbnI3n+1 (n = 1–3) were solved and refined using single-crystal X-ray crystallography. The results indicate a short I···I interlayer distance of 4.00–4.04 Å for the (mPDA)MAn–1PbnI3n+1 (n = 2 and 3) structures, which is the shortest among DJ perovskites. However, Pb–I–Pb angles are as small as 158–160°, reflecting the large distortion of the inorganic framework, which results in larger band gaps for these materials than those in other DJ analogues. Density functional theory calculations suggest appreciable dispersion in the stacking direction, unlike the band structures of the Ruddlesden–Popper phases, which exhibit flat bands along the stacking direction. This is a consequence of the short interlayer I···I distances that can lead to interlayer electronic coupling across the layers. The solution-deposited films (nominal (mPDA)MAn–1PbnI3n+1 compositions of n = 1–6) reveal improved surface coverage with increasing nominal n value with the higher n films being composed of a mixture of n = 1 and bulk three-dimensional MAPbI3 perovskites. The films made from solutions of these materials behave differently from those of other 2D iodide perovskites, and their solar cells have a mixture of n = 1 DJ and MAPbI3 as light-absorbing semiconductors.
Published: 2021
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37. Influence on photophysical properties of (de)protonation of phenol-substituted diazine chromophores: experimental and theoretical studies

Author: Maxime Hodée, Augustin Lenne, Julian Rodriguez-Lopez, Françoise Robin-Le Guen, Sylvain Achelle, Claudine Katan, Arnaud Fihey, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Instituto de Nanociencia, Nanotecnologia y Materiales Moleculares, Universidad de Castilla-La Mancha (INAMOL), Universidad de Castilla-La Mancha (UCLM), Calculations were performed at ISCR and the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2021-A0100800649 made by Grand Equipement National de Calcul Intensif (GENCI)., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidad de Castilla-La Mancha = University of Castilla-La Mancha (UCLM)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2021

38. The importance of relativistic effects on two-photon absorption spectra in metal halide perovskites

Author: Tom J. Savenije, Jos Thieme, Zimu Wei, Jacky Even, Claudine Katan, Valentina M. Caselli, Dengyang Guo, Delft University of Technology (TU Delft), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Absorption spectroscopy, Science, General Physics and Astronomy, Halide, Physics::Optics, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Two-photon absorption, Molecular physics, General Biochemistry, Genetics and Molecular Biology, Spectral line, Article, Condensed Matter::Materials Science, Tight binding, [CHIM]Chemical Sciences, Spectroscopy, Absorption (electromagnetic radiation), lcsh:Science, [PHYS]Physics [physics], Multidisciplinary, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Brillouin zone, Physical chemistry, OA-Fund TU Delft, Condensed Matter::Strongly Correlated Electrons, lcsh:Q, 0210 nano-technology, Materials for energy and catalysis
Abstract: Despite intense research into the optoelectronic properties of metal halide perovskites (MHPs), sub-bandgap absorption in MHPs remains largely unexplored. Here we recorded two-photon absorption spectra of MHPs using the time-resolved microwave conductivity technique. A two-step upward trend is observed in the two-photon absorption spectrum for methylammonium lead iodide, and some analogues, which implies that the commonly used scaling law is not applicable to MHPs. This aspect is further confirmed by temperature-dependent conductivity measurements. Using an empirical multiband tight binding model, spectra for methylammonium lead iodide were calculated by integration over the entire Brillouin zone, showing compelling similarity with experimental results. We conclude that the second upward trend in the two-photon absorption spectrum originates from additional optical transitions to the heavy and light electron bands formed by the strong spin-orbit coupling. Hence, valuable insight can be obtained in the opto-electronic properties of MHPs by sub-bandgap spectroscopy, complemented by modelling., Metal halide perovskites possess interesting properties but their sub-bandgap absorption remains largely unexplored. Here Wei et al. employ two-photon absorption spectroscopy with time-resolved microwave conductivity technique to confirm the existence of strong spin-orbit coupling effect.
Published: 2019
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39. Tuning Electronic Structure in Layered Hybrid Perovskites with Organic Spacer Substitution

Author: Amanda Neukirch, Aditya D. Mohite, Jacky Even, Joshua Leveillee, Claudine Katan, Wanyi Nie, Andre Schleife, Dibyajyoti Ghosh, Sergei Tretiak, University of Illinois at Urbana-Champaign [Urbana], University of Illinois System, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Los Alamos National Laboratory (LANL), DMR-1555153, National Science Foundation, State of Illinois, Los Alamos National Laboratory Directed Research and Development Funds, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Exciton, Bioengineering, 02 engineering and technology, Electronic structure, triplet light emission, 7. Clean energy, Condensed Matter::Materials Science, [CHIM]Chemical Sciences, exciton energy alignment, General Materials Science, Singlet state, Triplet state, Perovskite (structure), [PHYS]Physics [physics], Mechanical Engineering, organic spacer substitution, first-principles simulations, halide perovskite, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Chemical physics, Excited state, Light emission, Density functional theory, Layered hybrid organic−inorganic perovskites, 0210 nano-technology
Abstract: International audience; Two-dimensional layered halide organic perovskites (LHOPs) are promising candidates for many optoelectronic applications due to their interesting tunable properties. They provide a unique opportunity to control energy and charge dynamics via the independent tunability of the energy levels within the perovskite and the organic spacer for various optoelectronic applications. In the perovskite layer alone, one can replace the Pb (Sn), the halide (X=I,Br,Cl), the organic component, and the number of layers between the organic spacer layers. In addition, there are many possibilities for organic spacer layers between the perovskite layers, making it difficult for experimental methods to comprehensively explore such extensive combinatorial space. Of particular technological interest is alignment of electronic levels between the perovskite layer and the organic spacer layer, leading to desired transfer of energy or charge carriers between perovskite and organic components. For example, as band edge absorption is almost entirely attributed to the perovskite layer, one way to demonstrate energy transfer is to observe triplet emission from organic spacers. State-of-the-art computational chemistry tools can be used to predict the properties of many stoichiometries in search for LHOPs that have the most promising electronic structure features. In this first principles study, we survey a group of π-conjugated organic spacer candidates for use in triplet light emitting LHOPs. Utilizing density functional theory (DFT) and time-dependent DFT, we calculate the first singlet (S1) and triplet (T1) excitation energy in the ground-state geometry and the first triplet excitation energy in the excited triplet state relaxed geometry (T1*). By comparing these energies to the known lowest exciton energy level of PbnX(3n+1) perovskite layers (X=I, Br, Cl), organic spacer and perovskite layer pairings can be identified for possible transfer of Wannier excitons from the inorganic perovskite lattice to spin-triplet Frenkel excitons located on the organic cation. We successfully identify ten organic spacer candidates for possible pairing with perovskite layers of specific halide composition to achieve triplet light emission across the visible energy range. Molecular dynamics simulations predict that finite temperatures and perovskite environment have little influence on the excitation energies of the two common organic spacers naphthylethylammonium (NEA) and phenelethylammonium (PEA). We find significant thermal broadening up to 0.5 eV of the optical excitation energies appearing due to finite temperature effects. The findings herein provide insights into alignment of electronic levels of conjugated organic spacer with perovskite layer.
Published: 2019
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40. Halide Perovskite High-k Field Effect Transistors with Dynamically Reconfigurable Ambipolarity

Author: Boubacar Traoré, Aditya D. Mohite, Gary McCuistian, Bruce W. Alphenaar, Sergei Tretiak, Hugo Bellezza, Nicolo Zagni, Fangze Liu, Jared Crochet, Mercouri G. Kanatzidis, Kasun Fernando, Claudine Katan, Régis Rogel, Noelia Devesa Canicoba, Jacky Even, Muhammad Ashraf Alam, Jean-Christophe Blancon, Wanyi Nie, Laurent Le Brizoual, Hsinhan Tsai, Los Alamos National Laboratory (LANL), Institut d'Électronique et des Technologies du numéRique (IETR), Université de Nantes (UN)-Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Purdue University [West Lafayette], Rice University [Houston], Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Northwestern University [Evanston], University of Louisville, DE-FOA-0002022-1652, Office of Energy Efficiency and Renewable Energy, Laboratory Directed Research and Development, SC0012541, Office of Science, Institut Universitaire de France, CBET-1512106, Division of Chemical, Bioengineering, Environmental, and Transport Systems, Rice University, Nantes Université (NU)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Nantes (UN)-Université de Rennes 1 (UR1), École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [PHYS]Physics [physics], Materials science, business.industry, Ambipolar diffusion, General Chemical Engineering, Biomedical Engineering, Halide, 02 engineering and technology, Dielectric, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Hysteresis, Modulation, [CHIM]Chemical Sciences, Optoelectronics, General Materials Science, Field-effect transistor, 0210 nano-technology, business, High-κ dielectric, Perovskite (structure)
Abstract: International audience; Despite the remarkable optoelectronic properties of halide perovskites, achieving reproducible field effect transistor (FET) action in polycrystalline films at room temperature has been challenging and represents a fundamental bottleneck for understanding electronic charge transport in these materials. In this work, we report halide perovskite-based FET operation at room temperature with negligible hysteresis. Extensive measurements and device modeling reveal that incorporating high-k dielectrics enables modulation of the channel conductance. Furthermore, continuous bias cycling or resting allows dynamical reconfiguration of the FETs between p-type behavior and ambipolar FET with balanced electron and hole transport and an ON/OFF ratio up to 104 and negligible degradation in transport characteristics over 100 cycles. These results elucidate the path for achieving gate modulation in perovskite thin-films and provide a platform to understand the interplay between the perovskite structure, and external stimuli such as photons, fields and functional substrates, which will lead to novel and emergent properties.
Published: 2019
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41. Seven-Layered 2D Hybrid Lead Iodide Perovskites

Author: Claudine Katan, Weijun Ke, Jacky Even, Lingling Mao, Rhys M. Kennard, Mercouri G. Kanatzidis, Michael L. Chabinyc, Boubacar Traore, Constantinos C. Stoumpos, Northwestern University [Evanston], University of California [Santa Barbara] (UC Santa Barbara), University of California (UC), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), SC0012541, Basic Energy Sciences, A0010907682, Agence Nationale de la Recherche, N00014-17-1-2231, Office of Naval Research, ANR-15-CE05-0018,TRANSHYPERO,Vers une compréhension des propriétés de transport électronique des cellules solaires basées sur les pérovskites hybrides(2015), University of California [Santa Barbara] (UCSB), University of California, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), and Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)
Subjects: Materials science, Photoluminescence, General Chemical Engineering, Halide, 02 engineering and technology, Crystal structure, 010402 general chemistry, 01 natural sciences, Biochemistry, photoconductivity solar cells, Phase (matter), Materials Chemistry, Environmental Chemistry, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], 2D semiconductors, Photoconductivity, Biochemistry (medical), [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Absorption edge, Density of states, Density functional theory, 0210 nano-technology, organic-inorganic hybrids
Abstract: the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2017-A0010907682 made by GENCI; International audience; Two-dimensional hybrid halide perovskites offer high chemical versatility, strong potential in optoelectronics. Here, we report the highest layer thickness perovskites yet to be crystallographically characterized, for the Dion-Jacobson (DJ) family. The seven-layered DJ phase (4AMP)(MA) 6Pb 7I 22 (4AMP =4-aminomethylpyperidinium) shows less distortion in the crystal structure than the Ruddlesden-Popper (RP) phase (BA) 2(MA) 6Pb 7I 22 (BA = butylammonium). The comparison of the DJ and RP perovskites reveals that the fine structural details still influence the optical properties, with the DJ phase maintaining a lower energy absorption edge and photoluminescence emission (1.53 and 1.70 eV) than the RP phase (1.57 and 1.74 eV). Density functional theory (DFT) calculations show that the localized density of states of conduction band minimum and valence band maximum are situated at different parts of the layers, implying separate channels in the structure followed by electrons and holes. Unlocking high-layer-thickness layered perovskites provides accessibility to new perovskites for high-performance optoelectronics.
Published: 2019
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42. Two-Dimensional Dion–Jacobson Hybrid Lead Iodide Perovskites with Aromatic Diammonium Cations

Author: Weijun Ke, Mikael Kepenekian, Jacky Even, Ido Hadar, Xiaotong Li, Mercouri G. Kanatzidis, Peijun Guo, Richard D. Schaller, Claudine Katan, Boubacar Traore, Constantinos C. Stoumpos, Northwestern University [Evanston], Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Argonne National Laboratory [Lemont] (ANL), The Hebrew University of Jerusalem (HUJ), Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), W. M. Keck Foundation, Institut Universitaire de France, 1720139, Division of Materials Research, International Institute for Nanotechnology, Northwestern University, R?gion Bretagne, State of Illinois, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Photoluminescence, solar cell devices, Iodide, Stacking, Halide, Dielectric, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Biochemistry, Catalysis, chemistry.chemical_compound, Colloid and Surface Chemistry, halide perovskites, [CHIM]Chemical Sciences, Perovskite (structure), [PHYS]Physics [physics], chemistry.chemical_classification, General Chemistry, natural quantum-wells, 0104 chemical sciences, Crystallography, Octahedron, chemistry, dielectric constant, photoluminescence, Pyridinium, exciton binding energy
Abstract: International audience; Two-dimensional (2D) halide perovskites have extraordinary optoelectronic properties and structural tunability. Among them, the Dion-Jacobson phases with the inorganic layers stacking exactly on top of each other are less explored. Herein, we present the new series of 2D Dion-Jacobson halide perovskites, which adopt the general formula of A′An-1PbnI3n+1 (A′ = 4-(aminomethyl)pyridinium (4AMPY), A = methylammonium (MA), n = 1−4). By modifying the position of the -CH2NH3+ group from 4AMPY to 3AMPY (3AMPY = 3-(aminomethyl)pyridinium), the stacking of the inorganic layers changes from exactly eclipsed to slightly offset. The perovskite octahedra tilts are also different between the two series, with the 3AMPY series exhibiting smaller bandgaps than the 4AMPY series. Compared to the aliphatic cation of the same size (AMP = (aminomethyl)piperidinium), the aromatic spacers increase the rigidity of the cation, reduce the interlayer spacing and decrease the dielectric mismatch between inorganic layer and the organic spacer, showing the indirect but powerful influence of the organic cations on the structure and consequently on the optical properties of the perovskite materials. All A′An-1PbnI3n+1 compounds exhibit strong photoluminescence (PL) at room temperature. Preliminary solar cell devices based on the n = 4 perovskites as absorbers of both series exhibit promising performances, with a champion power conversion efficiency (PCE) of 9.20 % for (3AMPY)(MA)3Pb4I13 based devices, which is higher than the (4AMPY)(MA)3Pb4I13 and the corresponding aliphatic analogue (3AMP)(MA)3Pb4I13 based ones.
Published: 2019
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43. Density Functional Theory Simulations of Semiconductors for Photovoltaic Applications: Hybrid Organic-Inorganic Perovskites and III/V Heterostructures

Author: Jacky Even, Laurent Pedesseau, Eric Tea, Samy Almosni, Alain Rolland, Cédric Robert, Jean-Marc Jancu, Charles Cornet, Claudine Katan, Jean-François Guillemoles, and Olivier Durand
Subjects: Renewable energy sources, TJ807-830
Abstract: Potentialities of density functional theory (DFT) based methodologies are explored for photovoltaic materials through the modeling of the structural and optoelectronic properties of semiconductor hybrid organic-inorganic perovskites and GaAs/GaP heterostructures. They show how the properties of these bulk materials, as well as atomistic relaxations, interfaces, and electronic band-lineups in small heterostructures, can be thoroughly investigated. Some limitations of available standard DFT codes are discussed. Recent improvements able to treat many-body effects or based on density-functional perturbation theory are also reviewed in the context of issues relevant to photovoltaic technologies.
Published: 2014
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44. Structural and thermodynamic limits of layer thickness in 2D halide perovskites

Author: Mikael Kepenekian, Claudine Katan, Jacky Even, Laurent Pedesseau, Jean-Christophe Blancon, Aditya D. Mohite, Hsinhan Tsai, Duyen H. Cao, Alexandra Navrotsky, Ferdinand S. Melkonyan, Mercouri G. Kanatzidis, Wanyi Nie, Radha Shivaramaiah, Chan Myae Myae Soe, Boubacar Traore, Constantinos C. Stoumpos, Tobin J. Marks, G. P. Nagabhushana, Northwestern University [Evanston], Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, USA, Peter A. Rock Thermochemistry Laboratory, University of California Davis, University of California [Davis] (UC Davis), University of California-University of California, Los Alamos National Laboratory (LANL), Department of Chemical and Biomolecular Engineering, Rice University, Rice University [Houston], Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Department of materials science and technology, University of Crete, The work at ISCR was granted access to the high-performance computing resources of Très GrandCentre de Calcul/Centre Informatique National de l’Enseignement Supérieur/Institut du Développement et des Ressources en Informatique Scientifique underthe allocation 2017-A0010907682made by Grand Equipement National de CalculIntensif. J.E. acknowledges support by Institut Universitaire de France., ANR-15-CE05-0018,TRANSHYPERO,Vers une compréhension des propriétés de transport électronique des cellules solaires basées sur les pérovskites hybrides(2015), University of California (UC)-University of California (UC), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Ruddlesden–Popper halide perovskites, Iodide, Halide, Ruddlesden-Popper halide perovskites, 02 engineering and technology, Crystal structure, 010402 general chemistry, 7. Clean energy, 01 natural sciences, quantum confinement, Homologous series, chemistry.chemical_compound, Affordable and Clean Energy, homologous series, layered compounds, [CHIM.CRIS]Chemical Sciences/Cristallography, Perovskite (structure), chemistry.chemical_classification, formation enthalpy, Multidisciplinary, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, light emitting diodes, Standard enthalpy of formation, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, photovoltaics, Layered compounds, PNAS Plus, chemistry, Quantum dot, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Physical chemistry, Chemical stability, 0210 nano-technology, calorimetry
Abstract: In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A′)(2)(A)(n−1)M(n)X(3n+1) [where A = Cs(+), CH(3)NH(3)(+), HC(NH(2))(2)(+); A′ = ammonium cation acting as spacer; M = Ge(2+), Sn(2+), Pb(2+); and X = Cl(−), Br(−), I(−)] have recently made a critical entry. The n value defines the thickness of the 2D layers, which controls the optical and electronic properties. The 2D perovskites have demonstrated preliminary optoelectronic device lifetime superior to their 3D counterparts. They have also attracted fundamental interest as solution-processed quantum wells with structural and physical properties tunable via chemical composition, notably by the n value defining the perovskite layer thickness. The higher members (n > 5) have not been documented, and there are important scientific questions underlying fundamental limits for n. To develop and utilize these materials in technology, it is imperative to understand their thermodynamic stability, fundamental synthetic limitations, and the derived structure–function relationships. We report the effective synthesis of the highest iodide n-members yet, namely (CH(3)(CH(2))(2)NH(3))(2)(CH(3)NH(3))(5)Pb(6)I(19) (n = 6) and (CH(3)(CH(2))(2)NH(3))(2)(CH(3)NH(3))(6)Pb(7)I(22) (n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for “(CH(3)(CH(2))(2)NH(3))(2)(CH(3)NH(3))(8)Pb(9)I(28)” (“n = 9”). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (ΔH(f)), suggesting the formation of higher homologs to be challenging. Finally, we report preliminary n-dependent solar cell efficiency in the range of 9–12.6% in these higher n-members, highlighting the strong promise of these materials for high-performance devices.
Published: 2018
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45. Tetrazine-incorporating layered halide perovskites featuring type II electronic interface: a small cation with several optical and electronic resonances

Author: Emmanuelle Deleporte, Ferdinand Ledee, Pierre Audebert, Gaëlle Trippé-Allard, Laurent Galmiche, Damien Garrot, Marrot Jérôme, Jean‐sébastien Lauret, Claudine Katan, Jacky Even, Claudio Quarti, Laboratoire Lumière, Matière et Interfaces (LuMIn), CentraleSupélec-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Ecole Normale Supérieure Paris-Saclay (ENS Paris Saclay), Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Ecole Normale Supérieure Paris-Saclay (ENS Paris Saclay), Groupe d'Etude de la Matière Condensée (GEMAC), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Mons [Belgium] (UMONS), ANR-18-CE05-0026,MORELESS,Cellules solaires perovskite plus stables et à teneur réduite en plomb.(2018), ANR-18-CE24-0016,EMIPERO,Dispositifs émetteurs de lumière, pompés électriquement, à base de pérovskites hybrides(2018), European Project: 687008,H2020,H2020-FETOPEN-2014-2015-RIA,GOTSolar(2016), Université Paris-Saclay, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), and Université de Mons (UMons)
Subjects: [PHYS]Physics [physics], [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract: J.E and J.S.L acknowledges the financial support from the InstitutUniversitaire de France. Computational investigations were conducted thanks to HPC resourcesprovided by [TGCC/CINES/IDRIS] under the allocation 2020-A0010907682 made by GENCI.; National audience; Layered halide perovskites are a class of semiconductors easily produced via chemical approaches and showing unique optical and electronic properties. These materials have a natural quantum-well electronic structure, that is, the band-gap of the inorganic frame is embedded into that of the organic spacers,[1] and feature effective light absorption, positive in-plane transport properties, effective narrow linewidth emission and improved stability against their 3D counterpart.[2] On the other hand, confinement of semiconducting properties in an inorganic is not ideal for applications where photogenerated species are required to effectively travel within the optically active component. This is the typical case of photovoltaics, where ineffective out-of-plane charge transport results in depleted performances for layered halide perovskites, as compared to 3D analogues.[3] In this frame, substituting the (usually) electronic inert organic spacer with organic chromophores featuring extended -conjugated core can pave the way for layered materials showing improved charge and energy transport properties.[4] Indeed, the band-gap closing due to extended -electronic conjugation can result in the (de)stabilization of the frontier orbitals of the spacer, compared to those of the inorganic frame, resulting in the formation of a type II heterojunction at the organic/inorganic interface. Here, we discuss the related charge/energy transfer processes on the basis of recently reported PbX4 (X=Cl,Br) layered perovskite frame incorporating tetrazine derivative as organic spacer.[5] Thanks to the various energy resonances between the inorganic and the organic component, both at the level of the single particle electronic states and at the level of many-body exciton states, this system represents the ideal test case to discuss in the detail charge and energy transfer processes at the type II interface. Furthermore, the incorporation of this novel chromophore as spacer is based on a new design concept, which exploits heterocycles with large fraction of nitrogen, rather than extending the size of carbon-based -core.[6] Photoluminescence (PL) and Photoluminescence Excitation (PLE) measurements indicate partial energy transfer from the inorganic frame to the organic component. Furthermore, cutting-edge, periodic DFT simulations suggest potential exciton ionization as potential responsible for the suppressed light emission from the perovskite frame. REFERENCES[1] C. Katan, et al. Chem. Rev. 2019, 119, 3140−3192[2] M. D. Smith, et al., Chem. Rev. 2019, 119, 3104−3139[3] H. Tsai, et al., Nature 2016, 536, 312–316[4] D. B. Mitzi, et al., Inorg. Chem. 1999, 38, 6246-6256[5] F. Ledée et al., revised manuscript submitted to Mater. Horiz.[6] Y. Gao, Nat. Chem. 2019, 11, 1151–1157
Published: 2021

46. Effect of protonation on the photophysical properties of 4-substituted and 4,7-disubstituted quinazoline push-pull chromophores

Author: Arnaud Fihey, Claudine Katan, Françoise Robin-le Guen, Julián Rodríguez-López, Rodrigo Plaza-Pedroche, Sylvain Achelle, D. N. Georgiou, Mihalis Fakis, Facultad de Ciencias y Tecnologias Quimicas, Universidad de Castilla-La Mancha = University of Castilla-La Mancha (UCLM), University of Patras, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CTQ2017-84561-P, Ministerio de Economía y Competitividad, Agencia Estatal de Investigación, SBPLY/17/180501/000214, Junta de Comunidades de Castilla-La Mancha, Universidad de Castilla-La Mancha (UCLM), University of Patras [Patras], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Photoluminescence, Materials science, General Chemical Engineering, Protonation, 02 engineering and technology, 010402 general chemistry, Ring (chemistry), Photochemistry, 01 natural sciences, chemistry.chemical_compound, push-pull chromophores, White light, Quinazoline, quinazolines, Push pull, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Process Chemistry and Technology, Solvatochromism, white-light emission, Chromophore, 021001 nanoscience & nanotechnology, 0104 chemical sciences, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, fluorescence, 0210 nano-technology
Abstract: International audience; White-light emission from single molecular systems has attracted a great deal of attention due to their advantages over multicomponent emitters. Azaheterocyclic push-pull derivatives have been demonstrated to be white emitters by combining neutral and protonated forms in the appropriate ratio, although limited cases of white-light emission have been reported from quinazoline derivatives. Herein, we describe a series of push-pull 4-substituted and 4,7-disubstituted quinazolines that show white photoluminescence both in solution and in the solid state. All of the materials were prepared by straightforward Suzuki-Miyaura crosscoupling reactions and the compounds exhibited remarkable emission solvatochromism. In some cases the presence of acid prompted the appearance of emission bands of complementary colors. Thus, multicolor photoluminescence, including white light, could be finely tuned by the controlled protonation of the electron-deficient quinazoline ring.
Published: 2021
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47. DFT Simulations as Valuable Tool to Support NMR Characterization of Halide Perovskites: the Case of Pure and Mixed Halide Perovskites

Author: Eric Furet, Claudio Quarti, Claudine Katan, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), University of Mons [Belgium] (UMONS), Agence Nationale de la RechercheFrench National Research Agency (ANR) European Commission [ANR-18-CE05-0026], ANR-18-CE05-0026,MORELESS,Cellules solaires perovskite plus stables et à teneur réduite en plomb.(2018), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemistry, Organic Chemistry, structure elucidation, Halide, 02 engineering and technology, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Catalysis, periodic DFT calculations, 0104 chemical sciences, Characterization (materials science), Inorganic Chemistry, NMR spectroscopy, Drug Discovery, halide perovskites, Physical chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract: International audience; Solid state NMR spectroscopy is swiftly emerging as useful tool to characterize the structure, composition and dynamic properties of lead halide perovskites. On the other hand, interpretation of solid state NMR signatures is often challenging, because of the potential presence of many overlapping signals in small range of chemical shifts, hence complicating the extraction of detailed structural features. Here, we demonstrate the reliability of periodic Density Functional Theory in providing theoretical support for the NMR characterization of halide perovskite compounds, considering nuclei with spin I=1/2. For light H-1 and C-13 nuclei, we predict NMR chemical shifts in good agreement with experiment, further highlighting the effects of motional narrowing. Accurate prediction of the NMR response of Pb-207 nuclei is comparably more challenging, but we successfully reproduce the downshift in frequency when changing the halide composition from pure iodine to pure bromine. Furthermore, we confirm NMR as ideal tool to study mixed halide perovskite compounds, currently at the limelight for tandem solar cells and color-tunable light emission.
Published: 2021
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48. Memory Seeds Enable High Structural Phase Purity in 2D Perovskite Films for High‐Efficiency Devices

Author: Jacky Even, Amanda B. Marciel, Jean-Christophe Blancon, Yafei Wang, Claudine Katan, Mohammad H. K. Samani, Aditya D. Mohite, Siraj Sidhik, Hao Zhang, Justin M. Hoffman, Mercouri G. Kanatzidis, Michael S. Wong, Wenbin Li, Austin Fehr, Rice University [Houston], Northwestern University [Evanston], Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), and Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)
Subjects: Materials science, Dispersity, Nucleation, Halide, 02 engineering and technology, 2D perovskites, 010402 general chemistry, photostability, 01 natural sciences, intermediate phases, orientation, Crystallinity, [CHIM]Chemical Sciences, General Materials Science, Thin film, Dissolution, crystallinity, Perovskite (structure), [PHYS]Physics [physics], business.industry, Mechanical Engineering, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Mechanics of Materials, Optoelectronics, 0210 nano-technology, business, Layer (electronics)
Abstract: International audience; 2D perovskites are a class of halide perovskites offering a pathway for realizing efficient and durable optoelectronic devices. However, the broad chemical phase space and lack of understanding of film formation have led to quasi-2D perovskite films with polydispersity in perovskite layer thicknesses, which have hindered device performance and stability. Here, a simple and scalable approach is reported, termed as the “phase-selective method”, to fabricate 2D perovskite thin films with homogenous layer thickness (phase purity). The phase-selective method involves the dissolution of single-crystalline powders with a homogeneous perovskite layer thickness in desired solvents to fabricate thin films. In situ characterizations reveal the presence of sub-micrometer-sized seeds in solution that preserve the memory of the dissolved single crystals and dictate the nucleation and growth of grains with an identical thickness of the perovskite layers in thin films. Photovoltaic devices with a p–i–n architecture are fabricated with such films, which yield an efficiency of 17.1% enabled by an open-circuit voltage of 1.20 V, while preserving 97.5% of their peak performance after 800 h under illumination without any external thermal management.
Published: 2021
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49. Negative Pressure Engineering with Large Cage Cations in 2D Halide Perovskites Causes Lattice Softening

Author: Mercouri G. Kanatzidis, Xiaotong Li, Peijun Guo, Ido Hadar, Claudine Katan, Constantinos C. Stoumpos, Shelby A. Cuthriell, Yongping Fu, Jacky Even, Richard D. Schaller, Elad Harel, Laurent Pedesseau, Northwestern University [Evanston], Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Argonne National Laboratory [Lemont] (ANL), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Michigan State University System, SC0012541, Basic Energy Sciences, DE-AC02-06CH11357, Office of Science, Institut Universitaire de France, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [PHYS]Physics [physics], Photoluminescence, Chemistry, Band gap, Halide, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Bond length, symbols.namesake, Colloid and Surface Chemistry, Formamidinium, Chemical physics, Goldschmidt tolerance factor, symbols, [CHIM]Chemical Sciences, Raman spectroscopy, Perovskite (structure)
Abstract: International audience; Organic-inorganic hybrid halide perovskites are promising semiconductors with tailorable optical and electronic properties. The choice of A-site cation to support a three-dimensional (3D) perovskite structure AMX3 (where M is a metal, and X is a halide) is limited by the geometric Goldschmidt tolerance factor. However, this geometric constraint can be relaxed in two-dimensional (2D) perovskites, providing us an opportunity to understand how various the A-site cations modulate the structural properties and thereby the optoelectronic properties. Here, we report the synthesis and structures of single-crystals (BA)2(A)Pb2I7 where BA = butylammonium, and A = methylammonium (MA), formamidinium (FA), dimethylammonium (DMA) or guanidinium (GA), a series of A-site cation varied in size. Single-crystal X-ray diffraction reveals that the MA, FA, and GA structures crystallize in the same Cmcm space group, while the DMA imposes the Ccmb space group. We observe that as the A-site cation becomes larger, the Pb−I bond continuously elongates, expanding the volume of the perovskite cage, equivalent to exerting “negative pressure” on the perovskite structures. Optical studies and DFT calculations show the Pb−I bond length elongation reduces overlap of the Pb s- and I p-orbitals and increases the optical bandgap, while Pb−I−Pb angles play a secondary role. Raman spectra show lattice softening with increasing size of the A-site cation. These structural changes with enlarged A cations result in significant decreases in photoluminescence intensity and lifetime, consistent with a more pronounced nonradiative decay. Transient absorption microscopy (TAM) results suggest that the PL drop may derive from a higher concentration of traps or phonon-assisted nonradiative recombination. The results highlight that extending the range of Goldschmidt tolerance factors for 2D perovskites is achievable, enabling further tuning of the structure-property relationships in 2D perovskites.
Published: 2020
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50. Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D Hybrid Dion-Jacobson Lead Bromide Perovskites (A')(A)Pb

Author: Lingling, Mao, Peijun, Guo, Mikaël, Kepenekian, Ioannis, Spanopoulos, Yihui, He, Claudine, Katan, Jacky, Even, Richard D, Schaller, Ram, Seshadri, Constantinos C, Stoumpos, and Mercouri G, Kanatzidis
Abstract: Hybrid layered halide perovskites have achieved impressive performance in optoelectronics. New structural types in the two-dimensional (2D) halide system such as the Dion-Jacobson phases have attracted wide research attention due to the short interlayer distance and unique layer orientation that facilitate better charge-transport and higher stability in optoelectronic devices. Here, we report the first solid solution series incorporating both A and A' cations in the 2D Dion-Jacobson family, with the general formula (A')(A)Pb
Published: 2020

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