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Constantinos Stoumpos - One of the best experts on this subject based on the ideXlab platform.
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Insight into Layered and Deficient Metal Halide Perovskites from First Principles and Symmetry
2020Co-Authors: Claudio Quarti, Laurent Pedesseau, Jacky Even, Boubacar Traore, Mikael Kepenekian, Constantinos Stoumpos, Mercouri Kanatzidis, Nicolas Mercier, Claudine KatanAbstract:Abstract Body: Currently, many different perovskite -with corner-sharing octahedra- as well as non-perovskite metal-halide solids are synthetized worldwide entailing the need for in-depth understanding of their structure/property relationships. In this regard, combining the huge accumulated knowledge over the last decades, on halide but also oxide Perovskites, with modern atomic scale modeling as well as symmetry analysis has proved useful. Among others, new compositions such as A'2An-1MnX3n+1 (where A and A' are cations, X is halide and M is metal) afford layered structures with a controlled number (n, currently ? 7) of octahedra in the perovskite layer. Those correspond to innate heterostructures that offer an ideal platform for fundamental understanding such as effect of quantum or dielectric confinement.[1] Efforts have also been successful in building new perovskite structures with cations surpassing the Goldschmidt tolerance factor. For instance, this has been recently demonstrated for layered Perovskites with the use of ethylammonium, isopropylammonium or dimethylammonium as perovskitizer, having a perovskite sheet retaining its continuous corner-sharing connectivity.[2] On another note, new three dimensional networks have been achieved by mixing larger cations (e.g., hydroxyethylammonium) with the standard ones (e.g. methylammonium, formamidinium) leading to the formation of voids in the perovskite lattice, either disordered (Hollow Perovskites) or with structural signature of a periodic pattern (Deficient Perovskites).[3] In this talk, I will discuss some of our recent theoretical results paying attention on newly discovered halide perovskite phases and opportunities to further engineer their properties in connection with their use in devices. References including references therein: [1] C. Katan, N. Mercier, J. Even, Quantum and dielectric Confinement Effects in Lower-Dimensional Hybrid Perovskite Semiconductors, Chem. Rev. 119, 3140 (2019); [2] Y. Fu, X. Jiang, X. Li, B. Traore, I. Spanopoulos, C. Katan, J. Even, M. G. Kanatzidis, E. Harel, Cation Engineering in Two-Dimensional Ruddlesden-Popper Lead Iodide Perovskites with Mixed Large A-Site Cations in the Cages, J. Am. Chem. Soc. 142, 4008 (2020); X. Li, Y. Fu, L. Pedesseau, P. Guo, S. Cuthriell, I. Hadar, J. Even, C. Katan, C. C. Stoumpos, R. D. Schaller, E. Harel, M. G. Kanatzidis, Negative Pressure Engineering with Large Cage Cations in 2D Halide Perovskites Causes Lattice Softening, J. Am. Chem. Soc. (2020) DOI: 10.1021/jacs.0c03860; [3] A. Leblanc, N. Mercier, M. Allain, J. Dittmer, T. Pauporté, V. Fernandez, F. Boucher, M. Kepenekian, C. Katan, Enhanced Stability and Band Gap Tuning of ?-[HC(NH2)2]PbI3 Hybrid, ACS Appl. Mater. Interfaces, 11, 20743 (2019); C. Zheng, O. Rubel, M. Kepenekian, X. Rocquefelte, C. Katan, Electronic properties of Pb-I deficient lead halide Perovskites, J. Chem. Phys. 151, 234704 (2019); C. Quarti, C. Katan and J. Even, Physical properties of bulk, defective, 2D and 0D metal halide perovskite semiconductors from a symmetry perspective, under revision.
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Versatility of metal halide Perovskites: insight from atomic scale modelling
2019Co-Authors: Claudine Katan, Boubacar Traore, Mikael Kepenekian, Jean-christophe Blancon, Aditya Mohite, Sergei Tretiak, Constantinos Stoumpos, Mercouri Kanatzidis, Jacky EvenAbstract:Both all inorganic and hybrid halide Perovskites have recently demonstrated undeniably remarkable characteristics for a wide range of optoelectronic applications. The perovskite fever began with 3D halide Perovskites of chemical formula AMX3 with A a small organic (e.g. methylammonium, formamidinium) or an inorganic cation (e.g. Cs+), M a metal (Pb2+, Sn2+, Ge2+), and X a halogen (I-, Br-, Cl-), which have opened a route toward low-cost manufacture of solar cells while offering currently certified conversion efficiencies over 24%, at the level of the best known thin film technologies and not far from monocrystalline silicon (25%). Since the initial breakthrough mid-2012, halide Perovskites have attracted worldwide efforts from the scientific community leading to an extensive exploration of their structural versatility and an ever-growing diversity of structures. Prior to the perovskite fever, especially in the 80's and 90's, most experimental efforts on halide Perovskites were focused on chemistry and optical characterizations of monolayered halide Perovskites of chemical formula A'MX4, with A' a larger organic cation (e.g. alkylammonium). Currently, many different perovskite -with corner-sharing octahedra- as well as non-perovskite metal-halide networks are synthetized and their optoelectronic properties deserve to be unraveled. Among others, new compositions such as A'2An-1MnX3n+1 afford layered structures with a controlled number (n) of octahedra in the perovskite layer and thus offer an ideal platform for fundamental understanding.[6] Here, through a couple of recent examples including newly discovered halide perovskite phases as well as experimental data from the early 90's, we will discuss their optoelectronic properties based on first-principles calculations, semi-empirical and empirical modelling.
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two dimensional hybrid halide Perovskites principles and promises
Journal of the American Chemical Society, 2019Co-Authors: Lingling Mao, Constantinos Stoumpos, Mercouri G KanatzidisAbstract:Hybrid halide Perovskites have become the “next big thing” in emerging semiconductor materials, as the past decade witnessed their successful application in high-performance photovoltaics. This resurgence has encompassed enormous and widespread development of the three-dimensional (3D) Perovskites, spearheaded by CH3NH3PbI3. The next generation of halide Perovskites, however, is characterized by reduced dimensionality Perovskites, emphasizing the two-dimensional (2D) perovskite derivatives which expand the field into a more diverse subgroup of semiconducting hybrids that possesses even higher tunability and excellent photophysical properties. In this Perspective, we begin with a historical flashback to early reports before the “perovskite fever”, and we follow this original work to its fruition in the present day, where 2D halide Perovskites are in the spotlight of current research, offering characteristics desirable in high-performance optoelectronics. We approach the evolution of 2D halide Perovskites f...
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unraveling the chemical nature of the 3d hollow hybrid halide Perovskites
Journal of the American Chemical Society, 2018Co-Authors: Ioannis Spanopoulos, Constantinos Stoumpos, Ram Seshadri, Weijun Ke, Emily C Schueller, Oleg Y Kontsevoi, Mercouri G KanatzidisAbstract:The newly introduced class of 3D halide Perovskites, termed “hollow” Perovskites, has been recently demonstrated as light absorbing semiconductor materials for fabricating lead-free perovskite solar cells with enhanced efficiency and superior stability. Hollow Perovskites derive from three-dimensional (3D) AMX3 Perovskites (A = methylammonium (MA), formamidinium (FA); M = Sn, Pb; X = Cl, Br, I), where small molecules such as ethylenediammonium cations (en) can be incorporated as the dication without altering the structure dimensionality. We present in this work the inherent structural properties of the hollow Perovskites and expand this class of materials to the Pb-based analogues. Through a combination of physical and spectroscopic methods (XRD, gas pycnometry, 1H NMR, TGA, SEM/EDX), we have assigned the general formula (A)1–x(en)x(M)1–0.7x(X)3–0.4x to the hollow Perovskites. The incorporation of en in the 3D perovskite structure leads to massive M and X vacancies in the 3D [MX3] framework, thus the term...
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Critical Role of Interface and Crystallinity on the Performance and Photostability of Perovskite Solar Cell on Nickel Oxide
Advanced Materials, 2018Co-Authors: Wanyi Nie, Claudine Katan, Boubacar Traore, Mikael Kepenekian, Jean-christophe Blancon, Constantinos Stoumpos, Hsinhan Tsai, Fangze Liu, Olivier Durand, Sergei TretiakAbstract:Hybrid Perovskites are on a trajectory toward realizing the most efficient single-junction, solution-processed photovoltaic devices. However, a critical issue is the limited understanding of the correlation between the degree of crystallinity and the emergent perovskite/hole (or electron) transport layer on device performance and photostability. Here, the controlled growth of hybrid Perovskites on nickel oxide (NiO) is shown, resulting in the formation of thin films with enhanced crystallinity with characteristic peak width and splitting reminiscent of the tetragonal phase in single crystals. Photophysical and interface sensitive measurements reveal a reduced trap density at the perovskite/NiO interface in comparison with Perovskites grown on poly(3,4-ethylene dioxy thiophene) polystyrene sulfonate. Photovoltaic cells exhibit a high open circuit voltage (1.12 V), indicating a near-ideal energy band alignment. Moreover, photostability of photovoltaic devices up to 10-Suns is observed, which is a direct result of the superior crystallinity of perovskite thin films on NiO. These results elucidate the critical role of the quality of the perovskite/hole transport layer interface in rendering high-performance and photostable optoelectronic devices.
Aditya D. Mohite - One of the best experts on this subject based on the ideXlab platform.
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Metal Halide Perovskites: A New Class of Semiconductors
2019Co-Authors: Claudine Katan, Laurent Pedesseau, Boubacar Traore, Mikael Kepenekian, Jean-christophe Blancon, Sergei Tretiak, Joshua Leveillee, André Schleife, Amanda Neukirch, Aditya D. MohiteAbstract:Metal halide Perovskites have recently demonstrated undeniably remarkable characteristics for a wide range of optoelectronic applications. The perovskite fever began with 3D hybrid Perovskites of chemical formula AMX 3 , made of corner-sharing MX 6 with M a metal, X a halogen, and A a small organic cation. These Perovskites have opened a route toward low-cost manufacture of solar cells while offering currently certified conversion efficiencies over 24%, at the level of the best known thin film technologies and not far from monocrystalline silicon. Since the initial breakthrough mid-2012, halide Perovskites have attracted worldwide efforts from the scientific community leading to an extensive exploration of their structural versatility and an ever-growing diversity of composition with a revival of all inorganic metal halide Perovskites. Currently, many different metal-halide networks are synthetized and their optoelectronic properties deserve to be unraveled. Among others, new compositions such as A' 2 A n-1 M n X 3n+1 afford layered structures with a controlled number of octahedra in the perovskite layer interspaced with larger organic cations A' for most. Here, through a couple of recent examples including newly discovered halide perovskite phases as well as experimental data from the early 90's, we will discuss their optoelectronic properties based on first-principles calculations, semi-empirical and empirical modelling. Differences between this class of perovskite materials and conventional semiconductors will be highlighted. Impact of composition and structural pattern on properties will be inspected, with particular emphasis on the effect of quantum and dielectric confinements on charge carriers and excitons. Opportunities to further engineer halide perovskite properties will also be tackled in the prospect to provide guidance for the design of new synthetic targets.
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New Type of 2D Perovskites with Alternating Cations in the Interlayer Space, (C(NH2)3)(CH3NH3)nPbnI3n+1: Structure, Properties, and Photovoltaic Performance.
Journal of the American Chemical Society, 2017Co-Authors: Chan Myae Myae Soe, Claudine Katan, Boubacar Traore, Mikael Kepenekian, Constantinos Stoumpos, Hsinhan Tsai, Wanyi Nie, Binghao Wang, Ram Seshadri, Aditya D. MohiteAbstract:We present the new homologous series (C(NH2)3)(CH3NH3)nPbnI3n+1 (n = 1, 2, 3) of layered 2D Perovskites. Structural characterization by single-crystal X-ray diffraction reveals that these compounds adopt an unprecedented structure type, which is stabilized by the alternating ordering of the guanidinium and methylammonium cations in the interlayer space (ACI). Compared to the more common Ruddlesden–Popper (RP) 2D Perovskites, the ACI Perovskites have a different stacking motif and adopt a higher crystal symmetry. The higher symmetry of the ACI Perovskites is expressed in their physical properties, which show a characteristic decrease of the bandgap with respect to their RP perovskite counterparts with the same perovskite layer thickness (n). The compounds show a monotonic decrease in the optical gap as n increases: Eg = 2.27 eV for n = 1 to Eg = 1.99 eV for n = 2 and Eg = 1.73 eV for n = 3, which show slightly narrower gaps compared to the corresponding RP Perovskites. First-principles theoretical electron...
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new type of 2d Perovskites with alternating cations in the interlayer space c nh2 3 ch3nh3 npbni3n 1 structure properties and photovoltaic performance
Journal of the American Chemical Society, 2017Co-Authors: Chan Myae Myae Soe, Claudine Katan, Boubacar Traore, Mikael Kepenekian, Constantinos Stoumpos, Hsinhan Tsai, Wanyi Nie, Binghao Wang, Ram Seshadri, Aditya D. MohiteAbstract:We present the new homologous series (C(NH2)3)(CH3NH3)nPbnI3n+1 (n = 1, 2, 3) of layered 2D Perovskites. Structural characterization by single-crystal X-ray diffraction reveals that these compounds adopt an unprecedented structure type, which is stabilized by the alternating ordering of the guanidinium and methylammonium cations in the interlayer space (ACI). Compared to the more common Ruddlesden–Popper (RP) 2D Perovskites, the ACI Perovskites have a different stacking motif and adopt a higher crystal symmetry. The higher symmetry of the ACI Perovskites is expressed in their physical properties, which show a characteristic decrease of the bandgap with respect to their RP perovskite counterparts with the same perovskite layer thickness (n). The compounds show a monotonic decrease in the optical gap as n increases: Eg = 2.27 eV for n = 1 to Eg = 1.99 eV for n = 2 and Eg = 1.73 eV for n = 3, which show slightly narrower gaps compared to the corresponding RP Perovskites. First-principles theoretical electron...
Lioz Etgar - One of the best experts on this subject based on the ideXlab platform.
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fully inorganic mixed cation lead halide perovskite nanoparticles a study at the atomic level
Chemistry of Materials, 2020Co-Authors: Tal Binyamin, Laurent Pedesseau, Sergei Remennik, Amal Sawahreh, Jacky Even, Lioz EtgarAbstract:Mixed cation Perovskites are currently the most efficient perovskite materials used in perovskite solar cells. Mixing two cations inside a perovskite structure results in enhanced flexibility when ...
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Fully inorganic mixed cation lead halide perovskite nanoparticles: a study at the atomic level
Chemistry of Materials, 2020Co-Authors: Tal Binyamin, Laurent Pedesseau, Sergei Remennik, Amal Sawahreh, Jacky Even, Lioz EtgarAbstract:Mixed cation Perovskites are currently the most efficient perovskite materials used in perovskite solar cells. Mixing two cations inside a perovskite structure results in enhanced flexibility when designing interesting material properties. Moreover, using two inorganic cations in the same perovskite maintains the advantage of fully inorganic structures. A fascinating subject to investigate is therefore the nanoscale synthesis and the properties of such mixed inorganic cation Perovskites. In this work we mixed Rb and Cs inorganic atoms inside perovskite nanoparticles. We explored down to the atomic resolution different Rb and Cs concentrations and performed the chemical mapping of single nanoparticles. At medium concentrations, the Rb atoms are observed in the core of the particles, whereas the Cs atoms are located in the shell region, forming core shell structures. However, if there are high concentrations of Rb, a phase separation occurs because bulk perovskite based solely on Rb cations is not stable at room temperature. Density functional theory calculations support our experimental observations by showing that a stable nanoparticle is formed when the Rb atoms are located inside the particle and not on the surface. Our work demonstrates the importance of understanding the perovskite structure at the atomic level, leading to the formation of mixed cation bulk Perovskites and nanoparticles, and to improved perovskite stability. A new phase of cesium lead bromide (Cs6Pb5Br16) related to the Rb6Pb5Cl16 structure is also reported.
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Hole-transport material-free perovskite-based solar cells
Mrs Bulletin, 2015Co-Authors: Lioz EtgarAbstract:Recent discoveries have revealed a breakthrough in the photovoltaics (PVs) field using organometallic Perovskites as light harvesters in the solar cell. The organometal perovskite arrangement is self-assembled as alternate layers via a simple low-cost procedure. These organometal Perovskites promise several benefits not provided by the separate constituents. This overview concentrates on implementing Perovskites in PV cells such that the perovskite layers are used as the light harvester as well as the hole-conducting component. Eliminating hole-transport material (HTM) in this solar-cell structure avoids oxidation, reduces costs, and provides better stability and consistent results. Aspects of HTM-free perovskite solar cells discussed in this article include (1) depletion regions, (2) high voltages, (3) panchromatic responses, (4) chemical modifications, and (5) contacts in HTM-free perovskite solar cells. Elimination of HTM could expand possibilities to explore new interfaces in these solar cells, while over the long term, these uniquely structured HTM-free solar cells could offer valuable benefits for future PV and optoelectronics applications.
Boubacar Traore - One of the best experts on this subject based on the ideXlab platform.
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Insight into Layered and Deficient Metal Halide Perovskites from First Principles and Symmetry
2020Co-Authors: Claudio Quarti, Laurent Pedesseau, Jacky Even, Boubacar Traore, Mikael Kepenekian, Constantinos Stoumpos, Mercouri Kanatzidis, Nicolas Mercier, Claudine KatanAbstract:Abstract Body: Currently, many different perovskite -with corner-sharing octahedra- as well as non-perovskite metal-halide solids are synthetized worldwide entailing the need for in-depth understanding of their structure/property relationships. In this regard, combining the huge accumulated knowledge over the last decades, on halide but also oxide Perovskites, with modern atomic scale modeling as well as symmetry analysis has proved useful. Among others, new compositions such as A'2An-1MnX3n+1 (where A and A' are cations, X is halide and M is metal) afford layered structures with a controlled number (n, currently ? 7) of octahedra in the perovskite layer. Those correspond to innate heterostructures that offer an ideal platform for fundamental understanding such as effect of quantum or dielectric confinement.[1] Efforts have also been successful in building new perovskite structures with cations surpassing the Goldschmidt tolerance factor. For instance, this has been recently demonstrated for layered Perovskites with the use of ethylammonium, isopropylammonium or dimethylammonium as perovskitizer, having a perovskite sheet retaining its continuous corner-sharing connectivity.[2] On another note, new three dimensional networks have been achieved by mixing larger cations (e.g., hydroxyethylammonium) with the standard ones (e.g. methylammonium, formamidinium) leading to the formation of voids in the perovskite lattice, either disordered (Hollow Perovskites) or with structural signature of a periodic pattern (Deficient Perovskites).[3] In this talk, I will discuss some of our recent theoretical results paying attention on newly discovered halide perovskite phases and opportunities to further engineer their properties in connection with their use in devices. References including references therein: [1] C. Katan, N. Mercier, J. Even, Quantum and dielectric Confinement Effects in Lower-Dimensional Hybrid Perovskite Semiconductors, Chem. Rev. 119, 3140 (2019); [2] Y. Fu, X. Jiang, X. Li, B. Traore, I. Spanopoulos, C. Katan, J. Even, M. G. Kanatzidis, E. Harel, Cation Engineering in Two-Dimensional Ruddlesden-Popper Lead Iodide Perovskites with Mixed Large A-Site Cations in the Cages, J. Am. Chem. Soc. 142, 4008 (2020); X. Li, Y. Fu, L. Pedesseau, P. Guo, S. Cuthriell, I. Hadar, J. Even, C. Katan, C. C. Stoumpos, R. D. Schaller, E. Harel, M. G. Kanatzidis, Negative Pressure Engineering with Large Cage Cations in 2D Halide Perovskites Causes Lattice Softening, J. Am. Chem. Soc. (2020) DOI: 10.1021/jacs.0c03860; [3] A. Leblanc, N. Mercier, M. Allain, J. Dittmer, T. Pauporté, V. Fernandez, F. Boucher, M. Kepenekian, C. Katan, Enhanced Stability and Band Gap Tuning of ?-[HC(NH2)2]PbI3 Hybrid, ACS Appl. Mater. Interfaces, 11, 20743 (2019); C. Zheng, O. Rubel, M. Kepenekian, X. Rocquefelte, C. Katan, Electronic properties of Pb-I deficient lead halide Perovskites, J. Chem. Phys. 151, 234704 (2019); C. Quarti, C. Katan and J. Even, Physical properties of bulk, defective, 2D and 0D metal halide perovskite semiconductors from a symmetry perspective, under revision.
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(Invited) Intercalation engineering in layered Halide Perovskites
2019Co-Authors: Laurent Pedesseau, Claudine Katan, Boubacar Traore, Mikael Kepenekian, Jacky EvenAbstract:3D halide Perovskites are exciting materials for optoelectronic applications1 and amazing new solar cell devices2,3. 2D Halide Perovskites also allow both stabilizing and functionalizing the 3D structures. More, the number of available layered perovskite compounds is increasing rapidly. A simple spatial interruption in the 3D structure such as intercalation by a layer of molecules, or ions or even a mixture of molecules and ions can dramatically affect the intrinsic properties of the pristine Perovskites4. Here, a comparison of selected cases is proposed relying both on theoretical studies (quantum confinement effect, mixing of electronic states …) and experimental measurements (crystallography, spectroscopy, enthalpies of formation). The dielectric profiles along the stacking axis for different cases are also compared5,6. Finally, the limit to the thermodynamic stability7 is explored as a function of the number of layers in a single phase layered Perovskites. This project has received funding from the European Union’s Horizon 2020 research and innovation Programme under the grant agreement No 862656.
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Versatility of Halide Perovskites: Insight From Atomic Scale Modelling
2019Co-Authors: Claudine Katan, Boubacar Traore, Mikael Kepenekian, Sergei Tretiak, Joshua Leveillee, André Schleife, Amanda Neukirch, Jacky EvenAbstract:Both all inorganic and hybrid halide Perovskites have recently demonstrated undeniably remarkable characteristics for a wide range of optoelectronic applications. The perovskite fever began with 3D halide Perovskites of chemical formula AMX 3 with A a small organic (e.g. methylammonium, formamidinium) or an inorganic cation (e.g. Cs +), M a metal (Pb 2+ , Sn 2+ , Ge 2+), and X a halogen (I-, Br-, Cl-), which have opened a route toward low-cost manufacture of solar cells while offering currently certified conversion efficiencies over 24%, at the level of the best known thin film technologies and not far from monocrystalline silicon (25%). [1] Since the initial breakthrough mid-2012, [2] halide Perovskites have attracted worldwide efforts from the scientific community [3] leading to an extensive exploration of their structural versatility and an ever-growing diversity of structures. [4] Prior to the perovskite fever, especially in the 80's and 90's, most experimental efforts on halide Perovskites were focused on chemistry and optical characterizations of monolayered halide Perovskites of chemical formula A'MX 4 , with A' a larger organic cation (e.g. alkylammonium). [5] Figure 1. Layered metal-halide structures conceptually derived from the mother 3D perovskite network. Currently, many different perovskite-with corner-sharing octahedra-as well as non-perovskite metal-halide networks are synthetized and their optoelectronic properties deserve to be unraveled (Figure). Among others, new compositions such as A' 2 A n-1 M n X 3n+1 afford layered structures with a controlled number (n) of octahedra in the perovskite layer and thus offer an ideal platform for fundamental understanding. [6] Here, through a couple of recent examples including newly discovered halide perovskite phases as well as experimental data from the early 90's, we will discuss their optoelectronic properties based on first-principles calculations, semi-empirical and empirical modelling. Impact of composition and structural pattern on properties will be inspected, with particular emphasis on the effect of quantum and dielectric confinements on charge carriers and excitons. [6,7] Theoretical inspection of low energy states associated with electronic states localized on the edges of the perovskite layers will also be shown to provide guidance for the design of new synthetic targets [8] taking advantage of experimentally determined elastic constants. [9] Opportunities to engineer halide perovskite properties by considering dications or conjugated molecules in the interlayer will also be discussed. [10]
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Metal Halide Perovskites: A New Class of Semiconductors
2019Co-Authors: Claudine Katan, Laurent Pedesseau, Boubacar Traore, Mikael Kepenekian, Jean-christophe Blancon, Sergei Tretiak, Joshua Leveillee, André Schleife, Amanda Neukirch, Aditya D. MohiteAbstract:Metal halide Perovskites have recently demonstrated undeniably remarkable characteristics for a wide range of optoelectronic applications. The perovskite fever began with 3D hybrid Perovskites of chemical formula AMX 3 , made of corner-sharing MX 6 with M a metal, X a halogen, and A a small organic cation. These Perovskites have opened a route toward low-cost manufacture of solar cells while offering currently certified conversion efficiencies over 24%, at the level of the best known thin film technologies and not far from monocrystalline silicon. Since the initial breakthrough mid-2012, halide Perovskites have attracted worldwide efforts from the scientific community leading to an extensive exploration of their structural versatility and an ever-growing diversity of composition with a revival of all inorganic metal halide Perovskites. Currently, many different metal-halide networks are synthetized and their optoelectronic properties deserve to be unraveled. Among others, new compositions such as A' 2 A n-1 M n X 3n+1 afford layered structures with a controlled number of octahedra in the perovskite layer interspaced with larger organic cations A' for most. Here, through a couple of recent examples including newly discovered halide perovskite phases as well as experimental data from the early 90's, we will discuss their optoelectronic properties based on first-principles calculations, semi-empirical and empirical modelling. Differences between this class of perovskite materials and conventional semiconductors will be highlighted. Impact of composition and structural pattern on properties will be inspected, with particular emphasis on the effect of quantum and dielectric confinements on charge carriers and excitons. Opportunities to further engineer halide perovskite properties will also be tackled in the prospect to provide guidance for the design of new synthetic targets.
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Versatility of metal halide Perovskites: insight from atomic scale modelling
2019Co-Authors: Claudine Katan, Boubacar Traore, Mikael Kepenekian, Jean-christophe Blancon, Aditya Mohite, Sergei Tretiak, Constantinos Stoumpos, Mercouri Kanatzidis, Jacky EvenAbstract:Both all inorganic and hybrid halide Perovskites have recently demonstrated undeniably remarkable characteristics for a wide range of optoelectronic applications. The perovskite fever began with 3D halide Perovskites of chemical formula AMX3 with A a small organic (e.g. methylammonium, formamidinium) or an inorganic cation (e.g. Cs+), M a metal (Pb2+, Sn2+, Ge2+), and X a halogen (I-, Br-, Cl-), which have opened a route toward low-cost manufacture of solar cells while offering currently certified conversion efficiencies over 24%, at the level of the best known thin film technologies and not far from monocrystalline silicon (25%). Since the initial breakthrough mid-2012, halide Perovskites have attracted worldwide efforts from the scientific community leading to an extensive exploration of their structural versatility and an ever-growing diversity of structures. Prior to the perovskite fever, especially in the 80's and 90's, most experimental efforts on halide Perovskites were focused on chemistry and optical characterizations of monolayered halide Perovskites of chemical formula A'MX4, with A' a larger organic cation (e.g. alkylammonium). Currently, many different perovskite -with corner-sharing octahedra- as well as non-perovskite metal-halide networks are synthetized and their optoelectronic properties deserve to be unraveled. Among others, new compositions such as A'2An-1MnX3n+1 afford layered structures with a controlled number (n) of octahedra in the perovskite layer and thus offer an ideal platform for fundamental understanding.[6] Here, through a couple of recent examples including newly discovered halide perovskite phases as well as experimental data from the early 90's, we will discuss their optoelectronic properties based on first-principles calculations, semi-empirical and empirical modelling.
Mikael Kepenekian - One of the best experts on this subject based on the ideXlab platform.
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Insight into Layered and Deficient Metal Halide Perovskites from First Principles and Symmetry
2020Co-Authors: Claudio Quarti, Laurent Pedesseau, Jacky Even, Boubacar Traore, Mikael Kepenekian, Constantinos Stoumpos, Mercouri Kanatzidis, Nicolas Mercier, Claudine KatanAbstract:Abstract Body: Currently, many different perovskite -with corner-sharing octahedra- as well as non-perovskite metal-halide solids are synthetized worldwide entailing the need for in-depth understanding of their structure/property relationships. In this regard, combining the huge accumulated knowledge over the last decades, on halide but also oxide Perovskites, with modern atomic scale modeling as well as symmetry analysis has proved useful. Among others, new compositions such as A'2An-1MnX3n+1 (where A and A' are cations, X is halide and M is metal) afford layered structures with a controlled number (n, currently ? 7) of octahedra in the perovskite layer. Those correspond to innate heterostructures that offer an ideal platform for fundamental understanding such as effect of quantum or dielectric confinement.[1] Efforts have also been successful in building new perovskite structures with cations surpassing the Goldschmidt tolerance factor. For instance, this has been recently demonstrated for layered Perovskites with the use of ethylammonium, isopropylammonium or dimethylammonium as perovskitizer, having a perovskite sheet retaining its continuous corner-sharing connectivity.[2] On another note, new three dimensional networks have been achieved by mixing larger cations (e.g., hydroxyethylammonium) with the standard ones (e.g. methylammonium, formamidinium) leading to the formation of voids in the perovskite lattice, either disordered (Hollow Perovskites) or with structural signature of a periodic pattern (Deficient Perovskites).[3] In this talk, I will discuss some of our recent theoretical results paying attention on newly discovered halide perovskite phases and opportunities to further engineer their properties in connection with their use in devices. References including references therein: [1] C. Katan, N. Mercier, J. Even, Quantum and dielectric Confinement Effects in Lower-Dimensional Hybrid Perovskite Semiconductors, Chem. Rev. 119, 3140 (2019); [2] Y. Fu, X. Jiang, X. Li, B. Traore, I. Spanopoulos, C. Katan, J. Even, M. G. Kanatzidis, E. Harel, Cation Engineering in Two-Dimensional Ruddlesden-Popper Lead Iodide Perovskites with Mixed Large A-Site Cations in the Cages, J. Am. Chem. Soc. 142, 4008 (2020); X. Li, Y. Fu, L. Pedesseau, P. Guo, S. Cuthriell, I. Hadar, J. Even, C. Katan, C. C. Stoumpos, R. D. Schaller, E. Harel, M. G. Kanatzidis, Negative Pressure Engineering with Large Cage Cations in 2D Halide Perovskites Causes Lattice Softening, J. Am. Chem. Soc. (2020) DOI: 10.1021/jacs.0c03860; [3] A. Leblanc, N. Mercier, M. Allain, J. Dittmer, T. Pauporté, V. Fernandez, F. Boucher, M. Kepenekian, C. Katan, Enhanced Stability and Band Gap Tuning of ?-[HC(NH2)2]PbI3 Hybrid, ACS Appl. Mater. Interfaces, 11, 20743 (2019); C. Zheng, O. Rubel, M. Kepenekian, X. Rocquefelte, C. Katan, Electronic properties of Pb-I deficient lead halide Perovskites, J. Chem. Phys. 151, 234704 (2019); C. Quarti, C. Katan and J. Even, Physical properties of bulk, defective, 2D and 0D metal halide perovskite semiconductors from a symmetry perspective, under revision.
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(Invited) Intercalation engineering in layered Halide Perovskites
2019Co-Authors: Laurent Pedesseau, Claudine Katan, Boubacar Traore, Mikael Kepenekian, Jacky EvenAbstract:3D halide Perovskites are exciting materials for optoelectronic applications1 and amazing new solar cell devices2,3. 2D Halide Perovskites also allow both stabilizing and functionalizing the 3D structures. More, the number of available layered perovskite compounds is increasing rapidly. A simple spatial interruption in the 3D structure such as intercalation by a layer of molecules, or ions or even a mixture of molecules and ions can dramatically affect the intrinsic properties of the pristine Perovskites4. Here, a comparison of selected cases is proposed relying both on theoretical studies (quantum confinement effect, mixing of electronic states …) and experimental measurements (crystallography, spectroscopy, enthalpies of formation). The dielectric profiles along the stacking axis for different cases are also compared5,6. Finally, the limit to the thermodynamic stability7 is explored as a function of the number of layers in a single phase layered Perovskites. This project has received funding from the European Union’s Horizon 2020 research and innovation Programme under the grant agreement No 862656.
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Versatility of Halide Perovskites: Insight From Atomic Scale Modelling
2019Co-Authors: Claudine Katan, Boubacar Traore, Mikael Kepenekian, Sergei Tretiak, Joshua Leveillee, André Schleife, Amanda Neukirch, Jacky EvenAbstract:Both all inorganic and hybrid halide Perovskites have recently demonstrated undeniably remarkable characteristics for a wide range of optoelectronic applications. The perovskite fever began with 3D halide Perovskites of chemical formula AMX 3 with A a small organic (e.g. methylammonium, formamidinium) or an inorganic cation (e.g. Cs +), M a metal (Pb 2+ , Sn 2+ , Ge 2+), and X a halogen (I-, Br-, Cl-), which have opened a route toward low-cost manufacture of solar cells while offering currently certified conversion efficiencies over 24%, at the level of the best known thin film technologies and not far from monocrystalline silicon (25%). [1] Since the initial breakthrough mid-2012, [2] halide Perovskites have attracted worldwide efforts from the scientific community [3] leading to an extensive exploration of their structural versatility and an ever-growing diversity of structures. [4] Prior to the perovskite fever, especially in the 80's and 90's, most experimental efforts on halide Perovskites were focused on chemistry and optical characterizations of monolayered halide Perovskites of chemical formula A'MX 4 , with A' a larger organic cation (e.g. alkylammonium). [5] Figure 1. Layered metal-halide structures conceptually derived from the mother 3D perovskite network. Currently, many different perovskite-with corner-sharing octahedra-as well as non-perovskite metal-halide networks are synthetized and their optoelectronic properties deserve to be unraveled (Figure). Among others, new compositions such as A' 2 A n-1 M n X 3n+1 afford layered structures with a controlled number (n) of octahedra in the perovskite layer and thus offer an ideal platform for fundamental understanding. [6] Here, through a couple of recent examples including newly discovered halide perovskite phases as well as experimental data from the early 90's, we will discuss their optoelectronic properties based on first-principles calculations, semi-empirical and empirical modelling. Impact of composition and structural pattern on properties will be inspected, with particular emphasis on the effect of quantum and dielectric confinements on charge carriers and excitons. [6,7] Theoretical inspection of low energy states associated with electronic states localized on the edges of the perovskite layers will also be shown to provide guidance for the design of new synthetic targets [8] taking advantage of experimentally determined elastic constants. [9] Opportunities to engineer halide perovskite properties by considering dications or conjugated molecules in the interlayer will also be discussed. [10]
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Metal Halide Perovskites: A New Class of Semiconductors
2019Co-Authors: Claudine Katan, Laurent Pedesseau, Boubacar Traore, Mikael Kepenekian, Jean-christophe Blancon, Sergei Tretiak, Joshua Leveillee, André Schleife, Amanda Neukirch, Aditya D. MohiteAbstract:Metal halide Perovskites have recently demonstrated undeniably remarkable characteristics for a wide range of optoelectronic applications. The perovskite fever began with 3D hybrid Perovskites of chemical formula AMX 3 , made of corner-sharing MX 6 with M a metal, X a halogen, and A a small organic cation. These Perovskites have opened a route toward low-cost manufacture of solar cells while offering currently certified conversion efficiencies over 24%, at the level of the best known thin film technologies and not far from monocrystalline silicon. Since the initial breakthrough mid-2012, halide Perovskites have attracted worldwide efforts from the scientific community leading to an extensive exploration of their structural versatility and an ever-growing diversity of composition with a revival of all inorganic metal halide Perovskites. Currently, many different metal-halide networks are synthetized and their optoelectronic properties deserve to be unraveled. Among others, new compositions such as A' 2 A n-1 M n X 3n+1 afford layered structures with a controlled number of octahedra in the perovskite layer interspaced with larger organic cations A' for most. Here, through a couple of recent examples including newly discovered halide perovskite phases as well as experimental data from the early 90's, we will discuss their optoelectronic properties based on first-principles calculations, semi-empirical and empirical modelling. Differences between this class of perovskite materials and conventional semiconductors will be highlighted. Impact of composition and structural pattern on properties will be inspected, with particular emphasis on the effect of quantum and dielectric confinements on charge carriers and excitons. Opportunities to further engineer halide perovskite properties will also be tackled in the prospect to provide guidance for the design of new synthetic targets.
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Versatility of metal halide Perovskites: insight from atomic scale modelling
2019Co-Authors: Claudine Katan, Boubacar Traore, Mikael Kepenekian, Jean-christophe Blancon, Aditya Mohite, Sergei Tretiak, Constantinos Stoumpos, Mercouri Kanatzidis, Jacky EvenAbstract:Both all inorganic and hybrid halide Perovskites have recently demonstrated undeniably remarkable characteristics for a wide range of optoelectronic applications. The perovskite fever began with 3D halide Perovskites of chemical formula AMX3 with A a small organic (e.g. methylammonium, formamidinium) or an inorganic cation (e.g. Cs+), M a metal (Pb2+, Sn2+, Ge2+), and X a halogen (I-, Br-, Cl-), which have opened a route toward low-cost manufacture of solar cells while offering currently certified conversion efficiencies over 24%, at the level of the best known thin film technologies and not far from monocrystalline silicon (25%). Since the initial breakthrough mid-2012, halide Perovskites have attracted worldwide efforts from the scientific community leading to an extensive exploration of their structural versatility and an ever-growing diversity of structures. Prior to the perovskite fever, especially in the 80's and 90's, most experimental efforts on halide Perovskites were focused on chemistry and optical characterizations of monolayered halide Perovskites of chemical formula A'MX4, with A' a larger organic cation (e.g. alkylammonium). Currently, many different perovskite -with corner-sharing octahedra- as well as non-perovskite metal-halide networks are synthetized and their optoelectronic properties deserve to be unraveled. Among others, new compositions such as A'2An-1MnX3n+1 afford layered structures with a controlled number (n) of octahedra in the perovskite layer and thus offer an ideal platform for fundamental understanding.[6] Here, through a couple of recent examples including newly discovered halide perovskite phases as well as experimental data from the early 90's, we will discuss their optoelectronic properties based on first-principles calculations, semi-empirical and empirical modelling.
