Absence of Anomalous Electron-Phonon Coupling in the Temperature Renormalization of the Gap of CsPbBr$_3$ Nanocrystals
Shima Fasahat, Benedikt Schäfer, Kai Xu, Nadesh Fiuza-Maneiro, Sergio Gómez-Graña, M. Isabel Alonso, Lakshminarayana Polavarapu, Alejandro R. Goñi
备注：
29 pages, including 4 figures, a long table and 2 pages of Supporting Information
发表信息：
S. Fasahat, B. Schäfer, K. Xu, N. Fiuza-Maneiro, S. Gómez-Graña, M. I. Alonso, L. Polavarapu, A. R. Goñi, J. Phys. Chem. C \textbf{129}, 453-463 (2025)
Metal halide perovskites exhibit a fairly linear increase of the bandgap with increasing temperature, when crystallized in a tetragonal or cubic phase. In general, both thermal expansion and electron-phonon interaction effects contribute equally to this variation of the gap with temperature. Herein, we have disentangled both contributions in the case of colloidal CsPbBr$_3$ nanocrystals (NCs) by means of photoluminescence (PL) measurements as a function of temperature (from 80 K to ambient) and hydrostatic pressure (from atmospheric to ca. 1 GPa). At around room temperature, CsPbBr$_3$ NCs also show a linear increase of the bandgap with temperature with a slope similar to that of the archetypal methylammonium lead iodide (MAPbI$_3$) perovskite. This is somehow unexpected in view of the recent observations in mixed-cation Cs$_x$MA$_{1-x}$PbI$_3$ single crystals with low Cs content, for which Cs incorporation caused a reduction by a factor of two in the temperature slope of the gap. This effect was ascribed to an anomalous electron-phonon interaction induced by the coupling with vibrational modes admixed with the Cs translational dynamics inside the cage voids. Thus, no trace of anomalous coupling is found in CsPbBr$_3$ NCs. In fact, we show that the linear temperature renormalization exhibited by the gap of CsPbBr$_3$ NCs is shared with most metal halide perovskites, due to a common bonding/antibonding and atomic orbital character of the electronic band-edge states. In this way, we provide a deeper understanding of the gap temperature dependence in the general case when the A-site cation dynamics is not involved in the electron-phonon interaction.
Ligand-Controlled Phonon Dynamics in CsPbBr3 Nanocrystals Revealed by Machine-Learned Interatomic Potentials
Georgia Institute of Technology（佐治亚理工学院）；Queens College, City University of New York（纽约市立大学皇后学院）；The Graduate Center, City University of New York（纽约市立大学研究生中心）
Exciton Coherence in CsPbBr3 Nanocrystals is Bounded by Phonon-Mediated Bright-Triplet Relaxation
Massachusetts Institute of Technology（麻省理工学院）；Center for Hybrid Organic Inorganic Semiconductors for Energy（有机无机半导体混合能源中心）；National Laboratory of the Rockies（落基山国家实验室）；U.S. Naval Research Laboratory（美国海军研究实验室）；Lund University（隆德大学）
Model of luminescence and delayed luminescence correlated blinking in single CsPbBr$_3$ nanocrystals
Voevodsky Institute of Chemical Kinetics and Combustion SB RAS（伏耶沃德斯基化学动力学与燃烧研究所）；HSE University（高等经济大学）；Lebedev Physical Institute of the Russian Academy of Sciences, Troitsk Branch（俄罗斯科学院列别杰夫物理研究所特罗伊茨克分所）；School of Physics and Engineering, ITMO University（ITMO大学物理与工程学院）；Skolkovo Institute of Science and Technology（斯科尔科沃科学技术学院）；Institute of Spectroscopy of the Russian Academy of Sciences（俄罗斯科学院光谱学研究所）；Moscow Pedagogical State University (MPGU)（莫斯科国立师范大学）
Exogenous Metal Cations in the Synthesis of CsPbBr3 Nanocrystals and their Interplay with Tertiary Amines
Istituto Italiano di Tecnologia（意大利理工大学）；Lund University（隆德大学）；BCMaterials, Basque Center for Materials, Applications, and Nanostructures, UPV/EHU Science Park（巴斯克材料、应用与纳米结构中心（UPV/EHU科学园））；Ikerbasque Basque Foundation for Science（伊克尔巴斯科巴斯克科学基金会）
Improving the Stability of Colloidal CsPbBr3 Nanocrystals with an Alkylphosphonium Bromide as Surface Ligand Pair
Istituto Italiano di Tecnologia（意大利理工大学）；BCMaterials, Basque Center for Materials, Applications, and Nanostructures, UPV/EHU Science Park（巴斯克材料、应用与纳米结构中心，巴斯克国立科技大学科学园）；Ikerbasque Basque Foundation for Science（伊卡巴斯基巴斯克科学基金会）
Improvement of Photophysical Properties of CsPbBr$_3$ and Mn$^{2+}$:CsPb(Br,Cl)$_3$ Perovskite Nanocrystals by Sr$^{2+}$ Doping and Their Application in White-LEDs
Size-dependent Dielectric Permittivity of Perovskite Nanocrystals
Donostia International Physics Center (DIPC)（多诺斯蒂亚国际物理中心）；Centro de Física de Materiales (CFM-MPC)（材料物理中心）；University of the Basque Country (UPV/EHU)（巴斯克大学）；Uppsala University（乌普萨拉大学）
Nanocrystals Heterostructures based on Halide Perovskites and Metal Sulfides
Istituto Italiano di Tecnologia（意大利理工大学）；Università di Genova（热那亚大学）；Universidade de Vigo（维戈大学）；BCMaterials, Basque Center for Materials, Applications, and Nanostructures, UPV/EHU Science Park（巴斯克材料、应用和纳米结构中心，巴斯克国立科技大学科学园）；Ikerbasque Basque Foundation for Science Bilbao（毕尔巴鄂巴斯克科学基金会）
Why Fe doping kills photoluminescence in CsPbCl$_3$ but not in CsPbBr$_3$: Role of midgap Fe 3$d$ states and electron-phonon coupling
Theoretical Sciences Unit, Jawaharlal Nehru Centre for Advanced Scientific Research（贾瓦哈拉尔·尼赫鲁高级科学研究中心理论科学部）；Department of Science and Humanities, Audisankara (Deemed to be University)（奥迪桑卡拉大学（视为大学）科学与人文系）；Laboratory for Energy Materials, École Polytechnique Fédérale de Lausanne（洛桑联邦理工学院能源材料实验室）；New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research（贾瓦哈拉尔·尼赫鲁高级科学研究中心新化学单元）
Localized holes and delocalized electrons in photoexcited inorganic perovskites: Watching each atomic actor by picosecond X-ray absorption spectroscopy
Metal Halide Perovskite/Chalcohalide Heterojunctions for the Photoinduced Oxidative Coupling of p-substituted Thiophenols
Italian Institute of Technology（意大利理工大学）；Politecnico di Torino（都灵理工大学）；Lund University, Division of Chemical Physics（隆德大学化学物理系）；Institute of Molecular Science, University of Valencia（瓦伦西亚大学分子科学研究所）
