What is moving in hybrid halide perovskite solar cells?

Abstract

Organic-inorganic semiconductors, which adopt the perovskite crystal structure, have perturbed the landscape of contemporary photovoltaics research. In this Account, we discuss the internal motion of methylammonium lead iodide (CH${}_3$NH${}_3$PbI${}_3$) and formamidinium lead iodide ([CH(NH${}_2$)${}_2$]PbI${}_3$), covering: (i) molecular rotation-libration in the cuboctahedral cavity; (ii) drift and diffusion of large electron and hole polarons; (iii) transport of charged ionic defects. These processes give rise to a range of properties that are unconventional for photovoltaic materials, including frequency-dependent permittivity, low electron-hole recombination rates, and current-voltage hysteresis. Multi-scale simulations - drawing from electronic structure, ab initio molecular dynamic and Monte Carlo techniques - have been combined with neutron scattering and ultra-fast vibrational spectroscopy to qualify the nature and timescales of the motions. Recent experimental evidence and theoretical models for simultaneous electron transport and ion transport in these materials has been presented, suggesting they are mixed-mode conductors with similarities to metal oxide perovskites developed for battery and fuel cell applications. We expound on the implications of these effects for the photovoltaic action. The temporal behaviour found in hybrid perovskites introduces a sensitivity in materials characterisation to the time and length scale of the measurement, as well as the history of each sample. It also poses significant challenges for accurate materials and device simulations. Herein, we critically discuss the atomistic origin of the dynamic processes.

29 pages, 3 figures

References in corpus (3)

• Self-regulation mechanism for charged point defects in hybrid halide perovskites
• Molecular ferroelectric contributions to anomalous hysteresis in hybrid perovskite solar cells
• Ferroelectric Materials for Solar Energy Conversion: Photoferroics Revisited

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• Electronic Defects in Metal Oxide Photocatalysts
• Quantification of Ion Migration in CH3NH3PbI3 Perovskite Solar Cells by Transient Capacitance Measurements
• Optical Phonons in Methylammonium Lead Halide Perovskites and Implications for Charge Transport
• Exploring the properties of lead-free hybrid double perovskites using a combined computational-experimental approach
• Direct Observation of Dynamic Symmetry Breaking above Room Temperature in Methylammonium Lead Iodide Perovskite
• Microseconds, milliseconds and seconds: deconvoluting the dynamic behaviour of planar perovskite solar cells
• Understanding the Instability of the Halide Perovskite CsPbI${}_3$ through Temperature-Dependent Structural Analysis
• The Two Faces of Capacitance: New Interpretations for Electrical Impedance Measurements of Perovskite Solar Cells and Their Relation to Hysteresis
• First-Principles Lattice Dynamics Method for Strongly Anharmonic Crystals
• Perspective: Theory and simulation of hybrid halide perovskites
• Quantifying mobile ions in perovskite-based devices with temperature-dependent capacitance measurements: frequency versus time domain
• Optical Memory, Switching, and Neuromorphic Functionality in Metal Halide Perovskite Materials and Devices
• Deep Levels and Mixed Conductivity in Organometallic Halide Perovskites
• Temperature-dependent optical spectra of single-crystal (CH${}_3$NH${}_3$)PbBr${}_3$ cleaved in ultrahigh vacuum
• Structure and Binding in Halide Perovskites: Analysis of Static and Dynamic Effects from Dispersion-Corrected Density Functional Theory
• Excitonic States in Semiconducting Two-dimensional Perovskites
• Revealing the free energy landscape of halide perovskites: Metastability and transition characters in CsPbBr${}_3$ and MAPbI${}_3$
• The Effect of Ionic Composition on Acoustic Phonon Speeds in Hybrid Perovskites from Brillouin Spectroscopy and Density Functional Theory
• Using Pressure to Unravel the Structure-Dynamic-Disorder Relationship in Metal Halide Perovskites
• Improved evaluation of deep-level transient spectroscopy on perovskite solar cells reveals ionic defect distribution
• Numerical analysis of a hysteresis model in perovskite solar cells
• Characterization of the Ammonium Bending Vibrations in Two-Dimensional Hybrid Lead-Halide Perovskites from Raman Spectroscopy and First-Principles Calculations
• The effect of finite-temperature and anharmonic lattice dynamics on the thermal conductivity of ZrS2 monolayer: self-consistent phonon calculations
• Terahertz Kerr effect in a methylammonium lead bromide perovskite crystal
• Incommensurate chirality density wave transition in a hybrid molecular framework
• Lattice dynamics and spin excitations in the metal-organic framework [CH${}_3$NH${}_3$][Co(HCOO)${}_3$]
• Absence of Anomalous Electron-Phonon Coupling in the Temperature Renormalization of the Gap of CsPbBr${}_3$ Nanocrystals
• Coherent Transfer of Lattice Entropy via Extreme Nonlinear Phononics in Metal Halide Perovskites
• Role of host/guest coupling in stabilizing the phases of the over-tolerant hybrid perovskite MHyPbX3
• Ferroic Domains of Alternating Polar and Nonpolar Orders Regulate Photocurrent in Single Crystalline CH3NH3PbI3 Films Self-grown on FTO/TiO2 Substrate
• Iodide-methylammonium interaction is responsible for ferroelectricity in CH3NH3PbI3
• Design Rules for Optimizing Quaternary Mixed-Metal Chalcohalides
• Review: Solid-state physics of halide perovskites