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Journal ArticleDOI

Ab initio nonadiabatic molecular dynamics of charge carriers in metal halide perovskites

TL;DR: In this paper, a review of recent theoretical investigations of excited state dynamics in metal halide perovskites (MHPs), carried out using a state-of-the-art methodology combining nonadiabatic molecular dynamics with real-time time-dependent density functional theory, is presented.
Abstract: Photoinduced nonequilibrium processes in nanoscale materials play key roles in photovoltaic and photocatalytic applications. This review summarizes recent theoretical investigations of excited state dynamics in metal halide perovskites (MHPs), carried out using a state-of-the-art methodology combining nonadiabatic molecular dynamics with real-time time-dependent density functional theory. The simulations allow one to study evolution of charge carriers at the ab initio level and in the time-domain, in direct connection with time-resolved spectroscopy experiments. Eliminating the need for the common approximations, such as harmonic phonons, a choice of the reaction coordinate, weak electron–phonon coupling, a particular kinetic mechanism, and perturbative calculation of rate constants, we model full-dimensional quantum dynamics of electrons coupled to semiclassical vibrations. We study realistic aspects of material composition and structure and their influence on various nonequilibrium processes, including nonradiative trapping and relaxation of charge carriers, hot carrier cooling and luminescence, Auger-type charge–charge scattering, multiple excitons generation and recombination, charge and energy transfer between donor and acceptor materials, and charge recombination inside individual materials and across donor/acceptor interfaces. These phenomena are illustrated with representative materials and interfaces. Focus is placed on response to external perturbations, formation of point defects and their passivation, mixed stoichiometries, dopants, grain boundaries, and interfaces of MHPs with charge transport layers, and quantum confinement. In addition to bulk materials, perovskite quantum dots and 2D perovskites with different layer and spacer cation structures, edge passivation, and dielectric screening are discussed. The atomistic insights into excited state dynamics under realistic conditions provide the fundamental understanding needed for design of advanced solar energy and optoelectronic devices.
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TL;DR: In this paper , the role of functional motifs and their arrangement in materials, with representative examples, is presented, and the microscopic structures of these examples can be classified into six types on a length scale smaller than ∼10 nm with maximum subatomic resolution, i.e., crystal, magnetic, aperiodic, defect, local and electronic structures.
Abstract: Abstract As early as 2001, the need for the ‘functional motif theory’ was pointed out, to assist the rational design of functional materials. The properties of materials are determined by their functional motifs and how they are arranged in the materials. Uncovering functional motifs and their arrangements is crucial in understanding the properties of materials and rationally designing new materials of desired properties. The functional motifs of materials are the critical microstructural units (e.g. constituent components and building blocks) that play a decisive role in generating certain material functions, and can not be replaced with other structural units without the loss, or significant suppression, of relevant functions. The role of functional motifs and their arrangement in materials, with representative examples, is presented. The microscopic structures of these examples can be classified into six types on a length scale smaller than ∼10 nm with maximum subatomic resolution, i.e. crystal, magnetic, aperiodic, defect, local and electronic structures. Functional motif analysis can be employed in the function-oriented design of materials, as elucidated by taking infrared non-linear optical materials as an example. Machine learning is more efficient in predicting material properties and screening materials with high efficiency than high-throughput experimentation and high-throughput calculations. In order to extract functional motifs and find their quantitative relationships, the development of sufficiently reliable databases for material structures and properties is imperative.

31 citations

Journal ArticleDOI
TL;DR: In this article , the authors demonstrate that hole injection accelerates ion migration by decreasing the diffusion barrier and shortening the migration length, and the injected hole also promotes the nonradiative charge recombination by strengthening electron-phonon interactions in the low-frequency region and prolonging the quantum coherence time.
Abstract: Ion migration, hole trapping, and electron-hole recombination are common processes in metal halide perovskites. We demonstrate using ab initio non-adiabatic molecular dynamics and time-domain density functional theory that they are intricately related and strongly influence each other. The hole injection accelerates ion migration by decreasing the diffusion barrier and shortening the migration length. The injected hole also promotes the nonradiative charge recombination by strengthening electron-phonon interactions in the low-frequency region and prolonging the quantum coherence time. The synergy stems from the soft perovskite lattice and response of the valence band maximum to the Pb-I lattice distortion induced by the hole. This work provides important insights into the influence of ion mobility and hole injection on the performance of perovskite solar cells and suggests that high concentration of holes should be avoided.

29 citations

Journal ArticleDOI
TL;DR: In this article, the authors show that common intrinsic defects accelerate nonradiative charge recombination in lead-free metal halide perovskites without creating midgap traps.
Abstract: Lead-free metal halide perovskites are environmentally friendly and have favorable electro-optical properties; however, their efficiencies are significantly below the theoretical limit. Using ab initio nonadiabatic molecular dynamics, we show that common intrinsic defects accelerate nonradiative charge recombination in CsSnI3 without creating midgap traps. This is in contrast to Pb-based perovskites, in which many defects have little influence on and even prolong carrier lifetimes. Sn-related defects, such as Sn vacancies and replacement of Sn with Cs are most detrimental, since Sn removal breaks the largest number of bonds and strongly perturbs the Sn-I lattice that supports the carriers. The defects increase the nonadiabatic electron-vibrational coupling and interact strongly with free carrier states. Point defects associated with I atoms are less detrimental, and therefore, CsSnI3 synthesis should be performed in Sn rich conditions. The study provides an atomistic rationalization of why lead-free CsSnI3 exhibits lower photovoltaic efficiency compared to some lead-based perovskites.

22 citations

Journal ArticleDOI
TL;DR: In this article, the authors used unsupervised machine learning on the trajectories from a nonadiabatic molecular dynamics simulation with time-dependent Kohn-Sham density functional theory to elucidate the structural parameters with the largest influence on nonradiative recombination of charge carriers in CsPbI3, which forms the basis for solar energy and optoelectronic applications.
Abstract: Using unsupervised machine learning on the trajectories from a nonadiabatic molecular dynamics simulation with time-dependent Kohn-Sham density functional theory, we elucidated the structural parameters with the largest influence on nonradiative recombination of charge carriers in CsPbI3, which forms the basis for solar energy and optoelectronic applications. The I-I-I angles between PbI6 octahedra, followed by the Cs-I distance, have the strongest impact on the bandgap and the nonadiabatic coupling. The importance of the Cs-I distance is unexpected, because Cs does not contribute to electron and hole wave functions. The nonadiabatic coupling is most influenced by static properties, which is also surprising, given its explicit dependence on atomic velocities.

19 citations

Journal ArticleDOI
TL;DR: Using nonadiabatic molecular dynamics and time-domain density functional theory, the authors demonstrate that the DY− center forms a deep, highly localized hole trap, which accelerates nonradiative relaxation tenfold and is responsible for 90% of carrier losses.
Abstract: MAPbBr3 (MA = CH3NH3+) doping with bismuth increases electric conductivity, charge carrier density and photostability, reduces toxicity, and expands light absorption. However, Bi doping shortens excited-state lifetimes due to formation of DY− charge recombination centers. Using nonadiabatic molecular dynamics and time-domain density functional theory, we demonstrate that the DY− center forms a deep, highly localized hole trap, which accelerates nonradiative relaxation ten-fold and is responsible for 90% of carrier losses. Hole trapping occurs by coupling between the valence band and the trap state, facilitated by the Br atoms surrounding the Bi dopant. Passivation of the DY− center with chlorines heals the local geometry distortion, eliminates the trap state, and makes the carrier lifetimes longer than even in pristine MAPbBr3. The decreased charge recombination arises from reduced nonadiabatic coupling and shortened coherence time, due to diminished electron-hole overlap around the passivated defect. Our study demonstrates accelerated nonradiative recombination in Bi-doped MAPbBr3, suggests a strategy for defect passivation and reduction of nonradiative energy losses, and provides atomistic insights into unusual defect properties of metal halide perovskites needed for rational design of high-performance perovskite solar cells and optoelectronic devices.

19 citations

References
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Journal ArticleDOI
TL;DR: In this paper, the authors present an ab initio quantum-mechanical molecular-dynamics calculations based on the calculation of the electronic ground state and of the Hellmann-Feynman forces in the local density approximation.
Abstract: We present ab initio quantum-mechanical molecular-dynamics calculations based on the calculation of the electronic ground state and of the Hellmann-Feynman forces in the local-density approximation at each molecular-dynamics step. This is possible using conjugate-gradient techniques for energy minimization, and predicting the wave functions for new ionic positions using subspace alignment. This approach avoids the instabilities inherent in quantum-mechanical molecular-dynamics calculations for metals based on the use of a fictitious Newtonian dynamics for the electronic degrees of freedom. This method gives perfect control of the adiabaticity and allows us to perform simulations over several picoseconds.

32,798 citations

Journal ArticleDOI
TL;DR: QUANTUM ESPRESSO as discussed by the authors is an integrated suite of computer codes for electronic-structure calculations and materials modeling, based on density functional theory, plane waves, and pseudopotentials (norm-conserving, ultrasoft, and projector-augmented wave).
Abstract: QUANTUM ESPRESSO is an integrated suite of computer codes for electronic-structure calculations and materials modeling, based on density-functional theory, plane waves, and pseudopotentials (norm-conserving, ultrasoft, and projector-augmented wave). The acronym ESPRESSO stands for opEn Source Package for Research in Electronic Structure, Simulation, and Optimization. It is freely available to researchers around the world under the terms of the GNU General Public License. QUANTUM ESPRESSO builds upon newly-restructured electronic-structure codes that have been developed and tested by some of the original authors of novel electronic-structure algorithms and applied in the last twenty years by some of the leading materials modeling groups worldwide. Innovation and efficiency are still its main focus, with special attention paid to massively parallel architectures, and a great effort being devoted to user friendliness. QUANTUM ESPRESSO is evolving towards a distribution of independent and interoperable codes in the spirit of an open-source project, where researchers active in the field of electronic-structure calculations are encouraged to participate in the project by contributing their own codes or by implementing their own ideas into existing codes.

19,985 citations

Journal ArticleDOI
TL;DR: In this paper, a new hybrid density functional based on a screened Coulomb potential for the exchange interaction is proposed, which enables fast and accurate hybrid calculations, even of usually difficult metallic systems.
Abstract: Hybrid density functionals are very successful in describing a wide range of molecular properties accurately. In large molecules and solids, however, calculating the exact (Hartree–Fock) exchange is computationally expensive, especially for systems with metallic characteristics. In the present work, we develop a new hybrid density functional based on a screened Coulomb potential for the exchange interaction which circumvents this bottleneck. The results obtained for structural and thermodynamic properties of molecules are comparable in quality to the most widely used hybrid functionals. In addition, we present results of periodic boundary condition calculations for both semiconducting and metallic single wall carbon nanotubes. Using a screened Coulomb potential for Hartree–Fock exchange enables fast and accurate hybrid calculations, even of usually difficult metallic systems. The high accuracy of the new screened Coulomb potential hybrid, combined with its computational advantages, makes it widely applicable to large molecules and periodic systems.

13,446 citations

Journal ArticleDOI
TL;DR: In this article, an upper theoretical limit for the efficiency of p−n junction solar energy converters, called the detailed balance limit of efficiency, has been calculated for an ideal case in which the only recombination mechanism of holeelectron pairs is radiative as required by the principle of detailed balance.
Abstract: In order to find an upper theoretical limit for the efficiency of p‐n junction solar energy converters, a limiting efficiency, called the detailed balance limit of efficiency, has been calculated for an ideal case in which the only recombination mechanism of hole‐electron pairs is radiative as required by the principle of detailed balance. The efficiency is also calculated for the case in which radiative recombination is only a fixed fraction fc of the total recombination, the rest being nonradiative. Efficiencies at the matched loads have been calculated with band gap and fc as parameters, the sun and cell being assumed to be blackbodies with temperatures of 6000°K and 300°K, respectively. The maximum efficiency is found to be 30% for an energy gap of 1.1 ev and fc = 1. Actual junctions do not obey the predicted current‐voltage relationship, and reasons for the difference and its relevance to efficiency are discussed.

11,071 citations

Journal ArticleDOI
18 Oct 2013-Science
TL;DR: In this article, transient absorption and photoluminescence-quenching measurements were performed to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide and triiodide perovskite absorbers.
Abstract: Organic-inorganic perovskites have shown promise as high-performance absorbers in solar cells, first as a coating on a mesoporous metal oxide scaffold and more recently as a solid layer in planar heterojunction architectures. Here, we report transient absorption and photoluminescence-quenching measurements to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide (CH3NH3PbI(3-x)Cl(x)) and triiodide (CH3NH3PbI3) perovskite absorbers. We found that the diffusion lengths are greater than 1 micrometer in the mixed halide perovskite, which is an order of magnitude greater than the absorption depth. In contrast, the triiodide absorber has electron-hole diffusion lengths of ~100 nanometers. These results justify the high efficiency of planar heterojunction perovskite solar cells and identify a critical parameter to optimize for future perovskite absorber development.

8,199 citations