Tuning charge carrier dynamics through spacer cation functionalization in layered halide perovskites: an <i>ab initio</i> quantum dynamics study

Nayak, Pabitra K.; Ghosh, Dibyajyoti

doi:10.1039/d3tc00331k

Cited by 5 publications

(2 citation statements)

References 116 publications

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“…The thermal lattice fluctuations in MHPs substantially influence the photoexcited charge carrier dynamics activating nonradiative carrier recombination processes, which can reliably be modeled by combining the non-adiabatic molecular dynamics (NA-MD) with time-dependent density functional theory (TD-DFT). − The recombined carrier population along the NAMD trajectories illustrates faster nonradiative band-to-band charge recombination in MA 2 SnBr 6 than in inorganic VOHPs (Figure a). Furthermore, the nonradiative recombination rate of Cs 2 SnBr 6 is lower than that of Rb 2 SnBr 6 , depicting the subtle impact of A cations on charge carrier dynamics.…”

Section: Resultssupporting

confidence: 88%

A-Cation-Dependent Excited State Charge Carrier Dynamics in Vacancy-Ordered Halide Perovskites: Insights from Computational and Machine Learning Models

Nayak,

Mora Perez,

Liu

et al. 2024

Chem. Mater.

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Lead-free vacancy-ordered halide perovskites (VOHPs) are emerging as promising materials for environmentally friendly next-generation optoelectronic devices. However, a detailed atomistic understanding of charge carrier dynamics under ambient conditions ( 300 K) is lacking. Thus, attempts to refine the optoelectronic performance of VOHPs through material selection remain challenging. Here, we combine nonadiabatic molecular dynamics, time-domain density functional theory, and an unsupervised machine learning (ML) model for in-depth analyses of prevailing nonradiative carrier recombination and its entropy correlation with real-time structural dynamics. Our key findings illustrate that the thermal fluctuations are intricately linked to the performance-limiting nonradiative recombination in these perovskites. The detailed ML model-based analyses reveal the complex nonlinear correlations between photophysical properties and several structural features that dominantly influence excited state carrier dynamics. The atomistic insights unambiguously demonstrate that the organic methylammonium (MA) cation as the A cation in the lattice significantly impacts thermal fluctuations of the isolated inorganic metal halide octahedral subsystem. The stronger electron−phonon interactions introduce substantially faster nonradiative carrier relaxation over time. The inorganic elements, cesium and rubidium (A cations), largely restrict the lattice dynamics, weakening instantaneous nonradiative electron−phonon coupling in VOHPs. These inorganic VOHPs exhibit longer carrier lifetimes, depicting suppressed nonradiative carrier recombination processes. Our study emphasizes the decisive impacts of complex dynamic structure−excited state property correlations on the charge carrier dynamics in a group of primarily isostructural halide perovskites. This study provides valuable insights into the strategically designed lead-free perovskites for optoelectronic device applications.

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Section: Resultssupporting

confidence: 88%

A-Cation-Dependent Excited State Charge Carrier Dynamics in Vacancy-Ordered Halide Perovskites: Insights from Computational and Machine Learning Models

Nayak,

Mora Perez,

Liu

et al. 2024

Chem. Mater.

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“…The directional functionalization of spacer cations provides a considerable pathway for the stability and carrier dynamics of 2D perovskite structures. [ 26 ] This approach yields a substantial binding energy for excitons and facilitates fast and effective charge recombination. Additionally, it exerts a considerable influence on passivating grain boundaries (GBs), leading to inhomogeneous conductivity.…”

Section: D Perovskite Materials and 2d Pscsmentioning

confidence: 99%

The Key Role of Hole Transport Layer in Boosting Performance of Two‐Dimensional Perovskite Solar Cells

Li,

Yang,

Zhao

et al. 2024

Solar RRL

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Although currently in the nascent stages of research and development, two‐dimensional perovskite solar cells have showcased remarkable promise as the robust and efficient solar cell technology. Anticipated progressions and refinements in this domain are poised to establish two‐dimensional perovskite cells as instrumental catalysts in shaping the trajectory of renewable energy, heralding transformative breakthroughs. The hole transport layer plays an irreplaceable role in the charge carriers transport and interface effects in two‐dimensional perovskite devices. In this review, we start with the structural characteristics of two‐dimensional perovskite solar cells. The influence of the intrinsic characteristics of the perovskite active layer itself and the interaction of the perovskite/transport layer contact interface were analyzed. This discussion delves into the impact of intrinsic quantum confinement and the dielectric effect within the two‐dimensional perovskite structure on photovoltaic conversion efficiency. It also explores the energy level alignment between the clathrate active layer and the transport layer. The significance of the hole transport layer is emphasized, particularly regarding crystalline control, phase distribution, and interface passivation. Additionally, the crucial role of efficient carrier transport between the active layer and the transport layer is thoroughly examined.This article is protected by copyright. All rights reserved.

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Boosted Chirality Transfer in 2D Perovskites through Structural Isomer‐Driven Halogen–Halogen Interaction

Son,

Jang,

et al. 2024

Adv Funct Materials

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Chiral perovskites are promising materials due to their unique ability to interact with circularly polarized light (CPL), offering great potential in advanced photonic and spintronic applications. However, specific design principles for highly chiroptically active chiral perovskites remain unclear, hindering their practical exploitation. In this study, chiral cation fluorinated isomerization approach is employed to enhance the chiroptical response of chiral perovskites. Specifically, it is systematically discovered that incorporating ortho‐fluorinated chiral cations instead of para‐fluorinated cations induces a strong organic–inorganic halogen–halogen interaction due to the unique spatial arrangement. This boosted chirality transfer, mediated by the strong halogen–halogen interaction, resulting in a fivefold improvement in the circular dichroism compared to its para‐fluorinated counterpart. Consequently, a CPL photodetector utilizing the ortho‐fluorinated chiral perovskite exhibited superior CPL distinguishability of 0.288, the highest value among 2D lead‐iodide perovskite‐based devices. Furthermore, the photodetector incorporating these structural isomers demonstrated extended operational stability as well as high photodetecting performance.

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Tuning charge carrier dynamics through spacer cation functionalization in layered halide perovskites: an ab initio quantum dynamics study

Abstract: Dion-Jacobson (DJ) phase two-dimensional (2D) hybrid halide perovskites are promising for environmentally stable optoelectronic device applications due to their attractive photophysical properties, including long charge carrier lifetime and partially suppressed...

Cited by 5 publications

References 116 publications

A-Cation-Dependent Excited State Charge Carrier Dynamics in Vacancy-Ordered Halide Perovskites: Insights from Computational and Machine Learning Models

A-Cation-Dependent Excited State Charge Carrier Dynamics in Vacancy-Ordered Halide Perovskites: Insights from Computational and Machine Learning Models

The Key Role of Hole Transport Layer in Boosting Performance of Two‐Dimensional Perovskite Solar Cells

Boosted Chirality Transfer in 2D Perovskites through Structural Isomer‐Driven Halogen–Halogen Interaction

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