Exciton Bimolecular Annihilation Dynamics in Push-Pull Semiconductor Polymers

Fuente: arXiv
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Main Authors: Zheng, Yulong, Venkatesh, Rahul, Rojas-Gatjens, Esteban, Reichmanis, Elsa, Silva-Acuña, Carlos
Format: Preprint
Published: 2023
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author Zheng, Yulong
Venkatesh, Rahul
Rojas-Gatjens, Esteban
Reichmanis, Elsa
Silva-Acuña, Carlos
author_facet Zheng, Yulong
Venkatesh, Rahul
Rojas-Gatjens, Esteban
Reichmanis, Elsa
Silva-Acuña, Carlos
contents Exciton-exciton annihilation is a ubiquitous nonlinear dynamical phenomenon in materials hosting Frenkel excitons, that has been employed to probe exciton diffusion processes in conjugated polymeric materials. In this work, we investigate the nonlinear exciton dynamics of an electron push-pull conjugated polymer by fluence-dependent transient absorption and excitation-correlation photoluminescence spectroscopy, where we can quantitatively show the latter technique to be a more selective probe of the nonlinear dynamics. Simulations based on an exciton annihilation model that implements a simple (\textit{i.e.}\ time-independent) bimolecular rate constant decreasing trend for the extracted annihilation rates with excitation fluence. However, further investigation of the fluence-dependent transients suggests that the exciton-exciton annihilation bimolecular rate parameters are not constant in time, displaying a $t^{-1/2}$ time dependence, which we rationalize as reflective of anisotropic exciton diffusion. At ambient temperature, we estimate the exciton diffusion length to be $9 \pm 2$\,nm. In addition, exciton annihilation gives rise to a long-lived species that recombines on a nanosecond timescale. Our conclusions shed broad light onto nonlinear exciton dynamics in push-pull conjugated polymers.
format Preprint
id arxiv_https___arxiv_org_abs_2311_02716
institution arXiv
publishDate 2023
record_format arxiv
spellingShingle Exciton Bimolecular Annihilation Dynamics in Push-Pull Semiconductor Polymers
Zheng, Yulong
Venkatesh, Rahul
Rojas-Gatjens, Esteban
Reichmanis, Elsa
Silva-Acuña, Carlos
Materials Science
Chemical Physics
Exciton-exciton annihilation is a ubiquitous nonlinear dynamical phenomenon in materials hosting Frenkel excitons, that has been employed to probe exciton diffusion processes in conjugated polymeric materials. In this work, we investigate the nonlinear exciton dynamics of an electron push-pull conjugated polymer by fluence-dependent transient absorption and excitation-correlation photoluminescence spectroscopy, where we can quantitatively show the latter technique to be a more selective probe of the nonlinear dynamics. Simulations based on an exciton annihilation model that implements a simple (\textit{i.e.}\ time-independent) bimolecular rate constant decreasing trend for the extracted annihilation rates with excitation fluence. However, further investigation of the fluence-dependent transients suggests that the exciton-exciton annihilation bimolecular rate parameters are not constant in time, displaying a $t^{-1/2}$ time dependence, which we rationalize as reflective of anisotropic exciton diffusion. At ambient temperature, we estimate the exciton diffusion length to be $9 \pm 2$\,nm. In addition, exciton annihilation gives rise to a long-lived species that recombines on a nanosecond timescale. Our conclusions shed broad light onto nonlinear exciton dynamics in push-pull conjugated polymers.
title Exciton Bimolecular Annihilation Dynamics in Push-Pull Semiconductor Polymers
topic Materials Science
Chemical Physics
url https://arxiv.org/abs/2311.02716