Photoinduced polarons in polymers. Time-resolved ESR analysis of polaron pairs in polymer:fullerene blends

TL;DR

This study analyzes time-resolved ESR spectra of photoexcited polymer:fullerene blends, revealing how spin-coherent polaron pairs evolve over time and contribute to the spectra's features.

Contribution

It introduces a simple stochastic Liouville equation model to interpret the spin dynamics of polaron pairs in polymer:fullerene blends.

Findings

ESR spectra are superpositions of antiphase, CIDEP, and thermal contributions.

Sign changes in spectral contributions occur over time, matching experimental data.

The model accurately describes the evolution of polaron pair spin states.

Abstract

The work concerns the analysis of experimental time-resolved ESR spectra in photoexcited polymer:fullerene blend, consisting of poly(3-hexilthiophene) and fullerene [6,6]-phenyl C_{61} -butyric acid methyl ester (at low temperature T = 100 K). The spectra are assumed to be determined by spin-coherent pairs of charged polarons P^{+} and P^{-} generated in the singlet state. The analysis is made within simple model of a set of first order processes, in which P^{+}P$^{-}-pair spin evolution is described by the stochastic Liouville equation, allowing for fairly accurate description of experimental results. Simple analytical interpretation of obtained numerical results demonstrates that trESR spectra can be represented as a superposition of antiphase and CIDEP contributions together with the conventional thermal one. These contributions are shown to change their signs with the increase of time in agreement with experimental observations.