Reversible and Irreversible Interactions of Poly(3-hexylthiophene) with Oxygen Studied by Spin-Sensitive Methods

TL;DR

This study investigates how oxygen interacts with the polymer P3HT in organic solar cells, revealing reversible and irreversible pathways that affect stability, using advanced spin-sensitive spectroscopic methods.

Contribution

It introduces combined magneto-optical techniques to distinguish reversible and irreversible oxygen interactions with P3HT at the microscopic level.

Findings

Reversible formation of polymer:oxygen charge transfer complexes.

Irreversible formation of singlet oxygen involving triplet excitons.

Methanofullerenes provide a protective effect against triplet exciton formation.

Abstract

Understanding of degradation mechanisms in polymer:fullerene bulk-heterojunctions on the microscopic level aimed at improving their intrinsic stability is crucial for the breakthrough of organic photovoltaics. These materials are vulnerable to exposure to light and/or oxygen, hence they involve electronic excitations. To unambiguously probe the excited states of various multiplicities and their reactions with oxygen, we applied combined magneto-optical methods based on multifrequency (9 and 275 GHz) electron paramagnetic resonance (EPR), photoluminescence (PL), and PL-detected magnetic resonance (PLDMR) to the conjugated polymer poly(3-hexylthiophene) (P3HT) and polymer:fullerene bulk heterojunctions (P3HT:PCBM; PCBM = [6,6]-phenyl-C61-butyric acid methyl ester). We identified two distinct photochemical reaction routes, one being fully reversible and related to the formation of polymer:oxygen charge transfer complexes, the other one, irreversible, being related to the formation of singlet oxygen under participation of bound triplet excitons on the polymer chain. With respect to the blends, we discuss the protective effect of the methanofullerenes on the conjugated polymer bypassing the triplet exciton generation.