Multi-phase semicrystalline microstructures drive exciton dissociation in neat plastic semiconductors

The optoelectronic properties of macromolecular semiconductors depend fundamentally on their solid-state microstructure. For example, the molecular-weight distribution influences polymeric- semiconductor properties via diverse microstructures; polymers of low weight-average molecular weight (Mw) form unconnected, extended-chain crystals, usually of a paraffinic structure. Because of the non-entangled nature of the relatively short-chain macromolecules, this leads to a polycrystalline, one-phase morphology. In contrast, with high-Mw materials, where average chain lengths are longer than the length between entanglements, two-phase morphologies, comprised of crystalline moieties embedded in largely unordered (amorphous) regions, are obtained. We investigate charge photogeneration processes in neat regioregular poly(3-hexylthiophene) (P3HT) of varying Mw by means of time-resolved photoluminescence (PL) spectroscopy. At 10 K, PL originating from recombination of long-lived charge pairs decays over microsecond timescales. Both the amplitude and decay rate distribution depend strongly on Mw. In films with dominant one-phase chain-extended microstructures, the delayed PL is suppressed as a result of a diminished yield of photoinduced charges, and its decay is significantly faster than in two-phase microstructures. However, independent of Mw, charge recombination regenerates singlet excitons in torsionally disordered chains forming more strongly coupled photophysical aggregates than those in the steady-state ensemble, with delayed PL lineshape reminiscent of that in paraffinic morphologies at steady state. We conclude that highly delocalized excitons in disordered regions between crystalline and amorphous phases dissociate extrinsically with yield and spatial distribution that depend intimately upon microstructure.Comment: 19 pages, 4 figure

Effet de la microstructure sur les propriétés excitoniques des polymères semi-conducteurs semi-cristallins

Les polymères semi-conducteurs semicristallins sont utilisés au sein de diodes électroluminescentes, transistors ou dispositifs photovoltaïques organiques. Ces matériaux peuvent être traités à partir de solutions ou directement à partir de leur état solide et forment des agrégats moléculaires dont la morphologie dicte en grande partie leurs propriétés optoélectroniques. Le poly(3-hexylthiophène) est un des polymères semi-conducteurs les plus étudiés. Lorsque le poids moléculaire (Mw) des chaînes est inférieur à 50 kg/mol, la microstructure est polycristalline et composée de chaînes formant des empilements-π. Lorsque Mw>50 kg/mol, la morphologie est semicristalline et composée de domaines cristallins imbriquées dans une matrice de chaînes amorphes. À partir de techniques de spectroscopie en continu et ultrarapide et appuyé de modèles théoriques, nous démontrons que la cohérence spatiale des excitons dans ce matériau est légèrement anisotrope et dépend de Mw. Ceci nous permet d’approfondir la compréhension de la relation intime entre le couplage inter et intramoléculaire sur la forme spectrale en absorption et photoluminescence. De plus, nous démontrons que les excitations photogénérées directement aux interfaces entre les domaines cristallins et les régions amorphes génèrent des paires de polarons liés qui se recombinent par effet tunnel sur des échelles de temps supérieures à 10ns. Le taux de photoluminescence à long temps de vie provenant de ces paires de charges dépend aussi de Mw et varie entre ∼10% et ∼40% pour les faibles et hauts poids moléculaires respectivement. Nous fournissons un modèle permettant d’expliquer le processus de photogénération des paires de polarons et nous élucidons le rôle de la microstructure sur la dynamique de séparation et recombinaison de ces espèces.Microstructure plays a crucial role in defining the optoelectrical properties of conjugated polymeric semiconductors which can be used in light harvesting and generating devices such as organic light emitting diodes, field effect transistors or photovoltaic devices. These polymers can be processed from solution or solidstate and form photophysical aggregates, consequently providing a complex network which controls the fate of any photogenerated species. poly(3-hexylthiopene) is one of the most studied polymeric semiconductor. In this material, the molecular weight (Mw) of the polymer governs the microstructure and highly impact the optical and electronic properties. Below Mw≈ 50 kg/mol, the polymer chains forms polycrystalline domains of π-stacked molecules while high Mw (>50 kg/mol) consists of a two-phase morphology of molecularly ordered crystallites that are embedded in amorphous regions. Such morphology provides a bidimensionnal network hosting both neutral excitations, known as Frenkel excitons, and polarons. By means of steady-state and ultrafast spectroscopy experiment and backed up theoretical modeling, we demonstrate that the spatial coherence of such excitations are anisotropic in the lattice and depends on the Mw of the polymer, providing a deep understanding of the interplay between interchain (excitonic) and intrachain coupling in polymer aggregates. Moreover, we show that direct excitation at the interface between molecularly ordered and amorphous regions generates tightlybound charge pairs which decay via quantum tunneling over >10 ns. The yield of delayed photoluminescence arising from the recombination of those charge pairs varies between ∼10% and ∼40% for low and high Mw films respectively. We provide a quantitative model that describes the photogeneration process of those geminate polaron pairs and determine the role of the microstructure in the charge separation and recombination processes

Charge separation by photoexcitation in semicrystalline polymeric semiconductors: An intrinsic or extrinsic mechanism?

We probe charge photogeneration and subsequent recombination dynamics in neat regioregular poly(3-hexylthiophene) films over six decades in time by means of time-resolved photoluminescence spectroscopy. Exciton dissociation at 10K occurs extrinsically at interfaces between molecularly ordered and disordered domains. Polaron pairs thus produced recombine by tunnelling with distributed rates governed by the distribution of electron-hole radii. Quantum-chemical calculations suggest that hot-exciton dissociation at such interfaces results from a high charge-transfer character.Comment: 10 pages, 3 figure

Pelvis biomechanics during wheelchair propulsion: a state of the art

ESS 2022, 7th European Seating Symposium, Dublin, IRLANDE, 14-/06/2022 - 17/06/2022For wheelchair users, pelvis represents the basis of stability for movement and the soft tissues in this area can sustain pressure sore, it is important tounderstand its behavior