Publication

Electron and hole transfer dynamics of a triarylamine-based dye with peripheral hole acceptors on TiO2 in the absence and presence of solvent

Résumé

We investigated photoinduced primary charge transfer processes of the sensitizer E6 on TiO2 without solvent and in contact with the organic solvent acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium tetracyanoborate [C2mim]+[B(CN)4]- using transient absorption spectroscopy, spectroelectrochemistry, and DFT/TDDFT calculations. E6, which belongs to a family of triarylamine dyes for solar cell applications, features two peripheral triarylamine units which are connected via diether spacer groups to the core chromophore and are designed to act as hole traps. This function was confirmed by spectroelectrochemistry, where the E6 + radical cation shows a considerably blue-shifted absorption compared to dyes without these two substituents. This indicates that one of the terminal triarylamine units must carry the positive charge. After photoexcitation of E6 at 520 nm (S0 → S1 band), electrons are injected into TiO2 predominantly within the cross-correlation time (<80 fs), with some subsequent delayed electron injection (τ ca. 250 fs). Importantly, a transient Stark shift (electrochromism) is observed (time constants ca. 0.8 and 12 ps) which is related to a changing electric field generated by the E6+ radical cations and injected electrons. This field induces absorption shifts of the dye species on the surface. Interestingly, these dynamics are largely unaffected by solvent molecules. However, pronounced differences are observed on longer timescales. In contact with solvent, one observes an increase in the E6 + absorption band above 600 nm with a time constant of 75 ps. This is assigned to hole transfer from the core chromophore to one of the peripheral triarylamine substituents. Electron-cation recombination occurs on much longer timescales and is multiexponential, with time constants of ca. 100 μs, 1 ms and 15 ms. Because of hole trapping, it is slower than for similar dyes lacking the peripheral triarylamines. Additional experiments were performed for E6 attached to the wide band gap semiconductor ZrO2. Here, electron injection occurs into surface trap states with subsequent recombination. Another fraction of non-injecting E6 molecules in S1 quickly decays to S0 (time constants 1 and 35 ps). © 2014 the Partner Organisations.

À propos de ce résultat
Cette page est générée automatiquement et peut contenir des informations qui ne sont pas correctes, complètes, à jour ou pertinentes par rapport à votre recherche. Il en va de même pour toutes les autres pages de ce site. Veillez à vérifier les informations auprès des sources officielles de l'EPFL.
Concepts associés (34)
Cellule solaire à pigment photosensible
Une cellule solaire à pigment photosensible parfois appelée cellules Grätzel (en anglais, Dye-sensitized solar cell ou DSC) est un système photoélectrochimique inspiré de la photosynthèse végétale qui, exposé à la lumière (photons), produit de l’électricité. Elle est souvent désignée par l'acronyme dérivé de son appellation en anglais : dye-sensitized solar cell, DSC, DSSc voire DYSC). Les cellules Grätzel ont été nommées ainsi en référence à son concepteur, Michael Grätzel, de l’École polytechnique fédérale de Lausanne.
Cellule photovoltaïque
Une cellule photovoltaïque, ou cellule solaire, est un composant électronique qui, exposé à la lumière, produit de l’électricité grâce à l’effet photovoltaïque. La puissance électrique obtenue est proportionnelle à la puissance lumineuse incidente et elle dépend du rendement de la cellule. Celle-ci délivre une tension continue et un courant la traverse dès qu'elle est connectée à une charge électrique (en général un onduleur, parfois une simple batterie électrique).
Film photovoltaïque
Un film photovoltaïque ou cellule solaire en couche mince ou encore couche mince photovoltaïque est une technologie de cellules photovoltaïques de deuxième génération, consistant à l'incorporation d'une ou plusieurs couches minces (ou TF pour ) de matériau photovoltaïque sur un substrat, tel que du verre, du plastique ou du métal. Les couches minces photovoltaïques commercialisées actuellement utilisent plusieurs matières, notamment le tellurure de cadmium (de formule CdTe), le diséléniure de cuivre-indium-gallium (CIGS) et le silicium amorphe (a-Si, TF-Si).
Afficher plus
Publications associées (37)

Investigating the Effect of Crystal Morphology on Optoelectronic Properties of Zinc Phosphide Thin Films via Optical-pump Terahertz Probe Spectroscopy

Elias Zsolt Stutz, Jean-Baptiste Leran, Mahdi Zamani, Simon Robert Escobar Steinvall, Rajrupa Paul, Mirjana Dimitrievska, Léa Buswell

Zinc phosphide ( Zn3P2) is a promising earth-abundant material for solar cell applications but calls for the further understanding of its optoelectronic properties. In this work, we perform contact-free and noninvasive optical-pump terahertz probe (OPTP) s ...
New York2023

Revealing Exciton and Metal–Ligand Conduction Band Charge Transfer Absorption Spectra in Cu-Zn-In-S Nanocrystals

Jacques-Edouard Moser, Etienne Christophe Socie, Brener Rodrigo De Carvalho Vale

Copper indium sulfide quantum dots (QDs) have attracted substantial attention in recent years due to environmental issues and diverse applications. We report the synthesis and characterization of copper-zinc-indium-sulfide (CZIS) QDs and CZIS treated with ...
2020

Optimized Electrolyte Loading and Active Film Thickness for Sandwich Polymer Light-Emitting Electrochemical Cells

Frank Nüesch, Roland Hany, Matthias Diethelm

Effects of ion concentration and active layer thickness play a critical role on the performance of light-emitting electrochemical cells. Expanding on a pioneering materials system comprising the super yellow (SY) polymer and the electrolyte trimethylolprop ...
2019
Afficher plus
MOOCs associés (14)
Plasma Physics: Introduction
Learn the basics of plasma, one of the fundamental states of matter, and the different types of models used to describe it, including fluid and kinetic.
Plasma Physics: Introduction
Learn the basics of plasma, one of the fundamental states of matter, and the different types of models used to describe it, including fluid and kinetic.
Plasma Physics: Applications
Learn about plasma applications from nuclear fusion powering the sun, to making integrated circuits, to generating electricity.
Afficher plus