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Anchoring groups for dyes in p-DSSC application: insights from DFT

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Abstract

We present hybrid, periodic, spin-polarized density functional theory calculations of antiferromagnetic NiO bulk, of its clean (100) surface and of the binding on this latter of four different organic ligands, relevant for p-type dye-sensitized solar cells (p-DSSC) applications. We find evidence for a strong chemisorption of all ligands to the NiO surface in the form of short interatomic distances between surface Ni atoms and ligand atoms, confirmed by high binding energies. Although the analysis of the impact of the ligand adsorption on the density of states of the NiO substrate reveals significant modifications, the overall picture obtained is in line with the operation principles of p-DSSC in all cases. However, some of the considered ligands significantly shift the density of states to lower energies, which, in p-DSSCs employing these ligands to anchor dyes to NiO, could force the use of dyes with deeper HOMO energies and alternative redox couples capable of accepting electrons from the dye (assuming dye bandgaps in the UV/visible range).

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Acknowledgments

ANR is gratefully acknowledged for the financial support of this research through the program POSITIF (ANR-12-PRGE-0016-01). This work was granted access to the HPC resources of MesoPSL financed by the Région Ile-de-France and the project Equip@Meso (reference ANR-10-EQPX-29-01) of the program Investissements d’Avenir supervised by the Agence Nationale pour la Recherche.

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Authors and Affiliations

  1. Chimie Paristech-CNRS, Institut de Recherche de Chimie de Paris, PSL Research University, 75005, Paris, France

    Michael Wykes, Carlo Adamo, Ilaria Ciofini & Frédéric Labat

  2. CNRS, Chimie et Interdisciplinarité: Synthèse, Analyse, Modélisation (CEISAM), Université LUNAM, Université de Nantes, UMR 6230, 2 rue de la Houssinière, 44322, Nantes cedex 3, France

    Fabrice Odobel

  3. Institut Universitaire de France, 103 bd Saint-Michel, 75005, Paris, France

    Carlo Adamo

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  1. Michael Wykes
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  2. Fabrice Odobel
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Correspondence to Frédéric Labat.

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This work is dedicated to Henry Chermette for his significant contribution to the development of theoretical chemistry in France.

This paper belongs to Topical Collection Festschrift in Honor of Henry Chermette

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Wykes, M., Odobel, F., Adamo, C. et al. Anchoring groups for dyes in p-DSSC application: insights from DFT. J Mol Model 22, 289 (2016). https://doi.org/10.1007/s00894-016-3155-1

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