Single- and co-sensitization of triphenylamine-based and asymmetrical squaraine dyes on the anatase (001) surface for DSSC applications: Periodic DFT calculations

Ohoud S Al-Qurashi; Abdesslem Jedidi; Nuha Wazzan

doi:10.1016/j.jmgm.2021.107833

Single- and co-sensitization of triphenylamine-based and asymmetrical squaraine dyes on the anatase (001) surface for DSSC applications: Periodic DFT calculations

J Mol Graph Model. 2021 May:104:107833. doi: 10.1016/j.jmgm.2021.107833. Epub 2021 Jan 5.

Authors

Ohoud S Al-Qurashi¹, Abdesslem Jedidi², Nuha Wazzan³

Affiliations

¹ King Abdulaziz University, Chemistry Department, Faculty of Science, P.O Box 42805 Jeddah, 21589, Saudi Arabia; University of Jeddah, Chemistry Department, Faculty of Science, Jeddah, Saudi Arabia.
² King Abdulaziz University, Chemistry Department, Faculty of Science, P.O Box 42805 Jeddah, 21589, Saudi Arabia.
³ King Abdulaziz University, Chemistry Department, Faculty of Science, P.O Box 42805 Jeddah, 21589, Saudi Arabia. Electronic address: nwazzan@kau.edu.sa.

PMID: 33444981
DOI: 10.1016/j.jmgm.2021.107833

Abstract

Dye aggregation causes poor performance of dye-sensitized solar cell (DSSC) applications through faster charge recombination of the photosensitizer with electrolyte. Triphenylamine (TBA)-based dyes feature a higher molar absorption coefficient and broadened wavelength but cannot absorb sunlight in the near-infrared (NIR) region. In contrast, the squaraine (SQ) photosensitizer, which is also called an NIR photosensitizer, has a maximum wavelength in the NIR region with high intensity. However, SQ dye suffers from dye aggregation due to its planar structure. The use of a co-sensitizer is one well-tested way to increase the power conversion efficiency (η) of solar cells by reducing dye aggregation and charge recombination. Using density functional theory (DFT) and time-dependent DFT (TDDFT), this work explains from a theoretical perspective the higher η values of the TZC1 and TZC2 dyes compared to that of asymmetric the SQ sensitizer (YR6) as free dyes. The electronic properties, reorganization energies, absorption and emission spectra, ICT parameters, and photovoltage parameters of the TZC1, TZC2, and YR6 dyes were computed using the M06/6-31G(d,p) level of theory in the gas phase and CH₂Cl₂ solvent (CPCM method). Additionally, the mono- and co-adsorption processes of TZC-based sensitizers with YR6 on the anatase (001) surface were investigated using periodic DFT calculations with the PBE + U/PAW method and the dispersion correction of the Grimme method D3. The results reveal that the use of the co-sensitized led to significant stabilization of the formed complexes by at least 1.21 eV, the panchromatic effect on the absorption spectra, and an increase in the light-harvesting ability in the NIR region, which improves the performance of DSSCs.

Keywords: Aggregation; Asymmetrical squaraine (SQ) dye; Co-adsorption; DFT; Dye-synthesized solar cell (DSSC); Triphenylamine (TPA) dye.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Coloring Agents*
Cyclobutanes
Density Functional Theory
Models, Molecular
Phenols
Solar Energy*
Sunlight
Titanium

Substances

Coloring Agents
Cyclobutanes
Phenols
squaraine
titanium dioxide
Titanium