ZNO (10-10) SURFACE SENSITIZED WITH CYANOACRYLATED TERTHIOPHENE: A THEORETICAL INVESTIGATION OF THE PHOTO-EXCITED CHARGE-TRANSFER

Vinicius Alves Bastos; Tales José da Silva; Marilia Junqueira Caldas

Paper Title

Authors

Vinicius Alves Bastos
Tales José da Silva
Marilia Junqueira Caldas

Modality

Pôster

Subject area

Simulação computacional / Teoria

Publishing Date

12/12/2023

Country of Publishing

Brasil

Language of Publishing

Inglês

Paper Page

https://www.even3.com.br/anais/workshop-do-ineo-2023/611890-zno-(10-10)-surface-sensitized-with-cyanoacrylated-terthiophene--a-theoretical-investigation-of-the-photo-excited

ISBN

978-65-272-0088-8

Keywords

Dye-Sensitized Solar Cells, charge transfer, ZnO, oligothiophenes, DFT, GW, BSE

Summary

Dye-Sensitized Solar Cells (DSSCs) are an important class of photovoltaic devices in which the electron-transporting layer is sensitized by an organic dye to facilitate the charge transfer of electrons photo-generated in the active layer. Recently, Oerhlein et. al. [1] have investigated ZnO nanocrystals sensitized by cyanoacrylated oligothiophene molecules (nTCs), for application in DSSCs, and reported molecule-to-surface photo-excited charge transfer. Motivated by this work, we have performed a theoretical investigation of the ZnO (10-10) surface [2] functionalized by a cyanoacrylated terthiophene molecule (3TC), covering first the isolated systems, i.e., molecule and surface, proceeding to the chemically bonded system (3TC@ZnO). We adopted the local basis formulation of Density Functional Theory as implemented in the FHI-aims code [3] for treating the isolated 3TC, and the planewave formulation in the Quantum Espresso code [4] for the ZnO surface and the 3TC@ZnO bonded system. The PBE exchange-correlation functional [5] was used in the geometry optimizations and electronic structure calculations, and the PBE0 [6] for the final electronic structure analyses. Specifically for the isolated 3TC, we further performed a BSE-GW calculation [7] using FHI-aims on top of the PBE0 ground state. We find that 3TC displays a strong optical excitation around 2.7eV, due to the HOMO?LUMO transition, with the HOMO localized on the 3T part and the LUMO on the C termination, then characterizing a donor-acceptor system. Regarding the 3TC@ZnO, we obtained from the structural calculations a molecule-surface binding energy of -2.26eV, indicating stable chemical bonding [8]. The electronic structure results present appropriate molecule-substrate energy level alignment, i.e., the HOMO in the middle of the gap and the LUMO in the conduction band, and molecule-to-surface charge extension of the LUMO state. In summary, the 3TC@ZnO system shows encouraging features for application in DSSCs. [1] A. N. Oerhlein et al., Phys. Chem. Chem. Phys. 21, 6991 (2019); [2] A. Dominguez et al., J. Appl. Phys. 115, 203720 (2014); [3] V. Blum et al., Comput. Phys. Commun. 180, 2175 (2009); [4] P. Giannozzi et al., J. Phys. Condens. Matter. 21, 395502 (2009); [5] J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996); [6] C. Adamo and V. Barone, J. Chem. Phys. 110, 6158 (1999); [7] C. Liu et al., J. Chem. Phys. 152, 044105 (2020); [8] I. Arbouch et al., Phys. Chem. Chem. Phys. 19, 29389 (2017). The authors thank HPC-USP and CENAPAD-SP for computational resources, and CNPq and INCT-INEO for financial support.

Title of the Event: Workshop do INEO 2023
City of the Event: Nazaré Paulista
Title of the Proceedings of the event: Anais do Workshop INEO 2023
Name of the Publisher: Even3
Means of Dissemination: Meio Digital

How to cite

BASTOS, Vinicius Alves; SILVA, Tales José da; CALDAS, Marilia Junqueira. ZNO (10-10) SURFACE SENSITIZED WITH CYANOACRYLATED TERTHIOPHENE: A THEORETICAL INVESTIGATION OF THE PHOTO-EXCITED CHARGE-TRANSFER.. In: Anais do workshop INEO 2023. Anais...Nazaré Paulista(SP) Hotel Estância Atibainha, 2023. Available in: https//www.even3.com.br/anais/workshop-do-ineo-2023/611890-ZNO-(10-10)-SURFACE-SENSITIZED-WITH-CYANOACRYLATED-TERTHIOPHENE--A-THEORETICAL-INVESTIGATION-OF-THE-PHOTO-EXCITED. Access in: 18/03/2025