The N3/TiO2 interfacial structure is dependent on the pH conditions during sensitization

Farah, Yusef R.; Krummel, Amber T.

doi:10.1063/5.0099543

The N3/TiO₂ interfacial structure is dependent on the pH conditions during sensitization

Journal Article · Mon Aug 01 00:00:00 EDT 2022 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0099543· OSTI ID:1979126

Farah, Yusef R. ^[1]; ^[2]

Colorado State University, Fort Collins, CO (United States); Colorado State Univ., Fort Collins, CO (United States)
Colorado State University, Fort Collins, CO (United States)

The electronic structure of the N3/TiO₂ interface can directly influence the performance of a dye sensitized solar cell (DSSC). Therefore, it is crucial to understand the parameters that control the dye’s orientation on the semiconductor’s surface. A typical step in DSSC fabrication is to submerge the nanoparticulate semiconductor film in a solution containing the dye, the sensitizing solution. The pH of the N3 sensitizing solution determines the distribution of the N3 protonation states that exist in solution. Altering the pH of the sensitizing solution changes the N3 protonation states that exist in solution and, subsequently, the N3 protonation states that anchor to the TiO₂ substrate. We utilize the surface specific technique of heterodyne detected vibrational sum frequency generation spectroscopy to determine the binding geometry of N3 on a TiO₂ surface as a function of the sensitizing solution pH conditions. It is determined that significant reorientation of the dye occurs in pH ≤ 2.0 conditions due to the lack of N3-dye carboxylate anchoring groups participating in adsorption to the TiO₂ substrate. Consequently, the change in molecular geometry is met with a change in the interfacial electronic structure that can hinder electron transfer in DSSC architectures.

View Accepted Manuscript (DOE)

Research Organization:: Colorado State University, Fort Collins, CO (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: SC0016137

OSTI ID:: 1979126

Alternate ID(s):: OSTI ID: 2311840
OSTI ID: 1879118

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 157; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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The N3/TiO2 interfacial structure is dependent on the pH conditions during sensitization

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