Exploring Electron Transfer Dynamics of Novel Dye Sensitized Photocathodes Towards Solar Cells and Solar Fuels

Sammanfattning: The design of dyes for NiO-based dye-sensitized solar cells (DSSCs) has drawn attention owing to their potential applications in photocatalysis and because they are indispensable for the development of tandem dye-sensitized solar cells. The understanding of the electron transfer mechanisms and dynamics is beneficial to guide further dye design and further improve the performance of photocathode in solar cells and solar fuel devices.Time-resolved spectroscopy techniques, especially femtosecond and nanosecond transient absorption spectroscopy, supply sufficient resolution to get insights into the charge transfer processes in p-type dye sensitized solar cell and solar fuel devices. In paper I-V, several kinds of novel organic “push-pull” and inorganic charge transfer dyes for sensitization of p-type NiO, were systematically investigated by time-resolved spectroscopy, and photo-induced charge transfer dynamics of the organic/inorganic dyes were summarized. The excited state and reduced state intermediates were investigated in solution phase as references to confirm the charge injection and recombination on the NiO surface. The charge recombination kinetics is remarkably heterogeneous in some cases occurring on time scales spanning at least six orders of magnitude even for the same dye.In this thesis, we also proposed a novel concept of solid state p-type dye sensitized solar cells (p-ssDSSCs) for the first time (paper VI), using an organic dye P1 as sensitizer on mesoporous NiO and phenyl-C61-butyric acid methyl ester (PCBM) as electron conductor. Femtosecond and nanosecond transient absorption spectroscopy gave evidence for sub-ps hole injection from excited P1 to NiO, followed by electron transfer from P1●- to PCBM. The p-ssDSSCs device showed an impressive 620 mV open circuit photovoltage.Chapter 6 (paper VII) covers the study of electron transfer mechanisms in a covalently linked dye-catalyst (PB-2) sensitized NiO photocathode, towards hydrogen producing solar fuel devices. Hole injection from excited dye (PB-2') into NiO VB takes place on dual time scales, and the reduced PB-2 (PB-2●-) formed then donates an electron to the catalyst unit.  The subsequent regeneration efficiency of PB-2 by the catalyst unit (the efficiency of catalyst reduction) is determined to ca. 70%.