Surface Treatment of CdSe Nanoparticles for Application in Hybrid Solar Cells: The Effect of Multiple Ligand Exchange with Pyridine

Abstract

Colloidal CdSe quantum dots (QDs) are suitable as electron acceptors in polymer/nanoparticle bulk heterojunction hybrid solar cells. For this application, a thick organic ligand shell which is typically surrounding the QDs after synthesis needs to be removed. Ligand exchange with pyridine is the most widely used method for this purpose. Although this approach is already 15 years old, detailed studies on the effectiveness of ligand exchange with pyridine for solar cell applications are still missing. In the present work hybrid solar cells were prepared from CdSe QDs initially capped with oleic acid (OA), and the impact of single and multiple pyridine treatment was thoroughly investigated. NMR was applied to determine the composition of the ligand shell as well as to distinguish the bound and free ligands before and after ligand exchange. It is shown that after a single pyridine treatment some amount of OA is still present in the samples. By using thermal gravimetric analysis (TGA) we could obtain also quantitative information about the effectiveness of subsequent pyridine treatments. In a series of one-, two-, and threefold ligand exchange, the estimated surface coverage by OA decreased from 26% to 12%, whereas that of pyridine increased from 54% to 80%. Laboratory solar cells with pyridine-capped CdSe QDs and poly(3-hexylthiophene) (P3HT) were characterized by current−voltage (I−V) measurements, and in order to get deeper insight into charge carrier generation and recombination processes, CdSe/P3HT blends were studied by light-induced electron spin resonance (l-ESR). Although repeated pyridine treatment was found to have a beneficial effect in the sense that more complete ligand exchange was achieved, which in turn enabled more efficient charge transfer, the performance of the solar cells was found to be reduced. This fact correlates with increased aggregation tendency of repeatedly pyridine-treated particles, negatively influencing the morphology of the blends, as well as with a larger amount of surface defects in particles stabilized by the weak pyridine ligand shell.