AFM-IR of EHD-Printed PbS Quantum Dots: Quantifying Ligand Exchange at the Nanoscale

Colloidal quantum dots (cQDs) recently emerged as building blocks for semiconductor materials with tuneable properties. Electro-hydrodynamic printing can be used to obtain sub-micrometre patterns of cQDs without elaborate and aggressive photolithography steps. Post-deposition ligand exchange is necessary for the introduction of new functionalities into cQD solids. However, achieving a complete bulk exchange is challenging and conventional infrared spectroscopy lacks the required spatial resolution. Infrared nanospectroscopy (AFM-IR) enables quantitative analysis of the evolution of vibrational signals and structural topography on the nano-metre scale upon ligand substitution on lead sulphide (PbS) cQDs. A solution of ethane-dithiol in acetonitrile demonstrated rapid (~60 s) and controllable exchange of approximately 90% of the ligands, encompassing structures up to ~800 nm in thickness. Prolonged exposures (>1 h) led to the degradation of the microstructures, with a systematic removal of cQDs regulated by surface-to-bulk ratios and solvent interactions. This study establishes a method for the development of devices through a combination of tuneable photoactive materials, additive manufacturing of microstructures, and their quantitative nanometre-scale analysis.