Guanidinium-Pseudohalide Perovskite Interfaces Enable Surface Reconstruction of Colloidal Quantum Dots for Efficient...

Complete surface passivation of colloidal quantum dots (CQDs) and their strong electronic coupling are key factors toward high-performance CQD-based photovoltaics (CQDPVs). Also, the CQD matrices must be protected from oxidative environments, such as ambient air and moisture, to guarantee air-stable operation of the CQDPVs. Herein, we devise a complementary and effective approach to reconstruct the oxidized CQD surface using guanidinium and pseudohalide. Unlike conventional halides, thiocyanate anions provide better surface passivation with effective replacement of surface oxygen species and additional filling of defective sites, whereas guanidinium cations promote the construction of epitaxial perovskite bridges within the CQD matrix and augment electronic coupling. Additionally, we replace a defective 1,2-ethanedithiol-treated CQD hole transport layer (HTL) with robust polymeric HTLs, based on a judicious consideration of the energy level alignment established at the CQD/HTL interface. These efforts collectively result in high-performance and stable CQDPVs with photocurrents over 30 mA cm^-2, ∼80% quantum efficiency at excitonic peaks and stable operation under humid and ambient conditions. Elucidation of carrier dynamics further reveals that interfacial recombination associated with band alignment governs both the CQDPV performance and stability.