The Passivating Effect of Cadmium in PbS/CdS Colloidal Quantum Dots Probed by nm-Scale Depth Profiling

Pip Clark, Hanna Radtke, Atip Pengpad, Andrew Williamson, Ben Spencer, Samantha Hardman, Marina Leontiadou, D. C. J. Neo, Simon M Fairclough, A A R Watt, Igor Pis, Silvia Nappini , Federica Bondino, Elena Magnano, Karsten Handrup, Karina Schulte, Mathieu G. Silly, Fausto Sirotti, Wendy Flavell

    Research output: Contribution to journalArticlepeer-review


    Achieving control of the surface chemistry of colloidal quantum dots (CQDs) is essential to fully exploit their properties in solar cells, but direct measurement of the chemistry and electronic structure in the outermost atomic layers is challenging. Here we probe the surface oxidation and passivation of cation-exchanged PbS/CdS core/shell CQDs with sub nm-scale precision using synchrotron-radiation-excited depth-profiling photoemission. We investigate the surface composition of the topmost 1-2.5 nm of the CQDs as a function of depth, for CQDs of varying CdS shell thickness, and examine how the surface changes after prolonged air exposure. We demonstrate that the Cd is localized at the surface of the CQDs. The surface-localized products of oxidation are identified, and the extent of oxidation quantified. We show that oxidised sulfur species are progressively eliminated as Cd replaces Pb at the surface. A sub-monolayer surface 'decoration' of Cd is found to be effective in passivating the CQDs. We show that the measured energy-level alignments at PbS/CdS colloidal quantum dot surfaces differ from those expected on the basis of bulk band offsets, and are strongly affected by the oxidation products. We develop a model for the passivating action of Cd. The optimum shell thickness (of around 0.1 nm, previously found to give maximised power conversion efficiency in PbS/CdS solar cells) is found to correspond to a trade-off between the rate of oxidation and the introduction of a surface barrier to charge transport.
    Original languageEnglish
    Pages (from-to)6056-6067
    Number of pages12
    Early online date10 Apr 2017
    Publication statusPublished - 2017

    Research Beacons, Institutes and Platforms

    • Manchester Institute of Biotechnology


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