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The passivating effect of cadmium in PbS/CdS colloidal quantum dots probed by nm-scale depth profiling

Clark, Pip C.J.; Radtke, Hanna; Pengpad, Atip; Williamson, Andrew I.; Spencer, Ben F.; Hardman, Samantha J. O.; Leontiadou, Marina A.; Neo, Darren C.J.; Fairclough, Simon M. and Watt, Andrew A. R., et al. (2017) In Nanoscale 9(18). p.6056-6067
Abstract

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... (More)

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.

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published
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Nanoscale
volume
9
issue
18
pages
12 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85021780678
  • wos:000401146200036
ISSN
2040-3364
DOI
10.1039/c7nr00672a
language
English
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yes
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0f79557c-f120-4fdc-9749-ba8b7d29b7be
date added to LUP
2017-07-19 11:08:23
date last changed
2018-08-12 04:38:04
@article{0f79557c-f120-4fdc-9749-ba8b7d29b7be,
  abstract     = {<p>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.</p>},
  author       = {Clark, Pip C.J. and Radtke, Hanna and Pengpad, Atip and Williamson, Andrew I. and Spencer, Ben F. and Hardman, Samantha J. O. and Leontiadou, Marina A. and Neo, Darren C.J. and Fairclough, Simon M. and Watt, Andrew A. R. and Pis, Igor and Nappini, Silvia and Bondino, Federica and Magnano, Elena and Handrup, Karsten and Schulte, Karina and Silly, Mathieu G. and Sirotti, Fausto and Flavell, Wendy R.},
  issn         = {2040-3364},
  language     = {eng},
  month        = {05},
  number       = {18},
  pages        = {6056--6067},
  publisher    = {Royal Society of Chemistry},
  series       = {Nanoscale},
  title        = {The passivating effect of cadmium in PbS/CdS colloidal quantum dots probed by nm-scale depth profiling},
  url          = {http://dx.doi.org/10.1039/c7nr00672a},
  volume       = {9},
  year         = {2017},
}