Andrew Watt

The performance of devices containing colloidal quantum dot (CQD) films is strongly dependent on the surface chemistry of the CQDs they contain. Multistep surface treatments, which combine two or more strategies, are important for creating films with high carrier mobility that are well passivated against trap states and oxidation. Here, we examine the effect of a number of these surface treatments on PbS CQD films, including cation exchange to form PbS/CdS core/shell CQDs, and solid-state ligand-exchange treatments with Cl, Br, I, and 1,2-ethanedithiol (EDT) ligands. Using laboratory-based and synchrotron-radiation-excited X-ray photoelectron spectroscopy (XPS), we examine the compositions of the surface layer before and after treatment, and correlate this with the performance data and stability in air. We find that halide ion treatments may etch the CQD surfaces, with detrimental effects on the air stability and solar cell device performance caused by a reduction in the proportion of passivated surface sites. We show that films made up of PbS/CdS CQDs are particularly prone to this, suggesting Cd is more easily etched from the surface than Pb. However, by choosing a less aggressive ligand treatment, a good coverage of passivators on the surface can be achieved. We show that halide anions bind preferentially to surface Pb (rather than Cd). By isolating the part of XPS signal originating from the topmost surface layer of the CQD, we show that air stability is correlated with the total number of passivating agents (halide + EDT + Cd) at the surface.

© 2017 Elsevier B.V. The high throughput roll-to-roll patterning of metal thin films could be used to create organic functional devices. In this paper we present research into the compatibility of an in-vacuum selective metallization technique, which uses a sacrificial oil to define the metal electrode pattern for functional devices. The exact mechanism of the sacrificial oil masking, pattern definition and oil vaporization, due to the radiant heating from the thermal evaporation source, is described from previous research and experimental findings. The thermal modelling of this process develops further the requirements for the masking oil. It is found that in this particular system the oil thickness must be 1.63 ± 0.31 μm to match the radiative energy, and not be evaporated prior to leaving the metallization zone or to remain, as excess, after metallization is complete. The temperatures required are low and compatible with heat sensitive functional organic materials. The definition of the metal pattern edges is found to be like the liquid oil but thermal modelling still supports the theory of the oil vapor having the largest masking effect and concludes that the pattern definition quality does not depend on the sacrificial oil masking or vaporization effects but on the flexography patterning.

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.

Hybrid colloidal quantum dot (CQD) solar cells are fabricated from multilayer stacks of lead sulfide (PbS) CQD and single layer graphene (SG). The inclusion of graphene interlayers is shown to increase power conversion efficiency by 9.18%. It is shown that the inclusion of conductive graphene enhances charge extraction in devices. Photoluminescence shows that graphene quenches emission from the quantum dot suggesting spontaneous charge transfer to graphene. CQD photodetectors exhibit increased photoresponse and improved transport properties. We propose that the CQD/SG hybrid structure is a route to make CQD thin films with improved charge extraction, therefore resulting in improved solar cell efficiency.