Near-unity quantum yields from chloride treated CdTe colloidal quantum dots.

Colloidal quantum dots (CQDs) are promising materials for novel light sources and solar energy conversion. However, trap states associated with the CQD surface can produce non-radiative charge recombination that significantly reduces device performance. Here a facile post-synthetic treatment of CdTe CQDs is demonstrated that uses chloride ions to achieve near-complete suppression of surface trapping, resulting in an increase of photoluminescence (PL) quantum yield (QY) from ca. 5% to up to 97.2 ± 2.5%. The effect of the treatment is characterised by absorption and PL spectroscopy, PL decay, scanning transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. This process also dramatically improves the air-stability of the CQDs: before treatment the PL is largely quenched after 1 hour of air-exposure, whilst the treated samples showed a PL QY of nearly 50% after more than 12 hours.

Effect of Chloride Passivation on Recombination Dynamics in CdTe Colloidal Quantum Dots.

Colloidal quantum dots (CQDs) can be used in conjunction with organic charge-transporting layers to produce light-emitting diodes, solar cells and other devices. The efficacy of CQDs in these applications is reduced by the non-radiative recombination associated with surface traps. Here we investigate the effect on the recombination dynamics in CdTe CQDs of the passivation of these surface traps by chloride ions. Radiative recombination dominates in these passivated CQDs, with the radiative lifetime scaling linearly with CQD volume over τr =20-55 ns. Before chloride passivation or after exposure to air, two non-radiative components are also observed in the recombination transients, with sample-dependent lifetimes typically of less than 1 ns and a few ns. The non-radiative dynamics can be explained by Auger-mediated trapping of holes and the lifetimes of this process calculated by an atomistic model are in agreement with experimental values if assuming surface oxidation of the CQDs.

Size dependence of ultrafast charge dynamics in monodisperse Au nanoparticles supported on TiO2 colloidal spheres.

Sub-nanosecond charge dynamics in monodisperse Au nanoparticles (NPs) supported on TiO2 colloidal spheres are studied as a function of NP diameter using ultrafast transient absorption spectroscopy. The decay of the transmittance changes observed in the region of the plasmon resonance of the Au NPs following photoexcitation of the TiO2 spheres are well-described by a bi-exponential function consisting of a fast component of 2 ps duration associated with electron-phonon scattering, followed by a slow and relatively weak component associated with phonon-phonon scattering. The decay constant characterising the latter component was found to be dependent on the size of the Au NPs, rising from 49 ± 3 to 128 ± 6 ps as the diameter of the Au NPs increased from 12.2 ± 2.2 nm to 24.5 ± 2.8 nm, respectively.

Tunable structural and optical properties of CuInS2 colloidal quantum dots as photovoltaic absorbers.

Facile phase selective synthesis of CuInS2 (CIS) nanostructures has been an important pursuit because of the opportunity for tunable optical properties of the phases, and in this respect is investigated by hot-injection colloidal synthesis in this study. Relatively monodispersed colloidal quantum dots (3.8-5.6 nm) of predominantly chalcopyrite structure synthesized at 140, 180 and 210 °C over 60 minutes from copper(ii) hexafluoroacetylacetonate hydrate and indium(iii) diethyldithiocarbamate precursors exhibit temperature-dependent structural variability. The slightly off-stoichiometric quantum dots are copper-deficient in which copper vacancies , indium interstitials , indium-copper anti-sites and surface trapping states are likely implicated in broad photoluminescence emission with short radiative lifetimes, τ 1, τ 2, and τ 3 of 1.5-2.1, 7.8-13.9 and 55.2-70.8 ns and particle-size dependent tunable band gaps between 2.25 and 2.32 eV. Further structural and optical tunability (E g between 2.03 and 2.28 eV) is achieved with possible time-dependent wurtzite to chalcopyrite phase transformation at 180 °C likely involving a dynamic interplay of kinetic and thermodynamic factors.

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

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.

Erratum: Ultrafast Charge Dynamics in Trap-Free and Surface-Trapping Colloidal Quantum Dots.

[This corrects the article DOI: 10.1002/advs.201500088.].

Ultrafast Charge Dynamics in Trap-Free and Surface-Trapping Colloidal Quantum Dots.

Ultrafast transient absorption spectroscopy is used to study subnanosecond charge dynamics in CdTe colloidal quantum dots. After treatment with chloride ions, these can become free of surface traps that produce nonradiative recombination. A comparison between these dots and the same dots before treatment enables new insights into the effect of surface trapping on ultrafast charge dynamics. The surface traps typically increase the rate of electron cooling by 70% and introduce a recombination pathway that depopulates the conduction band minimum of single excitons on a subnanosecond timescale, regardless of whether the sample is stirred or flowed. It is also shown that surface trapping significantly reduces the peak bleach obtained for a particular pump fluence, which has important implications for the interpretation of transient absorption data, including the estimation of absorption cross-sections and multiple exciton generation yields.