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.
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.
The effects of the
sintering temperature on microstructures, electrical
properties, and dielectric response of 1%Cr3+/Ta5+ co-doped TiO2 (CrTTO) ceramics prepared using a solid-state
reaction method were studied. The mean grain size increased with an
increasing sintering temperature range of 1300–1500 °C.
The dielectric permittivity of CrTTO ceramics sintered at 1300 °C
was very low (ε′ ∼198). Interestingly, a low loss
tangent (tanδ ∼0.03–0.06) and high ε′
(∼1.61–1.9 × 104) with a temperature
coefficient less than ≤ ±15% in a temperature range of
−60 to 150 °C were obtained. The results demonstrated
a higher performance property of the acceptor Cr3+/donor
Ta5+ co-doped TiO2 ceramics compared to the
Ta5+-doped TiO2 and Cr3+-doped TiO2 ceramics. According to a first-principles study, high-performance
giant dielectric properties (HPDPs) did not originate from electron-pinned
defect dipoles. By impedance spectroscopy (IS), it was suggested that
the giant dielectric response was induced by interfacial polarization
at the internal interfaces rather than by the formation of complex
defect dipoles. X-ray photoelectron spectroscopy (XPS) results confirmed
the existence of Ti3+, resulting in the formation of semiconducting
parts in the bulk ceramics. Low tanδ and excellent temperature
stability were due to the high resistance of the insulating layers
with a very high potential barrier of ∼2.0 eV.
The dielectric properties of Cr3+/Ta3+ co-doped TiO2 can be significantly improved by triple doping with Al3+ due to the re-balance of charge compensation.
In this work, the colossal dielectric properties and Maxwell—Wagner relaxation of TiO2–rich Na1/2Y1/2Cu3Ti4+xO12 (x = 0–0.2) ceramics prepared by a solid-state reaction method are investigated. A single phase of Na1/2Y1/2Cu3Ti4O12 is achieved without the detection of any impurity phase. The highly dense microstructure is obtained, and the mean grain size is significantly reduced by a factor of 10 by increasing Ti molar ratio, resulting in an increased grain boundary density and hence grain boundary resistance (Rgb). The colossal permittivities of ε′ ~ 0.7–1.4 × 104 with slightly dependent on frequency in the frequency range of 102–106 Hz are obtained in the TiO2–rich Na1/2Y1/2Cu3Ti4+xO12 ceramics, while the dielectric loss tangent is reduced to tanδ ~ 0.016–0.020 at 1 kHz due to the increased Rgb. The semiconducting grain resistance (Rg) of the Na1/2Y1/2Cu3Ti4+xO12 ceramics increases with increasing x, corresponding to the decrease in Cu+/Cu2+ ratio. The nonlinear electrical properties of the TiO2–rich Na1/2Y1/2Cu3Ti4+xO12 ceramics can also be improved. The colossal dielectric and nonlinear electrical properties of the TiO2–rich Na1/2Y1/2Cu3Ti4+xO12 ceramics are explained by the Maxwell–Wagner relaxation model based on the formation of the Schottky barrier at the grain boundary.
ZnO dye-sensitized solar cells (ZnO DSSCs) with different thickness of NiO thin films coated in photo-electrode and counter-electrode were investigated. NiO thin films were prepared by thermal evaporation of NiO onto FTO glass substrate. The films were characterized by FE-SEM. For the photo-electrode, NiO thin films were coated on ZnO with 0.2, 0.6, 1.1 and 2.2 mg to form a barrier layer. For the counter-electrode, NiO thin films were coated on FTO glass with 5.4, 10.8, 16.2 and 21.6 mg in order to increase a surface-to-volume ratio. The photoconversion efficiency of ZnO DSSCs was measured under illumination of stimulated sunlight obtained from solar simulator with the radiant power of 100 mW/cm2. It was found that ZnO DSSCs coated with 0.6 mg NiO in photo-electrode and 10.8 mg in counter-electrode exhibited the highest photoconversion efficiency of 1.00% and 0.92%, respectively. The enhancement of photoconversion efficiency with NiO coating maybe explained by decreasing of charge recombination in photo-electrode and increasing of active surface area in counter-electrode.
Nanocrystals of CdTe with a zinc blende structure are described by D. J. Binks and co‐workers. The surface of each is passivated by a combination of oleylamine ligands and a varying number of chloride ions, shown in the cover image as yellow spheres, that result from the treatment described on page 1548, and which results in near‐unity photoluminesence quantum yields.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.