Control of Hot Carrier Relaxation in CsPbBr3 Nanocrystals Using Damping Ligands.

In photon-conversion processes, rapid cooling of photo-induced hot carriers is a dominant energy loss channel. We herein report a 3-fold reduced hot carrier cooling rate in CsPbBr3 nanocrystals capped with a cross-linked polysiloxane shell in comparison to single alkyl-chain oleylamine ligands. Relaxation of hot charge carriers depends on the carrier-phonon coupling (CPC) process as an important channel to dissipate energies in nanostructured perovskite materials. The CPC strengths in the two samples were measured through cryogenic photoluminescence spectroscopic measurements. The effect of organic ligands on the CPC in CsPbBr3 nanocrystals is elucidated based on a damped oscillation model. This supplements the conventional polaron-based CPC model, by involving a damping effect on the CPC from the resistance of the ligands against nanocrystal lattice vibrations. The model also accounts for the observed linear temperature-dependence of the CPC strength. Our work enables predictions about the effect of the ligands on the performance of perovskite nanocrystals in future applications.

Quantification of Material Gradients in Core/Shell Nanocrystals Using EXAFS Spectroscopy.

Core/shell nanocrystals with a graded interface between core and shell exhibit improved optoelectronic properties compared with particles with an abrupt, sharp interface. Material gradients mitigate interfacial defects and define the shape of the confinement potential. So far, few works exist that allow to quantify the width of the gradient. In this study, ZnSe/CdS nanocrystals with graded shells made at different temperatures are characterized using extended X-ray absorption fine structure (EXAFS) and Raman spectroscopies. The average coordination number of the probed element with respect to the two possible counterions is fit to a simple, geometric model. It is shown that at the lower temperature limit for shell growth (260 °C), substantial interfacial alloying can be attributed mainly to cation migration. At higher temperature (290 °C), strain minimization leads to atomic ordering of the metal ions and an anomalously low degree of phase mixing.

Sensibilization of p-NiO with ZnSe/CdS and CdS/ZnSe quantum dots for photoelectrochemical water reduction.

Core/shell quantum dots (QDs) paired with semiconductor photocathodes for water reduction have rarely been implemented so far. We demonstrate the integration of ZnSe/CdS and CdS/ZnSe QDs with porous p-type NiO photocathodes for water reduction. The QDs demonstrate appreciable enhancement in water-reduction efficiency, as compared with the bare NiO. Despite their different structure, both QDs generate comparable photocurrent enhancement, yielding a 3.8- and 3.2-fold improvement for the ZnSe/CdS@NiO and CdS/ZnSe@NiO system, respectively. Unraveling the carrier kinetics at the interface of these hybrid photocathodes is therefore critical for the development of efficient photoelectrochemical (PEC) proton reduction. In addition to examining the carrier dynamics by the Mott-Schottky technique and electrochemical impedance spectroscopy (EIS), we performed theoretical modelling for the distribution density of the carriers with respect to electron and hole wave functions. The electrons are found to be delocalized through the whole shell and can directly actuate the PEC-related process in the ZnSe/CdS QDs. The holes as the more localized carriers in the core have to tunnel through the shell before injecting into the hole transport layer (NiO). Our results emphasize the role of interfacial effects in core/shell QDs-based multi-heterojunction photocathodes.

The Future of Colloidal Semiconductor Magic-Size Clusters.

Atomically defined, zero-dimensional magic-size clusters play pivotal roles in the nucleation and growth of semiconductor nanocrystals. Thus, they provide new opportunities to understand and to control nucleation and growth reactions beyond classical nucleation theory and to employ these reactions in the colloidal synthesis of increasingly complex and anisotropic nanomaterials with atomic level monodispersity. Both challenges require reliable determination of the exact structure and size of these ultrasmall and metastable nanoclusters. In this Perspective, we review and discuss the current challenges in analytics of magic-size clusters, in elucidating their formation mechanism, and in using them as next-generation reagents in colloidal chemistry.

Rapid synthesis of vertically aligned α-MoO3 nanostructures on substrates.

We report a new procedure for large scale, reproducible and fast synthesis of polycrystalline, dense, vertically aligned α-MoO3 nanostructures on conducting (FTO) and non-conducting substrates (Si/SiO2) by using a simple, low-cost hydrothermal technique. The synthesis method consists of two steps, firstly formation of a thermally evaporated Cr/MoO3 seed layer, and secondly growth of the nanostructures in a highly acidic precursor solution. In this report, we document a growth process of vertically aligned α-MoO3 nanostructures with varying growth parameters, such as pH and precursor concentration influencing the resulting structure. Vertically aligned MoO3 nanostructures are valuable for different applications such as electrode material for organic and dye-sensitized solar cells, as a photocatalyst, and in Li-ion batteries, display devices and memory devices due to their high surface area.

Correction: Protic additives determine the pathway of CdSe nanocrystal growth.

Correction for 'Protic additives determine the pathway of CdSe nanocrystal growth' by Klaus Boldt et al., Nanoscale, 2018, 10, 18238-18248.

Controlled Preparation of Nanoparticle Gradient Materials by Diffusion.

Nanoparticle gradient materials combine a concentration gradient of nanoparticles with a macroscopic matrix. This way, specific properties of nanoscale matter can be transferred to bulk materials. These materials have great potential for applications in optics, electronics, and sensors. However, it is challenging to monitor the formation of such gradient materials and prepare them in a controlled manner. In this study, we present a novel universal approach for the preparation of this material class using diffusion in an analytical ultracentrifuge. The nanoparticles diffuse into a molten thermoreversible polymer gel and the process is observed in real-time by measuring the particle concentrations along the length of the material to establish a systematic understanding of the gradient generation process. We extract the apparent diffusion coefficients using Fick's second law of diffusion and simulate the diffusion behavior of the particles. When the desired concentration gradient is achieved the polymer solution is cooled down to fix the concentration gradient in the formed gel phase and obtain a nanoparticle gradient material with the desired property gradient. Gradients of semiconductor nanoparticles with different sizes, fluorescent silica particles, and spherical superparamagnetic iron oxide nanoparticles are presented. This method can be used to produce tailored nanoparticle gradient materials with a broad range of physical properties in a simple and predictable way.

Protic additives determine the pathway of CdSe nanocrystal growth.

The formation of semiconductor nanocrystals by hot-injection synthesis follows complex reaction mechanisms that are not yet fully understood. In particular the occurrence of intermediate species indicated by sharp, stationary spectral lines poses an important deviation from the predictions of classical nucleation theory. We show that trace amounts of water and other protic additives strongly impact the structure of these reaction intermediates, forming either coordination polymers under dry conditions or small clusters in the presence of moisture. These intermediates bind monomer during the initial nucleation phase. The structure of the intermediate determines the monomer release rate, either continuously or in a rapid dissolution event, and hence controls the reaction kinetics. From this we propose a kinetic model that allows us to predict secondary nucleation events. By directing the type of intermediate formed, protic additives provide a lever to manipulate this equilibrium and control nanocrystal synthesis in a rational fashion.

Morphogenesis of anisotropic nanoparticles: self-templating via non-classical, fibrillar Cd2Se intermediates.

A fibrillar, polymeric intermediate (Cd2Se)n was isolated from the synthesis of CdSe nanorods, which suggests that the reactants themselves can template anisotropic growth. It is shown that high monomer concentration is the principal factor favouring this reaction pathway. The intermediate is distinct from crystalline semiconductor or small clusters and is surprisingly temperature-stable below 250 °C.

Two Mechanisms Determine Quantum Dot Blinking.

Many potential applications of quantum dots (QDs) can only be realized once the luminescence from single nanocrystals (NCs) is understood. These applications include the development of quantum logic devices, single-photon sources, long-life LEDs, and single-molecule biolabels. At the single-nanocrystal level, random fluctuations in the QD photoluminescence occur, a phenomenon termed blinking. There are two competing models to explain this blinking: Auger recombination and surface trap induced recombination. Here we use lifetime scaling on core-shell chalcogenide NCs to demonstrate that both types of blinking occur in the same QDs. We prove that Auger-blinking can yield single-exponential on/off times in contrast to earlier work. The surface passivation strategy determines which blinking mechanism dominates. This study summarizes earlier studies on blinking mechanisms and provides some clues that stable single QDs can be engineered for optoelectronic applications.

Switchable dissociation of excitons bound at strained CdTe/CdS interfaces.

Charge carrier dynamics of semiconductor nano-heterostructures are determined by band alignment and lattice mismatch of the adjacent materials. However, quantum efficiencies for the separation of excited charge carriers at such an interface are hard to predict and cannot yet be easily controlled. In this work we examine nanorods with a severely strained, axial CdTe/CdS interface using femtosecond transient absorption spectroscopy. We show that charge separation is mitigated by equal contributions of valence band distortion and formation of coulomb pairs across the interface. Left undisturbed such localised excitons relax rapidly via non-radiative recombination channels. By adding a competitive hole acceptor that disrupts the coulomb interaction we overcome the synergetic co-localisation of the carriers and realise charge separation. The thus created long-lived state can be exploited for a broad range of applications such as photocatalysis, water splitting, and switchable nanodevices.

Increasing the Resistance of Living Cells against Oxidative Stress by Nonnatural Surfactants as Membrane Guards.

The importation of construction principles or even constituents from biology into materials science is a prevailing concept. Vice versa, the cellular level modification of living systems with nonnatural components is much more difficult to achieve. It has been done for analytical purposes, for example, imaging, to learn something about intracellular processes. Cases describing the improvement of a biological function by the integration of a nonnatural (nano)constituent are extremely rare. Because biological membranes contain some kind of a surfactant, for example, phospholipids, our idea is to modify cells with a newly synthesized surfactant. However, this surfactant is intended to possess an additional functionality, which is the reduction of oxidative stress. We report the synthesis of a surfactant with Janus-type head group architecture, a fullerene C60 modified by five alkyl chains on one side and an average of 20 oxygen species on the other hemisphere. It is demonstrated that the amphiphilic properties of the fullerenol surfactant are similar to that of lipids. Not only quenching of reactive oxygen species (superoxide, hydroxyl radicals, peroxynitrite, and hydrogen peroxide) was successful, but also the fullerenol surfactant exceeds benchmark antioxidant agents such as quercetin. The surfactant was then brought into contact with different cell types, and the viability even of delicate cells such as human liver cells (HepG2) and human dopaminergic neurons (LUHMES) has proven to be extraordinarily high. We could show further that the cells take up the fullerenol surfactant, and as a consequence, they are protected much better against oxidative stress.

Nanomorphology Effects in Semiconductors with Native Ferromagnetism: Hierarchical Europium (II) Oxide Tubes Prepared via a Topotactic Nanostructure Transition.

Semiconductors with native ferromagnetism barely exist and defined nanostructures are almost unknown. This lack impedes the exploration of a new class of materials characterized by a direct combination of effects on the electronic system caused by quantum confinement effects with magnetism. A good example is EuO for which currently no reliable routes for nanoparticle synthesis can be established. Bottom-up approaches applicable to other oxides fail because of the labile oxidation state +II. Instead of targeting a direct synthesis, the two steps-"structure control" and "chemical transformation"-are separated. The generation of a transitional, hybrid nanophase is followed by its conversion into EuO under full conservation of all morphological features. Hierarchical EuO materials are now accessible in the shape of oriented nanodisks stacked to tubular particles. Magnetically, the coupling of either vortex or onion states has been found. An unexpected temperature dependence is governed by thermally activated transitions between these states.

Comparative examination of the stability of semiconductor quantum dots in various biochemical buffers.

Due to their greater photostability compared to established organic fluorescence markers, semiconductor quantum dots provide an attractive alternative for the biolabeling of living cells. On the basis of a comparative investigation using differently sized thiol-stabilized CdTe nanocrystals in a variety of commonly used biological buffers, a method is developed to quantify the stability of such a multicomponent system. Above a certain critical size, the intensity of the photoluminescence of the nanocrystals is found to diminish with pseudo-zero-order kinetics, whereas for specific combinations of particle size, ligand, and buffer there appears to be no decay below this critical particle size, pointing out the necessity for thorough investigations of this kind in the view of prospect applications of semiconductor nanocrystals in the area of biolabeling.

Shell effects on hole-coupled electron transfer dynamics from CdSe/CdS quantum dots to methyl viologen.

Electron transfer (ET) dynamics from the 1Se electron state in quasi-type II CdSe/CdS core/shell quantum dots (QDs) to adsorbed methyl viologen (MV(2+)) were measured using femtosecond transient absorption spectroscopy. The intrinsic ET rate kET was determined from the measured average number of ET-active MV(2+) per QD, which permits reliable comparisons of variant shell thickness and different hole states. The 1Se electron was extracted efficiently from the CdSe core, even for CdS shells up to 20 Å thick. The ET rate decayed exponentially from 10(10) to 10(9) s(-1) for increasing CdS shell thicknesses with an attenuation factor ß≈ 0.13 Å(-1). We observed that compared to the ground state exciton 1Se1S3/2 the electron coupled to the 2S3/2 hot hole state exhibited slower ET rates for thin CdS shells. We attribute this behaviour to an Auger-assisted ET process (AAET), which depends on electron-hole coupling controlled by the CdS shell thickness.

Controlling Charge Carrier Overlap in Type-II ZnSe/ZnS/CdS Core-Barrier-Shell Quantum Dots.

We describe the synthesis and spectroscopic characterization of colloidal ZnSe/ZnS/CdS nanocrystals, which exhibit a type-II electronic structure and wave function overlap that is strongly dependent on the thickness of the ZnS barrier. Barrier thickness is controlled by both the amount of deposited material and the reaction and annealing temperature of CdS shell growth. The results show that a single monolayer of ZnS mitigates the overlap significantly, while four and more monolayers effectively suppress band edge absorption and emission. Transient absorption spectra reveal a broad distribution of excitons with mixed S and P symmetry, which become allowed due to alloy formation and contribute to charge carrier relaxation across the barrier. We present a model of the core/shell interface based on cation diffusion, which allows one to estimate the extent of the diffusion layer from optical spectra.

Characterization of the organic ligand shell of semiconductor quantum dots by fluorescence quenching experiments.

We present the characterization of the organic ligand shell of CdSe/Cd(x)Zn(1-x)S/ZnS nanoparticles by means of fluorescence quenching experiments. Both electron scavengers and acceptors for resonance energy transfer were employed as probes. Different quenching behavior for short and long chain thiol ligands in water was found. It could be shown that poly(ethylene oxide) (PEO)-capping of the particles comprises a densely packed inner shell and a loosely packed outer shell in which ions and small molecules diffuse unhindered. A quantitative uptake of quencher molecules into the PEO shell was observed, through which the particle volume including the ligand sphere could be determined.

Fluorescence properties of hydrophilic semiconductor nanoparticles with tridentate polyethylene oxide ligands.

In this contribution a facile, one-step synthesis of tridentate thiol-functionalized PEO ligands and their ability to stabilize CdSe/CdS/ZnS core-shell-shell nanoparticles in aqueous media are described. The PEO-coated quantum dots show colloidal stability as well as preserved fluorescence even at very low concentrations of a few nM. For improved ligand attachment and enhanced fluorescence properties a method for ligand exchange was developed, which includes formation of a ligand zinc complex before the actual exchange reaction. The stability and fluorescence properties in various aqueous buffers and cell media and at pH values down to pH 3 were investigated. The firm binding of the tridentate ligands to the particle surface makes this ligand-particle system a promising tool for biological applications. In addition, activation of the ligands' terminal hydroxyl group for covalent biofunctionalization by esterification with succinic acid is reported.