At present, the technical progress of secondary batteries employing metallic magnesium as the anode material has been severely hindered due to the low oxidation stability of state-of-the-art Mg ...electrolytes, which cannot be used to explore high-voltage (>3 V versus Mg2+/Mg) cathode materials. All known electrolytes based on oxidatively stable solvents and salts, such as Mg(ClO4)2 and Mg bis(trifluoromethanesulfonimide), react with the metallic magnesium anode, forming a passivating layer at its surface and preventing the reversible plating and stripping of Mg. Therefore, in a near-term effort to extend the upper voltage limit in the exploration of future candidate Mg-ion battery cathode materials, bismuth anodes have attracted considerable attention due to their efficient magnesiation and demagnesiation alloying reaction in such electrolytes. In this context, we present colloidal Bi nanocrystals (NCs) as a model anode material for the exploration of cathode materials for rechargeable Mg-ion batteries. Bi NCs demonstrate a stable capacity of 325 mAh g–1 over at least 150 cycles at a current density of 770 mA g–1, which is among the most-stable performance of Mg-ion battery anode materials. First-principles crystal structure prediction methodologies and ex situ X-ray diffraction measurements reveal that the magnesiation of Bi NCs leads to the simultaneous formation of the low-temperature trigonal structure, α-Mg3Bi2, and the high-temperature cubic structure, β-Mg3Bi2, which sheds insight into the high stability of this reversible alloying reaction. Furthermore, small-angle X-ray scattering measurements indicate that although the monodispersed, crystalline nature of the Bi NCs is indeed disturbed during the first discharge step, no notable morphological or structural changes occur in the following electrochemical cycles. The cost-effective and facile synthesis of colloidal Bi NCs and their remarkably high electrochemical stability upon magnesiation make them an excellent model anode material with which to accelerate progress in the field of Mg-ion secondary batteries.
Here, we present a hot injection synthesis of colloidal Ag chalcogenide nanocrystals (Ag2Se, Ag2Te, and Ag2S) that resulted in exceptionally small nanocrystal sizes in the range between 2 and 4 nm. ...Ag chalcogenide nanocrystals exhibit band gap energies within the near-infrared spectral region, making these materials promising as environmentally benign alternatives to established infrared active nanocrystals containing toxic metals such as Hg, Cd, and Pb. We present Ag2Se nanocrystals in detail, giving size-tunable luminescence with quantum yields above 1.7%. The luminescence, with a decay time on the order of 130 ns, was shown to improve due to the growth of a monolayer thick ZnSe shell. Photoconductivity with a quantum efficiency of 27% was achieved by blending the Ag2Se nanocrystals with a soluble fullerene derivative. The co-injection of lithium silylamide was found to be crucial to the synthesis of Ag chalcogenide nanocrystals, which drastically increased their nucleation rate even at relatively low growth temperatures. Because the same observation was made for the nucleation of Cd chalcogenide nanocrystals, we conclude that the addition of lithium silylamide might generally promote wet-chemical synthesis of metal chalcogenide nanocrystals, including in as-yet unexplored materials.
Various oleic acid salts are demonstrated to act as stabilizers for high-quality iron oxide nanocrystals, synthesized by thermal decomposition of ferric oleate. Changing the cation species in oleic ...acid salts allows different degrees of dissociation at high temperatures to be obtained, resulting in various stabilizer performances: Sodium oleate as stabilizer results in monodisperse iron oxide nanocrystals of cubic shape with precisely adjustable edge lengths between 7 and 23 nm. Dibutylammonium oleate and oleic acid, in contrast, induce growth of spherical nanocrystals in the same size range. Further adjustment of the growth conditions leads to {100}-bound bipyramidal nanocrystals with a single, (111) oriented twin plane. While the nanocrystal size is related to their superparamagnetic blocking temperature, the shape influences their magnetization hysteresis properties observed at low temperatures.
Epitaxial growth techniques enable nearly defect free heterostructures with coherent interfaces, which are of utmost importance for high performance electronic devices. While high-vacuum ...technology-based growth techniques are state-of-the art, here we pursue a purely solution processed approach to obtain nanocrystals with eptaxially coherent and quasi-lattice matched inorganic ligand shells. Octahedral metal-halide clusters, respectively 0-dimensional perovskites, were employed as ligands to match the coordination geometry of the PbS cubic rock-salt lattice. Different clusters (CH3NH3 +)(6–x)M(x+)Hal6(6–x)– (M x+ = Pb(II), Bi(III), Mn(II), In(III), Hal = Cl, I) were attached to the nanocrystal surfaces via a scalable phase transfer procedure. The ligand attachment and coherence of the formed PbS/ligand core/shell interface was confirmed by combining the results from transmission electron microscopy, small-angle X-ray scattering, nuclear magnetic resonance spectroscopy and powder X-ray diffraction. The lattice mismatch between ligand shell and nanocrystal core plays a key role in performance. In photoconducting devices the best performance (detectivity of 2 × 1011 cm Hz 1/2/W with > 110 kHz bandwidth) was obtained with (CH3NH3)3BiI6 ligands, providing the smallest relative lattice mismatch of ca. −1%. PbS nanocrystals with such ligands exhibited in millimeter sized bulk samples in the form of pressed pellets a relatively high carrier mobility for nanocrystal solids of ∼1.3 cm2/(V s), a carrier lifetime of ∼70 μs, and a low residual carrier concentration of 2.6 × 1013 cm–3. Thus, by selection of ligands with appropriate geometry and bond lengths optimized quasi-epitaxial ligand shells were formed on nanocrystals, which are beneficial for applications in optoelectronics.
Hydrogen‐bonded pigments are remarkably stable high‐crystal lattice energy organic solids. Here a lesser‐known family of compounds, the epindolidiones, which demonstrates electronic transport with ...extraordinary stability, even in highly demanding aqueous environments, is reported. Hole mobilities in the range 0.05–1 cm2 V–1 s–1 can be achieved, with lower electron mobilities of up to 0.1 cm2 V–1 s–1. To help understand charge transport in epindolidiones, X‐ray diffraction is used to solve the crystal structure of 2,8‐difluoroepindolidione and 2,8‐dichloroepindolidione. Both derivatives crystallize with a linear‐chain H‐bonding lattice featuring two‐dimensional π–π stacking. Powder diffraction indicates that the unsubstituted epindolidione has very similar crystallinity. All types of epindolidiones measured here display strong low‐energy optical emission originating from excimeric states, which coexists with higher‐energy fluorescence. This can be exploited in light‐emitting diodes, which show the same hybrid singlet and low‐energy excimer electroluminescence. Low‐voltage FETs are fabricated with epindolidione, which operate reliably under repeated cyclic tests in different ionic solutions within the pH range 3–10 without degradation. Finally, in order to overcome the insolubility of epindolidiones in organic solvents, a chemical procedure is devised to allow solution‐processing via the introduction of suitable thermolabile solubilizing groups. This work shows the versatile potential of epindolidione pigments for electronics applications.
Epindolidiones are H‐bonded organic pigment semiconductors with excellent operational stability, including in aqueous media. Their crystal structure, electrochemical properties, and photophysics, which are dominated by excimeric effects, are reported. Transistor and light‐emitting devices are demonstrated. Routes for solution processing of epindolidiones using transient solubilizing groups are explored.
It is a generally accepted perspective that type-II nanocrystal quantum dots (QDs) have low quantum yield due to the separation of the electron and hole wavefunctions. Recently, high quantum yield ...levels were reported for cadmium-based type-II QDs. Hence, the quest for finding non-toxic and efficient type-II QDs is continuing. Herein, we demonstrate environmentally benign type-II InP/ZnO/ZnS core/shell/shell QDs that reach a high quantum yield of ∼91%. For this, ZnO layer was grown on core InP QDs by thermal decomposition, which was followed by a ZnS layer via successive ionic layer adsorption. The small-angle X-ray scattering shows that spherical InP core and InP/ZnO core/shell QDs turn into elliptical particles with the growth of the ZnS shell. To conserve the quantum efficiency of QDs in device architectures, InP/ZnO/ZnS QDs were integrated in the liquid state on blue light-emitting diodes (LEDs) as down-converters that led to an external quantum efficiency of 9.4% and a power conversion efficiency of 6.8%, respectively, which is the most efficient QD-LED using type-II QDs. This study pointed out that cadmium-free type-II QDs can reach high efficiency levels, which can stimulate novel forms of devices and nanomaterials for bioimaging, display, and lighting.
When nanocrystals self assemble into ordered superstructures they form functional solids that may inherit the electronical properties of the single nanocrystals. To what extent these properties are ...enhanced depends on the positional and orientational order of the nanocrystals within the superstructure. Here, the formation of micrometer‐sized free‐standing supercrystals of faceted 20 nm Bi nanocrystals is investigated. The self‐assembly process, induced by nonsolvent into solvent diffusion, is probed in situ by synchrotron X‐ray scattering. The diffusion‐gradient is identified as the critical parameter for controlling the supercrystal‐structure as well as the alignment of the supercrystals with respect to the substrate. Monte Carlo simulations confirm the positional order of the nanocrystals within these superstructures and reveal a unique orientation phase: the nanocrystal shape, determined by the atomic Bi crystal structure, induces a total of 6 global orientations based on facet‐to‐facet alignment. This parallel alignment of facets is a prerequisite for optimized electronic and optical properties within designed nanocrystal solids.
The formation of colloidal supercrystals assembled from faceted 20 nm Bi nanocrystals is studied. The self‐assembly, induced by nonsolvent into solvent diffusion, is investigated by in situ synchrotron X‐ray scattering and Monte Carlo simulations. A unique orientation phase of the nanocrystals is revealed: their shape induces 6 distinct global orientations within the cubic superlattice based on a parallel facet‐to‐facet alignment.
The self‐assembly of 3D colloidal supercrystals built from faceted 20 nm Bi nanocrystals is studied by in situ synchrotron X‐ray scattering combined with Monte Carlo simulations. The assembly is ...driven by nonsolvent into solvent diffusion. In article number 1802078, Rainer T. Lechner and co‐workers reveal a unique orientation phase: the nanocrystals' shape induces 6 distinct global orientations within the cubic superlattice enabling parallel facet‐to‐facet alignment.
We reveal the existence of two different crystalline phases, i.e., the metastable rock salt and the equilibrium zinc blende phase within the CdS-shell of PbS/CdS core/shell nanocrystals formed by ...cationic exchange. The chemical composition profile of the core/shell nanocrystals with different dimensions is determined by means of anomalous small-angle X-ray scattering with subnanometer resolution and is compared to X-ray diffraction analysis. We demonstrate that the photoluminescence emission of PbS nanocrystals can be drastically enhanced by the formation of a CdS shell. Especially, the ratio of the two crystalline phases in the shell significantly influences the photoluminescence enhancement. The highest emission was achieved for chemically pure CdS shells below 1 nm thickness with a dominant metastable rock salt phase fraction matching the crystal structure of the PbS core. The metastable phase fraction decreases with increasing shell thickness and increasing exchange times. The photoluminescence intensity depicts a constant decrease with decreasing metastable rock salt phase fraction but shows an abrupt drop for shells above 1.3 nm thickness. We relate this effect to two different transition mechanisms for changing from the metastable rock salt phase to the equilibrium zinc blende phase depending on the shell thickness.
While over the past years the syntheses of colloidal quantum dots (CQDs) with core/shell structures were continuously improved to obtain highly efficient emission, it has remained a challenge to use ...them as active materials in laser devices. Here, we report random lasing at room temperature in films of CdSe/CdS CQDs with different core/shell band alignments and extra thick shells. Even though the lasing process is based on random scattering, we find systematic dependencies of the laser thresholds on morphology and laser spot size. To minimize laser thresholds, optimizing the film-forming properties of the CQDs, proven by small-angle X-ray scattering, was found to be more important than the optical parameters of the CQDs, such as biexciton lifetime and binding energy or fluorescence decay time. Furthermore, the observed systematic behavior turned out to be highly reproducible after storing the samples in air for more than 1 year. These highly reproducible systematic dependencies suggest that random lasing experiments are a valuable tool for testing nanocrystal materials, providing a direct and simple feedback for further development of colloidal gain materials toward lasing in continuous wave operation.
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