Surface Chemistry Dictates the Enhancement of Luminescence and Stability of InP QDs upon c-ALD ZnO Hybrid Shell Growth.

Indium phosphide quantum dots (InP QDs) are a promising example of Restriction of Hazardous Substances directive (RoHS)-compliant light-emitting materials. However, they suffer from low quantum yield and instability upon processing under ambient conditions. Colloidal atomic layer deposition (c-ALD) has been recently proposed as a methodology to grow hybrid materials including QDs and organic/inorganic oxide shells, which possess new functions compared to those of the as-synthesized QDs. Here, we demonstrate that ZnO shells can be grown on InP QDs obtained via two synthetic routes, which are the classical sylilphosphine-based route and the more recently developed aminophosphine-based one. We find that the ZnO shell increases the photoluminescence emission only in the case of aminophosphine-based InP QDs. We rationalize this result with the different chemistry involved in the nucleation step of the shell and the resulting surface defect passivation. Furthermore, we demonstrate that the ZnO shell prevents degradation of the InP QD suspension under ambient conditions by avoiding moisture-induced displacement of the ligands from their surface. Overall, this study proposes c-ALD as a methodology for the synthesis of alternative InP-based core@shell QDs and provides insight into the surface chemistry that results in both enhanced photoluminescence and stability required for application in optoelectronic devices and bioimaging.

Oxidation Kinetics of Nanocrystalline Hexagonal RMn1-xTixO3 (R = Ho, Dy).

Hexagonal manganites, RMnO3 (R = Sc, Y, Ho-Lu), are potential oxygen storage materials for air separation due to their reversible oxygen storage and release properties. Their outstanding ability to absorb and release oxygen at relatively low temperatures of 250-400 °C holds promise of saving energy compared to current industrial methods. Unfortunately, the low temperature of operation also implies slow kinetics of oxygen exchange in these materials, which would make them inefficient in applications such as chemical looping air separation. Here, we show that the oxidation kinetics of RMnO3 can be improved through Ti4+-doping as well as by increasing the rare earth cation size. The rate of oxygen absorption of nanocrystalline RMn1-xTixO3 (R = Ho, Dy; x = 0, 0.15) was investigated by thermogravimetric analysis, X-ray absorption near-edge structure, and high-temperature X-ray diffraction (HT-XRD) with in situ switching of atmosphere from N2 to O2. The kinetics of oxidation increases for larger R and even more with Ti4+ donor doping, as both induce expansion of the ab-plane, which reduces the electrostatic repulsion between oxygen in the lattice upon oxygen ion migration. Surface exchange rates and activation energies of oxidation were determined from changes in lattice parameters observed through HT-XRD upon in situ switching of atmosphere.

A new high temperature, high heating rate, low axial gradient capillary heater.

A new heater design, capable of fast heating and cooling to and from >1000°C, has been developed at the Swiss-Norwegian Beamlines, European Synchrotron Radiation Facility, France. The design uses a SiC head to distribute heat, and resistive Si3N4 heat cartridges to provide heat.

Hydrogen Interaction with Oxide Supports in the Presence and Absence of Platinum.

Oxides are essential catalysts and supports for noble metal catalysts. Their interaction with hydrogen enables, e.g., their use as a hydrogenation catalyst. Among the oxides considered reducible, substantial differences exist in their capability to activate hydrogen and how the oxide structure transforms due to this interaction. Noble metals, like platinum, generally enhance the oxide reduction by hydrogen spillover. This work presents a systematic temperature-programmed reduction study (300 to 873 K) of iron oxide, ceria, titania, zirconia, and alumina, with and without supported platinum. For all catalysts, platinum enhances the reducibility of the oxide. However, there are pronounced differences among all catalysts.

Hydrothermal synthesis of hexagonal YMnO3 and YbMnO3 below 250 °C.

The hydrothermal synthesis of hexagonal YMnO3 and YbMnO3 are reported using high KOH mineraliser concentrations (>10 M) and low temperatures (<240 °C). The relation between reaction parameters and resulting phase purity were mapped by ex situ and in situ X-ray diffraction. Excess Y2O3 resulted in two-phase product with hexagonal YMnO3 with different lattice parameters. An unusual microstructure was observed in which particles have a hexagonal shape with a highly crystalline edge and either a hollow or polycrystalline interior. An Ostwald ripening mechanism was proposed to explain this phenomenon. Solid-state reactions and density functional theory calculations were performed to determine plausible defect chemistry which can lead to the observed phases with different lattice parameters.

A Fast, Low-Temperature Synthesis Method for Hexagonal YMnO3 : Kinetics, Purity, Size and Shape as Studied by In Situ X-ray Diffraction.

The reaction mechanisms, phase development and kinetics of the hydrothermal synthesis of hexagonal-YMnO3 from Y2 O3 and Mn2 O3 using in situ X-ray diffraction are reported under different reaction conditions with temperatures ranging from 300 to 350 °C, and using 1, 5 and 10 m KOH, and 5 m NaOH mineraliser. Reactions initiated with Y2 O3 hydrating to Y(OH)3 , which then dehydrated to YO(OH). Higher temperatures and KOH concentrations led to faster, more complete dehydrations. However, 1 m KOH led to YO(OH) forming concurrently with Y(OH)3 before Y(OH)3 fully dehydrated but yielded a very low phase purity of hexagonal-YMnO3 . Using NaOH mineraliser, no YO(OH) was observed. Dehydration also initiated at a higher temperature in the absence of Mn2 O3 . The evolution of Rietveld refined scale factors was used to determine kinetic information and approximate activation energies for the reaction. The described hydrothermal synthesis offers a fast, low-temperature method for producing anisometric h-YMnO3 particles.

Assessing the suitability of copper thiocyanate as a hole-transport layer in inverted CsSnI3 perovskite photovoltaics.

We report the findings of a study into the suitability of copper (I) thiocyanate (CuSCN) as a hole-transport layer in inverted photovoltaic (PV) devices based on the black gamma phase (B-γ) of CsSnI3 perovskite. Remarkably, when B-γ-CsSnI3 perovskite is deposited from a dimethylformamide solution onto a 180-190 nm thick CuSCN film supported on an indium-tin oxide (ITO) electrode, the CuSCN layer is completely displaced leaving a perovskite layer with high uniformity and coverage of the underlying ITO electrode. This finding is confirmed by detailed analysis of the thickness and composition of the film that remains after perovskite deposition, together with photovoltaic device studies. The results of this study show that, whilst CuSCN has proved to be an excellent hole-extraction layer for high performance lead-perovskite and organic photovoltaics, it is unsuitable as a hole-transport layer in inverted B-γ-CsSnI3 perovskite photovoltaics processed from solution.

In situ neutron diffraction study of the formation of Ho2Ge2O7 pyrochlore at high temperature and pressure.

The formation of the spin-ice pyrochlore Ho2Ge2O7 by two different high temperature, high pressure routes has been explored using in situ neutron diffraction. The first route involves the solid-state reaction of Ho2O3 and GeO2, and formation of the pyrochlore phase is observed at 994(27) °C and 3.81(2) GPa, which are significantly milder conditions than those previously reported. The second route involves the hydrothermal synthesis of the tetragonal Ho2Ge2O7 pyrogermanate from Ho(NO3)3·5H2O and GeO2 and its subsequent transformation to the pyrochlore phase, which is observed at 683(23) °C and 3.89(3) GPa. The lowering of the formation temperature of high pressure phases by employment of a precursor of appropriate stoichiometry may also have applications in the wider field of solid-state chemistry.