Andreas Sternig

Optical Properties of Nanocrystal Interfaces in Compressed MgO Nanopowders

The optical properties and charge trapping phenomena observed on oxide nanocrystal ensembles can be strongly influenced by the presence of nanocrystal interfaces. MgO powders represent a convenient system to study these effects due to the well-defined shape and controllable size distributions of MgO nanocrystals. The spectroscopic properties of nanocrystal interfaces are investigated by monitoring the dependence of absorption characteristics on the concentration of the interfaces in the nanopowders. The presence of interfaces is found to affect the absorption spectra of nanopowders more significantly than changing the size of the constituent nanocrystals and, thus, leading to the variation of the relative abundance of light-absorbing surface structures. We find a strong absorption band in the 4.0−5.5 eV energy range, which was previously attributed to surface features of individual nanocrystals, such as corners and edges. These findings are supported by complementary first-principles calculations. The possibility to directly address such interfaces by tuning the energy of excitation may provide new means for functionalization and chemical activation of nanostructures and can help improve performance and reliability for many nanopowder applications.

Size effects in MgO cube dissolution.

Stability parameters and dissolution behavior of engineered nanomaterials in aqueous systems are critical to assess their functionality and fate under environmental conditions. Using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, we investigated the stability of cubic MgO particles in water. MgO dissolution proceeding via water dissociation at the oxide surface, disintegration of Mg(2+)-O(2-) surface elements, and their subsequent solvation ultimately leads to precipitation of Mg(OH)2 nanosheets. At a pH ≥ 10, MgO nanocubes with a size distribution below 10 nm quantitatively dissolve within few minutes and convert into Mg(OH)2 nanosheets. This effect is different from MgO cubes originating from magnesium combustion in air. With a size distribution in the range 10 nm ≤ d ≤ 1000 nm they dissolve with a significantly smaller dissolution rate in water. On these particles water induced etching generates (110) faces which, above a certain face area, dissolve at a rate equal to that of (100) planes.1 The delayed solubility of microcrystalline MgO is attributed to surface hydroxide induced self-inhibition effects occurring at the (100) and (110) microplanes. The present work underlines the importance of morphology evolution and surface faceting of engineered nanomaterials particles during their dissolution.

Zinc oxide scaffolds on MgO nanocubes

Powders of isolated and well-dispersed oxide nanocubes are promising components for photoelectronic applications that benefit from tunable optical properties, surface reactivity and the ease of realization of their controlled assembly. Here, we demonstrate that combustion of zinc and magnesium metal vapors at reduced pressures followed by subsequent vacuum annealing of the resulting nanoparticle powders yields single-crystalline Zn(x)Mg(1-x)O nanocubes of exceptional regular cubic shape and edge lengths below 25 nm. In line with ab initio calculations, which predict preferential Zn(2+) segregation into low coordinated surface elements of the MgO nanocubes, we track the occupation of edge sites by chains of Zn(2+)-O(2-) units through their spectroscopic signatures. As a method to generate composite nanostructures with controlled spatial distribution of the chemical components, the annealing induced ion segregation can be extended to other well-dispersed metastable nanoparticles. We expect that the energy of segregation mainly depends on the site coordination number, which can promote controlled demixing within the nanoparticles.

BaO Clusters on MgO Nanocubes: A Quantitative Analysis of Optical-Powder Properties

Uniformly sized and shaped nanoparticles are well suited for the quantitative characterization of optical-powder properties. For the first time, quantum yields related to photoluminescence emissions that originate from the photoexcitation of MgO nanocube corners and edges are measured. In addition, the surfaces of these nanoparticles are doped with submonolayer barium, which oxidizes during adsorption onto the MgO nanocrystal surfaces and transforms in O(2) atmosphere into BaO. UV-Vis diffuse reflectance and photoluminescence spectroscopy is employed to explore whether 10(-3) monolayer equivalents of these dopants affect the MgO specific optical properties. Surface-admixed BaO produces additional absorption and photoluminescence emission features but does not significantly affect those specific to MgO nanocubes. On this basis the number of optically active sites that can be sampled inside a powder of alkaline earth oxide nanoparticles using a standard spectrometer system is estimated.

Photoluminescence quenching in compressed MgO nanoparticle systems

Efficient use of highly dispersed metal oxides for lighting, energy conversion and catalysis requires knowledge about the impact of density and microstructure of the powders on the optical nanoparticle properties. For MgO nanocube powders we present a combined photoluminescence (PL) and electron paramagnetic resonance (EPR) approach which enables for samples of different aggregation states the quantification of the fractional powder volume that becomes illuminated with UV and visible light during the PL measurements. Using O2 as a PL emission quencher and - after light induced exciton separation and oxygen adsorption - as an EPR active adsorbate we observed clear aggregation dependent trends in PL emission quenching that originate from particle-particle contacts. Upon interaction of low coordinated surface elements with the surfaces of adjacent MgO nanocubes, which occurs even at powder consolidation levels that escape sorption analysis, the radiative decay of excited surface states becomes quenched down to 15% of the original intensity. Our results underline the critical role of microstructure and the aggregation state of a nanoparticle ensemble with respect to spectroscopic properties and related adsorption induced changes.

Surface Decoration of MgO Nanocubes with Sulfur Oxides:Experiment and Theory

We investigated the effect of surface sulfate formation on the structure and spectroscopic properties of MgO nanocubes using X-ray diffraction, electron microscopy, several spectroscopic techniques, and ab initio calculations. After CS2 adsorption and oxidative treatment at elevated temperatures the MgO particles remain cubic and retain their average size of ∼6 nm. Their low coordinated surface elements (corners and edges) were found to bind sulfite and sulfate groups even after annealing up to 1173 K. The absence of MgO corner specific photoluminescence emission bands at 3.4 and 3.2 eV substantiates that sulfur modifies the electronic properties of characteristic surface structures, which we attribute to the formation of (SO3)2– and (SO4)2– groups at corners and edges. Ab initio calculations support these conclusions and provide insight into the local atomic structures and spectroscopic properties of these groups.

Bulk and surface excitons in alloyed and phase-separated ZnO-MgO particulate systems.

The rational design of composite nanoparticles with desired optical and electronic properties requires the detailed analysis of surface and bulk contributions to the respective overall function. We use flame spray pyrolysis (FSP) to generate nanoparticles of the ternary Zn-Mg-O system the compositions of which range from solid solutions of Zn(2+) ions in periclase MgO to phase separated particle mixtures which consist of periclase (cubic) MgO and wurtzite (hexagonal) ZnO phases. The structure and composition of the composite Zn(x)Mg(1-x)O (0 ≤ x ≤ 0.3) particles are investigated using X-ray diffraction and high-resolution transmission electron microscopy, whereas UV diffuse reflectance and photoluminescence (PL) spectroscopy are used for the investigation of their optical properties. Vacuum annealing has been carried out to track the effects of stepwise elimination of surface adsorbates on the photoexcitation and PL emission properties. We demonstrate that for Zn(0.1)Mg(0.9)O particles, the admixed ZnO suppresses the MgO specific surface excitons and produces a PL emission band at 470 nm. Although gaseous oxygen partially reduces the emission intensity of hydroxylated particles, it leads to entire quenching in completely dehydroxylated samples after vacuum annealing at 1173 K. Consequently, surface hydroxyls at the solid-gas interface play a significant role as protecting groups against the PL-quenching effects of O(2). The obtained results are relevant for the characterization of ZnO-based devices as well as for other metal oxide materials where the impact of the surface composition on the photoelectronic properties is usually neglected.

Surface-specific visible light luminescence from composite metal oxide nanocrystals

Low-coordinated surface elements on metal oxide nanoparticles represent the basis for a new concept of luminescent nanoparticles made of abundant, non-toxic, and thermally stable materials. This combined experimental and theoretical study describes the generation and stability of Ba-doped MgO nanoparticle surfaces and their optical absorption and luminescence dependence on Ba loading. It is demonstrated that the vapor phase growth process employed here represents a particularly robust synthesis approach for particle powders with reproducibly adjustable photoluminescence emission properties in the range between blue and yellow light. Moreover, this in-depth characterization also provides an understanding of the electronic and optical characteristics of this nanoparticulate material with a so far unnoticed potential for solid-state light applications that are based on down conversion of UV light.

Thin water films and magnesium hydroxide fiber growth

Thin films of water covering highly dispersed metal oxides can give rise to the spontaneous and spatially controllable growth of hydroxide fibers in ambient air. Knowledge about the underlying formation mechanisms is key to the rational development of metal oxide nanomaterials and associated microstructures. We used SiCl4 as a water free chlorine ion source for the surface functionalization of MgO nanocubes and explored their subsequent transformation into magnesium oxychloride Mg3(OH)5Cl·4H2O fibers upon contact with water vapor. Specifically we show how the temperature of the functionalization process and material dispersion control the reaction pathway that can lead to very different products like Mg(OH)2, MgCl2·6H2O, or Mg3(OH)5Cl·4H2O and delineate a reaction mechanism. Lessons to be learned from this unique route to form hydroxide fibers under ambient conditions can be applied to a variety of microstructural evolution processes that involve metastable solids and superficial water acting both as a reactant and as a reaction medium for the hydration of metal oxide particles.

On the Entangled Growth of NaTaO3 Cubes and Na2Ti3O7 Wires in Sodium Hydroxide Solution

The entangled growth of sodium titanate Na2Ti3O7 nanowires and sodium tantalate NaTaO3 cubes was investigated with electron microscopy, X-ray diffraction, and UV diffuse reflectance spectroscopy. Depending on the composition of the Ta2O5- and TiO2-particle-based powder mixtures, which served as educts, we observed different types of hybridization effects. These include the titanium-induced contraction of the NaTaO3 perovskite-type unit cell and the generation of electronic defect states in NaTaO3 that give rise to optical subbandgap transitions and tantalum-induced limitations of the Na2Ti3O7 nanowire growth. The transformation from Ta2O5 to NaTaO3 occurs through a dissolution-recrystallization process. A systematic analysis of the impact of different titanium sources on NaTaO3 dispersion and, thus, on the properties of the entangled nanostructures revealed that a perfect intermixture of cubes and nanowires can only be achieved when titanate nanosheets emerge during transformation as reaction intermediates and shield nucleation and growth of isolated NaTaO3 cubes. The here demonstrated approach can be highly instrumental for understanding the nucleation and growth of composite and entangled nanostructures in solution and--at the same time--provides an interesting new class of photoactive composite materials.