Johannes Baier

Unexpected room-temperature ferromagnetism in bulk ZnO

It is demonstrated that a transition from paramagnetic behavior to clear room-temperature ferromagnetism (RTFM) exists in pure bulk ZnO. A significant enhancement of RTFM has been observed in argon-annealed ZnO samples. Quantitative chemical analysis unambiguously indicates that oxygen-related vacancies at surface play a crucial role in this observed RTFM. We suppose that the surface magnetic states, paramagnetic in the pure nanoparticles, are converted to ferromagnetic phase after mechanical compaction. Additionally, it is found that weakly adsorbed carbon species could block the exchange coupling between isolated magnetic moments in the surface layers.

The influence of ZnO-binding 12-mer peptides on bio-inspired ZnO formation

ZnO precipitation experiments were carried out in a Trizma (tris(hydroxymethyl)aminomethane)-buffered aqueous solution at 37 °C and in the presence of three ZnO-binding 12-mer peptide pairs, which have nearly the same isoelectric point (pI). With this new approach, the influence of peptide sequences on ZnO mineralization under moderate conditions was investigated. Previous work was focused on electrostatic interactions between inorganic-binding peptides and inorganic surfaces. The precipitates were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Furthermore, the peptide binding to crystallographic planes of ZnO crystals was modeled by molecular dynamics (MD) simulation in explicit water. The binding free energies of all ZnO-binding peptides were calculated. The combined experimental and modeled results demonstrated a direct correlation between the binding strength of the peptide and the morphology of the ZnO particle, due to differences in their specific binding strength towards polar ZnO (001) and nonpolar (100) surfaces. As a consequence, the ZnO-binding peptides inhibited the growth of ZnO crystals by selective adsorption on the polar or nonpolar ZnO surfaces. This was demonstrated by comparison with a precipitation experiment under peptide-free conditions.

Synthesis and characterization of textured Al-doped zinc oxide films prepared by template-directed deposition

Aluminum-doped ZnO (AZO) thin films were produced via template-directed deposition at 60 °C. By adding organic molecules to the deposition solution, it is possible to control the crystallite growth, and nanocrystallinity is achieved. An organic template, 3-aminopropyltriethoxysilane (APTES), is used to direct the attachment of the crystallites on the substrate. The optical properties and the incorporation of the aluminum from solution into the ZnO films were measured using photoluminescence (PL) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The morphology of the film was investigated using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The latter revealed a preferred orientation of the crystallites in the samples where more than 15 mol% Al was added to the stock solution. For values higher than 30 mol% Al in solution, no ZnO was found at all.

Influence of zinc on the calcium carbonate biomineralization of Halomonas halophila.

BackgroundThe salt tolerance of halophilic bacteria make them promising candidates for technical applications, like isolation of salt tolerant enzymes or remediation of contaminated saline soils and waters. Furthermore, some halophilic bacteria synthesize inorganic solids resulting in organic–inorganic hybrids. This process is known as biomineralization, which is induced and/or controlled by the organism. The adaption of the soft and eco-friendly reaction conditions of this formation process to technical syntheses of inorganic nano materials is desirable. In addition, environmental contaminations can be entrapped in biomineralization products which facilitate the subsequent removal from waste waters. The moderately halophilic bacteria Halomonas halophila mineralize calcium carbonate in the calcite polymorph. The biomineralization process was investigated in the presence of zinc ions as a toxic model contaminant. In particular, the time course of the mineralization process and the influence of zinc on the mineralized inorganic materials have been focused in this study.ResultsH. halophila can adapt to zinc contaminated medium, maintaining the ability for biomineralization of calcium carbonate. Adapted cultures show only a low influence of zinc on the growth rate. In the time course of cultivation, zinc ions accumulated on the bacterial surface while the medium depleted in the zinc contamination. Intracellular zinc concentrations were below the detection limit, suggesting that zinc was mainly bound extracellular. Zinc ions influence the biomineralization process. In the presence of zinc, the polymorphs monohydrocalcite and vaterite were mineralized, instead of calcite which is synthesized in zinc-free medium.ConclusionsWe have demonstrated that the bacterial mineralization process can be influenced by zinc ions resulting in the modification of the synthesized calcium carbonate polymorph. In addition, the shape of the mineralized inorganic material is chancing through the presence of zinc ions. Furthermore, the moderately halophilic bacterium H. halophila can be applied for the decontamination of zinc from aqueous solutions.

Chemical bath deposition of textured and compact zinc oxide thin films on vinyl-terminated polystyrene brushes

Summary In this study we investigated the influence of an organic polystyrene brush on the deposition of ZnO thin films under moderate conditions. On a non-modified SiOx surface, island growth is observed, whereas the polymer brush induces homogeneous film growth. A chemical modification of the polystyrene brushes during the mineralization process occurs, which enables stronger interaction between the then polar template and polar ZnO crystallites in solution. This may lead to oriented attachment of the crystallites so that the observed (002) texture arises. Characterization of the templates and the resulting ZnO films were performed with ζ-potential and contact angle measurements as well as scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). Infrared spectroscopy (IR) measurements were used to investigate the polystyrene brushes before and after modification.

Template-controlled mineralization: Determining film granularity and structure by surface functionality patterns.

Summary We present a promising first example towards controlling the properties of a self-assembling mineral film by means of the functionality and polarity of a substrate template. In the presented case, a zinc oxide film is deposited by chemical bath deposition on a nearly topography-free template structure composed of a pattern of two self-assembled monolayers with different chemical functionality. We demonstrate the template-modulated morphological properties of the growing film, as the surface functionality dictates the granularity of the growing film. This, in turn, is a key property influencing other film properties such as conductivity, piezoelectric activity and the mechanical properties. A very pronounced contrast is observed between areas with an underlying fluorinated, low energy template surface, showing a much more (almost two orders of magnitude) coarse-grained film with a typical agglomerate size of around 75 nm. In contrast, amino-functionalized surface areas induce the growth of a very smooth, fine-grained surface with a roughness of around 1 nm. The observed influence of the template on the resulting clear contrast in morphology of the growing film could be explained by a contrast in surface adhesion energies and surface diffusion rates of the nanoparticles, which nucleate in solution and subsequently deposit on the functionalized substrate.

Genesis of amorphous calcium carbonate containing alveolar plates in the ciliate Coleps hirtus (Ciliophora, Prostomatea).

In the protist world, the ciliate Coleps hirtus (phylum Ciliophora, class Prostomatea) synthesizes a peculiar biomineralized test made of alveolar plates, structures located within alveolar vesicles at the cell cortex. Alveolar plates are arranged by overlapping like an armor and they are thought to protect and/or stiffen the cell. Although their morphology is species-specific and of complex architecture, so far almost nothing is known about their genesis, their structure and their elemental and mineral composition. We investigated the genesis of new alveolar plates after cell division and examined cells and isolated alveolar plates by electron microscopy, energy-dispersive X-ray spectroscopy, FTIR and X-ray diffraction. Our investigations revealed an organic mesh-like structure that guides the formation of new alveolar plates like a template and the role of vesicles transporting inorganic material. We further demonstrated that the inorganic part of the alveolar plates is composed out of amorphous calcium carbonate. For stabilization of the amorphous phase, the alveolar vesicles, the organic fraction and the element phosphorus may play a role.