Daria Smazna

Hybridization of Zinc Oxide Tetrapods for Selective Gas Sensing Applications

In this work, the exceptionally improved sensing capability of highly porous three-dimensional (3-D) hybrid ceramic networks toward reducing gases is demonstrated for the first time. The 3-D hybrid ceramic networks are based on doped metal oxides (MexOy and ZnxMe1-xOy, Me = Fe, Cu, Al) and alloyed zinc oxide tetrapods (ZnO-T) forming numerous junctions and heterojunctions. A change in morphology of the samples and formation of different complex microstructures is achieved by mixing the metallic (Fe, Cu, Al) microparticles with ZnO-T grown by the flame transport synthesis (FTS) in different weight ratios (ZnO-T:Me, e.g., 20:1) followed by subsequent thermal annealing in air. The gas sensing studies reveal the possibility to control and change/tune the selectivity of the materials, depending on the elemental content ratio and the type of added metal oxide in the 3-D ZnO-T hybrid networks. While pristine ZnO-T networks showed a good response to H2 gas, a change/tune in selectivity to ethanol vapor with a decrease in optimal operating temperature was observed in the networks hybridized with Fe-oxide and Cu-oxide. In the case of hybridization with ZnAl2O4, an improvement of H2 gas response (to ∼7.5) was reached at lower doping concentrations (20:1), whereas the increase in concentration of ZnAl2O4 (ZnO-T:Al, 10:1), the selectivity changes to methane CH4 gas (response is about 28). Selectivity tuning to different gases is attributed to the catalytic properties of the metal oxides after hybridization, while the gas sensitivity improvement is mainly associated with additional modulation of the electrical resistance by the built-in potential barriers between n-n and n-p heterojunctions, during adsorption and desorption of gaseous species. Density functional theory based calculations provided the mechanistic insights into the interactions between different hybrid networks and gas molecules to support the experimentally observed results. The studied networked materials and sensor structures performances would provide particular advantages in the field of fundamental research, applied physics studies, and industrial and ecological applications.

Hierarchical self-entangled carbon nanotube tube networks

Three-dimensional (3D) assemblies based on carbon nanomaterials still lag behind their individual one-dimensional building blocks in terms of mechanical and electrical properties. Here we demonstrate a simple strategy for the fabrication of an open porous 3D self-organized double-hierarchical carbon nanotube tube structure with properties advantageous to those existing so far. Even though no additional crosslinking exists between the individual nanotubes, a high reinforcement effect in compression and tensile characteristics is achieved by the formation of self-entangled carbon nanotube (CNT) networks in all three dimensions, employing the CNTs in their high tensile properties. Additionally, the tubular structure causes a self-enhancing effect in conductivity when employed in a 3D stretchable conductor, together with a high conductivity at low CNT concentrations. This strategy allows for an easy combination of different kinds of low-dimensional nanomaterials in a tube-shaped 3D structure, enabling the fabrication of multifunctional inorganic-carbon-polymer hybrid 3D materials.Low-dimensional nanomaterials are crucial conducting components of stretchable electronics, but their mechanical reinforcement remains challenging. Here, the authors infiltrate carbon nanotubes into a porous ceramic network to produce a 3D nanofelted self-entangled assembly with high conductivity and mechanical stability.

Nanomechanics of individual aerographite tetrapods.

Carbon-based three-dimensional aerographite networks, built from interconnected hollow tubular tetrapods of multilayer graphene, are ultra-lightweight materials recently discovered and ideal for advanced multifunctional applications. In order to predict the bulk mechanical behaviour of networks it is very important to understand the mechanics of their individual building blocks. Here we characterize the mechanical response of single aerographite tetrapods via in situ scanning electron and atomic force microscopy measurements. To understand the acquired results, which show that the overall behaviour of the tetrapod is governed by the buckling of the central joint, a mechanical nonlinear model was developed, introducing the concept of the buckling hinge. Finite element method simulations elucidate the governing buckling phenomena. The results are then generalized for tetrapods of different size-scales and shapes. These basic findings will permit better understanding of the mechanical response of the related networks and the design of similar aerogels based on graphene and other two-dimensional materials.

Publisher Correction: Hierarchical self-entangled carbon nanotube tube networks

The original version of this Article was missing the ORCID ID of Professor Nicola Pugno.Also in the original version of this Article, the third to last sentence of the fourth paragraph of the Results incorrectly read ‘However, the stepwise addition of CNTs increases the self-entanglement and thereby the compressive strength value as well as the Young’s modulus (up to 2.5 MPa (normalized by density 6.4) and 24.5 MPa (normalized by density 62 MPa cm3 g−1).’ The correct version adds the units ‘MPa cm3 g−1’ to ‘6.4’.Finally, in the original version of this Article, the y-axis label of Figure 3f incorrectly read ‘Comp. strengthy’. The new version corrects that to ‘Comp. Strength’.These errors have now been corrected in both the PDF and the HTML versions of the Article.

Functional NiTi grids for in situ straining in the TEM

In situ measurements are a pivotal extension of conventional transmission electron microscopy (TEM). By means of the shape memory alloy NiTi thin film Functional Grids were produced for in situ straining as alternative or at least complement of expensive commercial holders. Due to the martensite-austenite transition temperature straining effects can be observed by use of customary heating holders in the range of 50 to 100°C. The grids can be produced in diversified designs to fit for different strain situations. Micro tensile tests were performed and compared with finite element simulations to estimate the applied forces on the sample and to predict the functionality of different grid designs. As a first example of this Functional Grid technology, we demonstrate the impact of applying a strain to a network of ZnO tetrapods.

Flame based growth of ZnO nano- and microstructures for advanced optical, multifunctional devices, and biomedical applications (Conference Presentation)

The recent flame based growth strategy offers a simple and versatile fabrication of various (one, two, and three-dimensional) nano- and microstructures from different metal oxides (ZnO, SnO2, Fe2O3, etc.) in a desired manner.[1] ZnO structures ranging from nanoscales wires to macroscopic and highly porous 3D interconnected tetrapod networks have been successfully synthesized, characterized and utilized for various applications. The ZnO micro- and nanoneedles grown at walls in silicon trenches showed excellent whispering gallery mode resonances and photocatalytic properties.[2] Using the same strategy, large polycrystalline micro- and nanostructured ZnO platelets can be grown with grains interconnected together via grain boundaries and these grain boundaries exhibit a higher conductivity as compared to individual grains.[3] This flame transport synthesis (FTS) approach offers the growth of a large amount of ZnO tetrapods which have shown interesting applications because of their 3D spatial shape and micro-and nanoscale size, for example, interconnected tetrapods based devices for UV-detection and gas sensing.[4-5] Because of their complex 3D shape, ZnO tetrapods can be used as efficient filler particles for designing self-reporting,[6] and other interesting composites. The nanostructured materials exhibit an important role with respect to advanced biomedical applications as grown ZnO structures have shown strong potentials for antiviral applications.[7] Being mechanically strong and micro-and nanoscale in dimensions, these ZnO tetrapods can be easily doped with other elements or hybridized with various nanoparticles in form of hybrid ZnO tetrapods which are suitable for various multifunctional applications, for example, these hybrid tetrapods showed improved gas sensing properties.[8] The sacrificial nature of ZnO allows the for growth of new tetrapods and 3D network materials for various advanced applications, for example, highly porous and ultra light carbon based Aerographite materials[9] and hollow silicon tetrapods.[10] These carbon based highly porous network can be further utilized for growth of new hybrid 3D nanomaterials, for example, Aerographite- GaN[11] and Aerographite-ZnO[12] for advanced optical and other applications.

Photocatalytic Applications of Doped Zinc Oxide Porous Films Grown by Magnetron Sputtering

Undoped, Al-doped and Sn-doped ZnO was sputter-deposited on glass substrates and on trenched Si substrates and some properties of these samples were evaluated. It was shown that the photocatalytic performance of the thin layers is improved by doping with Sn and Al. The samples doped with Al-doping provided a more pronounced effect compared to the control sample, as well as compared to the greater volume of undoped ZnO deposited on Si substrates. Morphology of produced particles was studied using transmission electron microscopy. Electron diffraction patterns were taken to confirm lattice parameters of the materials. Size and shape variations were monitored for un-doped, Al-doped and Sn-doped ZnO. EDX spectroscopy was utilized to assay chemical composition for doped and un-doped samples.