Aero-ZnS prepared by physical vapor transport on three-dimensional networks of sacrificial ZnO microtetrapods.

Aeromaterials represent a class of increasingly attractive materials for various applications. Among them, aero-ZnS has been produced by hydride vapor phase epitaxy on sacrificial ZnO templates consisting of networks of microtetrapods and has been proposed for microfluidic applications. In this paper, a cost-effective technological approach is proposed for the fabrication of aero-ZnS by using physical vapor transport with Sn2S3 crystals and networks of ZnO microtetrapods as precursors. The morphology of the produced material is investigated by scanning electron microscopy (SEM), while its crystalline and optical qualities are assessed by X-ray diffraction (XRD) analysis and photoluminescence (PL) spectroscopy, respectively. We demonstrate possibilities for controlling the composition and the crystallographic phase content of the prepared aerogels by the duration of the technological procedure. A scheme of deep energy levels and electronic transitions in the ZnS skeleton of the aeromaterial was deduced from the PL analysis, suggesting that the produced aerogel is a potential candidate for photocatalytic and sensor applications.

Protein-corona formation on aluminum doped zinc oxide and gallium nitride nanoparticles.

The interaction of semiconductor nanoparticles with bio-molecules attracts increasing interest of researchers, considering the reactivity of nanoparticles and the possibility to control their properties remotely giving mechanical, thermal, or electrical stimulus to the surrounding bio-environment. This work reports on a systematic comparative study of the protein-corona formation on aluminum doped zinc oxide and gallium nitride nanoparticles. Bovine serum albumin was chosen as a protein model. Dynamic light scattering, transmission electron microscopy and X-ray photoelectron spectroscopy techniques have been used to demonstrate the formation of protein-corona as well as the stability of the colloidal suspension given by BSA, which also works as a surfactant. The protein adsorption on the NPs surface studied by Bradford Assay showed the dependence on the quantity of proteins adsorbed to the available sites on the NPs surface, thus the saturation was observed at ratio higher than 5:1 (NPs:Proteins) in case of ZnO, these correlating with DLS results. Moreover, the kinetics of the proteins showed a relatively fast adsorption on the NPs surface with a saturation curve after about 25 min. GaN NPs, however, showed a very small amount of proteins adsorbed on the surface, a change in the hydrodynamic size being not observable with DLS technique or differential centrifugal sedimentation. The Circular Dichroism analysis suggests a drastic structural change in the secondary structure of the BSA after attaching on the NPs surface. The ZnO nanoparticles adsorb a protein-corona, which does not protect them against dissolution, and in consequence, the material proved to be highly toxic for Human keratinocyte cell line (HaCaT) at concentration above 25 µg/mL. In contrast, the GaN nanoparticles which do not adsorb a protein-corona, show no toxicity signs for HaCaT cells at concentration as high as 50 µg/mL, exhibiting much lower concentration of ions leakage in the culture medium as compared to ZnO nanoparticles.

Large-Sized Nanocrystalline Ultrathin ß-Ga2O3 Membranes Fabricated by Surface Charge Lithography.

Large-sized 2D semiconductor materials have gained significant attention for their fascinating properties in various applications. In this work, we demonstrate the fabrication of nanoperforated ultrathin ß-Ga2O3 membranes of a nanoscale thickness. The technological route includes the fabrication of GaN membranes using the Surface Charge Lithography (SCL) approach and subsequent thermal treatment in air at 900 °C in order to obtain ß-Ga2O3 membranes. The as-grown GaN membranes were discovered to be completely transformed into ß-Ga2O3, with the morphology evolving from a smooth topography to a nanoperforated surface consisting of nanograin structures. The oxidation mechanism of the membrane was investigated under different annealing conditions followed by XPS, AFM, Raman and TEM analyses.

Self-Propelled Aero-GaN Based Liquid Marbles Exhibiting Pulsed Rotation on the Water Surface.

We report on self-propelled rotating liquid marbles fabricated using droplets of alcoholic solution encapsulated in hollow microtetrapods of GaN with hydrophilic free ends of their arms and hydrophobic lateral walls. Apart from stationary rotation, elongated-spheroid-like liquid marbles were found, for the first time, to exhibit pulsed rotation on water surfaces characterized by a threshold speed of rotation, which increased with the weight of the liquid marble while the frequency of pulses proved to decrease. To throw light upon the unusual behavior of the developed self-propelled liquid marbles, we propose a model which takes into account skimming of the liquid marbles over the water surface similar to that inherent to flying water lily beetle and the so-called helicopter effect, causing a liquid marble to rise above the level of the water surface when rotating.

Highly Porous and Ultra-Lightweight Aero-Ga2O3: Enhancement of Photocatalytic Activity by Noble Metals.

A new type of photocatalyst is proposed on the basis of aero-ß-Ga2O3, which is a material constructed from a network of interconnected tetrapods with arms in the form of microtubes with nanometric walls. The aero-Ga2O3 material is obtained by annealing of aero-GaN fabricated by epitaxial growth on ZnO microtetrapods. The hybrid structures composed of aero-Ga2O3 functionalized with Au or Pt nanodots were tested for the photocatalytic degradation of methylene blue dye under UV or visible light illumination. The functionalization of aero-Ga2O3 with noble metals results in the enhancement of the photocatalytic performances of bare material, reaching the performances inherent to ZnO while gaining the advantage of the increased chemical stability. The mechanisms of enhancement of the photocatalytic properties by activating aero-Ga2O3 with noble metals are discussed to elucidate their potential for environmental applications.

Aero-Ga2O3 Nanomaterial Electromagnetically Transparent from Microwaves to Terahertz for Internet of Things Applications.

In this paper, fabrication of a new material is reported, the so-called Aero-Ga2O3 or Aerogallox, which represents an ultra-porous and ultra-lightweight three-dimensional architecture made from interconnected microtubes of gallium oxide with nanometer thin walls. The material is fabricated using epitaxial growth of an ultrathin layer of gallium nitride on zinc oxide microtetrapods followed by decomposition of sacrificial ZnO and oxidation of GaN which according to the results of X-ray diffraction (XRD) and X-ray photoemission spectroscopy (XPS) characterizations, is transformed gradually in ß-Ga2O3 with almost stoichiometric composition. The investigations show that the developed ultra-porous Aerogallox exhibits extremely low reflectivity and high transmissivity in an ultrabroadband electromagnetic spectrum ranging from X-band (8-12 GHz) to several terahertz which opens possibilities for quite new applications of gallium oxide, previously not anticipated.

Advanced Hybrid GaN/ZnO Nanoarchitectured Microtubes for Fluorescent Micromotors Driven by UV Light.

The development of functional microstructures with designed hierarchical and complex morphologies and large free active surfaces offers new potential for improvement of the pristine microstructures properties by the synergistic combination of microscopic as well as nanoscopic effects. In this contribution, dedicated methods of transmission electron microscopy (TEM) including tomography are used to characterize the complex hierarchically structured hybrid GaN/ZnO:Au microtubes containing a dense nanowire network on their interior. The presence of an epitaxially stabilized and chemically extremely stable ultrathin layer of ZnO on the inner wall of the produced GaN microtubes is evidenced. Gold nanoparticles initially trigger the catalytic growth of solid solution phase (Ga1- x Znx )(N1- x Ox ) nanowires into the interior space of the microtube, which are found to be terminated by AuGa-alloy nanodots coated in a shell of amorphous GaOx species after the hydride vapor phase epitaxy process. The structural characterization suggests that this hierarchical design of GaN/ZnO microtubes could offer the potential to exhibit improved photocatalytic properties, which are initially demonstrated under UV light irradiation. As a proof of concept, the produced microtubes are used as photocatalytic micromotors in the presence of hydrogen peroxide solution with luminescent properties, which are appealing for future environmental applications and active matter fundamental studies.

Light-Induced Motion of Microengines Based on Microarrays of TiO2 Nanotubes.

An electrochemical approach for manufacturing light-driven nanostructured titanium dioxide (TiO2 ) microengines with controlled spatial architecture for improved performance is reported. The microengines based on microscale arrays of TiO2 nanotubes with variable (50-120 nm) inner diameter show a quasi-ordered arrangement of nanotubes, being the smallest tubular entities for catalytic microengines reported to date. The nanotubes exhibit well defined crystalline phases depending upon the postfabrication annealing conditions that determine the microengines' efficiency. When exposed to UV-light, the microarrays of TiO2 nanotubes exhibiting conical internal shapes show directed motion in confined space, both in the presence and absence of hydrogen peroxide. In the former case, two different motion patterns related to diffusiophoresis and localized nanobubble generation inside of the tubes due to the photocatalytic decomposition of H2 O2 are disclosed. Controlled pick-up, transport, and release of individual and agglomerated particles are demonstrated using the UV light irradiation of microengines. The obtained results show that light-driven microengines based on microarrays of TiO2 nanotubes represent a promising platform for controlled micro/nanoscale sample transportation in fluids as well as for environmental applications, in particular, for the enhanced photocatalytic degradation of organic pollutants due to the improved intermixing taking place during the motion of TiO2 microengines.

Memristive GaN ultrathin suspended membrane array.

We show that ultrathin GaN membranes, with a thickness of 15 nm and planar dimensions of 12 × 184 µm(2), act as memristive devices. The memristive behavior is due to the migration of the negatively-charged deep traps, which form in the volume of the membrane during the fabrication process, towards the unoccupied surface states of the suspended membranes. The time constant of the migration process is of the order of tens of seconds and varies with the current or voltage sweep.