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.

Synthesis and Nanostructure Investigation of Hybrid ß-Ga2 O3 /ZnGa2 O4 Nanocomposite Networks with Narrow-Band Green Luminescence and High Initial Electrochemical Capacity.

The material design of functional "aero"-networks offers a facile approach to optical, catalytical, or and electrochemical applications based on multiscale morphologies, high large reactive area, and prominent material diversity. Here in this paper, the synthesis and structural characterization of a hybrid ß-Ga2 O3 /ZnGa2 O4 nanocomposite aero-network are presented. The nanocomposite networks are studied on multiscale with respect to their micro- and nanostructure by X-ray diffraction (XRD) and transmission electron microscopy (TEM) and are characterized for their photoluminescent response to UV light excitation and their electrochemical performance with Li-ion conversion reaction. The structural investigations reveal the simultaneous transformation of the precursor aero-GaN(ZnO) network into hollow architectures composed of ß-Ga2 O3 and ZnGa2 O4 nanocrystals with a phase ratio of ≈1:2. The photoluminescence of hybrid aero-ß-Ga2 O3 /ZnGa2 O4 nanocomposite networks demonstrates narrow band (λem  = 504 nm) green light emission of ZnGa2 O4 under UV light excitation (λex  = 300 nm). The evaluation of the metal-oxide network performance for electrochemical application for Li-ion batteries shows high initial capacities of ≈714 mAh g-1 at 100 mA g-1 paired with exceptional rate performance even at high current densities of 4 A g-1 with 347 mAh g-1 . This study provides is an exciting showcase example of novel networked materials and demonstrates the opportunities of tailored micro-/nanostructures for diverse applications a diversity of possible applications.

Ultralow voltage (1µV) electrical switching of SnS thin films driven by a vertical electric field.

In this paper, we show in a series of experiments on 10 nm thick SnS thin film-based back-gate transistors that in the absence of the gate voltage, the drain current versus drain voltage (ID-VD) dependence is characterized by a weak drain current and by an ambipolar transport mechanism. When we apply a gate voltage as low as 1µV, the current increases by several orders of magnitude and theID-VDdependence changes drastically, with the SnS behaving as ap-type semiconductor. This happens because the current flows from the source (S) to the drain (D) electrode through a discontinuous superficial region of the SnS film when no gate voltage is applied. On the contrary, when minute gate voltages are applied, the vertical electric field applied to the multilayer SnS induces a change in the flow path of the charge carriers, involving the inner and continuous SnS layer in the electrical conduction. Moreover, we show that high gate voltages can tune significantly the SnS bandgap.

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.

Ultrathin tin sulfide field-effect transistors with subthreshold slope below 60 mV/decade.

In this paper, we present for the first time a field-effect-transistor (FET) having a 10 nm thick tin sulfide (SnS) channel fabricated at the wafer scale with high reproducibility. SnS-based FETs are in on-state for increasing positive back-gate voltages up to 6 V, whereas the off-state is attained for negative back-gate voltages not exceeding -6 V, the on/off ratio being in the range 102-103depending on FET dimensions. The SnS FETs show a subthreshold slope (SS) below 60 mV/decade thanks to the in-plane ferroelectricity of SnS and attaining a minimum value SS = 21 mV/decade. Moreover, the low SS values can be explained by the existence of a negative value of the capacitance of the SnS thin film up to 10 GHz (for any DC bias voltage between 1 and 5 V), with the minimum value being -12.87 pF at 0.1 GHz.

The microwave properties of tin sulfide thin films prepared by RF magnetron sputtering techniques.

In this paper we present the microwave properties of tin sulfide (SnS) thin films with the thickness of just 10 nm, grown by RF magnetron sputtering techniques on a 4 inch silicon dioxide/high-resistivity silicon wafer. In this respect, interdigitated capacitors in coplanar waveguide technology were fabricated directly on the SnS film to be used as both phase shifters and detectors, depending on the ferroelectric or semiconductor behaviour of the SnS material. The ferroelectricity of the semiconducting thin layer manifests itself in a strong dependence of the electrical permittivity on the applied DC bias voltage, which induces a phase shift of 30 degrees mm-1at 1 GHz and of 8 degrees mm-1at 10 GHz, whereas the transmission losses are less than 2 dB in the frequency range 2-20 GHz. We have also investigated the microwave detection properties of SnS, obtaining at 1 GHz a voltage responsivity of about 30 mV mW-1in the unbiased case and with an input power level of only 16µW.

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.

Ultrafast Third-Order Nonlinear Optical Response Excited by fs Laser Pulses at 1550 nm in GaN Crystals.

The ultrafast third-order optical nonlinearity of c-plane GaN crystal, excited by ultrashort (fs) high-repetition-rate laser pulses at 1550 nm, wavelength important for optical communications, is investigated for the first time by optical third-harmonic generation in non-phase-matching conditions. As the thermo-optic effect that can arise in the sample by cumulative thermal effects induced by high-repetition-rate laser pulses cannot be responsible for the third-harmonic generation, the ultrafast nonlinear optical effect of solely electronic origin is the only one involved in this process. The third-order nonlinear optical susceptibility of GaN crystal responsible for the third-harmonic generation process, an important indicative parameter for the potential use of this material in ultrafast photonic functionalities, is determined.

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.

Mesenchymal stem cells proliferation and remote manipulation upon exposure to magnetic semiconductor nanoparticles.

In this paper, we report on spatial redistribution of bone marrow mesenchymal stem cells loaded with magnetic nanoparticles under the influence of continuously applied magnetic field. Semiconductor nanoparticles were synthesized by epitaxial growth of a GaN thin layer on magnetic sacrificial core consisting of ZnFe2O4 nanoparticles. Different quantities of nanoparticles were incubated in vitro with mesenchymal stem cells. High density of nanoparticles (50 µg/ml) leads to a decrease in the number of cells during incubation, while the density of nanoparticles as low as 10 µg/ml is enough to drag cells in culture and rearrange them according to the spatial distribution of the magnetic field intensity.

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.

Electromagnetic interference shielding in X-band with aero-GaN.

We investigate the electromagnetic shielding properties of an ultra-porous lightweight nanomaterial named aerogalnite (aero-GaN). Aero-GaN is made up of randomly arranged hollow GaN microtetrapods, which are obtained by direct growth using hydride vapor phase epitaxy of GaN on the sacrificial network of ZnO microtetrapods. A 2 mm thick aero-GaN sample exhibits electromagnetic shielding properties in the X-band similar to solid structures based on metal foams or carbon nanomaterials. Aero-GaN has a weight four to five orders of magnitude lower than the weight of metals.

Targeting Endothelial Cells with Multifunctional GaN/Fe Nanoparticles.

In this paper, we report on the interaction of multifunctional nanoparticles with living endothelial cells. The nanoparticles were synthesized using direct growth of gallium nitride on zinc oxide nanoparticles alloyed with iron oxide followed by core decomposition in hydrogen flow at high temperature. Using transmission electron microscopy, we demonstrate that porcine aortic endothelial cells take up GaN-based nanoparticles suspended in the growth medium. The nanoparticles are deposited in vesicles and the endothelial cells show no sign of cellular damage. Intracellular inert nanoparticles are used as guiding elements for controlled transportation or designed spatial distribution of cells in external magnetic fields.

Sensitivity of human pluripotent stem cells to insulin precipitation induced by peristaltic pump-based medium circulation: considerations on process development.

Controlled large-scale production of human pluripotent stem cells (hPSCs) is indispensable for their envisioned clinical translation. Aiming at advanced process development in suspension culture, the sensitivity of hPSC media to continuous peristaltic pump-based circulation, a well-established technology extensively used in hydraulically-driven bioreactors, was investigated. Unexpectedly, conditioning of low protein media (i.e. E8 and TeSR-E8) in a peristaltic pump circuit induced severe viability loss of hPSCs cultured as aggregates in suspension. Optical, biochemical, and cytological analyses of the media revealed that the applied circulation mode resulted in the reduction of the growth hormone insulin by precipitation of micro-sized particles. Notably, in contrast to insulin depletion, individual withdrawal of other medium protein components (i.e. bFGF, TGFß1 or transferrin) provoked minor reduction of hPSC viability, if any. Supplementation of the surfactant glycerol or the use of the insulin analogue Aspart did not overcome the issue of insulin precipitation. In contrast, the presence of bovine or human serum albumin (BSA or HSA, respectively) stabilized insulin rescuing its content, possibly by acting as molecular chaperone-like protein, ultimately supporting hPSC maintenance. This study highlights the potential and the requirement of media optimization for automated hPSC processing and has broad implications on media development and bioreactor-based technologies.

Viability and proliferation of endothelial cells upon exposure to GaN nanoparticles.

Nanotechnology is a rapidly growing and promising field of interest in medicine; however, nanoparticle-cell interactions are not yet fully understood. The goal of this work was to examine the interaction between endothelial cells and gallium nitride (GaN) semiconductor nanoparticles. Cellular viability, adhesion, proliferation, and uptake of nanoparticles by endothelial cells were investigated. The effect of free GaN nanoparticles versus the effect of growing endothelial cells on GaN functionalized surfaces was examined. To functionalize surfaces with GaN, GaN nanoparticles were synthesized on a sacrificial layer of zinc oxide (ZnO) nanoparticles using hydride vapor phase epitaxy. The uptake of GaN nanoparticles by porcine endothelial cells was strongly dependent upon whether they were fixed to the substrate surface or free floating in the medium. The endothelial cells grown on surfaces functionalized with GaN nanoparticles demonstrated excellent adhesion and proliferation, suggesting good biocompatibility of the nanostructured GaN.

Ultra-lightweight pressure sensor based on graphene aerogel decorated with piezoelectric nanocrystalline films.

In this paper, we report on a pressure sensor based on graphene aerogel functionalized with SnO2 or GaN thin films deposited by magnetron sputtering. Decoration by nanocrystalline SnO2 or GaN was found to enhance the piezoresistive response of the bare aerogel. The responsivity and pressure sensing range (from 1-5 atm) of the sensor are shown to be higher than those inherent in pressure sensors based on graphene membranes.

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.

Three-dimensional Aerographite-GaN hybrid networks: single step fabrication of porous and mechanically flexible materials for multifunctional applications.

Three dimensional (3D) elastic hybrid networks built from interconnected nano- and microstructure building units, in the form of semiconducting-carbonaceous materials, are potential candidates for advanced technological applications. However, fabrication of these 3D hybrid networks by simple and versatile methods is a challenging task due to the involvement of complex and multiple synthesis processes. In this paper, we demonstrate the growth of Aerographite-GaN 3D hybrid networks using ultralight and extremely porous carbon based Aerographite material as templates by a single step hydride vapor phase epitaxy process. The GaN nano- and microstructures grow on the surface of Aerographite tubes and follow the network architecture of the Aerographite template without agglomeration. The synthesized 3D networks are integrated with the properties from both, i.e., nanoscale GaN structures and Aerographite in the form of flexible and semiconducting composites which could be exploited as next generation materials for electronic, photonic, and sensors applications.