Vertically Aligned Nanowires and Quantum Dots: Promises and Results in Light Energy Harvesting.

The synthesis of crystals with a high surface-to-volume ratio is essential for innovative, high-performance electronic devices and sensors. The easiest way to achieve this in integrated devices with electronic circuits is through the synthesis of high-aspect-ratio nanowires aligned vertically to the substrate surface. Such surface structuring is widely employed for the fabrication of photoanodes for solar cells, either combined with semiconducting quantum dots or metal halide perovskites. In this review, we focus on wet chemistry recipes for the growth of vertically aligned nanowires and technologies for their surface functionalization with quantum dots, highlighting the procedures that yield the best results in photoconversion efficiencies on rigid and flexible substrates. We also discuss the effectiveness of their implementation. Among the three main materials used for the fabrication of nanowire-quantum dot solar cells, ZnO is the most promising, particularly due to its piezo-phototronic effects. Techniques for functionalizing the surfaces of nanowires with quantum dots still need to be refined to be effective in covering the surface and practical to implement. The best results have been obtained from slow multi-step local drop casting. It is promising that good efficiencies have been achieved with both environmentally toxic lead-containing quantum dots and environmentally friendly zinc selenide.

Self-Cleaning Bending Sensors Based on Semitransparent ZnO Nanostructured Films.

The design of multifunctional nanostructured materials is the key to the development of smart wearable devices. For instance, nanostructures endowed with both piezoelectric and photocatalytic activities could well be the workhorse for solar-light-driven self-cleaning wearable sensors. In this work, a simple strategy for the assembly of a flexible, semitransparent piezophotocatalytic system is demonstrated by leveraging rational wet chemistry synthesis of ZnO-based nanosheets/nanoflowers (NSs/NFs) under basic pH conditions onto flexible ITO/PET supports. A KMnO4 pretreatment before the ZnO synthesis (seeded ZnO) allows for the control of the density, size, and orientation of the NSs/NFs systems compared to the systems produced in the absence of seeding (seedless ZnO). The electrical response of the sensors is extracted at a 1 V bias as a function of bending in the interval between 0 and 90°, being the responsivity toward bending significantly enhanced by the KMnO4 treatment effect. The photocatalytic activity of the sensors is analyzed in aqueous solution (methylene blue, 25 µM) by a solar simulator, resulting in similar values between seedless and seeded ZnO. Upon bending the sensor, the photocatalytic activity of seedless ZnO is almost unaffected, whereas that of seeded ZnO is improved by about 25%. The sensor's reusability and repeatability are tested in up to three different cycles. These results open up the way toward the seamless integration of bending sensitivity and photocatalysis into a single device.

A Direct Catalytic Ethanol Fuel Cell (DCEFC) Modified by LDHs, or by Catalase-LDHs, and Improvement in Its Kinetic Performance: Applications for Human Saliva and Disinfectant Products for COVID-19.

In this work, it has been experimentally proven that the kinetic performance of a common Direct Catalytic Ethanol Fuel Cell (DCEFC) can be increased by introducing nanostructured (ZnII,AlIII(OH)2)+NO3-·H2O Layered Double Hydroxides (LDHs) into the anode compartment. Carrying out the measurements with the open-circuit voltage method and using a kinetic format, it has been shown that the introduction of LDHs in the anodic compartment implies a 1.3-fold increase in the calibration sensitivity of the method. This improvement becomes even greater in the presence of hydrogen peroxide in a solution. Furthermore, we show that the calibration sensitivity increased by 8-times, when the fuel cell is modified by the enzyme catalase, crosslinked on LDHs and in the presence of hydrogen peroxide. The fuel cell, thus modified (with or without enzyme), has been used for analytical applications on real samples, such as biological (human saliva) and hand disinfectant samples, commonly used for the prevention of COVID-19, obtaining very positive results from both analytical and kinetic points of view on ethanol detection. Moreover, if the increase in the calibration sensitivity is of great importance from the point of view of analytical applications, it must be remarked that the increase in the speed of the ethanol oxidation process in the fuel cell can also be extremely useful for the purposes of improving the energy performance of a DCEFC.

Novel Electrochemical Sensors Based on L-Proline Assisted LDH for H2O2 Determination in Healthy and Diabetic Urine.

In this paper, a novel non-enzymatic modified glassy carbon (GC) sensor, of the (GC-Agpaste)-catalytic proline-assisted LDH type, for H2O2 determination was fabricated, studied, characterized and employed to determine the hydrogen peroxide content in healthy and diabetic human urine. LDH (whose composition can be schematized as [ZnIIAlIII (OH)2]+ NO3-·nH2O) is glued to glassy carbon by means of silver paste, while proline, which increases the catalytic properties of LDH, is used free in solution in the phosphate buffer. A voltametric survey was first conducted to ascertain the positive effect induced by the presence of proline, i.e., the increase of sensor sensitivity. Then a deep study of the new three-electrode amperometric proline-assisted LDH sensor, whose working electrode was of the same type as the one used to perform the cyclic voltammetry, was carried out, working at first in static air, then in a nitrogen atmosphere. Possible interferences from various substances, both oxidants and antioxidants, were also investigated. Lastly, the new amperometric sensor was successfully used to determine the H2O2 level in human urine from both healthy and diabetic subjects. The effect of proline in enhancing the properties of the sensor system was also investigated. The limit of detection (LOD) of the new catalytic sensor was of the order of 0.15 mmol L-1, working in air, and of 0.05 µmol L-1, working in nitrogen atmosphere.

Chromium inhibition and size-selected Au nanocluster catalysis for the solution growth of low-density ZnO nanowires.

The wet chemical synthesis of nanostructures has many crucial advantages over high-temperature methods, including simplicity, low-cost, and deposition on almost arbitrary substrates. Nevertheless, the density-controlled solution growth of nanowires still remains a challenge, especially at the low densities (e.g. 1 to 10 nanowires/100 µm(2)) required, as an example, for intracellular analyses. Here, we demonstrate the solution-growth of ZnO nanowires using a thin chromium film as a nucleation inhibitor and Au size-selected nanoclusters (SSNCs) as catalytic particles for which the density and, in contrast with previous reports, size can be accurately controlled. Our results also provide evidence that the enhanced ZnO hetero-nucleation is dominated by Au SSNCs catalysis rather than by layer adaptation. The proposed approach only uses low temperatures (≤70 °C) and is therefore suitable for any substrate, including printed circuit boards (PCBs) and the plastic substrates which are routinely used for cell cultures. As a proof-of-concept we report the density-controlled synthesis of ZnO nanowires on flexible PCBs, thus opening the way to assembling compact intracellular-analysis systems, including nanowires, electronics, and microfluidics, on a single substrate.

InAs/GaAs Sharply Defined Axial Heterostructures in Self-Assisted Nanowires.

We present the fabrication of axial InAs/GaAs nanowire heterostructures on silicon with atomically sharp interfaces by molecular beam epitaxy. Our method exploits the crystallization at low temperature, by As supply, of In droplets deposited on the top of GaAs NWs grown by the self-assisted (self-catalyzed) mode. Extensive characterization based on transmission electron microscopy sets an upper limit for the InAs/GaAs interface thickness within few bilayers (≤1.5 nm). A detailed study of elastic/plastic strain relaxation at the interface is also presented, highlighting the role of nanowire lateral free surfaces.

Towards high-performance, low-cost quartz sensors with high-density, well-separated, vertically aligned ZnO nanowires by low-temperature, seed-less, single-step, double-sided growth.

Resonant sensors with nanostructured surfaces have long been considered as an emergent platform for high-sensitivity transduction because of the potentially very large sensing areas. Nevertheless, until now only complex, time-consuming, expensive and sub-optimal fabrication procedures have been described; in fact, especially with reference to in-liquid applications, very few devices have been reported. Here, we first demonstrate that, by immersing standard, ultra-low-cost quartz resonators with un-polished silver electrodes in a conventional zinc nitrate/HMTA equimolar nutrient solution, the gentle contamination from the metallic package allows direct growth on the electrodes of arrays of high-density (up to 10 µm⁻²) and well-separated (no fusion at the roots) ZnO nanowires without any seed layer or thermal annealing. The combination of high-density and good separation is ideal for increasing the sensing area; moreover, this uniquely simple, single-step process is suitable for conventional, ultra-low-cost and high-frequency quartzes, and results in devices that are already packaged and ready to use. As an additional advantage, the process parameters can be effectively optimized by measuring the quartz admittance before and after growth. As a preliminary test, we show that the sensitivity to the liquid properties of high-frequency (i.e. high sensitivity) quartzes can be further increased by nearly one order of magnitude and thus show the highest ever reported frequency shifts of an admittance resonance in response to immersion in both ethanol and water.