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Silicon is the most diffused material in the industry; thus, considering its high capacity for energy storage, silicon‐based materials are well studied as battery anodes and supercapacitors. Si nanowires (NWs) emerge due to the high surface to volume ratio, its compatibility with a wafer processing typical of microelectronics, and are studied as anodes for lithium batteries as well as coupled with other materials for supercapacitor application. In this article, the synthesis and application are reported as a lithium anode of 2D fractal arrays of ultrathin Si NWs obtained by a thin‐film metal‐assisted chemical etching (MACE). These Si NWs exhibit a density of about 1012 NWs cm−2, maximizing the surface to volume ratio compared to silver‐salts MACE and other NW fabrication approaches. By using 2.7 μm long NWs, a pseudo‐capacitor behavior with a specific capacitance of about 274.2 μF cm−2 at a scan rate of 50 mV s−1 is obtained. This specific capacitance is two orders of magnitude higher than the one obtained in the same condition by using NWs synthesized by silver‐salt MACE. In this result, the route is opened toward the application of these fractal arrays of ultrathin Si NWs as substrate for supercapacitors with improved efficiency.

Abstract The recent SARS‐CoV‐2 pandemic has highlighted the urgent need for novel point‐of‐care devices to be promptly used for a rapid and reliable large screening analysis of several biomarkers like genetic sequences and antibodies. Currently, one of the main limitations of rapid tests is the high percentage of false negatives in the presence of variants and, in particular for the Omicron one. We demonstrate in this work the detection of SARS‐CoV‐2 and the Omicron variant with a cost‐effective silicon nanosensor enabling high sensitivity, selectivity, and fast response. We have shown that a silicon (Si) nanowires (NW) platform detects both Sars‐CoV‐2 and its Omicron variant with a limit of detection (LoD) of four effective copies (cps), without any amplification of the genome, and with high selectivity. This ultrasensitive detection of 4 cps allows to obtain an extremely early diagnosis paving the way for efficient and widespread tracking. The sensor is made with industrially compatible techniques, which in perspective may allow easy and cost‐effective industrialization.

Lanthanide-doped yttrium oxide nanoparticles can display selective upconversion properties, rendering them invaluable in the field of nanomedicine for both sensing and diagnostics. Different syntheses of Er:Y2O3 and Nd:Y2O3 nanoparticles (NPs) were studied and optimized to obtain small particles of regular shape and good crystallinity. The morphological and compositional characterizations of the nanoparticles were obtained with different techniques and showed that both Er:Y2O3 and Nd:Y2O3 NPs were well dispersed, with dimensions of the order of a few tens of nanometers. The photoluminescence and cathodoluminescence measurements showed that both Er:Y2O3 and Nd:Y2O3 NPs had good emission as well as upconversion. The nanophosphors were functionalized by a pegylation procedure to suppress unwanted reactions of the NPs with other biological components, making the NP systems biocompatible and the NPs soluble in water and well dispersed. The pegylated core/shell nanoparticles showed the same morphological and optical characteristics as the core, promoting their strategic role as photoactive material for theragnostics and biosensing.

Air quality monitoring is an increasingly debated topic nowadays. The increasing spillage of waste products released into the environment has contributed to the increase in air pollution. Consequently, the production of increasingly performing devices in air monitoring is increasingly in demand. In this scenario, the attention dedicated to workplace safety monitoring has led to the developing and improving of new sensors. Despite technological advancements, sensors based on nanostructured materials are difficult to introduce into the manufacturing flow due to the high costs of the processes and the approaches that are incompatible with the microelectronics industry. The synthesis of a low-cost ultra-thin silicon nanowires (Si NWs)-based sensor is here reported, which allows us the detection of various dangerous gases such as acetone, ethanol, and the ammonia test as a proof of concept in a nitrogen-based mixture. A modified metal-assisted chemical etching (MACE) approach enables to obtain ultra-thin Si NWs by a cost-effective, rapid and industrially compatible process that exhibit an intense light emission at room temperature. All these gases are common substances that we find not only in research or industrial laboratories, but also in our daily life and can pose a serious danger to health, even at small concentrations of a few ppm. The exploitation of the Si NWs optical and electrical properties for the detection of low concentrations of these gases through their photoluminescence and resistance changes will be shown in a nitrogen-based gas mixture. These sensing platforms give fast and reversible responses with both optical and electrical transductions. These high performances and the scalable synthesis of Si NWs could pave the way for market-competitive sensors for ambient air quality monitoring.

Silicon nanowires (NWs) are appealing building blocks for low-cost novel concept devices with improved performances. In this research paper, we realized a hybrid platform combining an array of vertically oriented Si NWs with different types of bucky gels, obtained from carbon nanotubes (CNT) dispersed into an ionic liquid (IL) matrix. Three types of CNT bucky gels were obtained from imidazolium-based ionic liquids (BMIM-I, BIMI-BF4, and BMIM-Tf2N) and semiconductive CNTs, whose structural and optical responses to the hybrid platforms were analyzed and compared. We investigated the electrical response of the IL-CNT/NW hybrid junctions in dark and under illumination for each platform and its correlation to the ionic liquid characteristics and charge mobility. The reported results confirm the attractiveness of such IL-CNT/NW hybrid platforms as novel light-responsive materials for photovoltaic applications. In particular, our best performing cell reported a short-circuit current density of 5.6 mA/cm2 and an open-circuit voltage of 0.53 V.

Nanostructures are arising as novel biosensing platforms promising to surpass current performance in terms of sensitivity, selectivity, and affordability of standard approaches. However, for several nanosensors, the material and synthesis used make the industrial transfer of such technologies complex. Silicon nanowires (NWs) are compatible with Si-based flat architecture fabrication and arise as a hopeful solution to couple their interesting physical properties and surface-to-volume ratio to an easy commercial transfer. Among all the transduction methods, fluorescent probes and sensors emerge as some of the most used approaches thanks to their easy data interpretation, measure affordability, and real-time in situ analysis. In fluorescent sensors, Si NWs are employed as substrate and coupled with several fluorophores, NWs can be used as quenchers in stem-loop configuration, and have recently been used for direct fluorescent sensing. In this review, an overview on fluorescent sensors based on Si NWs is presented, analyzing the literature of the field and highlighting the advantages and drawbacks for each strategy.

The ever-stronger attention paid to enhancing safety in the workplace has led to novel sensor development and improvement. Despite the technological progress, nanostructured sensors are not being commercially transferred due to expensive and non-microelectronic compatible materials and processing approaches. In this paper, the realization of a cost-effective sensor based on ultrathin silicon nanowires (Si NWs) for the detection of nitrogen dioxide (NO2) is reported. A modification of the metal-assisted chemical etching method allows light-emitting silicon nanowires to be obtained through a fast, low-cost, and industrially compatible approach. NO2 is a well-known dangerous gas that, even with a small concentration of 3 ppm, represents a serious hazard for human health. We exploit the particular optical and electrical properties of these Si NWs to reveal low NO2 concentrations through their photoluminescence (PL) and resistance variations reaching 2 ppm of NO2. Indeed, these Si NWs offer a fast response and reversibility with both electrical and optical transductions. Despite the macro contacts affecting the electrical transduction, the sensing performances are of high interest for further developments. These promising performances coupled with the scalable Si NW synthesis could unfold opportunities for smaller sized and better performing sensors reaching the market for environmental monitoring.

Silicon nanowires (Si NWs) emerged in several application fields as a strategic element to surpass the bulk limits with a flat compatible architecture. The approaches used for the Si NW realization have a crucial impact on their final performances and their final cost. This makes the research on a novel and flexible approach for Si NW fabrication a crucial point for Si NW-based devices. In this work, the novelty is the study of the flexibility of thin film metal-assisted chemical etching (MACE) for the fabrication of Si NWs with the possibility of realizing different doped Si NWs, and even a longitudinal heterojunction p-n inside the same single wire. This point has never been reported by using thin metal film MACE. In particular, we will show how this approach permits one to obtain a high density of vertically aligned Si NWs with the same doping of the substrate and without any particular constraint on doping type and level. Fractal arrays of Si NWs can be fabricated without any type of mask thanks to the self-assembly of gold at percolative conditions. This Si NW fractal array can be used as a substrate to realize controllable artificial fractals, integrating other interesting elements with a cost-effective microelectronics compatible approach.

Silicon is the undisputed leader for microelectronics among all the industrial materials and Si nanostructures flourish as natural candidates for tomorrow’s technologies due to the rising of novel physical properties at the nanoscale. In particular, silicon nanowires (Si NWs) are emerging as a promising resource in different fields such as electronics, photovoltaic, photonics, and sensing. Despite the plethora of techniques available for the synthesis of Si NWs, metal-assisted chemical etching (MACE) is today a cutting-edge technology for cost-effective Si nanomaterial fabrication already adopted in several research labs. During these years, MACE demonstrates interesting results for Si NW fabrication outstanding other methods. A critical study of all the main MACE routes for Si NWs is here presented, providing the comparison among all the advantages and drawbacks for different MACE approaches. All these fabrication techniques are investigated in terms of equipment, cost, complexity of the process, repeatability, also analyzing the possibility of a commercial transfer of these technologies for microelectronics, and which one may be preferred as industrial approach.

Silicon nanowires (Si NWs) are emerging as an innovative building block in several fields, such as microelectronics, energetics, photonics, and sensing. The interest in Si NWs is related to the high surface to volume ratio and the simpler coupling with the industrial flat architecture. In particular, Si NWs emerge as a very promising material to couple the light to silicon. However, with the standard synthesis methods, the realization of quantum-confined Si NWs is very complex and often requires expensive equipment. Metal-Assisted Chemical Etching (MACE) is gaining more and more attention as a novel approach able to guarantee high-quality Si NWs and high density with a cost-effective approach. Our group has recently modified the traditional MACE approach through the use of thin metal films, obtaining a strong control on the optical and structural properties of the Si NWs as a function of the etching process. This method is Complementary Metal-Oxide-Semiconductors (CMOS)-technology compatible, low-cost, and permits us to obtain a high density, and room temperature light-emitting Si NWs due to the quantum confinement effect. A strong control on the Si NWs characteristics may pave the way to a real industrial transfer of this fabrication methodology for both microelectronics and optoelectronics applications.

In this paper, we report on the realization of a highly sensitive and low cost 3D surface-enhanced Raman scattering (SERS) platform. The structural features of the Ag dendrite network that characterize the SERS material were exploited, attesting a remarked self-similarity and scale invariance over a broad range of length scales that are typical of fractal systems. Additional structural and optical investigations confirmed the purity of the metal network, which was characterized by low oxygen contamination and by broad optical resonances introduced by the fractal behavior. The SERS performances of the 3D fractal Ag dendrites were tested for the detection of lysozyme as probe molecule, attesting an enhancement factor of ~2.4 × 106. Experimental results assessed the dendrite material as a suitable SERS detection platform for biomolecules investigations in hydration conditions.

In this paper, we present the realization by a low cost approach compatible with silicon technology of new nanostructures, characterized by the presence of different materials, such as copper iodide (CuI) and silicon nanowires (Si NWs). Silicon is the principal material of the microelectronics field for its low cost, easy manufacturing and market stability. In particular, Si NWs emerged in the literature as the key materials for modern nanodevices. Copper iodide is a direct wide bandgap p-type semiconductor used for several applications as a transparent hole conducting layers for dye-sensitized solar cells, light emitting diodes and for environmental purification. We demonstrated the preparation of a solid system in which Si NWs are embedded in CuI material and the structural, electrical and optical characterization is presented. These new combined Si NWs/CuI systems have strong potentiality to obtain new nanostructures characterized by different doping, that is strategic for the possibility to realize p-n junction device. Moreover, the combination of these different materials opens the route to obtain multifunction devices characterized by promising absorption, light emission, and electrical conduction.

The search for improved transducers to fabricate better-performing (bio)sensors is a challenging but rewarding endeavor aiming to better diagnose and treat diseases. In this paper, we report on the decoration of a dense vertical array of ultrathin silicon nanowires (Si NWs), produced by metal-assisted chemical etching, with 20 nm gold nanoparticles (Au NPs) for surface-enhanced Raman scattering (SERS) applications. To optimize the production of a uniform 3D SERS active platform, we tested different Si NW surface functionalizations with various alkoxysilanes before Au decoration. Scanning electron microscopy investigations confirm that Au NPs decorate both bare and (3-glycidiloxypropyl)trimethoxysilane (GPTMS)-modified Si NWs with a high surface coverage uniformity. The SERS response of the decorated NWs was probed using a model dye system (methylene blue; MB) at 633 and 785 nm excitation wavelengths. The GPTMS-modified NWs present the highest enhancements of 2.9 and 2.6 for the 450 cm−1 and 1625 cm−1 peaks under 785 nm excitation and of 10.8 and 5.3 for the 450 cm−1 and 1625 cm−1 peaks under 633 nm excitation. These results demonstrate the perspective role of Si NWs decorated with Au NPs as a low-cost 3D SERS platform.

Résumé Les Vésicules Extracellulaires (VE) sont des constituants d’origine membranaire contenant des protéines solubles ou membranaires, des lipides, des métabolites ou des acides nucléiques. Ces vésicules sont très hétérogènes en taille et en contenu. Trois catégories de VE ont été décrites dans le tractus génital mâle: les microvésicules, les myélinosomes et les exosomes. Les types de VE sont différents selon le lieu de production testiculaire, prostatique ou encore épididymaire. Il a été montré que les VE peuvent fusionner et délivrer une information à la cellule réceptrice, en l’occurrence le spermatozoïde dans le tractus génital mâle. La cryo-microscopie électronique reste la technique de référence pour déterminer la morphologie des VE mais la quantification de la concentration absolue de ces VE dans les liquides biologiques reste un challenge dans le cadre d’une approche clinique. Le domaine de la biodétection s’est. considérablement développé avec l’introduction des nanomatériaux dans les biocapteurs et va permettre de mieux comprendre l’impact de ces VE. Or les modifications fonctionnelles des gamètes mâles résultent d’interactions avec les composants du liquide intraluminal tout le long du tractus génital et dépendent de la sécrétion et de l’absorption de protéines et de lipides du microenvironnement local. On ne peut donc pas exclure la possibilité d’une modulation épigénétique des informations qui seront transmises à l’embryon donc à la génération suivante via les VE.

In this paper, we exploit the perspective of luminescent Si nanowires (NWs) in the growing field of commercial biosensing nanodevices for the selective recognition of proteins and pathogen genomes. We fabricated quantum confined fractal arrays of Si NWs with room temperature emission at 700 nm obtained by thin-film, metal-assisted, chemical etching with high production output at low cost. The fascinating optical features arising from multiple scattering and weak localization of light promote the use of Si NWs as optical biosensing platforms with high sensitivity and selectivity. In this work, label-free Si NW optical sensors are surface modified for the selective detection of C-reactive protein through antigen–gene interaction. In this case, we report the lowest limit of detection (LOD) of 1.6 fM, fostering the flexibility of different dynamic ranges for detection either in saliva or for serum analyses. By varying the NW surface functionalization with the specific antigen, the luminescence quenching of NW biosensors is used to measure the hepatitis B-virus pathogen genome without PCR-amplification, with an LOD of about 20 copies in real samples or blood matrix. The promising results show that NW optical biosensors can detect and isolate extracellular vesicles (EV) marked with CD81 protein with unprecedented sensitivity (LOD 2 × 105 sEV/mL), thus enabling their measurement even in a small amount of blastocoel fluid.

Gold nanoclusters (Au NCs) are attractive luminescent nanoprobes for biomedical applications. In vivo biosensing and bioimaging requires the delivery of the Au NCs into subcellular compartments. In this view, we explore here the possible encapsulation of ultra-small-sized red and blue emitting Au NCs into liposomes of various sizes and chemical compositions. Different methods were investigated to prepare vesicles containing Au NCs in their lumen. The efficiency of the process was correlated to the structural and morphological aspect of the Au NCs’ encapsulating vesicles thanks to complementary analyses by SAXS, cryo-TEM, and confocal microscopy techniques. Cell-like-sized vesicles (GUVs) encapsulating red or blue Au NCs were successfully obtained by an innovative method using emulsion phase transfer. Furthermore, exosome-like-sized vesicles (LUVs) containing Au NCs were obtained with an encapsulation yield of 40%, as estimated from ICP-MS.

The oocyte microenvironment constituted by the follicular fluid (FF) is a key for the optimal development of female gametes. Its composition reflects the physiological state of the ovarian follicle. The particularity of FF is to contain a huge diversity of extracellular vesicles specific to women, in the same way as seminal plasma in men. Here, we described and compared morphological aspects of broad subcategories of human FF-related Extracellular Vesicles (EVs). EVs participate in physiological and pathological processes and have potential applications in diagnostics or therapeutics. EVs isolated from FF are involved in different biological functions related to follicular growth, oocyte maturation, and embryo development. However, knowledge on the morphology of FF-derived EVs is limited, mainly due to their sub-micrometer size and to intrinsic limitations in methods applied for their characterization. The aim of this study was to provide a comprehensive morphological description of EVs from FF of healthy subjects and quantification. EVs separation was realized by centrifugation, with comparison of the EV yield obtained from differential centrifugation and one-step ultracentrifugation. Cryo-Transmission Electron Microscopy was used to reveal the morphology, size, and phenotype of EVs. Dynamic Light Scattering (DLS) and Nanoparticle Tracking Analysis (NTA) were used to quantify and analyze the size distribution for each centrifugation step. We performed a comprehensive inventory of human follicular fluid EVs. We show that human FF contains a huge diversity of EVs. This study brings novel insights on EVs from normal FF and provides a reference for further studies of EVs in ovarian diseases.

Molybdenum disulfide (MoS2) has attracted great attention for its unique chemical and physical properties. The applications of this transition metal dichalcogenide (TMDC) range from supercapacitors to dye-sensitized solar cells, Li-ion batteries and catalysis. This work opens new routes toward the use of electrodeposition as an easy, scalable and cost-effective technique to perform the coupling of Si with molybdenum disulfide. MoS2 deposits were obtained on n-Si (100) electrodes by electrochemical deposition protocols working at room temperature and pressure, as opposed to the traditional vacuum-based techniques. The samples were characterized by X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM) and Rutherford Back Scattering (RBS).

The continuing accumulation of mutations in the RNA genome of the SARS-CoV-2 virus generates an endless succession of highly contagious variants that cause concern around the world due to their antibody resistance and the failure of current diagnostic techniques to detect them in a timely manner. Raman spectroscopy represents a promising alternative to variants detection and recognition techniques, thanks to its ability to provide a characteristic spectral fingerprint of the biological samples examined under all circumstances. In this work we exploit the surface-enhanced Raman scattering (SERS) properties of a silver dendrite layer to explore, for the first time to our knowledge, the distinctive features of the Omicron variant genome. We obtain a complex spectral signal of the Omicron variant genome where the fingerprints of nucleobases in nucleosides are clearly unveiled and assigned in detail. Furthermore, the fractal SERS layer offers the presence of confined spatial regions in which the analyte remains trapped under hydration conditions. This opens up the prospects for a prompt spectral identification of the genome in its physiological habitat and for a study on its activity and variability.

Alzheimer’s disease (AD) is a neurodegenerative disorder that progressively compromises cognitive functions. Tumor necrosis factor (TNF)-Related Apoptosis Inducing Ligand (TRAIL), a proinflammatory cytokine belonging to the TNF superfamily, appears to be a key player in the inflammatory/immune orchestra of the AD brain. Despite the ability of an anti-TRAIL monoclonal antibody to reach the brain producing beneficial effects in AD mice, we attempted to develop such a TRAIL-neutralizing monoclonal antibody adsorbed on lipid and polymeric nanocarriers, for intranasal administration, in a valid approach to overcome issues related to both high dose and drug transport across the blood–brain barrier. The two types of nanomedicines produced showed physico-chemical characteristics appropriate for intranasal administration. As confirmed by enzyme-linked immunosorbent assay (ELISA), both nanomedicines were able to form a complex with the antibody with an encapsulation efficiency of ≈99%. After testing in vitro the immunoneutralizing properties of the nanomedicines, the latter were intranasally administered in AD mice. The antibody–nanocarrier complexes were detectable in the brain in substantial amounts at concentrations significantly higher compared to the free form of the anti-TRAIL antibody. These data support the use of nanomedicine as an optimal method for the delivery of the TRAIL neutralizing antibody to the brain through the nose-to-brain route, aiming to improve the biological attributes of anti-TRAIL-based therapy for AD treatment.

In this work, the optimal conditions for the electrodeposition of a CdSe film on n-Si were demonstrated. The structural and optical properties of the bare films and after annealing were studied. In particular, the crystallinity and photoluminescence of the samples were evaluated, and after annealing at 400 °C under a nitrogen atmosphere, a PL increase by almost an order of magnitude was observed. This paper opens the route towards the use of electrochemical deposition as a cost-effective and easy fabrication approach that can be used to integrate other interesting materials in the silicon-manufacturing processes for the realization of optoelectronic devices.

CdSe electrodeposition on n-Si (100) substrate was investigated in sulfuric acid solution. The behaviour and the deposition of the precursors (Cd and Se) were studied separately at first. Then, we explored both the alternated deposition, one layer by one, as well as the simultaneous co-deposition of the two elements to form the CdSe semiconductor. Varying the deposition conditions, we were able to obtain nanoparticles, or a thin film, on the surface of the electrode. The samples were then characterised microscopically and spectroscopically with SEM, XRD and XPS. Finally, we evaluated the induced photoemission of the deposit for the application in optoelectronics.

Abstract We report on the unconventional optical properties exhibited by a two-dimensional array of thin Si nanowires arranged in a random fractal geometry and fabricated using an inexpensive, fast and maskless process compatible with Si technology. The structure allows for a high light-trapping efficiency across the entire visible range, attaining total reflectance values as low as 0.1% when the wavelength in the medium matches the length scale of maximum heterogeneity in the system. We show that the random fractal structure of our nanowire array is responsible for a strong in-plane multiple scattering, which is related to the material refractive index fluctuations and leads to a greatly enhanced Raman scattering and a bright photoluminescence. These strong emissions are correlated on all length scales according to the refractive index fluctuations. The relevance and the perspectives of the reported results are discussed as promising for Si-based photovoltaic and photonic applications.

Silicon nanowires (SiNWs) decorated by pulsed laser ablation with gold or copper nanoparticles (labeled as AuNPs@SiNWs and CuNPs@SiNWs) were investigated for their catalytic properties. Results demonstrated high catalytic performances in the Caryl–N couplings and subsequent carbonylations for gold and copper catalysts, respectively, that have no precedents in the literature. The excellent activity, attested by the very high turn over number (TON) values, was due both to the uniform coverage along the NW length and to the absence of the chemical shell surrounding the metal nanoparticles (MeNPs). A high recyclability was also observed and can be ascribed to the strong covalent interaction at the Me–Si interface by virtue of metal “silicides” formation.