ICN2 Latest publications

  • Addressing the theoretical and experimental aspects of low-dimensional-materials-based fet immunosensors: A review

    Martins E.F., Pinotti L.F., Silva C.C.C., Rocha A.R. Chemosensors; 9 (7, 162) 2021. 10.3390/chemosensors9070162.

    Theory and Simulation

    Electrochemical immunosensors (EI) have been widely investigated in the last several years. Among them, immunosensors based on low-dimensional materials (LDM) stand out, as they could provide a substantial gain in fabricating point-of-care devices, paving the way for fast, precise, and sensitive diagnosis of numerous severe illnesses. The high surface area available in LDMs makes it possible to immobilize a high density of bioreceptors, improving the sensitivity in biorecognition events between antibodies and antigens. If on the one hand, many works present promising results in using LDMs as a sensing material in EIs, on the other hand, very few of them discuss the fundamental interactions involved at the interfaces. Understanding the fundamental Chemistry and Physics of the interactions between the surface of LDMs and the bioreceptors, and how the operating conditions and biorecognition events affect those interactions, is vital when proposing new devices. Here, we present a review of recent works on EIs, focusing on devices that use LDMs (1D and 2D) as the sensing substrate. To do so, we highlight both experimental and theoretical aspects, bringing to light the fundamental aspects of the main interactions occurring at the interfaces and the operating mechanisms in which the detections are based. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.


  • Low-Voltage Magnetoelectric Coupling in Fe0.5Rh0.5/0.68PbMg1/3Nb2/3O3-0.32PbTiO3 Thin-Film Heterostructures

    Zhao W., Kim J., Huang X., Zhang L., Pesquera D., Velarde G.A.P., Gosavi T., Lin C.-C., Nikonov D.E., Li H., Young I.A., Ramesh R., Martin L.W. Advanced Functional Materials; 2021. 10.1002/adfm.202105068. IF: 18.808

    Oxide Nanophysics

    The rapid development of computing applications demands novel low-energy consumption devices for information processing. Among various candidates, magnetoelectric heterostructures hold promise for meeting the required voltage and power goals. Here, a route to low-voltage control of magnetism in 30 nm Fe0.5Rh0.5/100 nm 0.68PbMg1/3Nb2/3O3-0.32PbTiO3 (PMN-PT) heterostructures is demonstrated wherein the magnetoelectric coupling is achieved via strain-induced changes in the Fe0.5Rh0.5 mediated by voltages applied to the PMN-PT. We describe approaches to achieve high-quality, epitaxial growth of Fe0.5Rh0.5 on the PMN-PT films and, a methodology to probe and quantify magnetoelectric coupling in small thin-film devices via studies of the anomalous Hall effect. By comparing the spin-flop field change induced by temperature and external voltage, the magnetoelectric coupling coefficient is estimated to reach ≈7 × 10−8 s m−1 at 325 K while applying a −0.75 V bias. © 2021 Wiley-VCH GmbH.


  • Tailoring plasmonic resonances in Cu-Ag metal islands films

    Bubaš M., Janicki V., Mezzasalma S.A., Spadaro M.C., Arbiol J., Sancho-Parramon J. Applied Surface Science; 564 (150260) 2021. 10.1016/j.apsusc.2021.150260. IF: 6.707

    Advanced Electron Nanoscopy

    The plasmonic response of Cu-Ag metal islands films is investigated. Films are obtained by subsequent electron beam deposition of Ag and Cu using different fabrication conditions: deposited mass thickness, substrate temperature and post-deposition annealing in vacuum. Optical properties of films are investigated by spectroscopic ellipsometry and correlated with the structural characterization results obtained by electron microscopy. It is observed that Ag enhances island growth and increases the percolation threshold of Cu films. The localized surface plasmon resonance of isolated particles shows signatures of both Cu and Ag. Moderate thermal annealing enhances island growth and favours Janus-like morphology, increasing the Ag contribution to the surface plasmon resonance. In case of percolated films, annealing-induced dewetting can lead to the appearance of large and irregular particles with a remarkable absorption peak in the near-infrared range. Composition and optical properties of the films can be further modified by Ag partial evaporation upon annealing at high temperatures. The variation of optical properties with aging is related to Cu oxidization and follows different trends depending on the sample morphology. Overall, it is shown that Cu-Ag island films are compelling systems for plasmonic applications, as their optical response can be widely and easily tuned by adjusting fabrication conditions. © 2021 Elsevier B.V.


  • Quantifying thermal transport in buried semiconductor nanostructures: Via cross-sectional scanning thermal microscopy

    Spièce J., Evangeli C., Robson A.J., El Sachat A., Haenel L., Alonso M.I., Garriga M., Robinson B.J., Oehme M., Schulze J., Alzina F., Sotomayor Torres C., Kolosov O.V. Nanoscale; 13 (24): 10829 - 10836. 2021. 10.1039/d0nr08768h. IF: 7.790

    Phononic and Photonic Nanostructures

    Managing thermal transport in nanostructures became a major challenge in the development of active microelectronic, optoelectronic and thermoelectric devices, stalling the famous Moore's law of clock speed increase of microprocessors for more than a decade. To find the solution to this and linked problems, one needs to quantify the ability of these nanostructures to conduct heat with adequate precision, nanoscale resolution, and, essentially, for the internal layers buried in the 3D structure of modern semiconductor devices. Existing thermoreflectance measurements and "hot wire"3ω methods cannot be effectively used at lateral dimensions of a layer below a micrometre; moreover, they are sensitive mainly to the surface layers of a relatively high thickness of above 100 nm. Scanning thermal microscopy (SThM), while providing the required lateral resolution, provides mainly qualitative data of the layer conductance due to undefined tip-surface and interlayer contact resistances. In this study, we used cross-sectional SThM (xSThM), a new method combining scanning probe microscopy compatible Ar-ion beam exit nano-cross-sectioning (BEXP) and SThM, to quantify thermal conductance in complex multilayer nanostructures and to measure local thermal conductivity of oxide and semiconductor materials, such as SiO2, SiGex and GeSny. By using the new method that provides 10 nm thickness and few tens of nm lateral resolution, we pinpoint crystalline defects in SiGe/GeSn optoelectronic materials by measuring nanoscale thermal transport and quantifying thermal conductivity and interfacial thermal resistance in thin spin-on materials used in extreme ultraviolet lithography (eUV) fabrication processing. The new capability of xSThM demonstrated here for the first time is poised to provide vital insights into thermal transport in advanced nanoscale materials and devices. © The Royal Society of Chemistry.


  • Pharmacokinetics, biodistribution, and biosafety of pegylated gold nanoparticles in vivo

    Kozics K., Sramkova M., Kopecka K., Begerova P., Manova A., Krivosikova Z., Sevcikova Z., Liskova A., Rollerova E., Dubaj T., Puntes V., Wsolova L., Simon P., Tulinska J., Gabelova A. Nanomaterials; 11 (7, 1702) 2021. 10.3390/nano11071702. IF: 5.076

    Inorganic Nanoparticles

    Despite the obvious advantages of gold nanoparticles for biomedical applications, controversial and incomplete toxicological data hamper their widespread use. Here, we present the results from an in vivo toxicity study using gold nanoparticles coated with polyethylene glycol (PEG-AuNPs). The pharmacokinetics and biodistribution of PEG-AuNPs were examined in the rat’s liver, lung, spleen, and kidney after a single i.v. injection (0.7 mg/kg) at different time intervals. PEG-AuNPs had a relatively long blood circulation time and accumulated primarily in the liver and spleen, where they remained for up to 28 days after administration. Increased cytoplasmic vacuolation in hepatocytes 24 h and 7 days after PEG-AuNPs exposure and apoptotic-like cells in white splenic pulp 24 h after administration has been detected, however, 28 days post-exposure were no longer observed. In contrast, at this time point, we identified significant changes in lipid metabolism, altered levels of liver injury markers, and elevated monocyte count, but without marked biological relevance. In blood cells, no DNA damage was present in any of the studied time intervals, with the exception of DNA breakage transiently detected in primary kidney cells 4 h post-injection. Our results indicate that the tissue accumulation of PEG-AuNPs might result in late toxic effects. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.


  • A method for the measurement of mass and number of graphene oxide sheets in suspension based on non-spherical approximations

    Crica L.E., Dennison T.J., Guerini E.A., Kostarelos K. 2D Materials; 8 (3, 035044) 2021. 10.1088/2053-1583/abfe01. IF: 7.103

    Nanomedicine

    Currently, particle analysis of 2D materials in suspension is commonly restricted to microscopic techniques in the dry state, and thus does not permit an accurate investigation of colloidal suspensions. Colloids in bulk can be assessed by light scattering and diffraction to investigate features such as their hydrodynamic size, charge and concentration. However, the main drawback of such techniques lies in the application of analytical and computational methods based on models assuming particle sphericity which are not representative for 2D materials. Resonance mass measurement (RMM) is a technique which can enable the analysis of 2D materials in suspension without the assumptions of spherical models. Here, we report the application of RMM to measure particle mass and concentration for three types of graphene oxide (GO) aqueous dispersions. Using micro- and nano-suspended resonating sensors, we were able to decipher gravimetric differences between GO and graphitic materials. Our results support the urge for proper definitions and standardisations of graphene based materials, and offer a new method of characterisation for 2D material colloids in liquid suspension. © 2021 The Author(s). Published by IOP Publishing Ltd.


  • Carbon Incorporation in MOCVD of MoS2Thin Films Grown from an Organosulfide Precursor

    Schaefer C.M., Caicedo Roque J.M., Sauthier G., Bousquet J., Hébert C., Sperling J.R., Pérez-Tomás A., Santiso J., Del Corro E., Garrido J.A. Chemistry of Materials; 2021. 10.1021/acs.chemmater.1c00646. IF: 9.811

    Nanomaterials Growth Unit | Advanced Electronic Materials and Devices

    With the rise of two-dimensional (2D) transition-metal dichalcogenide (TMD) semiconductors and their prospective use in commercial (opto)electronic applications, it has become key to develop scalable and reliable TMD synthesis methods with well-monitored and controlled levels of impurities. While metal-organic chemical vapor deposition (MOCVD) has emerged as the method of choice for large-scale TMD fabrication, carbon (C) incorporation arising during MOCVD growth of TMDs has been a persistent concern - especially in instances where organic chalcogen precursors are desired as a less hazardous alternative to more toxic chalcogen hydrides. However, the underlying mechanisms of such unintentional C incorporation and the effects on film growth and properties are still elusive. Here, we report on the role of C-containing side products of organosulfur precursor pyrolysis in MoS2 thin films grown from molybdenum hexacarbonyl Mo(CO)6 and diethyl sulfide (CH3CH2)2S (DES). By combining in situ gas-phase monitoring with ex situ microscopy and spectroscopy analyses, we systematically investigate the effect of temperature and Mo(CO)6/DES/H2 gas mixture ratios on film morphology, chemical composition, and stoichiometry. Aiming at high-quality TMD growth that typically requires elevated growth temperatures and high DES/Mo(CO)6 precursor ratios, we observed that temperatures above DES pyrolysis onset (≳600 °C) and excessive DES flow result in the formation of nanographitic carbon, competing with MoS2 growth. We found that by introducing H2 gas to the process, DES pyrolysis is significantly hindered, which reduces carbon incorporation. The C content in the MoS2 films is shown to quench the MoS2 photoluminescence and influence the trion-to-exciton ratio via charge transfer. This finding is fundamental for understanding process-induced C impurity doping in MOCVD-grown 2D semiconductors and might have important implications for the functionality and performance of (opto)electronic devices. ©


  • Viscoelastic surface electrode arrays to interface with viscoelastic tissues

    Tringides C.M., Vachicouras N., de Lázaro I., Wang H., Trouillet A., Seo B.R., Elosegui-Artola A., Fallegger F., Shin Y., Casiraghi C., Kostarelos K., Lacour S.P., Mooney D.J. Nature Nanotechnology; 2021. 10.1038/s41565-021-00926-z. IF: 39.213

    Nanomedicine

    Living tissues are non-linearly elastic materials that exhibit viscoelasticity and plasticity. Man-made, implantable bioelectronic arrays mainly rely on rigid or elastic encapsulation materials and stiff films of ductile metals that can be manipulated with microscopic precision to offer reliable electrical properties. In this study, we have engineered a surface microelectrode array that replaces the traditional encapsulation and conductive components with viscoelastic materials. Our array overcomes previous limitations in matching the stiffness and relaxation behaviour of soft biological tissues by using hydrogels as the outer layers. We have introduced a hydrogel-based conductor made from an ionically conductive alginate matrix enhanced with carbon nanomaterials, which provide electrical percolation even at low loading fractions. Our combination of conducting and insulating viscoelastic materials, with top-down manufacturing, allows for the fabrication of electrode arrays compatible with standard electrophysiology platforms. Our arrays intimately conform to the convoluted surface of the heart or brain cortex and offer promising bioengineering applications for recording and stimulation. © 2021, The Author(s), under exclusive licence to Springer Nature Limited.


  • Spontaneous interlayer compression in commensurately stacked van der Waals heterostructures

    Pike N.A., Dewandre A., Chaltin F., Garcia Gonzalez L., Pillitteri S., Ratz T., Verstraete M.J. Physical Review B; 103 (23, 235307) 2021. 10.1103/PhysRevB.103.235307. IF: 4.036

    Theory and Simulation

    Interest in layered two-dimensional materials, particularly stacked heterostructures of transition-metal dichalcogenides, has led to the need for a better understanding of the structural and electronic changes induced by stacking. Here, we investigate the effects of idealized heterostructuring, with periodic commensurate stacking, on the structural, electronic, and vibrational properties, when compared to the counterpart bulk transition-metal dichalcogenide. We find that in heterostructures with dissimilar chalcogen species there is a strong compression of the interlayer spacing, compared to the bulk compounds. This compression of the heterostructure is caused by an increase in the strength of the induced polarization interaction between the layers, but not a full charge transfer. We argue that this effect is real, not due to the imposed commensurability, and should be observable in heterostructures combining different chalcogens. Interestingly, we find that incommensurate stacking of Ti-based dichalcogenides can lead to the stabilization of the charge-density wave phonon mode, which is unstable in the 1T phase at low temperature. Mixed Ti- and Zr-based heterostructures are still dynamically unstable, but TiS2/ZrS2 becomes ferroelectric. © 2021 American Physical Society.


  • In situ nanoremediation of soils and groundwaters from the nanoparticle's standpoint: A review

    Marcon L., Oliveras J., Puntes V.F. Science of the Total Environment; 791 (148324) 2021. 10.1016/j.scitotenv.2021.148324. IF: 7.963

    Inorganic Nanoparticles

    Anthropogenic pollution coming from industrial processes, agricultural practices and consumer products, results in the release of toxic substances into rural and urban environments. Once released, these chemicals migrate through the atmosphere and water, and find their way into matrices such as sediments and groundwaters, thus making large areas potentially uninhabitable. Common pollutants, including heavy metal(loid)s, radionuclides, aliphatic hydrocarbons and halogenated organics, are known to adversely affect physiological systems in animal species. Pollution can be cleaned up using techniques such as coagulation, reverse osmosis, oxidation and biological methods, among others. The use of nanoparticles (NPs) extends the range of available technologies and offers particular benefits, not only by degrading, transforming and immobilizing contaminants, but also by reaching inaccessible areas and promoting biotic degradation. The development of NPs is understandably heralded as an environmentally beneficial technology; however, it is only now that the ecological risks associated with their use are being evaluated. This review presents recent developments in the use of engineered NPs for the in situ remediation of two paramount environmental matrices: soils and groundwaters. Emphasis will be placed on (i) the successful applications of nano-objects for environmental cleanup, (ii) the potential safety implications caused by the challenging requirements of [high reactivity toward pollutants] vs. [none reactivity toward biota], with a thorough view on their transport and evolution in the matrix, and (iii) the perspectives on scientific and regulatory challenges. To this end, the most promising nanomaterials will be considered, including nanoscale zerovalent iron, nano-oxides and carbonaceous materials. The purpose of the present review is to give an overview of the development of nanoremediators since they appeared in the 2000s, from their chemical modifications, mechanism of action and environmental behavior to an understanding of the problematics (technical limitations, economic constraints and institutional precautionary approaches) that will drive their future full-scale applications. © 2021