Electrical and Thermal Conductivities of Single CuxO Nanowires.

Copper oxide nanowires (NWs) are promising elements for the realization of a wide range of devices for low-power electronics, gas sensors, and energy storage applications, due to their high aspect ratio, low environmental impact, and cost-effective manufacturing. Here, we report on the electrical and thermal properties of copper oxide NWs synthetized through thermal growth directly on copper foil. Structural characterization revealed that the growth process resulted in the formation of vertically aligned NWs on the Cu growth substrate, while the investigation of chemical composition revealed that the NWs were composed of CuO rather than Cu2O. The electrical characterization of single-NW-based devices, in which single NWs were contacted by Cu electrodes, revealed that the NWs were characterized by a conductivity of 7.6 × 10-2 S∙cm-1. The effect of the metal-insulator interface at the NW-electrode contact was analyzed by comparing characterizations in two-terminal and four-terminal configurations. The effective thermal conductivity of single CuO NWs placed on a substrate was measured using Scanning Thermal Microscopy (SThM), providing a value of 2.6 W∙m-1∙K-1, and using a simple Finite Difference model, an estimate for the thermal conductivity of the nanowire itself was obtained as 3.1 W∙m-1∙K-1. By shedding new light on the electrical and thermal properties of single CuO NWs, these results can be exploited for the rational design of a wide range of optoelectronic devices based on NWs.

Effect of electrode materials on resistive switching behaviour of NbOx-based memristive devices.

Memristive devices that rely on redox-based resistive switching mechanism have attracted great attention for the development of next-generation memory and computing architectures. However, a detailed understanding of the relationship between involved materials, interfaces, and device functionalities still represents a challenge. In this work, we analyse the effect of electrode metals on resistive switching functionalities of NbOx-based memristive cells. For this purpose, the effect of Au, Pt, Ir, TiN, and Nb top electrodes was investigated in devices based on amorphous NbOx grown by anodic oxidation on a Nb substrate exploited also as counter electrode. It is shown that the choice of the metal electrode regulates electronic transport properties of metal-insulator interfaces, strongly influences the electroforming process, and the following resistive switching characteristics. Results show that the electronic blocking character of Schottky interfaces provided by Au and Pt metal electrodes results in better resistive switching performances. It is shown that Pt represents the best choice for the realization of memristive cells when the NbOx thickness is reduced, making possible the realization of memristive cells characterised by low variability in operating voltages, resistance states and with low device-to-device variability. These results can provide new insights towards a rational design of redox-based memristive cells.

Developing Quantitative Nondestructive Characterization of Nanomaterials: A Case Study on Sequential Infiltration Synthesis of Block Copolymers.

The sequential infiltration synthesis (SIS) of inorganic materials in nanostructured block copolymer templates has rapidly progressed in the last few years to develop functional nanomaterials with controllable properties. To assist this rapid evolution, expanding the capabilities of nondestructive methods for quantitative characterization of the materials properties is required. In this paper, we characterize the SIS process on three model polymers with different infiltration profiles through ex situ quantification by reference-free grazing incidence X-ray fluorescence. More qualitative depth distribution results were validated by means of X-ray photoelectron spectroscopy and scanning transmission electron microscopy combined with energy-dispersive X-ray spectroscopy.

Resistive switching and role of interfaces in memristive devices based on amorphous NbOx grown by anodic oxidation.

Memristive devices based on the resistive switching mechanism are continuously attracting attention in the framework of neuromorphic computing and next-generation memory devices. Here, we report on a comprehensive analysis of the resistive switching properties of amorphous NbOx grown by anodic oxidation. Besides a detailed chemical, structural and morphological analysis of the involved materials and interfaces, the mechanism of switching in Nb/NbOx/Au resistive switching cells is discussed by investigating the role of metal-metal oxide interfaces in regulating electronic and ionic transport mechanisms. The resistive switching was found to be related to the formation/rupture of conductive nanofilaments in the NbOx layer under the action of an applied electric field, facilitated by the presence of an oxygen scavenger layer at the Nb/NbOx interface. Electrical characterization including device-to-device variability revealed an endurance >103 full-sweep cycles, retention >104 s, and multilevel capabilities. Furthermore, the observation of quantized conductance supports the physical mechanism of switching based on the formation of atomic-scale conductive filaments. Besides providing new insights into the switching properties of NbOx, this work also highlights the perspective of anodic oxidation as a promising method for the realization of resistive switching cells.

Complex Phase-Fluctuation Effects Correlated with Granularity in Superconducting NbN Nanofilms.

Superconducting nanofilms are tunable systems that can host a 3D-2D dimensional crossover leading to the Berezinskii-Kosterlitz-Thouless (BKT) superconducting transition approaching the 2D regime. Reducing the dimensionality further, from 2D to quasi-1D superconducting nanostructures with disorder, can generate quantum and thermal phase slips (PS) of the order parameter. Both BKT and PS are complex phase-fluctuation phenomena of difficult experiments. We characterized superconducting NbN nanofilms thinner than 15 nm, on different substrates, by temperature-dependent resistivity and current-voltage (I-V) characteristics. Our measurements evidence clear features related to the emergence of BKT transition and PS events. The contemporary observation in the same system of BKT transition and PS events, and their tunable evolution in temperature and thickness was explained as due to the nano-conducting paths forming in a granular NbN system. In one of the investigated samples, we were able to trace and characterize the continuous evolution in temperature from quantum to thermal PS. Our analysis established that the detected complex phase phenomena are strongly related to the interplay between the typical size of the nano-conductive paths and the superconducting coherence length.

Liquid Phase Infiltration of Block Copolymers.

Novel materials with defined composition and structures at the nanoscale are increasingly desired in several research fields spanning a wide range of applications. The development of new approaches of synthesis that provide such control is therefore required in order to relate the material properties to its functionalities. Self-assembling materials such as block copolymers (BCPs), in combination with liquid phase infiltration (LPI) processes, represent an ideal strategy for the synthesis of inorganic materials into even more complex and functional features. This review provides an overview of the mechanism involved in the LPI, outlining the role of the different polymer infiltration parameters on the resulting material properties. We report newly developed methodologies that extend the LPI to the realisation of multicomponent and 3D inorganic nanostructures. Finally, the recently reported implementation of LPI into different applications such as photonics, plasmonics and electronics are highlighted.

Recommended implementation of electrical resistance tomography for conductivity mapping of metallic nanowire networks using voltage excitation.

The knowledge of the spatial distribution of the electrical conductivity of metallic nanowire networks (NWN) is important for tailoring the performance in applications. This work focuses on Electrical Resistance Tomography (ERT), a technique that maps the electrical conductivity of a sample from several resistance measurements performed on its border. We show that ERT can be successfully employed for NWN characterisation if a dedicated measurement protocol is employed. When applied to other materials, ERT measurements are typically performed with a constant current excitation; we show that, because of the peculiar microscopic structure and behaviour of metallic NWN, a constant voltage excitation protocols is preferable. This protocol maximises the signal to noise ratio in the resistance measurements-and thus the accuracy of ERT maps-while preventing the onset of sample alterations.

Recent Advances in Sequential Infiltration Synthesis (SIS) of Block Copolymers (BCPs).

In the continuous downscaling of device features, the microelectronics industry is facing the intrinsic limits of conventional lithographic techniques. The development of new synthetic approaches for large-scale nanopatterned materials with enhanced performances is therefore required in the pursuit of the fabrication of next-generation devices. Self-assembled materials as block copolymers (BCPs) provide great control on the definition of nanopatterns, promising to be ideal candidates as templates for the selective incorporation of a variety of inorganic materials when combined with sequential infiltration synthesis (SIS). In this review, we report the latest advances in nanostructured inorganic materials synthesized by infiltration of self-assembled BCPs. We report a comprehensive description of the chemical and physical characterization techniques used for in situ studies of the process mechanism and ex situ measurements of the resulting properties of infiltrated polymers. Finally, emerging optical and electrical properties of such materials are discussed.

Directed Self-Assembly of Polystyrene Nanospheres by Direct Laser-Writing Lithography.

In this work, we performed a systematic study on the effect of the geometry of pre-patterned templates and spin-coating conditions on the self-assembling process of colloidal nanospheres. To achieve this goal, large-scale templates, with different size and shape, were generated by direct laser-writer lithography over square millimetre areas. When deposited over patterned templates, the ordering dynamics of the self-assembled nanospheres exhibits an inverse trend with respect to that observed for the maximisation of the correlation length ξ on a flat surface. Furthermore, the self-assembly process was found to be strongly dependent on the height (H) of the template sidewalls. In particular, we observed that, when H is 0.6 times the nanospheres diameter and spinning speed 2500 rpm, the formation of a confined and well ordered monolayer is promoted. To unveil the defects generation inside the templates, a systematic assessment of the directed self-assembly quality was performed by a novel method based on Delaunay triangulation. As a result of this study, we found that, in the best deposition conditions, the self-assembly process leads to well-ordered monolayer that extended for tens of micrometres within the linear templates, where 96.2% of them is aligned with the template sidewalls.

Vortex Beam Generation by Spin-Orbit Interaction with Bloch Surface Waves.

Axis-symmetric grooves milled in metallic slabs have been demonstrated to promote the transfer of Orbital Angular Momentum (OAM) from far- to near-field and vice versa, thanks to spin-orbit coupling effects involving Surface Plasmons (SP). However, the high absorption losses and the polarization constraints, which are intrinsic in plasmonic structures, limit their effectiveness for applications in the visible spectrum, particularly if emitters located in close proximity to the metallic surface are concerned. Here, an alternative mechanism for vortex beam generation is presented, wherein a free-space radiation possessing OAM is obtained by diffraction of Bloch Surface Waves (BSWs) on a dielectric multilayer. A circularly polarized laser beam is tightly focused on the multilayer surface by means of an immersion optics, such that TE-polarized BSWs are launched radially from the focused spot. While propagating on the multilayer surface, BSWs exhibit a spiral-like wavefront due to the Spin-Orbit Interaction (SOI). A spiral grating surrounding the illumination area provides for the BSW diffraction out-of-plane and imparts an additional azimuthal geometric phase distribution defined by the topological charge of the spiral structure. At infinity, the constructive interference results into free-space beams with defined combinations of polarization and OAM satisfying the conservation of the Total Angular Momentum, based on the incident polarization handedness and the spiral grating topological charge. As an extension of this concept, chiral diffractive structures for BSWs can be used in combination with surface cavities hosting light sources therein.

Driving Cells with Light-Controlled Topographies.

Cell-substrate interactions can modulate cellular behaviors in a variety of biological contexts, including development and disease. Light-responsive materials have been recently proposed to engineer active substrates with programmable topographies directing cell adhesion, migration, and differentiation. However, current approaches are affected by either fabrication complexity, limitations in the extent of mechanical stimuli, lack of full spatio-temporal control, or ease of use. Here, a platform exploiting light to plastically deform micropatterned polymeric substrates is presented. Topographic changes with remarkable relief depths in the micron range are induced in parallel, by illuminating the sample at once, without using raster scanners. In few tens of seconds, complex topographies are instructed on demand, with arbitrary spatial distributions over a wide range of spatial and temporal scales. Proof-of-concept data on breast cancer cells and normal kidney epithelial cells are presented. Both cell types adhere and proliferate on substrates without appreciable cell damage upon light-induced substrate deformations. User-provided mechanical stimulation aligns and guides cancer cells along the local deformation direction and constrains epithelial colony growth by biasing cell division orientation. This approach is easy to implement on general-purpose optical microscopy systems and suitable for use in cell biology in a wide variety of applications.

Influence of the long-range ordering of gold-coated Si nanowires on SERS.

Controlling the location and the distribution of hot spots is a crucial aspect in the fabrication of surface-enhanced Raman spectroscopy (SERS) substrates for bio-analytical applications. The choice of a suitable method to tailor the dimensions and the position of plasmonic nanostructures becomes fundamental to provide SERS substrates with significant signal enhancement, homogeneity and reproducibility. In the present work, we studied the influence of the long-range ordering of different flexible gold-coated Si nanowires arrays on the SERS activity. The substrates are made by nanosphere lithography and metal-assisted chemical etching. The degree of order is quantitatively evaluated through the correlation length (ξ) as a function of the nanosphere spin-coating speed. Our findings showed a linear increase of the SERS signal for increasing values of ξ, coherently with a more ordered and dense distribution of hot spots on the surface. The substrate with the largest ξ of 1100 nm showed an enhancement factor of 2.6 · 103 and remarkable homogeneity over square-millimetres area. The variability of the signal across the substrate was also investigated by means of a 2D chemical imaging approach and a standard methodology for its practical calculation is proposed for a coherent comparison among the data reported in literature.

Hierarchical Order in Dewetted Block Copolymer Thin Films on Chemically Patterned Surfaces.

We investigated the dewetting process on flat and chemically patterned surfaces of ultrathin films (thickness between 2 and 15 nm) of a cylinder forming polystyrene- block-poly(methyl methacrylate) (PS- b-PMMA) spin coated on poly(styrene- r-methyl methacrylate) random copolymers (RCPs). When the PS- b-PMMA film dewets on a 2 nm-thick RCP layer, the ordering of the hexagonally packed PMMA cylinders in the dewetted structures extends over distances far exceeding the correlation length obtained in continuous block copolymer (BCP) films. As a result, micrometer-sized circular droplets featuring defectless single grains of self-assembled PS- b-PMMA with PMMA cylinders perpendicularly oriented with respect to the substrate are generated and randomly distributed on the substrate. Additionally, alignment of the droplets along micrometric lines was achieved by performing the dewetting process on large-scale chemically patterned stripes of 2 nm thick RCP films by laser lithography. By properly adjusting the periodicity of the chemical pattern, it was possible to tune and select the geometrical characteristics of the dewetted droplets in terms of maximum thickness, contact angle and diameter while maintaining the defectless single grain perpendicular cylinder morphology of the circular droplets.

Dimensional crossover and incipient quantum size effects in superconducting niobium nanofilms.

Superconducting and normal state properties of Niobium nanofilms have been systematically investigated as a function of film thickness, on different substrates. The width of the superconducting-to-normal transition for all films is remarkably narrow, confirming their high quality. The superconducting critical current density exhibits a pronounced maximum for thickness around 25 nm, marking the 3D-to-2D crossover. The magnetic penetration depth shows a sizeable enhancement for the thinnest films. Additional amplification effects of the superconducting properties have been obtained with sapphire substrates or squeezing the lateral size of the nanofilms. For thickness close to 20 nm we measured a doubled perpendicular critical magnetic field compared to its large thickness value, indicating shortening of the correlation length and the formation of small Cooper pairs. Our data analysis indicates an exciting interplay between quantum-size and proximity effects together with strong-coupling effects and the importance of disorder in the thinnest films, placing these nanofilms close to the BCS-BEC crossover regime.

Maskless X-Ray Writing of Electrical Devices on a Superconducting Oxide with Nanometer Resolution and Online Process Monitoring.

X-ray nanofabrication has so far been usually limited to mask methods involving photoresist impression and subsequent etching. Herein we show that an innovative maskless X-ray nanopatterning approach allows writing electrical devices with nanometer feature size. In particular we fabricated a Josephson device on a Bi2Sr2CaCu2O8+δ (Bi-2212) superconducting oxide micro-crystal by drawing two single lines of only 50 nm in width using a 17.4 keV synchrotron nano-beam. A precise control of the fabrication process was achieved by monitoring in situ the variations of the device electrical resistance during X-ray irradiation, thus finely tuning the irradiation time to drive the material into a non-superconducting state only in the irradiated regions, without significantly perturbing the crystal structure. Time-dependent finite element model simulations show that a possible microscopic origin of this effect can be related to the instantaneous temperature increase induced by the intense synchrotron picosecond X-ray pulses. These results prove that a conceptually new patterning method for oxide electrical devices, based on the local change of electrical properties, is actually possible with potential advantages in terms of heat dissipation, chemical contamination, miniaturization and high aspect ratio of the devices.

Toward Lateral Length Standards at the Nanoscale Based on Diblock Copolymers.

The self-assembly (SA) of diblock copolymers (DBCs) based on phase separation into different morphologies of small and high-density features is widely investigated as a patterning and nanofabrication technique. The integration of conventional top-down approaches with the bottom-up SA of DBCs enables the possibility to address the gap in nanostructured lateral length standards for nanometrology, consequently supporting miniaturization processes in device fabrication. On this topic, we studied the pattern characteristic dimensions (i.e., center-to-center distance L0 and diameter D) of a cylinder-forming polystyrene-b-poly( methyl methacrylate) PS-b-PMMA (54 kg mol-1, styrene fraction 70%) DBC when confined within periodic SiO2 trenches of different widths (W, ranging between 75 and 600 nm) and fixed length (l, 5.7 µm). The characteristic dimensions of the PMMA cylinder structure in the confined configurations were compared with those obtained on a flat surface (L0 = 27.8 ± 0.5 nm, D = 13.0 ± 1.0 nm). The analysis of D as a function of W evolution indicates that the eccentricity of the PMMA cylinders decreases as a result of the deformation of the cylinder in the direction perpendicular to the trenches. The center-to-center distance in the direction parallel to the long side of the trenches (L0l) is equal to L0 measured on the flat surface, whereas the one along the short side (L0w) is subjected to an appreciable variation (ΔL0w = 5 nm) depending on W. The possibility of finely tuning L0w maintaining constant L0l paves the way to the realization of a DBC-based transfer standard for lateral length calibration with periods in the critical range between 20 and 50 nm wherein no commercial transfer standards are available. A prototype transfer standard with cylindrical holes was used to calibrate the linear correction factor c(Δx')xx' of an atomic force microscope for a scan length of Δx' = 1 µm. The relative standard uncertainty of the correction factor was only 1.3%, and the second-order nonlinear correction was found to be significant.

4-Nitrobenzene Grafted in Porous Silicon: Application to Optical Lithography.

In this work, we report a method to process porous silicon to improve its chemical resistance to alkaline solution attacks based on the functionalization of the pore surface by the electrochemical reduction of 4-nitrobenzendiazonium salt. This method provides porous silicon with strong resistance to the etching solutions used in optical lithography and allows the fabrication of tailored metallic contacts on its surface. The samples were studied by chemical, electrochemical, and morphological methods. We demonstrate that the grafted samples show a resistance to harsh alkaline solution more than three orders of magnitude larger than that of pristine porous silicon, being mostly unmodified after about 40 min. The samples maintained open pores after the grafting, making them suitable for further treatments like filling by polymers. Optical lithography was performed on the functionalized samples, and electrochemical characterization results are shown.

Direct-Write X-ray Nanopatterning: A Proof of Concept Josephson Device on Bi2Sr2CaCu2O8+δ Superconducting Oxide.

We describe the first use of a novel photoresist-free X-ray nanopatterning technique to fabricate an electronic device. We have produced a proof-of-concept device consisting of a few Josephson junctions by irradiating microcrystals of the Bi2Sr2CaCu2O8+δ (Bi-2212) superconducting oxide with a 17.6 keV synchrotron nanobeam. Fully functional devices have been obtained by locally turning the material into a nonsuperconducting state by means of hard X-ray exposure. Nano-XRD patterns reveal that the crystallinity is substantially preserved in the irradiated areas that there is no evidence of macroscopic crystal disruption. Indications are that O ions have been removed from the crystals, which could make this technique interesting also for other oxide materials. Direct-write X-ray nanopatterning represents a promising fabrication method exploiting material/material rather than vacuum/material interfaces, with the potential for nanometric resolution, improved mechanical stability, enhanced depth of patterning, and absence of chemical contamination with respect to traditional lithographic techniques.

Thickness and Microdomain Orientation of Asymmetric PS-b-PMMA Block Copolymer Films Inside Periodic Gratings.

The ordering process of asymmetric PS-b-PMMA block copolymers (BCPs) is investigated on flat SiO2 surfaces and on topographically patterned substrates. The topographic patterns consist of periodic gratings of 10 trenches defined by conventional top-down approaches and subsequently neutralized using a P(S-r-MMA) random copolymer (RCP). When the ordering process is accomplished on a flat surface at a temperature ranging between 180 and 230 °C, cylindrical microdomains perpendicularly oriented with respect to the substrate are observed irrespective of annealing temperature. In contrast, when the ordering process occurs on topographically patterned substrates, different phenomena have to be considered. The simultaneous effect of the flow around the gratings and the BCP flux from the zone located between adjacent trenches (mesa) into the inner part of the trenches results in significant thickness variations of the confined BCP film. Therefore, the amount of BCP inside the trenches depends on the width of the mesa region, which acts as a BCP reservoir. Moreover, within each trench group, the BCP thickness progressively decreases from the external to the central trenches composing the periodic grating. The thickness variation of the BCP film within the trenches strongly affects the ordering process, ultimately leading to different orientations of the microdomains within the trenches. In particular, when the annealing temperature is 190 °C a precise confinement of the BCP within the trenches featuring a perpendicular cylinder morphology is observed. At higher temperatures, mixed or parallel orientations of the microdomains are obtained depending on the width of the trenches in the periodic grating.

Bessel-like photonic nanojets from core-shell sub-wavelength spheres.

It is accepted so far that the formation of photonic nanojets requires the use of large dielectric spheres (several wavelengths in diameter). Here we show both numerically and experimentally that similar effects can be obtained with properly engineered sub-wavelength core-shell colloids. The design of the spheres is strongly inspired by a far-field approach for the generation of Bessel beams.