Hyperbolic metamaterials by directed self-assembly of block copolymers

Hyperbolic materials are high uniaxial anisotropic materials that display hyperbolic dispersion with distinctive properties, including negative refraction index, control over light propagation and enhanced Purcell factor. Naturally-occurring hyperbolic materials exhibit these properties only in reduced wavelength ranges, thus limiting their implementation into integrated optical devices. In order to tune the hyperbolic dispersion over broader bandwidths, artificial structures capable to guarantee a greater flexibility, i.e. hyperbolic metamaterials (HMMs), are required. So far, the realization of HMMs that work in the visible and near-infrared wavelength regions has been limited to the out-of-plane configuration due to technological costraints in the fabrication of periodic structures at sub-wavelength dimensions. Here we propose a novel concept of HMMs working in the in-plane configuration, based on the use of block copolymers (BCPs) capable to self-assemble into highly ordered polimeric masks with nanometric feature sizes and periodicity, serving as templates for the subsequent fabrication of hybrid metal-dielectric HMMs. This new class of HMMs can be exploited for metrological applications such as the enhancement of single photon source's (SPS) emission properties

Memristive Devices for Quantum Metrology

As a consequence of the redefinition of the International System of Units (SI), where units are defined in terms of fundamental physical constants, memristive devices represent a promising platform for quantum metrology. Coupling ionics with electronics, memristive devices can exhibit conductance levels quantized in multiples of the fundamental quantum of conductance G(0) = 2e(2)/h. Since the fundamental quantum of conductance G(0) is related only to physical constants that assume fixed value in the revised SI, memristive devices can be exploited for the practical realization of a quantum-based resistance standard that, differently from quantum-Hall based devices conventionally adopted as resistance standards, can operate in different ambient conditions (air, vacuum, harsh environment), in a wide range of temperatures and without the need of an applied magnetic field In this work, the possibility of using memristive devices for quantum metrology is critically discussed, based on recent experimental and theoretical advances on quantum conductance phenomena reported in literature. Thanks to the high operational speed, high scalability down to the nanometer scale, and CMOS compatibility, memristive devices allow on-chip implementation of a resistance standard required for the realization of self-calibrating electrical systems and equipment with zero-chain traceability in accordance with the revised SI

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

Hyperbolic Metamaterials via Hierarchical Block Copolymer Nanostructures

Hyperbolic metamaterials (HMMs) offer unconventional properties in the field of optics, enabling opportunities for confinement and propagation of light at the nanoscale. In‐plane orientation of the optical axis, in the direction coinciding with the anisotropy of the HMMs, is desirable for a variety of novel applications in nanophotonics and imaging. Here, a method for creating localized HMMs with in‐plane optical axis, based on block copolymer (BCP) blend instability, is introduced. The dewetting of BCP thin film over topographically defined substrates generates droplets composed of highly ordered lamellar nanostructures in hierarchical configuration. The hierarchical nanostructures represent a valuable platform for the subsequent pattern transfer into a Au/air HMM, exhibiting hyperbolic behavior in a broad wavelength range in the visible spectrum. A computed Purcell factor as high as 32 at 580 nm supports the strong reduction in the fluorescence lifetime of defects in nanodiamonds placed on top of the HMM

Ultrathin random copolymer-grafted layers for block copolymer self-assembly

Hydroxyl-terminated P(S-r-MMA) random copolymers (RCPs) with molecular weights (Mn) from 1700 to 69000 and a styrene unit fraction of approximately 61% were grafted onto a silicon oxide surface and subsequently used to study the orientation of nanodomains with respect to the substrate, in cylinder-forming PS-b-PMMA block copolymer (BCP) thin films. When the thickness (H) of the grafted layer is greater than 5-6 nm, a perpendicular orientation is always observed because of the efficient decoupling of the BCP film from the polar SiO2 surface. Conversely, if H is less than 5 nm, the critical thickness of the grafted layer, which allows the neutralization of the substrate and promotion of the perpendicular orientation of the nanodomains in the BCP film, is found to depend on the Mn of the RCP. In particular, when Mn = 1700, a 2.0 nm thick grafted layer is sufficient to promote the perpendicular orientation of the PMMA cylinders in the PS-b-PMMA BCP film. A proximity shielding mechanism of the BCP molecules from the polar substrate surface, driven by chain stretching of the grafted RCP molecules, is proposed

Structure and stability of 7-mercapto-4-methylcoumarin self-assembled monolayers on gold: an experimental and computational analysis

Self-assembled monolayers (SAM) of 7-mercapto-4-methylcoumarin (MMC) on a flat gold surface were studied by molecular dynamics (MD) simulations, reference-free grazing incidence X-ray fluorescence (GIXRF) and X-ray photoelectron spectroscopy (XPS), to determine the maximum monolayer density and to investigate the nature of the molecule/surface interface. In particular, the protonation state of the sulfur atom upon adsorption was analyzed, since some recent literature presented evidence for physisorbed thiols (preserving the S-H bond), unlike the common picture of chemisorbed thiyls (losing the hydrogen). MD with a specifically tailored force field was used to simulate either thiol or thiyl monolayers with increasing number of molecules, to determine the maximum dynamically stable densities. This result was refined by computing the monolayer chemical potential as a function of the density with the bennet acceptance ratio method, based again on MD simulations. The monolayer density was also measured with GIXRF, which provided the absolute quantification of the number of sulfur atoms in a dense self-assembled monolayer (SAM) on flat gold surfaces. The sulfur core level binding energies in the same monolayers were measured by XPS, fitting the recorded spectra with the binding energies proposed in the literature for free or adsorbed thiols and thiyls, to get insight on the nature of the molecular species present in the layer. The comparison of theoretical and experimental SAM densities, and the XPS analysis strongly support the picture of a monolayer formed by chemisorbed, dissociated thiyls

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

Total Reflection X-ray Fluorescence Reference Materials for Cascade Impactor Air Quality Monitoring Systems

The 12th International Conference on “Instrumental Methods of Analysis” www.ima2021.gr (accessed on 8 November 2021)), was organized by the Aristotle University of Thessaloniki and National Technical University of Athens, during 20–23 September 2021 as a virtual event, providing the opportunity for high-level analytical scientists from all around the world to promote their relevant research. IMA is a biannual series of conferences that started in 1999 and cover all areas of Chemical Analysis, including the development of new techniques, modern trends, and applications in a wide range of scientific disciplines. To date, several leading analytical chemists from Greece and abroad have presented their research work at previous IMA meetings. The 12th IMA conference (in a virtual format for the first time), had the ambition to bring together some of the most talented and innovative analytical chemists from all over the world for an excellent scientific online conference. The program of the 4-day event attended by 260 participants from 23 countries, included 14 invited speakers, 73 oral presentations, and 98 poster contributions. Covered topics included: spectrometric and electrometric analysis; chromatographic, mass spectrometric, microscopic, and thermal analysis methods; proteomics, metabolomics, metallomics, and elemental speciation analysis; chemical and biosensors; field analysis—mobile analytical instruments; miniaturized analytical systems (lab-on-a-chip), micro-, and nanofluidics; immunoassays and electrophoretic separation techniques; sampling techniques and strategies; robotics and automation; quality control—quality assurance in analysis; metrology; data processing and chemometrics; environmental analysis; biomedical (ecotoxicological and clinical) and pharmaceutical analysis; food analysis; materials analysis (nanomaterials, smart/advanced materials, and surface analysis); archaeometry; and analytical chemistry markets and possibilities for commercialization. Special sessions, focused on aerosol metrology (supported by EU Project AEROMET II), advanced X-ray techniques (supported by the European X-ray Spectrometry Association), and application of chemical analysis in the study of virus spread analytics (airborne and wastewaters), were also organized within the frame of IMA-2021

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