Nanoscale Study of the Tarnishing Process in Electron Beam Lithography-Fabricated Silver Nanoparticles for Plasmonic Applications

Scuderi, M.; Esposito, Marco; Todisco, Francesco; Simeone, D.; Tarantini, Iolena; Marco, Luisa De; Giorgi, Milena De; Nicotra, Giuseppe; Carbone, Luigi; Sanvitto, D.; Passaseo, A.; Gigli, Giuseppe; Cuscunà, Massimo

doi:10.1021/acs.jpcc.6b03963

Cited by 52 publications

(51 citation statements)

References 57 publications

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“…Silverhasbeenusedinartandjewelleryfor millennia, and it is nowadays ubiquitously adopted for technologically important devices such as catalysts, [1] electric equipment, [2] and localized surface-plasmon nanochips. [3] These applications share ac ommon problem:s ilver corrosion, where the early stage is called tarnishing.A gc orrosion is critical in the electronics industry, [2][3][4] since Ag is used in printed circuit boards (PCBs) as af inish material and both to build electronic components and to assemble them on PCBs. Because PCBs are used in applications where they are exposed to air, Ag-corrosion-related failures are not uncommon [4] and represent an economic burden as well as aperformance and reliability issue.…”

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confidence: 99%

Silver Tarnishing Mechanism Revealed by Molecular Dynamics Simulations

Saleh

Sanvito

2019

Angew Chem Int Ed

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The mechanism of silver-oxygen and silver-sulfur reactions is revealed by means of molecular dynamics simulations,performed with reactive force fields purposely built and extensively tested against quantum-chemical results.D ifferent reaction mechanisms and rates for Ag-O and Ag-S emerge. This study solves the long-lasting question why silver exposed to the environment is strongly vulnerable to sulfur corrosion (tarnishing) but hardly reacts with O 2 ,d espite the thermodynamic prediction that both oxide and sulfide should form. The reliability of the simulation results is confirmed by the agreement with am ultitude of experimental results from the literature.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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mentioning

confidence: 99%

Silver Tarnishing Mechanism Revealed by Molecular Dynamics Simulations

Saleh

Sanvito

2019

Angew Chem Int Ed

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“…To protect the silver nanostructures from oxidizing, a 2 nm thick Al 2 O 3 layer was deposited in a low temperature atomic layer deposition process at 50 °C . Another option to prevent oxidation was to apply a self‐assembled monolayer of hexanethiols …”

Section: Methodsmentioning

confidence: 99%

High‐Efficiency, Extreme‐Numerical‐Aperture Metasurfaces Based on Partial Control of the Phase of Light

Hail

Poulikakos

Eghlidi

2018

Advanced Optical Materials

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add phase shifts ranging from 0-2π to the electric field at the interface via nanoscale scatterers. [4] However, refracting light to large angles requires the ability to introduce large phase differences over a short distance. In single-layer metasurfaces, these phase gradients are introduced by varying the resonance phase or the Pancharatnam-Berry (PB) phase. While the former method uses V-shaped plasmonic antenna modes [4,5,11] or Mie-type scattering of high-index dielectric structures, [12,13] the latter employs simple (rod-shaped) plasmonic antennas [14,15] or propagation through dielectric structures [8,16] (see Figure 1a,b). Recently, metasurfaces based on low-loss dielectric structures have demonstrated high anomalous transmission efficiencies. [12,16,17] However, in plasmonic metasurfaces, the required polarization conversion intrinsically limits the corresponding transmission efficiency of these surfaces to below 25%, [18] with the largest measured efficiency of 15% for focusing light. [19] Moreover, in both plasmonic and dielectric surfaces, it is challenging to efficiently introduce large phase gradients for large angle refraction, since the scatterer size and near-field interactions restrict the distance between phase-shifting elements. [20] Diffractive flat optical elements, while functionally similar, have their own working principle and limitations for large angle deflection or focusing (multiple real and virtual focal points, limited efficiency). [21][22][23] In this work, we show how a high degree of wavefront manipulation can be achieved with only a partial control of the phase (i.e., less than 0-2π, see Figure 1c,d). With this relaxed phase requirement, the choice of scatterers is less restrictive. As a result, more compact scatterers, for example, simple nanorods (Figure 1c), with reduced near-field interactions can be used to introduce large phase gradients by placing them at smaller distances from each other. This allows, in principle, accessing phase gradients for anomalous refraction at extreme angles, up to 90° in air or in dielectrics, otherwise not feasible with full phase coverage surfaces. [24] Furthermore, these metasurfaces do not rely on polarization conversion and can generate scattered light with the same polarization as the impinging light (i.e., the co-polarized beam). In contrast to single-layer plasmonic phase gradient surfaces, there is thus no limitation in efficiency due to a polarization conversion. [18] One period of a phase gradient metasurface with partial phase High-quality flat optical elements require efficient light deflection to large angles and over a wide wavelength spectrum. Although phase gradient metasurfaces achieve this by continuously adding phase shifts in the range of 0-2π to the electric field with subwavelength-sized scatterers, their performance is limited by the spatial resolution of phase modulation at the interface. Here, a new class of metasurfaces is introduced, where the phase shifts cover less than the full 0-2π range, offering significant adva...

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“…Silver has been used in art and jewellery for millennia, and it is nowadays ubiquitously adopted for technologically important devices such as catalysts, electric equipment, and localized surface‐plasmon nanochips . These applications share a common problem: silver corrosion, where the early stage is called tarnishing.…”

Section: Figurementioning

confidence: 99%

“…These applications share a common problem: silver corrosion, where the early stage is called tarnishing. Ag corrosion is critical in the electronics industry, since Ag is used in printed circuit boards (PCBs) as a finish material and both to build electronic components and to assemble them on PCBs. Because PCBs are used in applications where they are exposed to air, Ag‐corrosion‐related failures are not uncommon and represent an economic burden as well as a performance and reliability issue.…”

Section: Figurementioning

confidence: 99%

Silver Tarnishing Mechanism Revealed by Molecular Dynamics Simulations

Saleh

Sanvito

2019

Angewandte Chemie

View full text Add to dashboard Cite

The mechanism of silver–oxygen and silver–sulfur reactions is revealed by means of molecular dynamics simulations, performed with reactive force fields purposely built and extensively tested against quantum‐chemical results. Different reaction mechanisms and rates for Ag–O and Ag–S emerge. This study solves the long‐lasting question why silver exposed to the environment is strongly vulnerable to sulfur corrosion (tarnishing) but hardly reacts with O2, despite the thermodynamic prediction that both oxide and sulfide should form. The reliability of the simulation results is confirmed by the agreement with a multitude of experimental results from the literature.

show abstract

Nanoscale Study of the Tarnishing Process in Electron Beam Lithography-Fabricated Silver Nanoparticles for Plasmonic Applications

Cited by 52 publications

References 57 publications

Silver Tarnishing Mechanism Revealed by Molecular Dynamics Simulations

Silver Tarnishing Mechanism Revealed by Molecular Dynamics Simulations

High‐Efficiency, Extreme‐Numerical‐Aperture Metasurfaces Based on Partial Control of the Phase of Light

Silver Tarnishing Mechanism Revealed by Molecular Dynamics Simulations

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