Monocrystalline Silver Research Articles

Interfacial Second-Harmonic Generation via Superposition of Symmetries in a Double-Resonance-Enhanced Plasmonic Nanocavity.

Second-harmonic generation (SHG) has rapidly advanced with the miniaturization of on-chip devices and has found many applications, including optical frequency conversion, nonlinear imaging, and quantum technology. However, owing to the obvious phase-matching constraints involved in nonlinear optical interactions in bulk crystals and the decrease in the length and strength of nonlinear interactions in nanophotonic and surface/interface systems, improving the SHG efficiency and manipulating its optical properties at the nanoscale are challenging tasks. Herein, a monocrystalline silver microplate and nanocube-coupled nanocavity with double-resonance plasmonic modes and an ultrasmall gap were constructed, resulting in efficiently enhanced SHG. In particular, the SHG from the silver microplate (111) is polarization-dependent, and the anisotropy of the SHG in the plasmonic nanocavity can be further controlled via the superposition of symmetries at the interface and plasmonic waveguide-cavity modes. The interfacial SHG provides technology for developing lattice surface atomic arrangement and nanostructure rapid characterization, nonlinear light sources, and on-chip nonlinear nanophotonic devices.

Crystallinity as a factor of SERS stability of silver nanoparticles formed by Ar+ irradiation

The plasmonic sensors based on silver nanoparticles are limited in application due to their relatively fast degradation in the ambient atmosphere. The technology of ion-beam modification for the creation of monocrystalline silver nanoparticles (NPs) with stable plasmonic properties will expand the application of silver nanostructures. In the present study, highly-stable monocrystalline NPs were formed on the basis of a thin silver film by low-energy ion irradiation. Combined with lithography, this technique allows the creation of nanoparticle ensembles in variant forms. The characterization of the nanoparticles formed by ion-beam modification showed long-term outstanding for Ag nanoparticles stability of their plasmonic properties due to their monocrystalline structure. According to optical spectroscopy data, the reliable plasmonic properties in the ambient atmosphere are preserved for up to 39 days. The mapping of crystal violet dye via surface-enhanced Raman spectroscopy (SERS) revealed a strong amplification factor sustaining at least thrice as long as the one of similarly sized polycrystalline silver NPs formed by annealing. The plasmonic properties sustain more than a month of storage in the ambient atmosphere. Thus, ion-beam modification of silver film makes it possible to fabricate NPs with stable plasmonic properties and form clusters of NPs for sensor technology and SERS applications.

On the slip burst amplitude cutoff in dislocation-rich microcrystals

The plastic deformation of small-scale face-centered cubic metals exhibits intermittent slip burst events that appear on stress-strain curves as sudden strain jumps and/or load drops. These events are generally attributed to the avalanche-like cooperative motion of several dislocations, or to the repeated activation of single-arm dislocation sources. We explore the influence of the load train compliance on the amplitude of such slip bursts by testing in tension microcast monocrystalline silver specimens 3.4 µm in diameter under two different load-train compliance conditions. Resulting data show that the statistics of slip burst amplitudes in the higher-amplitude, cutoff, regime depend on the compliance of the total testing load train, whereas the stress drop distributions do not. We propose a mechanism and derive an expression for the slip burst cutoff by assuming that higher-intensity slip bursts are driven by the stochastic activation of dislocation sources induced by forest dislocation motion. The resulting expression accounts for the influence of the load train compliance on the statistics of larger-amplitude slip bursts, resembles the expression for the slip amplitude cutoff that was proposed by Zaiser and Nikitas, and agrees with observed cutoff amplitude data from this and earlier studies on microcast FCC single crystals tested in tension.

Selective Mapping of Tip-Launched Near-Field Scattering of Surface Plasmon Polaritons for Retrieving Dispersion Relation in Silver Nanoflakes

Scattering-type near-field scanning optical microscopy (s-NSOM) has been beneficial for observing various nano-optical phenomena by overcoming the spatial resolution diffraction limit, creating optical dispersion, and investigating optoelectronic systems. We used s-NSOM on mono-crystalline silver nanoflakes to selectively decompose tip-launched surface plasmon polariton (SPP) signals and suppress the undesired geometrical effects arising from the silver nanoflakes and s-NSOM tips. Comparing the Fourier transform analysis data from all the edges of silver nanoflakes, we successfully identified the momentum of tip-launched SPPs. We have conducted energy spectral measurements on mono-crystalline silver nanoflakes and applied a geometry-independent factor: tip-launched SPP. We neglected the additional complex contribution from various shapes of the nanoflakes in the visible-near infrared regime. These experimentally obtained momentums of SPPs have a good agreement with analytical calculations. We observed that the propagation of the SPP increases with a decrease in excitation energy even without additional destructive fabrications on the surface, although the surface quality of silver nanoflakes is affected by dirt and oxidation. This study provides a precise interpretation of the experimental studies on the various polariton studies using s-NSOM.

Simultaneous Detection of Spin and Orbital Angular Momentum of Light through Scattering from a Single Silver Nanowire

AbstractIn recent times the spin angular momentum (SAM) and orbital angular momentum (OAM) of light have gained prominence because of their significance in optical communication systems, micromanipulation, and sub‐wavelength position sensing. To this end, simultaneous detection of SAM and OAM of light beam is one of the important topics of research from both application and fundamental spin‐orbit interaction (SOI) point of view. While interferometry and metasurface based approaches have been able to detect the states, the presented approach involves elastic scattering from a monocrystalline silver nanowire for the simultaneous detection of SAM and OAM state of a circularly polarized Laguerre–Gaussian beam. By employing Fourier plane (FP) microscopy, the transmitted scattered light intensity distribution in the FP is analyzed to reconstruct the SAM and OAM state unambiguously. The SAM and OAM induced transverse energy flow as well as the polarization dependent scattering characteristics of the nanowire is investigated to understand the detection mechanism. This method is devoid of complex nanofabrication techniques and to the authors' knowledge, is a first example of single nano‐object based simultaneous SAM and OAM detection. The study will further the understanding of SOI effects and can be useful for on‐chip optical detection and manipulation.

Highly-efficient electrically-driven localized surface plasmon source enabled by resonant inelastic electron tunneling

On-chip plasmonic circuitry offers a promising route to meet the ever-increasing requirement for device density and data bandwidth in information processing. As the key building block, electrically-driven nanoscale plasmonic sources such as nanoLEDs, nanolasers, and nanojunctions have attracted intense interest in recent years. Among them, surface plasmon (SP) sources based on inelastic electron tunneling (IET) have been demonstrated as an appealing candidate owing to the ultrafast quantum-mechanical tunneling response and great tunability. However, the major barrier to the demonstrated IET-based SP sources is their low SP excitation efficiency due to the fact that elastic tunneling of electrons is much more efficient than inelastic tunneling. Here, we remove this barrier by introducing resonant inelastic electron tunneling (RIET)—follow a recent theoretical proposal—at the visible/near-infrared (NIR) frequencies and demonstrate highly-efficient electrically-driven SP sources. In our system, RIET is supported by a TiN/Al2O3 metallic quantum well (MQW) heterostructure, while monocrystalline silver nanorods (AgNRs) were used for the SP generation (localized surface plasmons (LSPs)). In principle, this RIET approach can push the external quantum efficiency (EQE) close to unity, opening up a new era of SP sources for not only high-performance plasmonic circuitry, but also advanced optical sensing applications.

Nanocube Imprint Lithography.

In recent years, imprint lithography has emerged as a promising patterning technique capable of high-speed and volume production. In this work, we report highly reproducible one-step printing of metal nanocubes. A dried film of monocrystalline silver cubes serves as the resist, and a soft polydimethylsiloxane stamp directly imprints the final pattern. The use of atomically smooth and sharp faceted nanocubes facilitates the printing of high-resolution and well-defined patterns with face-to-face alignment between adjacent cubes. It also permits digital control over the line width of patterns such as straight lines, curves, and complex junctions over an area of several square millimeters. Single-particle lattices as well as three-dimensional nanopatterns are also demonstrated with an aspect ratio up to 5 in the vertical direction. The high-fidelity nanocube patterning combined with the previously demonstrated epitaxial overgrowth can enable curved (single) crystals from solution at room temperature or highly efficient transparent conductors.

Underpotential‐Assisted Electrodeposition of Highly Crystalline and Smooth Thin Film of Bismuth

AbstractIn this work, the electrodeposition of smooth bismuth thin films was investigated. Bismuth is known for its peculiar magnetic, thermal and electrical properties but the deposition of a uniform and flat film, which are features required for its application in electronic devices, is not trivial. We investigated the morphology of Bi film electrodeposited at increasing overpotential on a monocrystalline silver electrode. We found that the presence of an underpotential deposition (UPD) layer, previously deposited on the surface, drives the overpotential deposition to a smoother growth. The samples were investigated by means of different techniques: atomic force microscopy (AFM) and scanning electron microscopy combined with energy dispersive X‐ray spectroscopy (SEM‐EDS) to study the morphology, X‐ray photoemission spectroscopy (XPS) to assess the composition and X‐ray diffraction spectroscopy (XRD) to check the crystallinity. We also found an unexpected form birefringence behaviour, which has been preliminary investigated with cross polarized light microscopy (CPL).

Selective embedment of silver nanocrystals into spatially segregated domains in thin polymer films for controlled fabrication of functional nanocomposites.

Fabrication of polymer-nanoparticle nanocomposites typically relies on mixing nanoparticle and polymer solutions, which renders little control over nanoparticle incorporation, and homogeneity of the resulting composite material. This work focuses on the thermally induced embedment of monocrystalline silver nanocubes (AgNCs) into polymer surfaces. The AgNCs are initially deposited through a Langmuir approach onto films of immiscible blended polymer films, which allows fine control over nanoparticle density and aggregation state. This nanoparticle/polymer composite is then heated above the glass transition temperature (Tg) of a polymer, which initiates the irreversible embedding of the AgNCs. The immiscible ternary polymer films featured discrete domains (with different Tgs), which were altered by changing the amount of polystyrene, poly(2-vinylpyridine) and poly(methyl methacrylate) within the polymer solution. The Tg dependence of the embedding process allowed the selective embedment of AgNCs into discrete polymer domains. The process was monitored in real time by using spatially separated hybrid plasmon modes, through peak shifts observed in a UV-vis spectrum. Enhanced surface confinement was observed for certain tripolymer films when compared to polystyrene–AgNC nanocomposites, due to changes in the surface energy within the blend. This work brings interesting insight on nanoparticle-blended polymer interactions and provides a fairly universal approach for the fabrication of these polymer–metal nanoparticle nanocomposites, which is of particular interest in fields that require fine control over nanoparticle incorporation within segregated polymer domains.

Extremely Confined Gap-Plasmon Waveguide Modes Excited by Nitrogen-Vacancy Centers in Diamonds

Quantum emitters with high emission rates and efficiently coupled to optical waveguides are in demand for various applications in quantum information technologies. Accurate positioning of a quantum emitter within a strongly confined gap-plasmon waveguide (GPW) mode would allow one to significantly enhance the decay rate and efficiency of channeling of emitted photons into the waveguide mode. Here, we present experimental results on the GPW mode excitation in a gap between a monocrystalline silver nanowire and a monocrystalline silver flake by using a single nitrogen-vacancy center in a nanodiamond. The coupled systems containing a nanodiamond and the structure supporting the GPW mode are created by a combination of electron beam lithography and nanomanipulation with an atomic force microscope (AFM). In these systems, we find decay rate enhancements of up to ∼50 and the efficiency of channeling of photons into the GPW mode of up to 82%, resulting in an exceptionally high figure-of-merit of 212 for the emit...

Highly stable silver nanoparticles for SERS applications

Plasmonics sensor configurations utilizing localized plasmon resonances in silver nanostructures typically suffer from rapid degradation of silver in ambient atmospheric conditions. In this work, we report on the fabrication and detailed characterization of ensembles of monocrystalline silver nanoparticles (NPs), which exhibit a long-term stability of optical properties under ambient conditions without any protective treatments. Ensembles with different densities (surface coverages) of size-selected NPs (diameters from 12.5 to 24 nm) on quartz substrates are fabricated using the cluster-beam technique and characterized by linear spectroscopy, surface-enhanced Raman scattering microscopy as well as transmission electron, helium-ion and atomic force microscopies. It is found that the fabricated ensembles of monocrystalline silver NPs preserve their plasmonic properties (monitored with optical spectroscopy) and strong field enhancements (revealed by surface enhanced Raman spectroscopy) at least 5 times longer as compared to chemically synthesized silver NPs with similar sizes. The obtained results are of high practical relevance for the further development of sensors, resonators and metamaterials utilizing plasmonic properties of silver NPs.

Degradation of the chemotherapy drug 5-fluorouracil on medical-grade silver surfaces

The degradation of the chemotherapy drug 5-fluorouracil by a non-pristine metal surfaces is studied. Using density functional theory, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy we show that the drug is entirely degraded by medical-grade silver surfaces, already at body temperature, and that all of the fluorine has left the molecule, presumably as HF. Remarkably, this degradation is even more severe than that reported previously for 5-fluorouracil on a pristine monocrystalline silver surface (in which case 80% of the drug reacted at body temperature) [1].We conclude that the observed reaction is due to a reaction pathway, driven by H to F attraction between molecules on the surface, which results in the direct formation of HF; a pathway which is favoured when competing pathways involving reactive Ag surface sites are made unavailable by environmental contamination. Our measurements indicate that realistically cleaned, non-pristine silver alloys, which are typically used in medical applications, can result in severe degradation of 5-fluorouracil, with the release of HF – a finding which may have important implications for the handling of chemotherapy drugs.

Highly Stable Monocrystalline Silver Clusters for Plasmonic Applications.

Plasmonic sensor configurations utilizing localized plasmon resonances in silver nanostructures typically suffer from the rapid degradation of silver under ambient atmospheric conditions. In this work, we report on the fabrication and detailed characterization of ensembles of monocrystalline silver nanoparticles (NPs), which exhibit a long-term stability of optical properties under ambient conditions without any protective treatments. Ensembles with different densities (surface coverages) of size-selected NPs (mean diameters of 12.5 and 24 nm) on quartz substrates are fabricated using the cluster-beam technique and characterized by linear spectroscopy, two-photon-excited photoluminescence, surface-enhanced Raman scattering microscopy, and transmission electron, helium ion, and atomic force microscopies. It is found that the fabricated ensembles of monocrystalline silver NPs preserve their plasmonic properties (monitored with optical spectroscopy) and strong field enhancements (revealed by surface-enhanced Raman spectroscopy) at least 5 times longer as compared to chemically synthesized silver NPs with similar sizes. The obtained results are of high practical relevance for the further development of sensors, resonators, and metamaterials utilizing the plasmonic properties of silver NPs.

Ultrabright Linearly Polarized Photon Generation from a Nitrogen Vacancy Center in a Nanocube Dimer Antenna.

We demonstrate an exceptionally bright photon source based on a single nitrogen-vacancy center (NV center) in a nanodiamond (ND) placed in the nanoscale gap between two monocrystalline silver cubes in a dimer configuration. The system is operated near saturation at a stable photon rate of 850 kcps, while we further achieve strongly polarized emission and high single photon purity, evident by the measured autocorrelation with a g(2)(0) value of 0.08. These photon source features are key parameters for quantum technological applications, such as secure communication based on quantum key distribution. The cube antenna is assembled with an atomic force microscope, which allows us to predetermine the dipole orientation of the NV center and optimize cube positioning accordingly, while also tracking the evolution of emission parameters from isolated ND to the one- and two-cube configuration. The experiment is well described by finite element modeling, assuming an instrinsic quantum efficiency of 0.35. We attribute the large photon rate of the assembled photon source, to increased quantum efficiency of the NV center and high antenna efficiency.

Monocrystalline Nanopatterns Made by Nanocube Assembly and Epitaxy.

Monocrystalline materials are essential for optoelectronic devices such as solar cells, LEDs, lasers, and transistors to reach the highest performance. Advances in synthetic chemistry now allow for high quality monocrystalline nanomaterials to be grown at low temperature in solution for many materials; however, the realization of extended structures with control over the final 3D geometry still remains elusive. Here, a new paradigm is presented, which relies on epitaxy between monocrystalline nanocube building blocks. The nanocubes are assembled in a predefined pattern and then epitaxially connected at the atomic level by chemical growth in solution, to form monocrystalline nanopatterns on arbitrary substrates. As a first demonstration, it is shown that monocrystalline silver structures obtained with such a process have optical properties and conductivity comparable to single-crystalline silver. This flexible multiscale process may ultimately enable the implementation of monocrystalline materials in optoelectronic devices, raising performance to the ultimate limit.

Pancharatnam–Berry Phase Manipulating Metasurface for Visible Color Hologram Based on Low Loss Silver Thin Film

This study demonstrates visible color hologram using a plasmonic metasurface. The metasurface is fabricated by perforating nanoslits in a 50 nm thick monocrystalline silver film that is ultrasmooth and has ultralow loss compared to conventional polycrystalline silver films commonly used in plasmonics. The designed plasmonic hologram is the thinnest metasurface hologram operating in transmission mode to the best of our knowledge. Holograms of three individual component colors (red, green, and blue) are demonstrated in transmission mode, and a scheme for generating polychromatic hologram is illustrated. By adjusting the slit dimensions and orientation, the phase of a visible spectrum light can be controlled, paving the way to applications of ultracompact polychromatic plasmonic metasurfaces for advanced light manipulation.

Bio-mediated silver nanoparticle synthesis: mechanism and microbial inactivation

ABSTRACTEven though plenty of literature is available on the biosynthesis of metal nanoparticles, there are serious lacunae on the mechanisms of their formation. In the present study, the mechanism of formation of mono-crystalline silver nanoparticles using a fruit extract of the ornamental tree Thevetia peruviana is emphasized, i.e. how the pH of the reaction mixture affected reaction kinetics and size of the nanoparticles. The facilitation of formation of Ag2O at higher pH resulted in a faster rate of particle formation. The diameter of the bare particles at neutral pH determined by field emission scanning electron microscopy and the hydrodynamic diameter determined by dynamic light scattering were 53 and 104 nm, respectively. The silver nanoparticles exhibited good inactivation of Escherichia coli due to participation of free radicals as evidenced by electron spin resonance spectroscopy.

Enhanced Electronic Properties of Pt@Ag Heterostructured Nanoparticles

Platinum coated by silver nanoparticles was synthesized, which displays a unique structure where polycrystalline platinum particles are completely encapsulated in continuous monocrystalline silver shells. These particles display accentuated electronic properties, where the silver shells gain electron density from the platinum cores, imparting enhanced properties such as oxidation resistance. This electron transfer phenomenon is highly interfacial in nature, and the degree of electron transfer decreases as the thickness of silver shell increases. The nanoparticle structure and electronic properties are studied and the implication to creating sensing probes with enhanced robustness, sensitivity and controllable plasmonic properties is discussed.

Simulation of electromigration effects on voids in monocrystalline Ag films

We developed a three-dimensional, atomistic model based on the kinetic Monte Carlo method to investigate how voids penetrating a monocrystalline silver film are affected by electromigration. The simulations show a clear dependency between the nonequilibrium shape of the voids and the crystallographic orientation of the film. The simulation results are in accordance with experimental results on bicrystalline silver wires.

Simulation of Electromigration Effects on Voids in Monocrystalline Ag

ABSTRACTUnderstanding electromigration effects in monocrystalline metal becomes of increasing interest with decreasing width and thickness of interconnects. Using a three-dimensional, atomistic model based on the Kinetic Monte Carlo method, we investigate voids in monocrystalline silver. Subject to electromigration, voids begin to drift. We show that the drift velocity not only depends on the void size, but also on the electromigration force direction, with respect to the crystallographic orientation.