Interparticle Separation Research Articles

Reversible Modulation of Plasmonic Coupling of Gold Nanoparticles Confined within Swellable Polymer Colloidal Spheres.

Dynamic optical modulation in response to stimuli provides exciting opportunities for designing novel sensing, actuating, and authentication devices. Here, we demonstrate that the reversible swelling and deswelling of crosslinked polymer colloidal spheres in response to pH and temperature changes can be utilized to drive the assembly and disassembly of the embedded gold nanoparticles (AuNPs), inducing their plasmonic coupling and decoupling and, correspondingly, color changes. The multi-responsive colloids are created by depositing a monolayer of AuNPs on the surface of resorcinol-formaldehyde (RF) nanospheres, then overcoating them with an additional RF layer, followed by a seeded growth process to enlarge the AuNPs and reduce their interparticle separation to induce significant plasmonic coupling. This configuration facilitates dynamic modulation of plasmonic coupling through the reversible swelling/deswelling of the polymer spheres in response to pH and temperature changes. The rapid and repeatable transitions between coupled and decoupled plasmonic states of AuNPs enable reversible color switching when the polymer spheres are in colloidal form or embedded in hydrogel substrates. Furthermore, leveraging the photothermal effect and stimuli-responsive plasmonic coupling of the embedded AuNPs enables the construction of hybrid hydrogel films featuring switchable anticounterfeiting patterns, showcasing the versatility and potential of this multi-stimuli-responsive plasmonic system.

Multi-wavelength and broadband plasmonic switching with V-shaped plasmonic nanostructures on a VO2 coated plasmonic substrate

In this paper, periodic arrays of identical V-shaped gold nanostructures and variable V-shaped gold nanostructures are designed on top of a gold-coated silicon dioxide (SiO2) substrate with a thin spacer layer of vanadium dioxide (VO2) to realize multi-wavelength and broadband plasmonic switches, respectively. The periodic array of identical V-shaped nanostructures (IVNSs) with small inter-particle separation leads to coupled interactions of the elementary plasmons of a V-shaped nanostructure (VNS), resulting in a hybridized plasmon response with two longitudinal plasmonic modes in the reflectance spectra of the proposed switches when the incident light is polarized in the x-direction. The x-direction is oriented along the axis that joins the V-junctions of all VNSs in one unit cell of the periodic array. On exposure to temperature, electric field, or optical stimulus, the VO2 layer transforms from its monoclinic semiconducting state to its rutile metallic state, leading to an overall change in the reflectance spectra obtained from the proposed nanostructures and resulting in an efficient multi-wavelength switching action. Finite difference time domain modelling is employed to demonstrate that an extinction ratio (ER) >12 dB at two wavelengths can be achieved by employing the proposed switches based on periodic arrays of IVNSs. Further, plasmonic switches based on variable V-shaped nanostructures—i.e. multiple VNSs with variable arm lengths in one unit cell of a periodic array—are proposed for broadband switching. In the broadband operation mode, we report an ER >5 dB over an operational wavelength range >1400 nm in the near-IR spectral range spanning over all optical communication bands, i.e. the O, E, S, C, L and U bands. Further, it is also demonstrated that the wavelength of operation for these switches can be tuned by varying the geometrical parameters of the proposed switches. These switches have the potential to be employed in communication networks where ultrasmall and ultrafast switches with multi-wavelength operation or switching over a wide operational bandwidth are inevitably required.

Direct measurement of repulsive and attractive pair potentials using pairs of optical traps

We present a technique for measuring the interactions between pairs of colloidal particles in two optical traps. This method is particularly suitable for measuring strongly attractive potentials, an otherwise challenging task. The interaction energy is calculated from the distribution of inter-particle separations by accounting for the contribution from the optical traps with arbitrary trap profiles. The method is simple to implement and applicable to different types of pair potentials and optical trapping geometries. We apply the method to measure dipolar pair interactions in experiments with paramagnetic colloids in external magnetic fields. We obtain consistent and accurate results in all regimes, from strongly attractive to repulsive potentials. By means of computer simulations, we demonstrate that the proposed method can be successfully applied to systems with complex pair interactions characterized by multiple attractive and repulsive regimes, which are ubiquitous in soft and biological matter.

Cavity-mediated long-range interactions in levitated optomechanics

AbstractThe ability to engineer cavity-mediated interactions has emerged as a powerful tool for the generation of non-local correlations and the investigation of non-equilibrium phenomena in many-body systems. Levitated optomechanical systems have recently entered the multiparticle regime, which promises the use of arrays of strongly coupled massive oscillators to explore complex interacting systems and sensing. Here we demonstrate programmable cavity-mediated interactions between nanoparticles in vacuum by combining advances in multiparticle optical levitation and cavity-based quantum control. The interaction is mediated by photons scattered by spatially separated particles in a cavity, resulting in strong coupling that is long-range in nature. We investigate the scaling of the interaction strength with cavity detuning and interparticle separation and demonstrate the tunability of interactions between different mechanical modes. Our work will enable the exploration of many-body effects in nanoparticle arrays with programmable cavity-mediated interactions, generating entanglement of motion, and the use of interacting particle arrays for optomechanical sensing.

Conducting Gold Nanoparticle Films via Sessile Drop Evaporation.

The deposit patterns obtained from the evaporation of drops containing insoluble solute particles are vital for several technologies, including inkjet printing and optical and electronic device manufacturing. In this work, we consider the evaporation of an aqueous reaction mixture typically used for gold nanoparticle (AuNP) synthesis. The patterns obtained from the evaporation-driven assembly of in situ generated AuNPs are studied using optical microscopy and SEM analyses. The evaporation of drops withdrawn at different reaction times is found to significantly influence the distribution of AuNPs in the dried patterns. The evolution of the deposit patterns is also explored by drying multiple drops on the solid substrate, wherein a drop of a fresh reaction mixture is introduced over the deposit pattern left by the evaporation of the drop dispensed at an earlier time. Using quantitative image analysis, we show that the interparticle separation between the AuNPs in the dried patterns left on the solid substrate decreases when the number of drops is increased. We find optimal conditions to achieve solid-supported AuNP films, wherein the particles are in close physical contact, leading to a conducting deposit. The current through the AuNP deposit is found to increase with increase in the number of drops due to evaporation-driven self-assembly of AuNPs into branch-like structures with reduced interparticle separation. In addition, we also show that it is possible to produce conducting AuNP deposits by drying multiple drops withdrawn from the same reaction mixture. The evaporation-driven assembly of the in situ grown nanoparticles from a reaction mixture presented in this work can be further exploited in optical and electronic device fabrication.

Soft colloidal monolayers with reflection symmetry through confined drying.

Colloidal monolayers serve as fundamental building blocks in fabricating diverse functional materials, pivotal for surface modifications, chemical reactivity, and controlled assembly of nanoparticles. In this article, we report the formation of colloidal monolayers generated by drying an aqueous droplet containing soft colloids confined between two hydrophilic parallel plates. The analysis of the kinetics of evaporation in this confined mode showed that: (i) for a significant portion of the drying time, the drops adopt a catenoid configuration; (ii) in the penultimate stage of drying, the catenoid structure undergoes division into two daughter droplets; (iii) the three-phase contact line remains pinned at a specific location while it continuously slips at all other locations. The interplay between interface-assisted particle deposition onto the solid substrate and the time evolution of particle concentration within the droplet during evaporation results in unique microstructural features in the deposited patterns. Notably, these deposit patterns exhibit reflection symmetry. The microstructural features of the dried deposits are further quantified by calculating the particle number density, inter-particle separation, areal disorder parameter, and bond orientational order parameter. The variation of these parameters for deposits formed under different conditions, such as by altering the spacing between parallel plates and the concentration of microgel particles in the droplet, is discussed.

Computational investigation of the effects of polymer grafting on the effective interaction between silica nanoparticles in water.

Understanding and control of the effective interaction between nanoscale building blocks (colloids or nanoparticles) dispersed in a solvent is an important prerequisite for the development of bottom-up design strategies for soft functional materials. Here, we have employed all-atom molecular dynamics simulations to investigate the impact of polymer grafting on the solvent-mediated effective interaction between the silica nanoparticles (Si-NPs) in water, and in turn, on its bulk structural and thermodynamic properties. We found that the nature of the short grafting polymers [characterized by their interaction with water (hydrophobicity or hydrophilicity) and molecular weight] has a profound effect on the range and strength of the effective interaction between the Si-NPs. The hydrophobic polymer [such as polyethylene (PE)]-grafting of Si-NP gives rise to a more attractive interaction between the Si-NPs compared to the hydrophilic polymer [such as polyethylene glycol (PEG)] and non-grafted cases. This study further provides fundamental insights into the molecular origin of the observed behavior of the effective pair interactions between the grafted Si-NPs. For PE-grafted Si-NPs, the confined water (water inside the cavity formed by a pair of Si-NPs) undergoes a partial dewetting transition on approaching below a critical inter-particle separation leading to a stronger attractive interaction. Furthermore, we report that the effective attraction between the PE-grafted Si-NPs can be reliably controlled by changing the grafting PE density. We have also investigated the bulk structural and thermodynamic behavior of the coarse-grained Si-NP system where the particles interact via effective interaction in the absence of water. We believe that the insights gained from this work are important prerequisites for formulating rational bottom-up design strategies for functional materials where nano- (or, colloidal) particles are the building blocks.

Shape anisotropy induced jamming of nanoparticles at liquid interfaces: a tensiometric study.

The intersection of nanotechnology and interfacial science has opened up new avenues for understanding complex phenomena occurring at liquid interfaces. The assembly of nanoparticles at liquid/liquid interfaces provides valuable insights into their interactions with fluid interfaces, essential for various applications, including drug delivery. In this study, we focus on the shape and concentration effects of nanoscale particles on interfacial affinity. Using pendant drop tensiometry, we monitor the real-time interfacial tension between an oil droplet and an aqueous solution containing nanoparticles. We measure two different types of nanoparticles: spherical gold nanoparticles (AuNPs) and anisotropic gold nanorods (AuNRs), each functionalized with surfactants to facilitate interaction at the interface. We observe that the interface equilibrium behaviour is mediated by kinetic processes, namely, diffusion, adsorption and rearrangement of particles. For anisotropic AuNRs, we observe shape-induced jamming of particles at the interface, as evidenced by their slower diffusivity and invariant rearrangement rate. In contrast, the adsorption of spherical AuNPs is dynamic and requires more time to reach equilibrium, indicating weaker interface affinity. By detailed analysis of the interfacial tension data and interaction energy calculations, we show that the anisotropic particle shape achieves stable equilibrium inter-particle separation compared to the isotropic particles. Our findings demonstrate that anisotropic particles are a better design choice for drug delivery applications as they provide better affinity for fluid interface attachment, a crucial requirement for efficient drug transport across cell membranes. Additionally, anisotropic shapes can stabilize interfaces at low particle concentrations compared to isotropic particles, thus minimizing side effects associated with biocompatibility and toxicity.

Quantum-mechanical four-body versus semi-classical three-body theories for double charge exchange in collisions of fast alpha particles with helium targets

AbstractWithin the two-channel distorted wave second-order perturbative theoretical formalism, we study capture of both electrons from helium-like targets by heavy nuclei as projectiles at intermediate and high impact energies. The emphasis is on the four-body single-double scattering (SDS-4B) method and the three-body continuum distorted wave impact parameter method (CDW-3B-IPM). The SDS-4B method deals with the full quantum-mechanical correlative dynamics of all the four interactively participating particles (two electrons, two nuclei). The CDW-3B-IPM is a semi-classical three-body independent particle model (one electron, two nuclei), using a combinatorial calculus to describe double capture by a product of two uncorrelated probabilities, integrated over impact parameters. Both theories share a common feature in having altogether two electronic full Coulomb continuum wave functions. One such function is centered on the projectile nucleus in the entrance channel, whereas the other is centered on the target nucleus in the exit channel. These two methods satisfy the correct initial and final Coulomb boundary conditions in the asymptotic region of scattering, at infinitely large inter-particle separations. Yet, it is presently demonstrated that most of the available experimental data on total cross sections for the double capture from helium by alpha particles distinctly favor the SDS-4B method. This is especially true at intermediate energies. Such energies are critically important in versatile applications under the general umbrella of ion transport in matter, including thermonuclear fusion (plasma physics) and ion therapy (medicine).

Nanostructured anti-reflection coating for absorption enhancement in perovskite silicon tandem solar cells

Perovskite-silicon tandem solar cells have captured the attention of the solar cell research community due to the advantages of perovskites, such as, an easy fabrication process using sol-gel methods and silicon bottom cells that can be fabricated using well-established fabrication techniques. The present study discusses the design, optimization, and numerical analysis related to the role of nanostructured anti-reflection coating design for perovskite (MAPbI3) silicon tandem solar cells. In the design, the top cell is taken as MAPbI3 and the bottom cell is C-silicon. The anti-reflection coating is designed with SiO2 nanoparticles embedded in ITO. These nanostructured top anti-reflection coating results are compared with its planar top cell counterpart. SiO2 nanoparticle diameter and interparticle separation are optimized to get maximum absorption in the top cell. Upon optimization, it was found that a design having SiO2 nanoparticles with a diameter of 60 nm and no interparticle separation showed the most reduction in reflection, which in turn led to an increase in absorption in the top cell. The proposed structure enhances current density by 8.3% over the planar cell. This top cell current is matched to the bottom silicon thickness. These findings were validated using Mie scattering and the Bruggmann effective medium approximation.

Tuning perovskite nanocrystal superlattices for superradiance in the presence of disorder.

The cooperative emission of interacting nanocrystals is an exciting topic fueled by recent reports of superfluorescence and superradiance in assemblies of perovskite nanocubes. Several studies estimated that coherent coupling is localized to a small fraction of nanocrystals (10-7-10-3) within the assembly, raising questions about the origins of localization and ways to overcome it. In this work, we examine single-excitation superradiance by calculating radiative decays and the distribution of superradiant wave function in two-dimensional CsPbBr3 nanocube superlattices. The calculations reveal that the energy disorder caused by size distribution and large interparticle separations reduces radiative coupling and leads to the excitation localization, with the energy disorder being the dominant factor. The single-excitation model clearly predicts that, in the pursuit of cooperative effects, having identical nanocubes in the superlattice is more important than achieving a perfect spatial order. The monolayers of large CsPbBr3 nanocubes (LNC = 10-20nm) are proposed as model systems for experimental tests of superradiance under conditions of non-negligible size dispersion, while small nanocubes (LNC = 5-10nm) are preferred for realizing the Dicke state under ideal conditions.

Fabrication of Au‐Decorated Al Nanoconcavities Platform for Augmented SERS

AbstractA robust and competitive technology to synthesize arranged high‐density gold nanoparticles on highly uniform Al nanoconcavities substrates is presented. The nanoparticles are formed through sputtering and thermal annealing treatment on Al templates, which are synthesized through particular removal of nanoporous anodic alumina structure with controlled anodization conditions and with phosphoric acid as electrolyte. This scalable fabrication mechanism regulates the particle size, arrangement, shape and interparticle separation across large surface areas, which empowers the optimization of their surface enhanced Raman scattering (SERS) activities. 4‐mercaptopyridine is selected as a probe molecule. Analysis reveals that Au‐decorated Al nanoconcavities substrates are highly competitive for the enhancement of Raman signals and could be employed as self‐sustaining nanosensors. By using these templates, a concentration as low as 10−7 M of 4‐mercaptopyridine is easily detected. Finally, the calculated EF factor of 1.1 × 107 confirms the suitability for effective and sensitive SERS detection of the developed substrates.

Cluster formation and relaxation in particle rafts under uniform radial expansion.

Particle rafts floating at an air-liquid interface exhibit a variety of behaviors when interfacial flow is introduced. Motivated by previous experimental observations, the failure pattern of particle rafts under uniform radial expansion is reported in this paper. The expansion process is specifically designed to expand the system affinely in the radial direction and to keep the velocity gradient constant throughout. A strong resemblance to the results of particle rafts under uniform uniaxial expansion is found. The size of the cluster emerging as the rafts are pulled apart scales inversely with the pulling velocity. This is a result of two competing velocities: the interparticle separation speed provided by the flow and a size-dependent relaxation speed for clustering. A model, generalized from a one-dimensional linear (in)stability calculation, is in agreement with the failure morphology found for this radially expanded system. Nonlinear relaxation and particle rearrangement are observed after the initial clustering occurs. This is a feature unique to a two-dimensional system. With its easily accessible particle dynamics at the microscopic level, this system provides insights into the morphology controlled by two competing mechanisms in two or higher dimensions and across different scales.

Nanoscale goldbeating: Solid-state transformation of 0D and 1D gold nanoparticles to anisotropic 2D morphologies.

Goldbeating is the ancient craft of thinning bulk gold (Au) into gossamer leaves. Pioneered by ancient Egyptian craftsmen, modern mechanized iterations of this technique can fabricate sheets as thin as ∼100 nm. We take inspiration from this millennia-old craft and adapt it to the nanoscale regime, using colloidally synthesized 0D/1D Au nanoparticles (AuNPs) as highly ductile and malleable nanoscopic Au ingots and subjecting them to solid-state, uniaxial compression. The applied stress induces anisotropic morphological transformation of AuNPs into 2D leaf form and elucidates insights into metal nanocrystal deformation at the extreme length scales. The induced 2D morphology is found to be dependent on the precursor 0D/1D NP morphology, size (0D nanosphere diameter and 1D nanorod diameter and length), and their on-substrate arrangement (e.g., interparticle separation and packing order) prior to compression. Overall, this versatile and generalizable solid-state compression technique enables new pathways to synthesize and investigate the anisotropic morphological transformation of arbitrary NPs and their resultant emergent phenomena.

Influence of Interparticle Separation Distance on the Fresh and Hardened Behavior of Ecoefficient Cement Pastes

Influence of Interparticle Separation Distance on the Fresh and Hardened Behavior of Ecoefficient Cement Pastes

On the radiative and multiple reflection corrections of the van der Waals force between two particles/atoms: dipolar contribution

We present a theoretical formalism based on fluctuational electrodynamics and the Maxwell-stress tensor for describing the impact of radiative and multiple reflections corrections on the van der Waals force between two nanoscale spherical particles and a pair of atoms in the dipolar approximation. Particularly, we examine the van der Waals forces for two metallic particles whose dielectric constant is represented by the Drude model, for two dielectric particles in which their material response has phononic resonances, and for two atoms with dynamic polarizabilities containing a single resonant frequency. For the metallic particles, in relation to the case in which the aforementioned effects are omitted, the van der Waals force is unchanged by the radiative corrections of the polarizabilities, whereas the mechanism of multiple reflections perturbs force about a few percentage points when the spheres nearly touch each other. In contrast to the the metallic case, the radiative corrections of the polarizabilities of the dielectric particles modify peculiarly the van der Waals force in comparison to the case where such corrections are neglected; there is a critical interparticle separation that divides two regimes: when the interparticle separation is smaller (larger) than this critical distance the force with radiative corrections is smaller (greater) than that without these corrections. Moreover, the van der Waals force is practically unchanged when effect of multiple reflections is taken into account. For the atomic case, the deviation of the van der Waals force due to multiple reflections is about a few percentage points when the interatomic separation corresponds to twice the van der Waals radius, and this deviation can reach about seventeen percent at a separation of 2.5 times the atomic radius. This work might have implications concerning the fine-tuning between theoretical and experimental outcomes of the van der Waals forces.

Getting over the hump with KAMEL-LOBE: Kernel-averaging method to eliminate length-of-bin effects in radial distribution functions.

Radial distribution functions (RDFs) are widely used in molecular simulation and beyond. Most approaches to computing RDFs require assembling a histogram over inter-particle separation distances. In turn, these histograms require a specific (and generally arbitrary) choice of discretization for bins. We demonstrate that this arbitrary choice for binning can lead to significant and spurious phenomena in several commonplace molecular-simulation analyses that make use of RDFs, such as identifying phase boundaries and generating excess entropy scaling relationships. We show that a straightforward approach (which we term Kernel-Averaging Method to Eliminate Length-Of-Bin Effects) mitigates these issues. This approach is based on systematic and mass-conserving mollification of RDFs using a Gaussian kernel. This technique has several advantages compared to existing methods, including being useful for cases where the original particle kinematic data have not been retained, and the only available data are the RDFs themselves. We also discuss the optimal implementation of this approach in the context of several application areas.

Nonlinear laser absorption on metal surface embedded with nanoparticles in the presence of external magnetic field

A nonlinear analytical model is developed for the absorption of a p-polarized laser that is obliquely incident on a metal surface embedded with metallic nanoparticles under the influence of an external magnetic field. The model suggests that the absorption coefficient is proportional to the angle of incidence and cube of nanoparticle-radius, but inversely proportional to the square of interparticle separation. Obtained results show that the laser absorption by the nanoparticles is substantially amplified due to plasmon resonance in the presence of an external magnetic field. The absorption coefficient has a sharp peak at surface plasma resonance where is the plasma frequency and it shows explicit dependence on the amplitude transmission coefficient of the incident wave. Absorption coefficient is obtained for gold nanoparticles for different incident angles, radii and interparticle separations and this study is of direct relevance in high performance optoelectronic devices, solar cells and nanomedicines.

Plasmon-enhanced photoluminescence and Raman spectroscopy of silver nanoparticles grown by solid state dewetting

The growth of the metallic nanoparticles (NPs) on the solid substrate with the desired shape and size is a critical issue for application of these NPs in solid-state devices. Solid state dewetting (SSD) technique is simple, low cost and can be used to fabricate the metallic NPs with control on the shape and size on different substrates. In this work, silver NPs (Ag NPs) were grown on corning glass substrate by SSD of silver precursor thin film deposited at different substrate temperatures by RF sputtering. The influence of the substrate temperature on the growth of Ag NPs and their several properties like localized surface plasmon resonance (LSPR), photoluminescence (PL), and Raman spectroscopy is studied. The size of the NPs was found to vary from 25 nm to 70 nm with the variation in substrate temperature from room temperature (RT) to . For the RT films, the LSPR peak position of Ag NPs is around 474 nm. A red shift in LSPR peak for films deposited at higher temperature is observed due to change in the particle size and interparticle separation. Photoluminescence spectra suggests the presence of two photoluminescence bands at 436 and 474 nm corresponding to Ag NPs radiative interband transition and LSPR band. An intense Raman peak was observed at 1587 cm−1. Enhancement in PL peak intensity and Raman peak intensity is found to be in accordance with the LSPR of Ag NPs.

Hibridon: A program suite for time-independent non-reactive quantum scattering calculations

Hibridon is a program package to solve the close-coupled equations which occur in the time independent quantum treatment of inelastic atomic and molecular collisions. Gas-phase scattering, photodissociation, collisions of atoms and/or molecules with flat surfaces, and bound states of weakly-bound complexes can be treated. From calculation of the S matrix, integral and differential cross sections, stereodynamic (alignment and steric asymmetry) cross sections, as well as more specialized quantities, such as transport and tensor cross sections, and cross sections between hyperfine levels, and photodissociation amplitudes can be obtained. The program is capable of treating closed-shell systems where the nuclear motion takes place on a single Born-Oppenheimer potential as well as open-shell systems for which the nuclear motion can evolve on several coupled electronic (Born-Oppenheimer) potentials. Program summaryProgram Title: HibridonCPC Library link to program files:https://doi.org/10.17632/sk9zcvz8vs.1Developer's repository link:https://doi.org/10.5281/zenodo.7551616Licensing provisions: GPLv3Programming language: Fortran 90External routines/libraries: LAPACK, BLASNature of problem: Solution of the time-independent Schrödinger equation for the inelastic scattering of atoms and molecules, for the photodissociation of molecules, and for the ro-vibrational motion of weakly bound molecular complexes.Solution method: The scattering wavefunction is expanded in a set of internal states of the system, constructed as direct products of the internal states of one (or both) fragments and angular functions which describe the rotation of one collision partner about the other. The Schrödinger equation for the nuclear motion is solved by determining the expansion coefficients as a function of the interparticle separation starting from the short-range classically forbidden region outwards to the asymptotic region. The S matrix is given by the asymptotic behavior of the wavefunction. Integral and differential cross sections, as well as other scattering and photodissociation quantities are calculated from the S matrix.