Yueying Wu

Self-Assembly versus Directed Assembly of Nanoparticles via Pulsed Laser Induced Dewetting of Patterned Metal Films

A nanoscale, synthetic perturbation was all that was required to nudge a natural, self-assembly process toward significantly higher order. Metallic thin film strips were transformed into nanoparticle arrays by nanosecond, liquid-phase dewetting. Arrays formed according to an evolving Rayleigh-Plateau instability, yet nanoparticle diameter and pitch were poorly controlled. However, by patterning a nanoscale sinusoid onto the original strip edge, a precise nanoparticle diameter and pitch emerged superseding the naturally evolving Rayleigh-Plateau instability.

On the breakup of patterned nanoscale copper rings into droplets via pulsed-laser-induced dewetting: competing liquid-phase instability and transport mechanisms.

Nanolithographically patterned copper rings were synthesized, and the self-assembly of the rings into ordered nanoparticle/nanodrop arrays was accomplished via nanosecond pulsed laser heating above the melt threshold. The resultant length scale was correlated to the transport and instability growths that occur during the liquid lifetime of the melted copper rings. For 13-nm-thick rings, a change in the nanoparticle spacing with the ring width is attributed to a transition from a Raleigh-Plateau instability to a thin film instability because of competition between the cumulative transport and instability timescales. To explore the competition between instability mechanisms further, we carried out experiments with 7-nm-thick rings. In agreement with the theoretical predictions, these rings break up in both the azimuthal and radial directions, confirming that a simple hydrodynamic model captures the main features of the processes leading to the breakup.

Competing Liquid Phase Instabilities during Pulsed Laser Induced Self-Assembly of Copper Rings into Ordered Nanoparticle Arrays on SiO2

Nanoscale copper rings of different radii, thicknesses, and widths were synthesized on silicon dioxide thin films and were subsequently liquefied via a nanosecond pulse laser treatment. During the nanoscale liquid lifetimes, the rings experience competing retraction dynamics and thin film and/or Rayleigh-Plateau types of instabilities, which lead to arrays of ordered nanodroplets. Surprisingly, the results are significantly different from those of similar experiments carried out on a Si surface. We use hydrodynamic simulations to elucidate how the different liquid/solid interactions control the different instability mechanisms in the present problem.

Directed Liquid Phase Assembly of Highly Ordered Metallic Nanoparticle Arrays

Directed assembly of nanomaterials is a promising route for the synthesis of nanoscale materials. In this paper, we demonstrate the directed-assembly of highly ordered two-dimensional arrays of hierarchical nanostructures with tunable size, spacing and composition. The directed assembly is achieved on lithographically patterned metal films that are subsequently pulse-laser melted; during the brief liquid lifetime, the pattened nanostructures assemble into highly ordered primary and secondary nanoparticles, with sizes below that which was originally patterned. Complementary fluid-dynamics simulations emulate the resultant patterns and show how the competition of capillary forces and liquid metal-solid substrate interaction potential drives the directed assembly. As an example of the enhanced functionality, a full-wave electromagnetic analysis has been performed to identify the nature of the supported plasmonic resonances.

Hierarchical Nanoparticle Ensembles Synthesized by Liquid Phase Directed Self-Assembly

A liquid metal filament supported on a dielectric substrate was directed to fragment into an ordered, mesoscale particle ensemble. Imposing an undulated surface perturbation on the filament forced the development of a single unstable mode from the otherwise disperse, multimodal Rayleigh-Plateau instability. The imposed mode paved the way for a hierarchical spatial fragmentation of the filament into particles, previously seen only at much larger scales. Ultimately, nanoparticle radius control is demonstrated using a micrometer scale switch.

Real-time observation of nanosecond liquid-phase assembly of nickel nanoparticles via pulsed-laser heating.

Using pump-probe electron microscopy techniques, the dewetting of thin nickel films exposed to a pulsed nanosecond laser was monitored at tens of nanometers spatial and nanosecond time scales to provide insight into the liquid-phase assembly dynamics. Thickness-dependent and correlated time and length scales indicate that a spinodal instability drives the assembly process. Measured lifetimes of the liquid metal are consistent with finite-difference simulations of the laser-irradiated film and are consistent with estimated and observed spinodal time scales. These results can be used to design improved synthesis and assembly routes toward achieving advanced functional nanomaterials and devices.

Solid-Solution CrCoCuFeNi High-Entropy Alloy Thin Films Synthesized by Sputter Deposition

The concept of high configurational entropy requires that the high-entropy alloys (HEAs) yield single-phase solid solutions. However, phase separations are quite common in bulk HEAs. A five-element alloy, CrCoCuFeNi, was deposited via radio frequency magnetron sputtering and confirmed to be a single-phase solid solution through the high-energy synchrotron X-ray diffraction, energy-dispersive spectroscopy, wavelength-dispersive spectroscopy, and transmission electron microscopy. The formation of the solid-solution phase is presumed to be due to the high cooling rate of the sputter-deposition process.

Instability of liquid Cu films on a SiO2 substrate.

We study the instability of nanometric Cu thin films on SiO2 substrates. The metal is melted by means of laser pulses for some tens of nanoseconds, and during the liquid lifetime, the free surface destabilizes, leading to the formation of holes at first and then in later stages of the instability to metal drops on the substrate. By analyzing the Fourier transforms of the SEM (scanning electron microscope) images obtained at different stages of the metal film evolution, we determine the emerging length scales at relevant stages of the instability development. The results are then discussed within the framework of a long-wave model. We find that the results may differ whether early or final stages of the instability are considered. On the basis of the interpretation of the experimental results, we discuss the influence of the parameters describing the interaction of the liquid metal with the solid substrate. By considering both the dependence of dominant length scales on the film thickness and the measured contact angle, we isolate a model which predicts well the trends found in the experimental data.

Examining Substrate-Induced Plasmon Mode Splitting and Localization in Truncated Silver Nanospheres with Electron Energy Loss Spectroscopy.

Motivated by the need to study the size dependence of nanoparticle-substrate systems, we present a combined experimental and theoretical electron energy loss spectroscopy (EELS) study of the plasmonic spectrum of substrate-supported truncated silver nanospheres. This work spans the entire classical range of plasmonic behavior probing particles of 20-1000 nm in diameter, allowing us to map the evolution of localized surface plasmons into surface plasmon polaritons and study the size dependence of substrate-induced mode splitting. This work constitutes the first nanoscopic characterization and imaging of these effects in truncated nanospheres, setting the stage for the systematic study of plasmon-mediated energy transfer in nanoparticle-substrate systems.

Simultaneous In‐Situ Synthesis and Characterization of Co@Cu Core‐Shell Nanoparticle Arrays

Core-shell particle ensembles are fabricated by pulsed-laser-induced dewetting of initially continuous, ultrathin alloy films through a combination of morphological and chemical instability. The synthesis of these arrays is monitored in situ with high spatial and temporal resolutions, which, when combined with ex situ composition analysis, provides insight to the morphological and chemical evolution pathways leading to core-shell particle formation.