Sagar Yadavali

Self-organization of nanoscale multilayer liquid metal films: experiment and theory.

Surfaces made from composite nanostructured materials are potential multifunctional platforms for detection, sensing, and energy harvesting in biological and inorganic systems. However, robust and cost-effective synthesis routes are required to create the required arrays of nanostructures with tailorable size, morphology, and composition. Here we show that self-organization via spontaneous pattern formation in nanometer thick bilayer liquid films could lead to such nanostructure arrays. Experimentally, bilayers of immiscible metallic liquids show different self-organized patterning characteristics based on their order of arrangement on a substrate. Energy rate theory based on equating the rate of free energy change to viscous dissipation was used to explain this result. The different bilayer arrangements change the signs of intermolecular interactions, which changes the mode of coupled deformations and the patterning characteristics. Patterning length scale characteristics from nanosecond pulsed laser induced self-organization of Ag and Co liquids on SiO₂ substrate were in good agreement with theory.

Self-organized bimetallic Ag-Co nanoparticles with tunable localized surface plasmons showing high environmental stability and sensitivity.

We demonstrate a promising synthesis route based on pulsed laser dewetting of bilayer films (Ag and Co) to make bimetallic nanoparticle arrays. By combining experiment and theory we establish a parameter space for the independent control of composition and diameter for the bimetallic nanoparticles. As a result, physical properties, such as the localized surface plasmon resonance (LSPR), that depend on particle size and composition can be readily tuned over a wavelength range one order of magnitude greater than for pure Ag nanoparticles. The LSPR detection sensitivity of the bimetallic nanoparticles with narrow size distribution was found to be high-comparable with pure Ag (∼60 nm/RIU). Moreover, they showed significantly higher long-term environmental stability over pure Ag.

Oxidation-resistant silver nanostructures for ultrastable plasmonic applications.

Reduced degradation (oxidation) of silver nanoparticles (NPs) is achieved by contacting Ag with immiscible Co NPs. The relative decay of the plasmon peak (plot) shows that pure Ag NPs (blue dashed curve) decay by 25% in ca 20 days, whereas AgCo NPs last about 10 times longer, requiring nearly five months for a similar decay (red solid curve). The TEM images for both Ag and AgCo were taken after 50 days of storage under ambient conditions.

Ferroplasmons: Intense Localized Surface Plasmons in Metal-Ferromagnetic Nanoparticles

Interaction of photons with matter at length scales far below their wavelengths has given rise to many novel phenomena, including localized surface plasmon resonance (LSPR). However, LSPR with narrow bandwidth (BW) is observed only in a select few noble metals, and ferromagnets are not among them. Here, we report the discovery of LSPR in ferromagnetic Co and CoFe alloy (8% Fe) in contact with Ag in the form of bimetallic nanoparticles prepared by pulsed laser dewetting. These plasmons in metal-ferromagnetic nanostructures, or ferroplasmons (FP) for short, are in the visible spectrum with comparable intensity and BW to those of the LSPRs from the Ag regions. This finding was enabled by electron energy-loss mapping across individual nanoparticles in a monochromated scanning transmission electron microscope. The appearance of the FP is likely due to plasmonic interaction between the contacting Ag and Co nanoparticles. Since there is no previous evidence for materials that simultaneously show ferromagnetism and such intense LSPRs, this discovery may lead to the design of improved plasmonic materials and applications. It also demonstrates that materials with interesting plasmonic properties can be synthesized using bimetallic nanostructures in contact with each other.

Formation of organized nanostructures from unstable bilayers of thin metallic liquids

Dewetting of pulsed-laser irradiated, thin (<20 nm), optically reflective metallic bilayers on an optically transparent substrate with a reflective support layer is studied within the lubrication equations model. A steady-state bilayer film thickness (h) dependent temperature profile is derived based on the mean substrate temperature estimated from the elaborate thermal model of transient heating and melting/freezing. Large thermocapillary forces are observed along the plane of the liquid-liquid and liquid-gas interfaces due to this h-dependent temperature, which, in turn, is strongly influenced by the h-dependent laser light reflection and absorption. Consequently the dewetting is a result of the competition between thermocapillary and intermolecular forces. A linear analysis of the dewetting length scales established that the non-isothermal calculations better predict the experimental results as compared to the isothermal case within the bounding Hamaker coefficients. Subsequently, a computational non-l...

Transformation of irregular shaped silver nanostructures into nanoparticles by under water pulsed laser melting.

The ability to easily manufacture nanostructures with a desirable attribute, such as well-defined size and shape, especially from any given initial shapes or sizes of the material, will be helpful towards accelerating the use of nanomaterials in various applications. In this work we report the transformation of discontinuous irregular nanostructures (DIN) of silver metal by rapid heating under a bulk fluid layer. Ag films were changed into DIN by dewetting in air and subsequently heated by nanosecond laser pulses under water. Our findings show that the DIN first ripens into elongated structures and then breaks up into nanoparticles. From the dependence of this behavior on laser fluence we found that under water irradiation reduced the rate of ripening and also decreased the characteristic break-up length scale of the elongated structures. This latter result was qualitatively interpreted as arising from a Rayleigh-Plateau instability modified to yield significantly smaller length scales than the classical process due to pressure gradients arising from the rapid evaporation of water during laser melting. These results demonstrate that it is possible to fabricate a dense collection of monomodally sized Ag nanoparticles with significantly enhanced plasmonic quality starting from the irregular shaped materials. This can be beneficial towards transforming discontinuous Ag films into nanostructures with useful plasmonic properties, that are relevant for biosensing applications.

Nanomaterials synthesis by a novel phenomenon: The nanoscale Rayleigh-Taylor instability

The Rayleigh-Taylor (RT) interfacial instability has been attributed to physical phenomenon in a wide variety of macroscopic systems, including black holes, laser generated plasmas, and thick fluids. However, evidence for its existence in the nanoscale is lacking. Here we first show theoretically that this instability can occur in films with thickness negligible compared to the capillary length when they are heated rapidly inside a bulk fluid. Pressure gradients developed in the evaporated fluid region produce large forces causing the instability. Experiments were performed by melting Au films inside glycerol fluid by nanosecond laser pulses. The ensuing nanoparticles had highly monomodal size distributions. Importantly, the spacing of the nanoparticles was independent of the film thickness and could be tuned by the magnitude of the pressure gradients. Therefore, this instability can overcome some of the limitations of conventional thin self-organization techniques that rely on film thickness to control l...

DC electric field induced phase array self-assembly of Au nanoparticles

In this work we report the discovery of phase array self-assembly, a new way to spontaneously make periodic arrangements of metal nanoparticles. An initially random arrangement of gold (Au) or silver (Ag) nanoparticles on SiO2/Si substrates was irradiated with linearly polarized (P) laser light in the presence of a dc electric (E) field applied to the insulating substrate. For E fields parallel to the laser polarization (E||P), the resulting periodic ordering was single-crystal like with extremely low defect density and covered large macroscopic areas. The E field appears to be modifying the phase between radiation scattered by the individual nanoparticles thus leading to enhanced interference effects. While phase array behavior is widely known in antenna technology, this is the first evidence that it can also aid in nanoscale self-assembly. These results provide a simple way to produce periodic metal nanoparticles over large areas.

Pulsed-laser induced Rayleigh-Taylor instabilities of ultrathin metal films inside homogeneous liquid mixtures

Nanosecond pulsed laser melting of ultrathin gold films immersed inside glycerol-water mixtures assemble into monomodal sized nanoparticles with small spacing. This is a result of the large vapor pressure gradient created at the metal-fluid interface.