Exploiting the Marangoni Effect To Initiate Instabilities and Direct the Assembly of Liquid Metal Filaments.

Utilization of the Marangoni effect in a liquid metal is investigated, focusing on initiating instabilities to direct material assembly via the Rayleigh-Plateau instability. Thin (2 nm) copper (Cu) films are lithographically patterned onto thick (12 nm) nickel (Ni) strips to induce a surface energy gradient at the maximum wavelength of the filament instability predicted by Rayleigh-Plateau instability analysis. The pattern is irradiated with an 18 ns pulsed laser such that the pattern melts and the resultant Ni-Cu surface tension gradient induces Marangoni flows due to the difference in surface energies. The experimental results, supported by extensive direct numerical simulations, demonstrate that the Marangoni flow exceeds the capillary flow induced by the initial geometry, guiding instabilities such that final nanoparticle location is directed toward the regions of higher surface energy (Ni regions). Our work shows a route for manipulation, by means of the Marangoni effect, to direct the evolution of the surface instabilities and the resulting pattern formation.

Instability of Nano- and Microscale Liquid Metal Filaments: Transition from Single Droplet Collapse to Multidroplet Breakup.

We carry out experimental and numerical studies to investigate the collapse and breakup of finite size, nano- and microscale, liquid metal filaments supported on a substrate. We find the critical dimensions below which filaments do not break up but rather collapse to a single droplet. The transition from collapse to breakup can be described as a competition between two fluid dynamic phenomena: the capillary driven end retraction and the Rayleigh-Plateau type instability mechanism that drives the breakup. We focus on the unique spatial and temporal transition region between these two phenomena using patterned metallic thin film strips and pulsed-laser-induced dewetting. The experimental results are compared to an analytical model proposed by Driessen et al. and modified to include substrate interactions. In addition, we report the results of numerical simulations based on a volume-of-fluid method to provide additional insight and highlight the importance of liquid metal resolidification, which reduces inertial effects.

Electron nanoprobe induced oxidation: a simulation of direct-write purification.

Electron beam direct-write has recently taken a large step forward with the advent of methods to purify deposits. This development has opened the door for future direct-write device prototyping and editing. In one such approach, an additional beam scanning procedure removes carbonaceous impurities via oxidation from metal-carbon deposits (e.g., PtC5) in the presence of H2O or O2 after deposition. So far, critical aspects of the oxidation reaction remain unclear; experiments reveal clearly that electron stimulated oxidation drives the process yet it is not understood why H2O purifies by a bottom-up mechanism while O2 purifies from the top-down. The simulation results presented here suggest that the chemisorption of dissolved O2 at buried Pt nanoparticle surfaces controls purification in the top-down case while both the high relative solubility coupled with weak physisorption of H2O explains the bottom-up process. Crucial too is the role that the carbonaceous contaminant itself has on the dissolution and diffusion of O2 and H2O. These results pave the way for simulation driven experiments where (1) the transient densification of the deposit can be accounted for in the initial deposit design stage and (2) the deposition and purification steps can be combined.

Pulsed laser-assisted focused electron-beam-induced etching of titanium with XeF2: enhanced reaction rate and precursor transport.

In order to enhance the etch rate of electron-beam-induced etching, we introduce a laser-assisted focused electron-beam-induced etching (LA-FEBIE) process which is a versatile, direct write nanofabrication method that allows nanoscale patterning and editing. The results demonstrate that the titanium electron stimulated etch rate via the XeF2 precursor can be enhanced up to a factor of 6 times with an intermittent pulsed laser assist. The evolution of the etching process is correlated to in situ stage current measurements and scanning electron micrographs as a function of time. The increased etch rate is attributed to photothermally enhanced Ti-F reaction and TiF4 desorption and in some regimes enhanced XeF2 surface diffusion to the reaction zone.

Monte Carlo simulations of nanoscale focused neon ion beam sputtering of copper: elucidating resolution limits and sub-surface damage.

A three dimensional Monte Carlo simulation program was developed to model physical sputtering and to emulate vias nanomachined by the gas field ion microscope. Experimental and simulation results of focused neon ion beam induced sputtering of copper are presented and compared to previously published experiments. The simulation elucidates the nanostructure evolution during the physical sputtering of high aspect ratio nanoscale features. Quantitative information such as the energy-dependent sputtering yields, dose dependent aspect ratios, and resolution-limiting effects are discussed. Furthermore, the nuclear energy loss and implant concentration beneath the etch front is correlated with the sub-surface damage revealed by transmission electron microscopy at different beam energies.

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.

Synthesis of nanowires via helium and neon focused ion beam induced deposition with the gas field ion microscope.

The ion beam induced nanoscale synthesis of platinum nanowires using the trimethyl (methylcyclopentadienyl)platinum(IV) (MeCpPt(IV)Me3) precursor is investigated using helium and neon ion beams in the gas field ion microscope. The He(+) beam induced deposition resembles material deposited by electron beam induced deposition with very small platinum nanocrystallites suspended in a carbonaceous matrix. The He(+) deposited material composition was estimated to be 16% Pt in a matrix of amorphous carbon with a large room-temperature resistivity (∼3.5 × 10(4)-2.2 × 10(5) µΩ cm) and temperature-dependent transport behavior consistent with a granular material in the weak intergrain tunnel coupling regime. The Ne(+) deposited material has comparable composition (17%), however a much lower room-temperature resistivity (∼600-3.0 × 10(3) µΩ cm) and temperature-dependent electrical behavior representative of strong intergrain coupling. The Ne(+) deposited nanostructure has larger platinum nanoparticles and is rationalized via Monte Carlo ion-solid simulations which show that the neon energy density deposited during growth is much larger due to the smaller ion range and is dominated by nuclear stopping relative to helium which has a larger range and is dominated by electronic stopping.

Synthesis and electroplating of high resolution insulated carbon nanotube scanning probes for imaging in liquid solutions.

High resolution and isolated scanning probe microscopy (SPM) is in demand for continued development of energy storage and conversion systems involving chemical reactions at the nanoscale as well as an improved understanding of biological systems. Carbon nanotubes (CNTs) have large aspect ratios and, if leveraged properly, can be used to develop high resolution SPM probes. Isolation of SPM probes can be achieved by depositing a dielectric film and selectively etching at the apex of the probe. In this paper the fabrication of a high resolution and isolated SPM tip is demonstrated using electron beam induced etching of a dielectric film deposited onto an SPM tip with an attached CNT at the apex.

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.

An optimized nanoparticle separator enabled by electron beam induced deposition.

Size-based separations technologies will inevitably benefit from advances in nanotechnology. Direct-write nanofabrication provides a useful mechanism for depositing/etching nanoscale elements in environments otherwise inaccessible to conventional nanofabrication techniques. Here, electron beam induced deposition was used to deposit an array of nanoscale features in a 3D environment with minimal material proximity effects outside the beam-interaction region. Specifically, the membrane component of a nanoparticle separator was fabricated by depositing a linear array of sharply tipped nanopillars, with a singular pitch, designed for sub-50 nm nanoparticle permeability. The nanopillar membrane was used in a dual capacity to control the flow of nanoparticles in the transaxial direction of the array while facilitating the sealing of the cellular-sized compartment in the paraxial direction. An optimized growth recipe resulted which (1) maximized the growth efficiency of the membrane (which minimizes proximity effects) and (2) preserved the fidelity of the spacing between nanopillars (which maximizes the size-based gating quality of the membrane) while (3) maintaining sharp nanopillar apexes for impaling an optically transparent polymeric lid critical for device sealing.

Pulsed laser dewetting of nickel catalyst for carbon nanofiber growth.

We present a pulsed laser dewetting technique that produces single nickel catalyst particles from lithographically patterned disks for subsequent carbon nanofiber growth through plasma enhanced chemical vapor deposition. Unlike the case for standard heat treated Ni catalyst disks, for which multiple nickel particles and consequently multiple carbon nanofibers (CNFs) are observed, single vertically aligned CNFs could be obtained from the laser dewetted catalyst. Different laser dewetting parameters were tested in this study, such as the laser energy density and the laser processing time measured by the total number of laser pulses. Various nickel disk radii and thicknesses were attempted and the resultant number of carbon nanofibers was found to be a function of the initial disk dimension and the number of laser pulses.

A nanoscale three-dimensional Monte Carlo simulation of electron-beam-induced deposition with gas dynamics.

A computer simulation was developed to simulate electron-beam-induced deposition (EBID). Simulated growth produced high-aspect-ratio, nanoscale pillar structures by simulating a stationary Gaussian electron beam. The simulator stores in memory the spatial and temporal coordinates of deposited atoms in addition to the type of electron, either primary (PE), back-scattered (BSE), or secondary (SE), that induced its deposition. The results provided in this paper apply to tungsten pillar growth by EBID on a tungsten substrate from WF(6) precursor, although the simulation may be applied to any substrate-precursor set. The details of the simulation are described including the Monte Carlo electron-solid interaction simulation used to generate scattered electron trajectories and SE generation, the probability of molecular dissociation of the precursor gas when an electron traverses the surface, and the gas dynamics which control the surface coverage of the WF(6) precursor on the substrate and pillar surface. In this paper, three specific studies are compared: the effects of beam energy, mass transport versus reaction-rate-limited growth, and the effects of surface diffusion on the EBID process.

Formation of ultrasharp vertically aligned Cu-Si nanocones by a DC plasma process.

We report an effective method for the production of ultrasharp vertically oriented silicon nanocones with tip radii as small as 5 nm. These silicon nanostructures were shaped by a high-temperature acetylene and ammonia dc plasma reactive ion etch (RIE) process. Thin-film copper deposited onto Si substrates forms a copper silicide (Cu3Si) during plasma processing, which subsequently acts as a seed material masking the single-crystal cones while the exposed silicon areas are reactive ion etched. In this process, the cone angle is sharpened continually as the structure becomes taller. Furthermore, by lithographically defining the seed material as well as employing an etch barrier material such as titanium, the cone location and substrate topography can be controlled effectively.