In Situ Mitigation of Subsurface and Peripheral Focused Ion Beam Damage via Simultaneous Pulsed Laser Heating.

Focused helium and neon ion (He(+)/Ne(+)) beam processing has recently been used to push resolution limits of direct-write nanoscale synthesis. The ubiquitous insertion of focused He(+)/Ne(+) beams as the next-generation nanofabrication tool-of-choice is currently limited by deleterious subsurface and peripheral damage induced by the energetic ions in the underlying substrate. The in situ mitigation of subsurface damage induced by He(+)/Ne(+) ion exposures in silicon via a synchronized infrared pulsed laser-assisted process is demonstrated. The pulsed laser assist provides highly localized in situ photothermal energy which reduces the implantation and defect concentration by greater than 90%. The laser-assisted exposure process is also shown to reduce peripheral defects in He(+) patterned graphene, which makes this process an attractive candidate for direct-write patterning of 2D materials. These results offer a necessary solution for the applicability of high-resolution direct-write nanoscale material processing via focused ion beams.

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.

Enhanced by-product desorption via laser assisted electron beam induced deposition of W(CO)6 with improved conductivity and resolution.

Nanowires with higher tungsten (W) concentration and enhanced conductivity were grown via the laser assisted electron beam induced deposition (LAEBID) technique using tungsten hexacarbonyl W(CO)6 as the gas precursor. Periodic, pulsed laser irradiation facilitated CO desorption during growth by heating the deposit. Deposit purity improved with laser pulse width up to the threshold for pyrolytic laser chemical vapor deposition (LCVD). Higher resolution was also observed and was attributed to reduced CO incorporation and higher deposit density. The optimal composition and lowest resistivity was achieved by synchronizing the electron beam induced deposition and laser assist such that (1) the electron beam induced deposit is less than a monolayer per cycle and (2) the laser induced heating is just below the LCVD threshold.

3D Nanoprinting Replication Enhancement Using a Simulation-Informed Analytical Model for Electron Beam Exposure Dose Compensation.

3D nanoprinting, using focused electron beam-induced deposition, is prone to a common structural artifact arising from a temperature gradient that naturally evolves during deposition, extending from the electron beam impact region (BIR) to the substrate. Inelastic electron energy loss drives the Joule heating and surface temperature variations lead to precursor surface concentration variations due, in most part, to temperature-dependent precursor surface desorption. The result is unwanted curvature when prescribing linear segments in 3D objects, and thus, complex geometries contain distortions. Here, an electron dose compensation strategy is presented to offset deleterious heating effects; the Decelerating Beam Exposure Algorithm, or DBEA, which corrects for nanowire bending a priori, during computer-aided design, uses an analytical solution derived from information gleaned from 3D nanoprinting simulations. Electron dose modulation is an ideal solution for artifact correction because variations in electron dose have no influence on temperature. Thus, the generalized compensation strategy revealed here will help advance 3D nanoscale printing fidelity for focused electron beam-induced deposition.

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.

Competition between collapse and breakup in nanometer-sized thin rings using molecular dynamics and continuum modeling.

We consider nanometer-sized fluid annuli (rings) deposited on a solid substrate and ask whether these rings break up into droplets due to the instability of Rayleigh-Plateau-type modified by the presence of the substrate, or collapse to a central drop due to the presence of azimuthal curvature. The analysis is carried out by a combination of atomistic molecular dynamics simulations and a continuum model based on a long-wave limit of Navier-Stokes equations. We find consistent results between the two approaches, and demonstrate characteristic dimension regimes which dictate the assembly dynamics.

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.

Optical and Magnetic Properties of Ag-Ni Bimetallic Nanoparticles Assembled via Pulsed Laser-Induced Dewetting.

Pulsed laser-induced dewetting (PLiD) of Ag0.5Ni0.5 thin films results in phase-separated bimetallic nanoparticles with size distributions that depend on the initial thin film thickness. Co-sputtering of Ag and Ni is used to generate the as-deposited (AD) nanogranular supersaturated thin films. The magnetic and optical properties of the AD thin films and PLiD nanoparticles are characterized using a vibrating sample magnetometer, optical absorption spectroscopy, and electron energy loss spectroscopy (EELS). Magnetic measurements demonstrate that Ag0.5Ni0.5 nanoparticles are ferromagnetic at room temperature when the nanoparticle diameters are >20 nm and superparamagnetic <20 nm. Optical measurements show that all nanoparticle size distributions possess a local surface plasmon resonance (LSPR) peak that red-shifts with increasing diameter. Following PLiD, a Janus nanoparticle morphology is observed in scanning transmission electron microscopy, and low-loss EELS reveals size-dependent Ag and Ni LSPR dipole modes, while higher order modes appear only in the Ag hemisphere. PLiD of Ag-Ni thin films is shown to be a viable technique to generate bimetallic nanoparticles with both magnetic and plasmonic functionality.

High-Resolution Laser-Induced Graphene. Flexible Electronics beyond the Visible Limit.

Laser-induced graphene (LIG) is a multifunctional graphene foam that is commonly direct-written with an infrared laser into a carbon-based precursor material. Here, a visible 405 nm laser is used to directly convert polyimide into LIG. This enabled the formation of LIG with a spatial resolution of ∼12 µm and a thickness of <5 µm. The spatial resolution enabled by the relatively smaller focused spot size of the 405 nm laser represents a >60% reduction in LIG feature sizes reported in prior publications. This process occurs in situ in an SEM chamber, thus allowing direct observation of LIG formation. The reduced size of the LIG features enables the direct-write formation of flexible electronics that are not visible to the unaided eye. A humidity sensor is demonstrated which could detect human breath with a response time of 250 ms. With the growing interest in LIG for flexible electronics and sensors, finer features can greatly expand its utility.

Direct Write of 3D Nanoscale Mesh Objects with Platinum Precursor via Focused Helium Ion Beam Induced Deposition.

The next generation optical, electronic, biological, and sensing devices as well as platforms will inevitably extend their architecture into the 3rd dimension to enhance functionality. In focused ion beam induced deposition (FIBID), a helium gas field ion source can be used with an organometallic precursor gas to fabricate nanoscale structures in 3D with high-precision and smaller critical dimensions than focused electron beam induced deposition (FEBID), traditional liquid metal source FIBID, or other additive manufacturing technology. In this work, we report the effect of beam current, dwell time, and pixel pitch on the resultant segment and angle growth for nanoscale 3D mesh objects. We note subtle beam heating effects, which impact the segment angle and the feature size. Additionally, we investigate the competition of material deposition and sputtering during the 3D FIBID process, with helium ion microscopy experiments and Monte Carlo simulations. Our results show complex 3D mesh structures measuring ~300 nm in the largest dimension, with individual features as small as 16 nm at full width half maximum (FWHM). These assemblies can be completed in minutes, with the underlying fabrication technology compatible with existing lithographic techniques, suggesting a higher-throughput pathway to integrating FIBID with established nanofabrication techniques.

An in vivo imaging-based assay for detecting protein interactions over a wide range of binding affinities.

Identifying and characterizing protein interactions are fundamental steps toward understanding and modeling biological networks. Methods that detect protein interactions in intact cells rather than buffered solutions are likely more relevant to natural systems since molecular crowding events in the cytosol can influence the diffusion and reactivity of individual proteins. One in vivo, imaging-based method relies on the colocalization of two proteins of interest fused to DivIVA, a cell division protein from Bacillus subtilis, and green fluorescent protein (GFP). We have modified this imaging-based assay to facilitate rapid cloning by constructing new vectors encoding N- and C-terminal DivIVA or GFP molecular tag fusions based on site-specific recombination technology. The sensitivity of the assay was defined using a well-characterized protein interaction system involving the eukaryotic nuclear import receptor subunit, Importin alpha (Imp alpha), and variant nuclear localization signals (NLS) representing a range of binding affinities. These data demonstrate that the modified colocalization assay is sensitive enough to detect protein interactions with K(d) values that span over four orders of magnitude (1 nM to 15 microM). Lastly, this assay was used to confirm numerous protein interactions identified from mass spectrometry-based analyses of affinity isolates as part of an interactome mapping project in Rhodopseudomonas palustris.

Nanoparticle assembly via the dewetting of patterned thin metal lines: understanding the instability mechanisms.

Nanosecond pulsed laser heating was used to control the assembly of spatially correlated nanoparticles from lithographically patterned pseudo-one-dimensional nickel lines. The evolution of the nickel line instabilities and nanoparticle formation with a correlated size and spacing was observed after a series of laser pulses. To understand the instabilities that direct the nanoparticle assembly, we have carried out nonlinear time-dependent simulations and linear stability analysis based on a simple hydrodynamic model. We find that the simulated time scales and length scales agree well with the experimental results. Interestingly, in both experiments and simulations, the instabilities associated with the line edge, and with the surface perturbation-driven mechanism, are found to result in similar particle sizes and spacings.

Simulation Informed CAD for 3D Nanoprinting.

A promising 3D nanoprinting method, used to deposit nanoscale mesh style objects, is prone to non-linear distortions which limits the complexity and variety of deposit geometries. The method, focused electron beam-induced deposition (FEBID), uses a nanoscale electron probe for continuous dissociation of surface adsorbed precursor molecules which drives highly localized deposition. Three dimensional objects are deposited using a 2D digital scanning pattern-the digital beam speed controls deposition into the third, or out-of-plane dimension. Multiple computer-aided design (CAD) programs exist for FEBID mesh object definition but rely on the definition of nodes and interconnecting linear nanowires. Thus, a method is needed to prevent non-linear/bending nanowires for accurate geometric synthesis. An analytical model is derived based on simulation results, calibrated using real experiments, to ensure linear nanowire deposition to compensate for implicit beam heating that takes place during FEBID. The model subsequently compensates and informs the exposure file containing the pixel-by-pixel scanning instructions, ensuring nanowire linearity by appropriately adjusting the patterning beam speeds. The derivation of the model is presented, based on a critical mass balance revealed by simulations and the strategy used to integrate the physics-based analytical model into an existing 3D nanoprinting CAD program is overviewed.

Impact of Electron-Beam Heating during 3D Nanoprinting.

An artifact limiting the reproduction of three-dimensional (3D) designs using nanoprinting has been quantified. Beam-induced heating was determined through complementary experiments, models, and simulations to affect the deposition rate during the 3D nanoprinting of mesh objects using focused electron beam induced deposition (FEBID). The mesh objects are constructed using interconnected nanowires. During nanowire growth, the beam interaction driving deposition also causes local heating. The temperature at the beam impact region progressively rises as thermal resistance increases with nanowire growth. Heat dissipation resembles the classical mode of heat transfer from extended surfaces; heat must flow through the mesh object to reach the substrate sink. Simulations reveal that beam heating causes an increase in the rate of precursor desorption at the BIR, causing a concomitant decrease in the deposition rate, overwhelming an increase in the deposition rate driven by thermally enhanced precursor surface diffusion. Temperature changes as small as 10 K produce noticeable changes in deposit geometry; nanowires appear to deflect and curve toward the substrate because the vertical growth rate decreases. The 3D FEBID naturally ensues from the substrate surface upward, inducing a vertical temperature gradient along the deposit. Simulations, experiments, temperature-controlled studies, and process current monitoring all confirm the cause of nanowire distortion as beam-induced heating while also revealing the rate-determining physics governing the final deposit shape.

Focused Electron Beam-Based 3D Nanoprinting for Scanning Probe Microscopy: A Review.

Scanning probe microscopy (SPM) has become an essential surface characterization technique in research and development. By concept, SPM performance crucially depends on the quality of the nano-probe element, in particular, the apex radius. Now, with the development of advanced SPM modes beyond morphology mapping, new challenges have emerged regarding the design, morphology, function, and reliability of nano-probes. To tackle these challenges, versatile fabrication methods for precise nano-fabrication are needed. Aside from well-established technologies for SPM nano-probe fabrication, focused electron beam-induced deposition (FEBID) has become increasingly relevant in recent years, with the demonstration of controlled 3D nanoscale deposition and tailored deposit chemistry. Moreover, FEBID is compatible with practically any given surface morphology. In this review article, we introduce the technology, with a focus on the most relevant demands (shapes, feature size, materials and functionalities, substrate demands, and scalability), discuss the opportunities and challenges, and rationalize how those can be useful for advanced SPM applications. As will be shown, FEBID is an ideal tool for fabrication / modification and rapid prototyping of SPM-tipswith the potential to scale up industrially relevant manufacturing.

Pore-scale hydrodynamics influence the spatial evolution of bacterial biofilms in a microfluidic porous network.

Bacteria occupy heterogeneous environments, attaching and growing within pores in materials, living hosts, and matrices like soil. Systems that permit high-resolution visualization of dynamic bacterial processes within the physical confines of a realistic and tractable porous media environment are rare. Here we use microfluidics to replicate the grain shape and packing density of natural sands in a 2D platform to study the flow-induced spatial evolution of bacterial biofilms underground. We discover that initial bacterial dispersal and grain attachment is influenced by bacterial transport across pore space velocity gradients, a phenomenon otherwise known as rheotaxis. We find that gravity-driven flow conditions activate different bacterial cell-clustering phenotypes depending on the strain's ability to product extracellular polymeric substances (EPS). A wildtype, biofilm-producing bacteria formed compact, multicellular patches while an EPS-defective mutant displayed a linked-cell phenotype in the presence of flow. These phenotypes subsequently influenced the overall spatial distribution of cells across the porous media network as colonies grew and altered the fluid dynamics of their microenvironment.

Pulsed Laser-Assisted Helium Ion Nanomachining of Monolayer Graphene-Direct-Write Kirigami Patterns.

A helium gas field ion source has been demonstrated to be capable of realizing higher milling resolution relative to liquid gallium ion sources. One drawback, however, is that the helium ion mass is prohibitively low for reasonable sputtering rates of bulk materials, requiring a dosage that may lead to significant subsurface damage. Manipulation of suspended graphene is, therefore, a logical application for He+ milling. We demonstrate that competitive ion beam-induced deposition from residual carbonaceous contamination can be thermally mitigated via a pulsed laser-assisted He+ milling. By optimizing pulsed laser power density, frequency, and pulse width, we reduce the carbonaceous byproducts and mill graphene gaps down to sub 10 nm in highly complex kiragami patterns.

Low-Temperature Charging Dynamics of the Ionic Liquid and Its Gating Effect on FeSe0.5Te0.5 Superconducting Films.

Ionic liquids (ILs) have been investigated extensively because of their unique ability to form the electric double layer (EDL), which induces high electrical field. For certain materials, low-temperature IL charging is needed to limit the electrochemical etching. Here, we report our investigation of the low-temperature charging dynamics in two widely used ILs-DEME-TF2N and C4mim-TF2N. Results show that the formation of the EDL at ∼220 K requires several hours relative to milliseconds at room temperature, and an equivalent voltage Ve is introduced as a measure of the EDL formation during the biasing process. The experimental observation is supported by molecular dynamics simulation, which shows that the dynamics are logically a function of gate voltage, time, and temperature. To demonstrate the importance of understanding the charging dynamics, a 140 nm thick FeSe0.5Te0.5 film was biased using the DEME IL, showing a tunable Tc between 18 and 35 K. Notably, this is the first observation of the tunability of the Tc in thick film FeSe0.5Te0.5 superconductors.

Understanding the kinetics and nanoscale morphology of electron-beam-induced deposition via a three-dimensional Monte Carlo simulation: the effects of the precursor molecule and the deposited material.

The electron-beam-induced deposition of silicon oxide from tetraethyorthosilicate and tungsten from tungsten hexafluoride is simulated via a Monte Carlo simulation. Pseudo one-dimensional nanopillars are grown using comparable electron-beam parameters and a comparison of the vertical and lateral growth rate and the pillar morphology is correlated to the precursor and deposited material parameters. The primary and secondary electrons (type I) are found to dominate the vertical growth rate and the lateral growth rate is dominated by forward and secondary electrons (type II). The resolution and morphology of the nanopillars are affected by the effective electron interaction volume and the resultant surface coverage of the precursor species in the effective electron interaction region. Finally, the simulated results are compared to previously reported experimental results.