P. D. Rack

Focused, nanoscale electron-beam-induced deposition and etching

Focused electron-beam-induced (FEB-induced) deposition and etching are versatile, direct-write nanofabrication schemes that allow for selective deposition or removal of a variety of materials. Fundamentally, these processes are governed by an electron-induced reaction with a precursor vapor, which may either result in decomposition to a solid deposit or formation of a volatile etch by-product. The ability to induce such localized reactions by placement of a nanometer-sized focused electron probe has recently drawn considerable attention. In response, we have reviewed much of the relevant literature pertaining to both focused electron-beam-induced etching and deposition. Because these nanoscale processing techniques are still in their relative infancy, a significant amount of scientific research is being conducted to understand, and hence improve, the processes. This article summarizes the associated physics of electron-solid-vapor interactions, discusses related physical processes, and provides an introduction to electron-beam-induced etching (EBIE) and electron-beam-induced deposition (EBID). Additionally, specific applications of FEB-induced processes are discussed and several FEB computer model and simulation results are reviewed.

Focused electron-beam-induced etching of silicon dioxide

Focused electron-beam (FEB)-induced etching of silicon dioxide with xenon difluoride has been investigated as a selective nanoscale etching technique. In order to gain an understanding of the parameters that control etch rate and etch efficiency, the effects of beam current, beam energy, and scan rate conditions on the FEB process were examined. High etch rates were obtained for low beam energy, high beam current, and high scan rates. Experimental results also indicated that the FEB etch process is governed by the electron-stimulated desorption of oxygen from the SiO2 matrix, and subsequently rate limited by XeF2 availability. Based on experimental evidence and existing literature, a simple, two-step model was introduced to qualitatively describe the etch mechanism. The model involves a cyclical process, which is initiated by the reduction of a surface layer of SiO2 to elemental silicon. The exposed silicon surface is then removed by a chemical-mediated etch reaction.

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.

Effects of heat generation during electron-beam-induced deposition of nanostructures

To elucidate the effects of beam heating in electron-beam-induced deposition (EBID), a Monte Carlo electron-solid interaction model has been employed to calculate the energy deposition profiles in bulk and nanostructured SiO2. Using these profiles, a finite element model was used to predict the nanostructure tip temperatures for standard experimental EBID conditions. Depending on the beam energy, beam current, and nanostructure geometry, the heat generated can be substantial. This heat source can subsequently limit the EBID growth by thermally reducing the mean stay time of the precursor gas. Temperature-dependent EBID growth experiments qualitatively verified the results of the electron-beam-heating model. Additionally, experimental trends for the growth rate as a function of deposition time supported the conclusion that electron-beam-induced heating can play a major role in limiting the EBID growth rate of SiO2 nanostructures.

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.

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.

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.

Control of carbon nanostructure: From nanofiber toward nanotube and back

The unique properties of carbon nanofibers (CNFs) make them attractive for numerous applications ranging from field emitters to biological probes. In particular, it is the deterministic synthesis of CNFs, which requires precise control over geometrical characteristics such as location, length, diameter, and alignment, that enables the diverse applications. Catalytic plasma enhanced chemical vapor deposition of vertically aligned CNFs is a growth method that offers substantial control over the nanofiber geometry. However, deterministic synthesis also implies control over the nanofiber’s physical and chemical properties that are defined by internal structure. Until now, true deterministic synthesis has remained elusive due to the lack of control over internal graphitic structure. Here we demonstrate that the internal structure of CNFs can be influenced by catalyst preparation and ultimately defined by growth conditions. We have found that when the growth rate is increased by 100-fold, obtained through maxim...

Integrated tungsten nanofiber field emission cathodes selectively grown by nanoscale electron beam-induced deposition

We report on the fabrication and operation of integrated field emission cathodes containing single tungsten (W) nanofibers selectively grown by nanoscale electron beam induced deposition (EBID). A nonorganometallic precursor, WF6, was used to deposit metallic W fibers. Vacuum electrical testing reveals electrons were successfully extracted from the W nanofiber tip and were collected by a phosphor anode. Direct current versus voltage (I–V) curves exhibited Fowler–Nordheim behavior, indicating the occurrence of cold field emission. Electrical testing of these devices indicated that EBID direct-write is a promising technique for direct production or repair of field emission cathodes.

PVD synthesis and high-throughput property characterization of Ni–Fe–Cr alloy libraries

Three methods of alloy library synthesis, thick-layer deposition followed by interdiffusion, composition-spread codeposition and electron-beam melting of thick deposited layers, have been applied to Ni–Fe–Cr ternary and Ni–Cr binary alloys. Structural XRD mapping and mechanical characterization by means of nanoindentation have been used to characterize the properties of the libraries. The library synthesis methods are compared from the point of view of the structural and mechanical information they can provide.