J. D. Fowlkes

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.

Silicon microcolumn arrays grown by nanosecond pulsed-excimer laser irradiation

Arrays of high aspect ratio silicon microcolumns that protrude well above the initial surface have been formed by cumulative nanosecond pulsed-excimer laser irradiation of silicon. Microcolumn growth is strongly affected by the gas environment, being enhanced in air or other oxygen-containing ambient. It is proposed that microcolumn growth occurs through a combination of pulsed-laser melting of the tips of the columns and deposition of silicon from the intense flux of silicon-rich vapor produced by ablation of the surface regions between columns. The molten tips of the columns are strongly preferred sites for deposition, resulting in a very high axial growth rate. The growth process is conceptually similar to the vapor–liquid–solid method used to grow silicon whiskers. However, in the present case the pulsed-laser radiation fulfills two roles almost simultaneously, viz., providing the flux of silicon-containing molecules and melting the tips of the columns.

Early Stages of Pulsed-Laser Growth of Silicon Microcolumns and Microcones in Air and SF6

Dense arrays of high-aspect-ratio silicon microcolumns and microcones are formed by cumulative nanosecond pulsed excimer laser irradiation of single-crystal silicon in oxidizing atmospheres such as air and SF6. Growth of such surface microstructures requires a redeposition model and also involves elements of self-organization. The shape of the microstructures, i.e., straight columns vs. steeply sloping cones and connecting walls, is governed by the type and concentration of the oxidizing species, e.g., oxygen vs. fluorine. Growth is believed to occur by a “catalyst-free” VLS (vapor–liquid–solid) mechanism that involves repetitive melting of the tips of the columns/cones and deposition there of the ablated flux of Si-containing vapor. Results are presented of a new investigation of how such different final microstructures as microcolumns or microcones joined by walls nucleate and develop. The changes in silicon surface morphology were systematically determined and compared as the number of pulsed KrF (248 nm) laser shots was increased from 25 to several thousand in both air and SF6. The experiments in air and SF6 reveal significant differences in initial surface cracking and pattern formation. Consequently, local protrusions are first produced and column or cone/wall growth is initiated by different processes and at different rates. Differences in the spatial organization of column or cone/wall growth also are apparent.

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.

Surface microstructuring and long-range ordering of silicon nanoparticles

Pulsed-laser irradiation was used to induce the formation of linear arrays of nanoparticles that can extend over millimeter distances. On flat surfaces, the irradiation induces the fragmentation and clustering of a thin silicon film pulsed-laser deposited on silicon into nanoparticles that grow to 30–40 nm in diameter. The nanoparticles aggregate into clusters that migrate, forming short curvilinear groups that exhibit a short-range ordering. If a region containing a microscopic roughness is introduced, the nanoparticles are forced to align into long and remarkably straight lines with line spacing very close to the laser wavelength. A close connection is established between the nanoparticle alignment and the evolution of laser-induced periodic surface structures. The microscopic roughness solely serves as a trigger to produce the alignment.

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.

Microstructural Evolution of Laser-Exposed Silicon Targets in SF6 Atmospheres

The microstructures formed at the surface of silicon during pulsed-laser irradiation in SF6-rich atmospheres consist of an array of microholes surrounded by microcones. It is shown that there is a dynamic interplay between the formation of microholes and microcones. Fluorine produced by the laser-induced decomposition of SF6 is most likely responsible for the etching/ablation process. It is proposed that silicon-rich molecules and clusters that form in and are ejected from the continually deepening microholes sustain the axial and lateral growth of the microcones. The laser-melted layer at the tip and sides of the cones efficiently collects the silicon-rich products formed upon ablation. The total and partial pressures of SF6 in the chamber play a major role in cone development, a clear indication that it is the laser-generated plasma that controls the growth of these cones.

Surface micro-structuring of silicon by excimer-laser irradiation in reactive atmospheres

Abstract The formation mechanisms of cones and columns by pulsed-laser irradiation in reactive atmospheres were studied using scanning electron microscopy and profilometry. Deep etching takes place in SF 6 - and O 2 - rich atmospheres and consequently, silicon-containing molecules and clusters are released. Transport of silicon from the etched/ablated regions to the tip of columns and cones and to the side of the cones is required because both structures, columns and cones, protrude above the initial surface. The laser-induced micro-structure is influenced not only by the nature but also by the partial pressure of the reactive gas in the atmosphere. Irradiation in Ar following cone formation in SF 6 produced no additional growth but rather melting and resolidification. Subsequent irradiation using again a SF 6 atmosphere lead to cone restructuring and growth resumption. Thus the effects of etching plus re-deposition that produce column/cone formation and growth are clearly separated from the effects of just melting. On the other hand, irradiation continued in air after first performed in SF 6 resulted in: (a) an intense etching of the cones and a tendency to transform them into columns; (b) growth of new columns on top of the existing cones and (c) filamentary nano-structures coating the sides of the columns and cones.

Controlling thin film structure for the dewetting of catalyst nanoparticle arrays for subsequent carbon nanofiber growth

Vertically aligned carbon nanofiber (CNF) growth is a catalytic chemical vapor deposition process in which structure and functionality is controlled by the plasma conditions and the properties of the catalyst nanoparticles that template the fiber growth. We have found that the resultant catalyst nanoparticle network that forms by the dewetting of a continuous catalyst thin film is dependent on the initial properties of the thin film. Here we report the ability to tailor the crystallographic texture and composition of the nickel catalyst film and subsequently the nanoparticle template by varying the rf magnetron sputter deposition conditions. After sputtering the Ni catalyst thin films, the films are heated and exposed to an ammonia dc plasma, to chemically reduce the native oxide on the films and induce dewetting of the film to form nanoparticles. Subsequent nanoparticle treatment in an acetylene plasma at high substrate temperature results in CNF growth. Evidence is presented that the texture and composition of the nickel thin film has a significant impact on the structure and composition of the formed nanoparticle, as well as the resultant CNF morphology. Nickel films with a preferred (111) or (100) texture were produced and conditions favoring interfacial silicidation reactions were identified and investigated. Both compositional and structural analysis of the films and nanoparticles indicate that the properties of the as-deposited Ni catalyst film influences the subsequent nanoparticle formation and ultimately the catalytic growth of the carbon nanofibers.