Electron Beam Induced Etching Research Articles

Probing the interaction range of electron beam-induced etching in STEM by a non-contact electron beam

Beside its main purpose as a high-end tool in material analysis reaching the atomic scale for structure, chemical and electronic properties, aberration-corrected scanning transmission electron microscopy (STEM) is increasingly used as a tool to manipulate materials down to that very same scale. In order to obtain exact and reproducible results, it is essential to consider the interaction processes and interaction ranges between the electron beam and the involved materials. Here, we show in situ that electron beam-induced etching in a low-pressure oxygen atmosphere can extend up to a distance of several nm away from the Ångström-size electron beam, usually used for probing the sample. This relatively long-range interaction is related to beam tails and inelastic scattering involved in the etching process. To suppress the influence of surface diffusion, we measure the etching effect indirectly on isolated nm-sized holes in a 2 nm thin amorphous carbon foil that is commonly used as sample support in STEM. During our experiments, the electron beam is placed inside the nanoholes so that most electrons cannot directly participate in the etching process. We characterize the etching process from measuring etching rates at multiple nanoholes with different distances between the hole edge and the electron beam.

Sidewall angle tuning in focused electron beam-induced processing.

Structures fabricated using focused electron beam-induced deposition (FEBID) have sloped sidewalls because of the very nature of the deposition process. For applications this is highly undesirable, especially when neighboring structures are interconnected. A new technique combining FEBID and focused electron beam-induced etching (FEBIE) has been developed to fabricate structures with vertical sidewalls. The sidewalls of carbon FEBID structures have been modified by etching with water and it is shown, using transmission electron microscopy imaging, that the sidewall angle can be tuned from outward to inward by controlling the etch position on the sidewall. A surprising under-etching due to the emission of secondary electrons from the deposit was observed, which was not indicated by a simple model based on etching. An analytical model was developed to include continued etching once the deposit has been removed at the exposed pixel. At this stage the secondary electrons from the substrate then cause the adsorbed water molecules to become effective in etching the deposit from below, resulting in under-etched structures. The evolution of the sidewall angle during etching has also been experimentally observed in a scanning electron microscope by continuously monitoring the secondary electron detector signal.

Selected Area Manipulation of MoS2 via Focused Electron Beam-Induced Etching for Nanoscale Device Editing.

We demonstrate direct-write patterning of single and multilayer MoS2 via a focused electron beam-induced etching (FEBIE) process mediated with the XeF2 precursor. MoS2 etching is performed at various currents, areal doses, on different substrates, and characterized using scanning electron and atomic force microscopies as well as Raman and photoluminescence spectroscopies. Scanning transmission electron microscopy reveals a sub-40 nm etching resolution and the progression of point defects and lateral etching of the consequent unsaturated bonds. The results confirm that the electron beam-induced etching process is minimally invasive to the underlying material in comparison to ion beam techniques, which damage the subsurface material. Single-layer MoS2 field-effect transistors are fabricated, and device characteristics are compared for channels that are edited via the selected area etching process. The source-drain current at constant gate and source-drain voltage scale linearly with the edited channel width. Moreover, the mobility of the narrowest channel width decreases, suggesting that backscattered and secondary electrons collaterally affect the periphery of the removed area. Focused electron beam doses on single-layer transistors below the etching threshold were also explored as a means to modify/thin the channel layer. The FEBIE exposures showed demonstrative effects via the transistor transfer characteristics, photoluminescence spectroscopy, and Raman spectroscopy. While strategies to minimize backscattered and secondary electron interactions outside of the scanned regions require further investigation, here, we show that FEBIE is a viable approach for selective nanoscale editing of MoS2 devices.

Electron beam-induced etching of SiO2, Si3N4, and poly-Si assisted by CF4/O2 remote plasma

Electron-stimulated etching of surfaces functionalized by remote plasma is a flexible and novel approach for material removal. In comparison with plasma dry etching, which uses the ion-neutral synergistic effect to control material etching, electron beam-induced etching (EBIE) uses an electron-neutral synergistic effect. This approach appears promising for the reduction of plasma-induced damage (PID), including atomic displacement and lateral straggling, along with the potential for greater control and lateral resolution. One challenge for EBIE is the limited selection of chemical precursor molecules that can be used to produce functionalized materials suitable for etching under electron beam irradiation. In this work, we studied a new experimental approach that utilizes a remote plasma source to functionalize substrate surfaces in conjunction with electron beam irradiation by an electron flood gun. Etching rates (ERs) of SiO2, Si3N4, and poly-Si are reported in a broad survey of processing conditions. The parametric dependence of the ER of these Si-based materials on the operating parameters of the flood gun and the remote plasma source is evaluated. We also identified the processing parameters that enable the realization of material selective removal, i.e., the etching selectivity of Si3N4 over SiO2 and poly-Si over SiO2. Additionally, surface characterization of etched materials is used to clarify the effects of the co-introduction of particle fluxes from the remote plasma and flood gun sources on surface chemistry.

SiO2 etching and surface evolution using combined exposure to CF4/O2 remote plasma and electron beam

Electron-based surface activation of surfaces functionalized by remote plasma appears like a flexible and novel approach to atomic scale etching and deposition. Relative to plasma-based dry etching that uses ion bombardment of a substrate to achieve controlled material removal, electron beam-induced etching (EBIE) is expected to reduce surface damage, including atom displacement, surface roughness, and undesired material removal. One of the issues with EBIE is the limited number of chemical precursors that can be used to functionalize material surfaces. In this work, we demonstrate a new configuration that was designed to leverage flexible surface functionalization using a remote plasma source, and, by combining with electron beam bombardment to remove the chemically reacted surface layer through plasma-assisted electron beam-induced etching, achieve highly controlled etching. This article describes the experimental configuration used for this demonstration that consists of a remote plasma source and an electron flood gun for enabling electron beam-induced etching of SiO2 with Ar/CF4/O2 precursors. We evaluated the parametric dependence of SiO2 etching rate on processing parameters of the flood gun, including electron energy and emission current, and of the remote plasma source, including radiofrequency source power and flow rate of CF4/O2, respectively. Additionally, two prototypical processing cases were demonstrated by temporally combining or separating remote plasma treatment and electron beam irradiation. The results validate the performance of this approach for etching applications, including photomask repair and atomic layer etching of SiO2. Surface characterization results that provide mechanistic insights into these processes are also presented and discussed.

Nanoscale Ruthenium-Containing Deposits from Ru(CO)4I2 via Simultaneous Focused Electron Beam-Induced Deposition and Etching in Ultrahigh Vacuum: Mask Repair in Extreme Ultraviolet Lithography and Beyond

Nanoscale Ruthenium-Containing Deposits from Ru(CO)₄I₂ via Simultaneous Focused Electron Beam-Induced Deposition and Etching in Ultrahigh Vacuum: Mask Repair in Extreme Ultraviolet Lithography and Beyond

Combined Focused Electron Beam-Induced Deposition and Etching for the Patterning of Dense Lines without Interconnecting Material.

High resolution dense lines patterned by focused electron beam-induced deposition (FEBID) have been demonstrated to be promising for lithography. One of the challenges is the presence of interconnecting material, which is often carbonaceous, between the lines as a result of the Gaussian line profile. We demonstrate the use of focused electron beam-induced etching (FEBIE) as a scanning electron microscope (SEM)-based direct-write technique for the removal of this interconnecting material, which can be implemented without removing the sample from the SEM for post processing. Secondary electron (SE) imaging has been used to monitor the FEBIE process, and atomic force microscopy (AFM) measurements confirm the fabrication of well separated FEBID lines. We further demonstrate the application of this technique for removing interconnecting material in high resolution dense lines using backscattered electron (BSE) imaging to monitor the process.

Role of knock-on in electron beam induced etching of diamond

Electron beam induced etching (EBIE) has recently emerged as a promising direct-write nanofabrication technique. EBIE is typically assumed to proceed entirely through chemical pathways driven by electron-electron interactions. Here we show that knock-on (i.e., momentum transfer from electrons to nuclei) can play a significant role in EBIE, even at electron beam energies as low as 1.5 keV. Specifically, we calculate knock-on cross-sections for H, D, O and CO on the surface of diamond and show experimentally that they affect the kinetics of EBIE performed using oxygen, hydrogen and deuterium etch precursors. Our results advance basic understanding of electron-adsorbate interactions, particularly in relation to EBIE and the related techniques of electron beam-induced deposition and surface functionalisation.

Photonic Nanostructures from Hexagonal Boron Nitride

AbstractGrowing interest in devices based on layered van der Waals (vdW) materials is motivating the development of new nanofabrication methods. Hexagonal boron nitride (hBN) is one of the most promising materials for studies of quantum photonics and phonon polaritonics. A promising nanofabrication process used to fabricate several hBN photonic devices using a hybrid reactive ion etching (RIE) and electron beam‐induced etching (EBIE) technique is reported in detail here. The shortcomings and benefits of RIE and EBIE are highlighted and the utility of the hybrid approach for the fabrication of suspended and supported device structures with nanoscale features and highly vertical sidewalls are demonstrated. Functionality of the fabricated devices is proven by measurements of high‐quality cavity optical modes (Q ≈ 1500). This nanofabrication approach constitutes an advance toward an integrated, monolithic quantum photonics platform based on hBN and other layered vdW materials.

Deterministic Nanopatterning of Diamond Using Electron Beams.

Diamond is an ideal material for a broad range of current and emerging applications in tribology, quantum photonics, high-power electronics, and sensing. However, top-down processing is very challenging due to its extreme chemical and physical properties. Gas-mediated electron beam-induced etching (EBIE) has recently emerged as a minimally invasive, facile means to dry etch and pattern diamond at the nanoscale using oxidizing precursor gases such as O2 and H2O. Here we explain the roles of oxygen and hydrogen in the etch process and show that oxygen gives rise to rapid, isotropic etching, while the addition of hydrogen gives rise to anisotropic etching and the formation of topographic surface patterns. We identify the etch reaction pathways and show that the anisotropy is caused by preferential passivation of specific crystal planes. The anisotropy can be controlled by the partial pressure of hydrogen and by using a remote RF plasma source to radicalize the precursor gas. It can be used to manipulate the geometries of topographic surface patterns as well as nano- and microstructures fabricated by EBIE. Our findings constitute a comprehensive explanation of the anisotropic etch process and advance present understanding of electron-surface interactions.

Electron beam induced etching of carbon nanotubes enhanced by secondary electrons in oxygen

Multi-walled carbon nanotubes (CNTs) are subjected to electron-beam-induced etching (EBIE) in oxygen. The EBIE process is observed in situ by environmental transmission electron microscopy. The partial pressure of oxygen (10 and 100 Pa), energy of the primary electrons (80 and 200 keV), and environment of the CNTs (suspended or supported on a silicon nitride membrane) are investigated as factors affecting the etching rate. The EBIE rate of CNTs was markedly promoted by the effects of secondary electrons that were emitted from a silicon nitride membrane under irradiation by primary electrons. Membrane supported CNTs can be cut by EBIE with a spatial accuracy better than 3 nm, and a nanogap of 2 nm can be successfully achieved between the ends of two suspended CNTs.

Maskless Direct-Write Etching of Nanopit Arrays in Si Using Focused Electron Beam Induced Etching

We have used a focused electron beam and chlorine injection in order to etch nanopits on predefined positions of a Si sample. With other methods it is often difficult to get exactly positioned nanopits. With this maskless, resistless direct-write approach nanopits with a diameter below 100 nm has been fabricated. We will report on the optimum processing conditions and present different geometries fabricated wit this technique. Finally, application examples will be given.

Dynamic Pattern Formation in Electron-Beam-Induced Etching.

We report highly ordered topographic patterns that form on the surface of diamond, span multiple length scales, and have a symmetry controlled by the precursor gas species used in electron-beam-induced etching (EBIE). The pattern formation dynamics reveals an etch rate anisotropy and an electron energy transfer pathway that is overlooked by existing EBIE models. We, therefore, modify established theory such that it explains our results and remains universally applicable to EBIE. The patterns can be exploited in controlled wetting, optical structuring, and other emerging applications that require nano- and microscale surface texturing of a wide band-gap material.

Using an energized oxygen micro-jet for improved graphene etching by focused electron beam

We report on an improved Focused Electron Beam Induced Etching (FEBIE) process, which exploits heated oxygen delivery via a continuous supersonic micro-jet resulting in faster graphene patterning and better etch feature definition. Positioning a micro-jet in close proximity to a graphene surface with minimal jet spreading due to a continuous regime of gas flow at the exit of the 10 μm inner diameter capillary allows for focused exposure of the surface to reactive oxygen at high mass flux and impingement energy of a supersonic gas stream localized to a small etching area exposed to electron beam. These unique benefits of focused supersonic oxygen delivery to the surface enable a dramatic increase in the etch rate of graphene with no parasitic carbon “halo” deposition due to secondary electrons from backscattered electrons (BSE) in the area surrounding the etched regions. Increase of jet temperature via local nozzle heating provides means for enhancing kinetic energy of impinging oxygen molecules, which further speed up the etch, thus minimizing the beam exposure time and required electron dose, before parasitic carbon film deposition due to BSE mediated decomposition of adsorbed hydrocarbon contaminants has a measurable impact on quality of graphene etched features. Interplay of different physical mechanisms underlying an oxygen micro-jet assisted FEBIE process is discussed with support from experimental observations.

Localized Probing of Gas Molecule Adsorption Energies and Desorption Attempt Frequencies

Gas-mediated electron beam induced etching (EBIE) and deposition (EBID) can be used to measure activation energies that are interpreted as the adsorption energies of surface-adsorbed precursor molecules. However, the measured quantities often disagree with adsorption energies measured by conventional analysis techniques such as thermally programmed desorption and have anomalous dependencies on parameters such as the electron beam current used to perform EBID. Here, we use the theory of EBIE and EBID rate kinetics to explain this behavior and identify conditions under which the activation energies and the associated pre-exponential factors correspond to gas molecule adsorption energies and desorption attempt frequencies, respectively. Under these conditions, EBIE and EBID can be used as robust, nanoscale techniques for the analysis of adsorbates.

Cryogenic electron beam induced chemical etching.

Cryogenic cooling is used to enable efficient, gas-mediated electron beam induced etching (EBIE) in cases where the etch rate is negligible at room and elevated substrate temperatures. The process is demonstrated using nitrogen trifluoride (NF3) as the etch precursor, and Si, SiO2, SiC, and Si3N4 as the materials volatilized by an electron beam. Cryogenic cooling broadens the range of precursors that can be used for EBIE, and enables high-resolution, deterministic etching of materials that are volatilized spontaneously by conventional etch precursors as demonstrated here by NF3 and XeF2 EBIE of silicon.

Advances in gas-mediated electron beam-induced etching and related material processing techniques

Electron beam-induced etching (EBIE) has traditionally been used for top-down, direct-write, chemical dry etching, and iterative editing of materials. The present article reviews recent advances in EBIE modeling and emerging applications, with an emphasis on use cases in which the approaches that have conventionally been used to realize EBIE are instead used for material analysis, surface functionalization, or bottom-up growth of nanostructured materials. Such applications are used to highlight the shortcomings of existing quantitative EBIE models and to identify physicochemical phenomena that must be accounted for in order to enable full exploitation and predictive modeling of EBIE and related electron beam fabrication techniques.

Dynamic Surface Site Activation: A Rate Limiting Process in Electron Beam Induced Etching

We report a new mechanism that limits the rate of electron beam induced etching (EBIE). Typically, the etch rate is assumed to scale directly with the precursor adsorbate dissociation rate. Here, we show that this is a special case, and that the rate can instead be limited by the concentration of active sites at the surface. Novel etch kinetics are expected if surface sites are activated during EBIE, and observed experimentally using the electron sensitive material ultra nanocrystalline diamond (UNCD). In practice, etch kinetics are of interest because they affect resolution, throughput, proximity effects, and the topography of nanostructures and nanostructured devices fabricated by EBIE.

Electron beam induced chemical dry etching and imaging in gaseous NH3 environments

We report the use of ammonia (NH3) vapor as a new precursor for nanoscale electron beam induced etching (EBIE) of carbon, and an efficient imaging medium for environmental scanning electron microscopy (ESEM). Etching is demonstrated using amorphous carbonaceous nanowires grown by electron beam induced deposition (EBID). It is ascribed to carbon volatilization by hydrogen radicals generated by electron dissociation of NH3 adsorbates. The volatilization process is also effective at preventing the buildup of residual hydrocarbon impurities that often compromise EBIE, EBID and electron imaging. We also show that ammonia is a more efficient electron imaging medium than H2O, which up to now has been the most commonly used ESEM imaging gas.

3D Nanofluidic Channels Shaped by Electron‐Beam‐Induced Etching

In-plane nanofluidic channels with 3D topography are fabricated. Nanochannel masters are written by electron beam lithography in SU-8 resist and shaped by electron-beam-induced etching (EBIE) with water as the precursor gas. Nanofunnel replicas cast from unmodified and EBIE-modified masters show that the funnel tip dimensions decrease from a 150-nm depth and 80-nm width to a 70-nm depth and 40-nm width.