Focused Electron Beam Induced Processing Research Articles

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.

Pushing the limits of EUV mask repair: addressing sub-10 nm defects with the next generation e-beam-based mask repair tool

Mask repair is an essential step in the manufacturing process of extreme ultraviolet (EUV) masks. Its key challenge is to continuously improve resolution and control to enable the repair of the ever-shrinking feature sizes on mask along the EUV roadmap. The state-of-the-art mask repair method is gas-assisted electron-beam (e-beam) lithography also referred to as focused electron-beam induced processing (FEBIP). We discuss the principles of the FEBIP repair process, along with the criteria to evaluate the repairs, and identify the major contributions determining the achievable resolution. As key results, we present several high-end repairs on EUV masks including a sub-10-nm extrusion achieved with the latest generation of e-beam-based mask repair tools, the MeRiT® LE. Furthermore, we demonstrate the corresponding repair verification using at-wavelength (actinic) measurements.

Exploring the fabrication and transfer mechanism of metallic nanostructures on carbon nanomembranes via focused electron beam induced processing.

Focused electron beam-induced processing is a versatile method for the fabrication of metallic nanostructures with arbitrary shape, in particular, on top of two-dimensional (2D) organic materials, such as self-assembled monolayers (SAMs). Two methods, namely electron beam-induced deposition (EBID) and electron beam-induced surface activation (EBISA) are studied with the precursors Fe(CO)5 and Co(CO)3NO on SAMs of 1,1′,4′,1′′-terphenyl-4-thiol (TPT). For Co(CO)3NO only EBID leads to deposits consisting of cobalt oxide. In the case of Fe(CO)5 EBID and EBISA yield deposits consisting of iron nanocrystals with high purity. Remarkably, the EBISA process exhibits a strong time dependence, which is analyzed in detail for different electron doses. This time dependence is a new phenomenon, which, to the best of our knowledge, was not reported before. The electron-induced cross-linking of the SAM caused by the cleavage of C–H bonds and the subsequent formation of new C–C bonds between neighboring molecules also seems to play a crucial role in the EBISA process. Previous studies showed that iron nanostructures fabricated on top of a cross-linked SAM on Au/mica can be transferred to solid substrates and grids without any changes, aside from oxidation. Here we demonstrate that iron as well as cobalt oxide structures on top of a cross-linked SAM on Ag/mica do change more significantly. The Fe(NO3)3 solution used for etching of the Ag layer also dissolves the cobalt oxide structures and causes dissolution and reduction of the iron structures. These results demonstrate that the fabrication of hybrids of metallic nanostructures onto organic 2D materials is an intrinsically complex procedure. The interactions among the metallic deposits, the substrate for the growth of the SAM, and the associated etching/dissolving agent need to be considered and further studied.

Ultrathin Carbon Nanomembranes from 5,10,15,20-Tetraphenylporphyrin: Electron Beam Induced Fabrication and Functionalization via Focused Electron Beam Induced Processing

Two-dimensional (2D) materials are promising candidates as main components for future applications in electronics, optics, and magnetics due to their specific properties. One method to fabricate su...

Controlled Electron-Induced Fabrication of Metallic Nanostructures on 1 nm Thick Membranes.

Functional hybrids comprising metallic nanostructures connected and protected by nonmetallic 2D materials are envisioned as miniaturized components for applications in optics, electronics, and magnetics. A promising strategy to build such elements is the direct writing of metallic nanostructures by focused electron beam induced processing (FEBIP) onto insulating 2D materials. Carbon nanomembranes (CNMs), produced via electron-induced crosslinking of self-assembled monolayers (SAMs), are ultrathin and flexible films; their thickness as well as their mechanical and electrical properties are determined by the specific choice of self-assembling molecules. In this work, functionalized CNMs are produced via electron beam induced deposition of Fe(CO)5 onto terphenylthiol SAMs. Clean iron nanostructures of arbitrary size and shape are deposited on the SAMs, and the SAMs are then crosslinked into CNMs. The functionalized CNMs are then transferred onto either solid substrates or onto grids to obtain freestanding metal/CNM hybrid structures. Iron nanostructures with predefined shapes on top of 1 nm thin freestanding CNMs are realized; they stay intact during the fabrication procedures and remain mechanically stable. Combining the ease and versatility of SAMs with the flexibility of FEBIP thus leads to a route for the fabrication of functional hybrid nanostructures.

Adaptive simulations enable computational design of electron beam processing of nanomaterials with supersonic micro-jet precursor

Focused Electron Beam Induced Processing (FEBIP) is a powerful tool for the “direct-write” of nanomaterials with the possibility of atomistic control on suspended 2D material substrates. FEBIP capabilities have been significantly expanded by using a localized jet-based delivery of precursors, and especially when a thermally energized supersonic micro-jet enhances the delivery of mass flux along with controlling the far-from-equilibrium thermodynamic state of adsorbed adatoms. The possibilities of growing nanomaterials with “dialed-in” composition with ultra-high growth rates and aspect ratios up to 100:1 have been demonstrated using the supersonic micro-jet-FEBIP. Bringing this scientific discovery to the level of maturity required for practical applications in additive nanomanufacturing requires simulation tools that are capable of capturing the complex flow physics of micro-jet-substrate interactions that bridge a wide range of flow regimes from the high-density gas micro-jet expanding into the vacuum environment of FEBIP. To address this significant computational challenge, a new approach has been developed and described in this work for a multiscale adaptive DSMC (Direct Simulation Monte Carlo) algorithm to predict the micro-jet gas dynamics in an FEBIP environment, spanning the full range of flow regimes from low Knudsen (Kn) number O(0.01) continuum flow to high Kn of O(10) for the molecular flow within a unified computational framework. The fundamental principles of the adaptive DSMC algorithm are described, its viability as a DSMC technique is demonstrated, and computational improvements for the benchmark cases are discussed in the context of advancing 3D nanofabrication with FEBIP. Ultimately, combining the first principle simulations via adaptive DSMC with the complementary experimental data will enable the creation of the powerful CAD tools for in silico design and optimal operation of micro-jet-FEBIP.

High-Resolution Three-Dimensional Sculpting of Two-Dimensional Graphene Oxide by E-Beam Direct Write.

On-demand switchable "additive/subtractive" patterning of two-dimensional (2D) nanomaterials is an essential capability for developing new concepts of functional nanomaterials and their device realizations. Traditionally, this is performed via a multistep process using photoresist coating and patterning by conventional photo or electron beam lithography, which is followed by bulk dry/wet etching or deposition. This limits the range of functionalities and structural topologies that can be achieved as well as increases the complexity, cost, and possibility of contamination, which are significant barriers to device fabrication from highly sensitive 2D materials. Focused electron beam-induced processing (FEBIP) enables a material chemistry/site-specific, high-resolution multimode atomic scale processing and provides unprecedented opportunities for "direct-write", single-step surface patterning of 2D nanomaterials with an in situ imaging capability. It allows for realizing a rapid multiscale/multimode approach, ranging from an atomic scale manipulation (e.g., via targeted defect introduction as an active site) to a large-area surface modification on nano- and microscales, including patterned doping and material removal/deposition with 2D (in-plane)/three-dimensional (3D) (out-of-plane) control. In this work, we report on a new capability of FEBIP for nanoscale patterning of graphene oxide via removal of oxygenated carbon moieties with no use of reactive gas required for etching complemented by carbon atom deposition using a focused electron beam. The mechanism of experimentally observed phenomena is explored using the density functional theory (DFT) calculations, revealing that interactions of e-beam that liberated reactive oxygen radicals with carbon atoms on the graphene basal plane lead to the creation of atomic vacancies in the material. The reaction byproducts are volatile carbon dioxides, which are dissociated and volatilized from the graphene oxide surface functional groups by interactions with an energetic focused electron beam. Along with selective subtractive patterning of graphene oxide, the same electron beam with increased irradiation doses can deposit out-of-plane 3D carbon nanostructures on top of or around the 2D etched pattern, thus forming a hybrid 2D/3D nanocomposite with a feature control down to a few nanometers. This in operando dual nanofabrication capability of FEBIP is unmatched by any other nanopatterning techniques and opens a new design window for forming 2D/3D complex nanostructures and functional nanodevices.

Additive Nano-Lithography with Focused Soft X-rays: Basics, Challenges, and Opportunities.

Focused soft X-ray beam induced deposition (FXBID) is a novel technique for direct-write nanofabrication of metallic nanostructures from metal organic precursor gases. It combines the established concepts of focused electron beam induced processing (FEBIP) and X-ray lithography (XRL). The present setup is based on a scanning transmission X-ray microscope (STXM) equipped with a gas flow cell to provide metal organic precursor molecules towards the intended deposition zone. Fundamentals of X-ray microscopy instrumentation and X-ray radiation chemistry relevant for FXBID development are presented in a comprehensive form. Recently published proof-of-concept studies on initial experiments on FXBID nanolithography are reviewed for an overview on current progress and proposed advances of nanofabrication performance. Potential applications and advantages of FXBID are discussed with respect to competing electron/ion based techniques.

Surface-Anchored Metal-Organic Frameworks as Versatile Resists for Gas-Assisted E-Beam Lithography: Fabrication of Sub-10 Nanometer Structures.

We demonstrate that surface-anchored metal-organic frameworks (SURMOFs) are extraordinary well-suited as resists for high-resolution focused electron beam induced processing (FEBIP) techniques. The combination of such powerful lithographic protocols with the huge versatility of MOF materials are investigated in respect to their potential in nanostructures fabrication. The applied FEBIP methods rely on the local decomposition of Fe(CO)5 and Co(CO)3NO as precursors, either by the direct impact of the focused electron beam (electron beam induced deposition, EBID) or through the interaction of the precursor molecules with preirradiated/activated SURMOF areas (electron beam induced surface activation, EBISA). We demonstrate the huge potential of the approach for two different types of MOFs (HKUST-1 and Zn-DPDCPP). Our "surface science" approach to FEBIP, yields well-defined deposits with each investigated precursor/SURMOF combination. Local Auger electron spectroscopy reveals clean iron deposits from Fe(CO)5; deposits from Co(CO)3NO contain cobalt, nitrogen, and oxygen. EBISA experiments were successful with Fe(CO)5. Remarkably EBISA with Co(CO)3NO does not result in deposit formation on both resists, making the process chemically selective. Most importantly we demonstrate the fabrication of "nested-L" test structures with Fe(CO)5 on HKUST-1 with extremely narrow line widths of partially less than 8 nm, due to reduced electron proximity effects within the MOF-based resists. Considering that the actual diameter of the electron beam was larger than 6 nm, we see a huge potential for significant reduction of the structure sizes. In addition, the role and high potential of loading and transport of the precursor molecules within the porous SURMOF materials is discussed.

On the Principles of Tweaking Nanostructure Fabrication via Focused Electron Beam Induced Processing Combined with Catalytic Growth Processes

Novel pathways to use a focused electron beam in ultrahigh vacuum in combination with catalytic growth protocols are explored for the fabrication of well-defined nanostructures. Thereby, the basic process is the local deposition of material from different precursor molecules (Co(CO)3 NO, Fe(CO)5). This can be realized with a focused electron beam by direct deposition of the precursor or by a chemical modification of the substrate, such that it becomes activated toward the decomposition of the precursor. For both methods, autocatalytic growth (AG) processes can occur, yielding the deposition of additional material. Interestingly, significantly different chemical selectivities for the two precursors are found, which can drastically change upon subtle changes of the surface. It is demonstrated that AG can be tweaked by the choice of the substrate/precursor combination. One possibility to quench catalytic activity of a substrate is the preparation of a thin layer of organic molecules, here porphyrins, which enables the fabrication of hybrid metal–organic nanostructures with line widths below 20 nm. Based on these findings, corresponding techniques are developed which exploit (auto)catalytic effects for the controlled fabrication of nanostructures. These results indicate that every substrate is applicable to electron beam induced surface activation by preparation of a thin porphyrin layer.

History and modern applications of nano-composite materials carrying GA/cm2 current density due to a Bose-Einstein Condensate at room temperature produced by Focused Electron Beam Induced Processing for many extraordinary novel technical applications

The discovery of Focused Electron Beam Induced Processing and early applications of this technology led to the possible use of a novel nanogranular material “Koops-GranMat®” using Pt/C and Au/C material. which carries at room temperature a current density > 50 times the current density which high TC superconductors can carry. The explanation for the characteristics of this novel material is given. This fact allows producing novel products for many applications using Dual Beam system having a gas supply and X.Y.T stream data programming and not using GDSII layout pattern control software. Novel products are possible for energy transportation. -distribution.-switching, photon-detection above 65 meV energy for very efficient energy harvesting, for bright field emission electron sources used for vacuum electronic devices like amplifiers for HF electronics, micro-tubes, 30 GHz to 6 THz switching amplifiers with signal to noise ratio >10(!), THz power sources up to 1 Watt, in combination with miniaturized vacuum pumps, vacuum gauges, IR to THz detectors, EUV- and X-Ray sources. Since focusing electron beam induced deposition works also at low energy, selfcloning multibeam-production machines for field emitter lamps, displays, multi-beam - lithography, - imaging, and - inspection, energy harvesting, and power distribution with switches controlling field-emitter arrays for KA of currents but with < 100 V switching voltage are possible. Finally the replacement of HTC superconductors and its applications by the Koops-GranMat® having Koops-Pairs at room temperature will allow the investigation devices similar to Josephson Junctions and its applications now called QUIDART (Quantum interference devices at Room Temperature). All these possibilities will support a revolution in the optical, electric, power, and electronic technology.

Focused particle beam-induced processing.

Focused particle beam-induced processing.

Continuum models of focused electron beam induced processing.

Focused electron beam induced processing (FEBIP) is a suite of direct-write, high resolution techniques that enable fabrication and editing of nanostructured materials inside scanning electron microscopes and other focused electron beam (FEB) systems. Here we detail continuum techniques that are used to model FEBIP, and release software that can be used to simulate a wide range of processes reported in the FEBIP literature. These include: (i) etching and deposition performed using precursors that interact with a surface through physisorption and activated chemisorption, (ii) gas mixtures used to perform simultaneous focused electron beam induced etching and deposition (FEBIE and FEBID), and (iii) etch processes that proceed through multiple reaction pathways and generate a number of reaction products at the substrate surface. We also review and release software for Monte Carlo modeling of the precursor gas flux which is needed as an input parameter for continuum FEBIP models.

The future of focused electron beam-induced processing

A perspective is sketched for the field of focused electron beam-induced processing (FEBIP). The FEBIP lithography technique is compared to the very successful resist-based electron beam lithography (EBL) technique. The advantages of FEBIP over EBL are identified, the main advantage being its high spatial resolution. This will enable FEBIP to become an important lithography technique for the fabrication of devices with critical dimension in the range between 1 and 20 nm and serve as a complementary technique to EBL. It will be discussed what needs to be done to achieve this and what the potential applications are.

Focused-electron-beam-induced processing (FEBIP) for emerging applications in carbon nanoelectronics

Focused-electron-beam-induced processing (FEBIP), a resist-free additive nanomanufacturing technique, is an actively researched method for “direct-write” processing of a wide range of structural and functional nanomaterials, with high degree of spatial and time-domain control. This article attempts to critically assess the FEBIP capabilities and unique value proposition in the context of processing of electronics materials, with a particular emphasis on emerging carbon (i.e., based on graphene and carbon nanotubes) devices and interconnect structures. One of the major hurdles in advancing the carbon-based electronic materials and device fabrication is a disjoint nature of various processing steps involved in making a functional device from the precursor graphene/CNT materials. Not only this multi-step sequence severely limits the throughput and increases the cost, but also dramatically reduces the processing reproducibility and negatively impacts the quality because of possible between-the-step contamination, especially for impurity-susceptible materials such as graphene. The FEBIP provides a unique opportunity to address many challenges of carbon nanoelectronics, especially when it is employed as part of an integrated processing environment based on multiple “beams” of energetic particles, including electrons, photons, and molecules. This avenue is promising from the applications’ prospective, as such a multi-functional (electron/photon/molecule beam) enables one to define shapes (patterning), form structures (deposition/etching), and modify (cleaning/doping/annealing) properties with locally resolved control on nanoscale using the same tool without ever changing the processing environment. It thus will have a direct positive impact on enhancing functionality, improving quality and reducing fabrication costs for electronic devices, based on both conventional CMOS and emerging carbon (CNT/graphene) materials.

Industrial perspective on focused electron beam-induced processes

After a short overview of the historical developments of the technique of gas-assisted focused electron beam-induced processing (mostly deposition and etching), this paper deals with the applications of this technology to photolithographic mask repair. A commented list of results is shown on different mask types, for different types of defects, and at different node generations. The scope of this article is double: summarize the state of the art in a fast-paced highly specific industrial environment driven by “Moore’s law” and feedback to academic researchers some technologically relevant directions for further investigations.

Electron beam induced surface activation: a method for the lithographic fabrication of nanostructures via catalytic processes

In focused electron beam induced processing (FEBIP), the very narrow electron beam of a scanning electron microscope or transmission electron microscope is used to locally modify matter on the nanometer scale. Recently, the family of FEBIP could be considerably expanded by the technique of focused electron beam induced surface activation (EBISA). In EBISA, the surface itself gets chemically activated by the impact of the electron beam without the presence of precursor molecules. In the second EBISA processing step, the surface is exposed to a precursor molecule which is then catalytically decomposed at the pre-irradiated/activated areas and eventually continues to grow autocatalytically upon prolonged precursor dosage. In this way, electron irradiation and precursor dosage are effectively separated. One of the advantages is that, due to the autocatalytic growth, the size of the corresponding nanostructures can be controlled by the precursor dosage and corresponding electron proximity effects can be omitted. Another advantage is the parallel processing of the pre-irradiated regions during precursor dosage. This bears the potential to significantly reduce the fabrication times for larger deposits compared to the classical electron beam induced deposition approach, in which precursor molecules are sequentially dissociated by the impact of the electron. The fundamentals and apparent further developments as well as the potential and challenges of the comparably new EBISA technique, and more general of catalytic effects in FEBIP are presented and discussed.

Size and shape control of sub-20 nm patterns fabricated using focused electron beam-induced processing

In a first study to analyze the feasibility of electron beam-induced deposition (EBID) for creating certain patterns in advanced lithography, line patterns were fabricated on silicon wafers using EBID. The growth conditions were such that the growth rate is fully determined by the electron flux (the current limited growth regime). It is experimentally verified that different patterning strategies, such as serial versus parallel patterning and single pass patterning versus multiple pass patterning, all lead to the same result in this growth regime. Images of EBID lines, imaged in a scanning electron microscope, were analyzed to determine the position of the lines, the width of the lines, and the linewidth roughness (LWR). The results are that the lines have an average width of 13.7 nm, an average standard deviation of 1.6 nm in the center position of the lines, and an average LWR of 4.5 nm (1? value). As an example of the capabilities of EBID, a logic-resembling lithography pattern was fabricated

Fabrication of cobalt trifluoride (CoF3) phase from metallic cobalt by XeF2-assisted Focused Electron Beam Induced Processing

Focused Electron Beam Induced Processing (FEBIP) using XeF2 gas injection is routinely applied in circuit editing, mask repair and nanolithography to etch semiconducting or metallic materials. Here, we report the use of XeF2-assisted FEBIP for a novel application: the formation of a metal fluoride from a metal layer in the area scanned by the electron beam. Our study focuses on the reaction of cobalt into cobalt trifluoride (CoF3). The objective of the present study is to locally obtain the CoF3 compound out of a cobalt nanostructure. The CoF3 phase has been reported in the past to show antiferromagnetic properties at room temperature, thus ferromagnetic/antiferromagnetic (Co/CoF3) bilayer structures with magnetic exchange bias phenomena could be engineered at the micro/nano scale. Electron Energy Loss Spectroscopy studies presented here demonstrate that CoF3 is efficiently obtained out of Co by means of XeF2-assisted FEBIP, opening the route for future Co/CoF3-based devices.

The role of electron-stimulated desorption in focused electron beam induced deposition

We present the results of our study about the deposition rate of focused electron beam induced processing (FEBIP) as a function of the substrate temperature with the substrate being an electron-transparent amorphous carbon membrane. When W(CO)6 is used as a precursor it is observed that the growth rate is lower at higher substrate temperatures. From Arrhenius plots we calculated the activation energy for desorption, Edes, of W(CO)6. We found an average value for Edes of 20.3 kJ or 0.21 eV, which is 2.5–3.0 times lower than literature values. This difference between estimates for Edes from FEBIP experiments compared to literature values is consistent with earlier findings by other authors. The discrepancy is attributed to electron-stimulated desorption, which is known to occur during electron irradiation. The data suggest that, of the W(CO)6 molecules that are affected by the electron irradiation, the majority desorbs from the surface rather than dissociates to contribute to the deposit. It is important to take this into account during FEBIP experiments, for instance when determining fundamental process parameters such as the activation energy for desorption.