Electron Beam Induced Deposition Research Articles

Tuning dissipation dilution in 2D material resonators by MEMS-induced tension

Resonators based on two-dimensional (2D) materials have exceptional properties for application as nanomechanical sensors, which allows them to operate at high frequencies with high sensitivity. However, their performance as nanomechanical sensors is currently limited by their low quality (Q)-factor. Here, we make use of micro-electromechanical systems (MEMS) to apply pure in-plane mechanical strain, enhancing both their resonance frequency and Q-factor. In contrast to earlier work, the 2D material resonators are fabricated on the MEMS actuators without any wet processing steps using a dry-transfer method. A platinum clamp, which is deposited by electron beam-induced deposition, is shown to be effective in fixing the 2D membrane to the MEMS and preventing slippage. By in-plane straining the membranes in a purely mechanical fashion, we increase the tensile energy, thereby diluting dissipation. This way, we show how dissipation dilution can increase the Q-factor of 2D material resonators by 91%. The presented MEMS actuated dissipation dilution method does not only pave the way toward higher Q-factors in resonators based on 2D materials, but also provides a route toward studies of the intrinsic loss mechanisms of 2D materials in the monolayer limit.

Electron-induced deposition using Fe(CO)4MA and Fe(CO)5 - effect of MA ligand and process conditions.

The electron-induced decomposition of Fe(CO)4MA (MA = methyl acrylate), which is a potential new precursor for focused electron beam-induced deposition (FEBID), was investigated by surface science experiments under UHV conditions. Auger electron spectroscopy was used to monitor deposit formation. The comparison between Fe(CO)4MA and Fe(CO)5 revealed the effect of the modified ligand architecture on the deposit formation in electron irradiation experiments that mimic FEBID and cryo-FEBID processes. Electron-stimulated desorption and post-irradiation thermal desorption spectrometry were used to obtain insight into the fate of the ligands upon electron irradiation. As a key finding, the deposits obtained from Fe(CO)4MA and Fe(CO)5 were surprisingly similar, and the relative amount of carbon in deposits prepared from Fe(CO)4MA was considerably less than the amount of carbon in the MA ligand. This demonstrates that electron irradiation efficiently cleaves the neutral MA ligand from the precursor. In addition to deposit formation by electron irradiation, the thermal decomposition of Fe(CO)4MA and Fe(CO)5 on an Fe seed layer prepared by EBID was compared. While Fe(CO)5 sustains autocatalytic growth of the deposit, the MA ligand hinders the thermal decomposition in the case of Fe(CO)4MA. The heteroleptic precursor Fe(CO)4MA, thus, offers the possibility to suppress contributions of thermal reactions, which can compromise control over the deposit shape and size in FEBID processes.

Atomic force microscopy in mechanical measurements of single nanowires

In this paper, we present the results of mechanical measurement of single nanowires (NWs) in a repeatable manner. Substrates with specifically designed mechanical features were used for NW placement and localization for measurements of properties such as Young's modulus or tensile strength of NW with an atomic force microscopy (AFM) system. Dense arrays of zinc oxide (ZnO) nanowires were obtained by one-step anodic oxidation of metallic Zn foil in a sodium bicarbonate electrolyte and thermal post-treatment. ZnO NWs with a hexagonal wurtzite structure were fixed to the substrates using focused electron beam-induced deposition (FEBID) and were annealed at different temperatures in situ. We show a 10-fold change in the properties of annealed materials as well as a difference in the properties of the NW materials from their bulk values with pre-annealed Young modulus at the level of 20 GPa and annealed reaching 200 GPa. We found the newly developed method to be much more versatile, allowing for in situ operations of NWs, including measurements with different methods of scanning probe microscopy.

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.

Design, fabrication, and characterization of kinetic-inductive force sensors for scanning probe applications.

We describe a transducer for low-temperature atomic force microscopy based on electromechanical coupling due to a strain-dependent kinetic inductance of a superconducting nanowire. The force sensor is a bending triangular plate (cantilever) whose deflection is measured via a shift in the resonant frequency of a high-Q superconducting microwave resonator at 4.5 GHz. We present design simulations including mechanical finite-element modeling of surface strain and electromagnetic simulations of meandering nanowires with large kinetic inductance. We discuss a lumped-element model of the force sensor and describe the role of an additional shunt inductance for tuning the coupling to the transmission line used to measure the microwave resonance. A detailed description of our fabrication is presented, including information about the process parameters used for each layer. We also discuss the fabrication of sharp tips on the cantilever using focused electron beam-induced deposition of platinum. Finally, we present measurements that characterize the spread of mechanical resonant frequency, the temperature dependence of the microwave resonance, and the sensor's operation as an electromechanical transducer of force.

Focused Helium Ion and Electron Beam-Induced Deposition of Organometallic Tips for Dynamic Atomic Force Microscopy of Biomolecules in Liquid.

We demonstrate the fabrication of sharp nanopillars of high aspect ratio onto specialized atomic force microscopy (AFM) microcantilevers and their use for high-speed AFM of DNA and nucleoproteins in liquid. The fabrication technique uses localized charged-particle-induced deposition with either a focused beam of helium ions or electrons in a helium ion microscope (HIM) or scanning electron microscope (SEM). This approach enables customized growth onto delicate substrates with nanometer-scale placement precision and in situ imaging of the final tip structures using the HIM or SEM. Tip radii of <10 nm are obtained and the underlying microcantilever remains intact. Instead of the more commonly used organic precursors employed for bio-AFM applications, we use an organometallic precursor (tungsten hexacarbonyl) resulting in tungsten-containing tips. Transmission electron microscopy reveals a thin layer of carbon on the tips. The interaction of the new tips with biological specimens is therefore likely very similar to that of standard carbonaceous tips, with the added benefit of robustness. A further advantage of the organometallic tips is that compared to carbonaceous tips they better withstand UV-ozone cleaning treatments to remove residual organic contaminants between experiments, which are inevitable during the scanning of soft biomolecules in liquid. Our tips can also be grown onto the blunted tips of previously used cantilevers, thus providing a means to recycle specialized cantilevers and restore their performance to the original manufacturer specifications. Finally, a focused helium ion beam milling technique to reduce the tip radii and thus further improve lateral spatial resolution in the AFM scans is demonstrated.

Pillar Growth by Focused Electron Beam-Induced Deposition Using a Bimetallic Precursor as Model System: High-Energy Fragmentation vs. Low-Energy Decomposition.

Electron-induced fragmentation of the HFeCo3(CO)12 precursor allows direct-write fabrication of 3D nanostructures with metallic contents of up to >95 at %. While microstructure and composition determine the physical and functional properties of focused electron beam-induced deposits, they also provide fundamental insights into the decomposition process of precursors, as elaborated in this study based on EDX and TEM. The results provide solid information suggesting that different dominant fragmentation channels are active in single-spot growth processes for pillar formation. The use of the single source precursor provides a unique insight into high- and low-energy fragmentation channels being active in the same deposit formation process.

Structural Analysis of Si(OEt)4 Deposits on Au(111)/SiO2 Substrates at the Nanometer Scale Using Focused Electron Beam-Induced Deposition.

The focused electron beam-induced deposition (FEBID) process was used by employing a GeminiSEM with a beam characteristic of 1 keV and 24 pA to deposit pillars and line-shaped nanostructures with heights between 9 nm and 1 μm and widths from 5 nm to 0.5 μm. All structures have been analyzed to their composition looking at a desired Si/O/C content measuring a 1:2:0 ratio. The C content of the structure was found to be ∼over 60% for older deposits kept in air (∼at room temperature) and less than 50% for later deposits, only 12 h old. Upon depositing Si(OEt)4 at high rates and at a deposition temperature of under 0 °C, the obtained Si content of our structures was between 10 and 15 atom % (compositional percentage). The FEBID structures have been deposited on Au(111)/SiO2. The Au(111) was chosen as a substrate for the deposition of Si(OEt)4 due to its structural and morphological properties. With its surface granulation following a Chevron pattern and surface defects having an increased contribution to the changes in the composition of the final structure content, the Au(111) surface characteristic behavior at the deposition of Si(OEt)4 is an increase in the O ratio and a reduction in the nanodeposit heights.

Dissociative electron attachment to gold(I)-based compounds: 4,5-dichloro-1,3-diethyl-imidazolylidene trifluoromethyl gold(I).

With the use of proton-NMR and powder XRD (XRPD) studies, the suitability of specific Au-focused electron beam induced deposition (FEBID) precursors has been investigated with low electron energy, structure, excited states and resonances, structural crystal modifications, flexibility, and vaporization level. 4,5-Dichloro-1,3-diethyl-imidazolylidene trifluoromethyl gold(I) is a compound that is a uniquely designed precursor to meet the needs of focused electron beam-induced deposition at the nanostructure level, which proves its capability in creating high purity structures, and its growing importance in other AuImx and AuClnB (where x and n are the number of radicals, B = CH, CH3, or Br) compounds in the radiation cancer therapy increases the efforts to design more suitable bonds in processes of SEM (scanning electron microscopy) deposition and in gas-phase studies. The investigation performed of its powder shape using the XRPD XPERT3 panalytical diffractometer based on CoKα lines shows changes to its structure with change in temperature, level of vacuum, and light; the sensitivity of this compound makes it highly interesting in particular to the radiation research. Used in FEBID, though its smaller number of C, H, and O atoms has lower levels of C contamination in the structures and on the surface, it replaces these bonds with C-Cl and C-N bonds that have lower bond-breaking energy. However, it still needs an extra purification step in the deposition process, either H2O, O2, or H jets.

Role of the Molecular Environment in Quenching the Irradiation-Driven Fragmentation of Fe(CO)5: A Reactive Molecular Dynamics Study

Irradiation-driven fragmentation and chemical transformations of molecular systems play a key role in nanofabrication processes where organometallic compounds break up due to the irradiation with focused particle beams. In this study, reactive molecular dynamics simulations have been performed to analyze the role of the molecular environment on the irradiation-induced fragmentation of molecular systems. As a case study, we consider the dissociative ionization of iron pentacarbonyl, Fe(CO)5, a widely used precursor molecule for focused electron beam-induced deposition. In connection to recent experiments, the irradiation-induced fragmentation dynamics of an isolated Fe(CO)5+ molecule is studied and compared with that of Fe(CO)5+ embedded into an argon cluster. The appearance energies of different fragments of isolated Fe(CO)5+ agree with the recent experimental data. For Fe(CO)5+ embedded into an argon cluster, the simulations reproduce the experimentally observed suppression of Fe(CO)5+ fragmentation and provide an atomistic-level understanding of this effect. Understanding irradiation-driven fragmentation patterns for molecular systems in environments facilitates the advancement of atomistic models of irradiation-induced chemistry processes involving complex molecular systems.

Superconducting single-photon detectors fabricated via a focused electron beam-induced deposition process

Superconducting detectors have become essential devices for high-performance single-photon counting over a wide wavelength range with excellent time resolution. Detector fabrication typically relies on resist-based lithography processes, which can limit possibilities for device integration, e.g., on unconventional substrates. Here, we demonstrate a resist-free fabrication route for realizing superconducting nanowire single-photon detectors based on focused electron beam-induced deposition. Utilizing direct writing of a Pt–C mask, we achieved nanowire meanders with linewidths below 100 nm, operated them as superconducting devices for the detection of visible and near-infrared photons, and showed detector integration on side-polished optical fibers. Being compatible with device fabrication on curved irregular surfaces, our approach could enable superconducting detector integration in complex configurations.

Additive Manufacturing of Co3Fe Nano-Probes for Magnetic Force Microscopy.

Magnetic force microscopy (MFM) is a powerful extension of atomic force microscopy (AFM), which mostly uses nano-probes with functional coatings for studying magnetic surface features. Although well established, additional layers inherently increase apex radii, which reduce lateral resolution and also contain the risk of delamination, rendering such nano-probes doubtful or even useless. To overcome these limitations, we now introduce the additive direct-write fabrication of magnetic nano-cones via focused electron beam-induced deposition (FEBID) using an HCo3Fe(CO)12 precursor. The study first identifies a proper 3D design, confines the most relevant process parameters by means of primary electron energy and beam currents, and evaluates post-growth procedures as well. That way, highly crystalline nano-tips with minimal surface contamination and apex radii in the sub-15 nm regime are fabricated and benchmarked against commercial products. The results not only reveal a very high performance during MFM operation but in particular demonstrate virtually loss-free behavior after almost 8 h of continuous operation, thanks to the all-metal character. Even after more than 12 months of storage in ambient conditions, no performance loss is observed, which underlines the high overall performance of the here-introduced FEBID-based Co3Fe MFM nano-probes.

Long-Term Performance of Magnetic Force Microscopy Tips Grown by Focused Electron Beam Induced Deposition

High-resolution micro- and nanostructures can be grown using Focused Electron Beam Induced Deposition (FEBID), a direct-write, resist-free nanolithography technology which allows additive patterning, typically with sub-100 nm lateral resolution, and down to 10 nm in optimal conditions. This technique has been used to grow magnetic tips for use in Magnetic Force Microscopy (MFM). Due to their high aspect ratio and good magnetic behavior, these FEBID magnetic tips provide several advantages over commercial magnetic tips when used for simultaneous topographical and magnetic measurements. Here, we report a study of the durability of these excellent candidates for high-resolution MFM measurements. A batch of FEBID-grown magnetic tips was subjected to a systematic analysis of MFM magnetic contrast for 30 weeks, using magnetic storage tape as a test specimen. Our results indicate that these FEBID magnetic tips operate effectively over a long period of time. The magnetic signal was well preserved, with a maximum reduction of 60% after 21 weeks of recurrent use. No significant contrast degradation was observed after 30 weeks in storage.

Novel type of whisker-tip cantilever based on GaN microrods for atomic force microscopy

High-resolution scanning probe microscopy (SPM) is a fundamental and efficient technology for surface characterization of modern materials at the subnanometre scale. The bottleneck of SPM is the probe and scanning tip. Materials with stable electrical, thermal, and mechanical properties for high-aspect-ratio (AR) tips are continuously being developed to improve their accuracy. Among these, GaN is emerging as a significant contender that serves as a replacement for standard Si probes. In this paper, for the first time, we present an approach that demonstrates the application of GaN microrods (MRs) as high-AR SPM probes. GaN MRs were grown using molecular beam epitaxy, transferred and mounted on a cantilever using focused electron beam-induced deposition and milled in a whisker tip using a focused ion beam in a scanning electron/ion microscope. The presence of a native oxide layer covering the GaN MR surface was confirmed by X-ray photoelectron spectroscopy. Current-voltage map measurements are also presented to indicate the elimination of the native oxide layer from the tip surface. The utility of the designed probes was tested using conductive atomic force microscopy and a 24-hour durability test in contact mode atomic force microscopy. Subsequently, the graphene stacks were imaged.

Nanostructured Poly(ethylene glycol) Diacrylate-Based Hydrogels Printed by Focused Electron Beam-Induced Deposition: Implications for Nanosensors

Hydrogels, especially poly(ethylene glycol)-based hydrogels, have received considerable attention due to their excellent performance. However, the commonly used millimeter or micron size of hydrogels limits their higher resolution sensing applications. Using liquid-phase, focused electron-beam-induced deposition is a feasible way to print nanostructured hydrogels. In this work, a device based on a scanning electron microscope was designed to fabricate nanopatterned hydrogels and the electron scattering distribution to induce hydrogel cross-linking was obtained by an optimized Monte Carlo simulation with a Pearson correlation coefficient analysis. We discuss the factors affecting the swelling ratio of the poly(ethylene glycol)diacrylate hydrogel and conclude that the feature size of the hydrogel is about 280 nm in diameter under certain conditions. This study provides a solution for the miniaturized preparation of nanohydrogels, which will help improve the ability of nanosensors to obtain more high density of arrays.

One-Step Synthesis of Functional Sulfonated Polynaphthoylenebenzimidazoles for Biosensing Applications

Polynaphthoylenebenzimidazoles containing functional sulfo groups were synthesized by a one-step method in a sulfuric acid medium with oleum. A polymer-analogous transformation of these polymers with aqueous solutions of metal salts (K, Ca, and Cr) was carried out. Their chemical structure was characterized by FTIR, NMR, and elemental analysis. Polymer salt coatings were deposited on QCM sensor surfaces by electron beam-induced vacuum deposition. The morphology of the coatings was characterized by AFM. It was shown that the coatings formed from a series of polymer salts have different adsorption activity in acetaminophen–water solution compared to distilled water. The QCM results indicate that sensor signal correlates with polymer coating thickness, morphology, and its chemical composition.

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.

Atomistic modeling of thermal effects in focused electron beam-induced deposition of Me$$_2$$Au(tfac)

The role of thermal effects in the focused electron beam induced deposition (FEBID) process of Me$_2$Au(tfac) is studied by means of irradiation-driven molecular dynamics simulations. The FEBID of Me$_2$Au(tfac), a commonly used precursor molecule for the fabrication of gold nanostructures, is simulated at different temperatures in the range of $300-450$ K. The deposit's structure, morphology, growth rate, and elemental composition at different temperatures are analyzed. The fragmentation cross section for Me$_2$Au(tfac) is evaluated on the basis of the cross sections for structurally similar molecules. Different fragmentation channels involving the dissociative ionization (DI) and dissociative electron attachment (DEA) mechanisms are considered. The conducted simulations of FEBID confirm experimental observations that deposits consist of small gold clusters embedded into a carbon-rich organic matrix. The simulation results indicate that accounting for both DEA- and DI-induced fragmentation of all the covalent bonds in Me$_2$Au(tfac) and increasing the amount of energy transferred to the system upon fragmentation increase the concentration of gold in the deposit. The simulations predict an increase in Au:C ratio in the deposit from 0.18 to 0.25 upon the temperature increase from 300 K to 450 K, being within the range of experimentally reported values.

Charge Transport inside TiO2 Memristors Prepared via FEBID

We fabricated memristive devices using focused electron beam-induced deposition (FEBID) as a direct-writing technique employing a Pt/TiO2/Pt sandwich layer device configuration. Pinching in the measured current-voltage characteristics (i-v), the characteristic fingerprint of memristive behavior was clearly observed. The temperature dependence was measured for both high and low resistive states in the range from 290 K down to about 2 K, showing a stretched exponential behavior characteristic of Mott-type variable-range hopping. From this observation, a valence change mechanism of the charge transport inside the TiO2 layer can be deduced.

Hafnium oxide films grown on silicon substrates by electron beam-induced deposition

Electron beam-induced deposition (EBID) is an effective technique for directly fabricating materials with arbitrary shapes on substrates. EBID techniques have mostly been applied to the deposition of metals; however, only a few methods have been applied to metal oxides. As an application of metal oxides in EBID, I report on the fabrication of hafnium oxide (HfO2) films and their structural analysis using transmission electron microscopy techniques. Hafnium tetra-tert-butoxide [Hf(OC4H9)4] was supplied as a precursor from the gas injection system to deposit HfO2 films on silicon substrates. As a result of structural analysis, the grain size of the HfO2 film was less than 1 nm and residual carbon in the film remained. Although deposition conditions to reduce or remove residual carbon in the films need to be improved, the results demonstrate the applicability of one method of HfO2 fabrication and the potential of the EBID method for various metal oxide depositions.