Electron-induced ligand loss from iron tetracarbonyl methyl acrylate.

We probe the separation of ligands from iron tetracarbonyl methyl acrylate (Fe(CO)4(C4H6O2) or Fe(CO)4MA) induced by the interaction with free electrons. The motivation comes from the possible use of this molecule as a nanofabrication precursor and from the corresponding need to understand its elementary reactions fundamental to the electron-induced deposition. We utilize two complementary electron collision setups and support the interpretation of data by quantum chemical calculations. This way, both the dissociative ionization and dissociative electron attachment fragmentation channels are characterized. Considerable differences in the degree of precursor fragmentation in these two channels are observed. Interesting differences also appear when this precursor is compared to structurally similar iron pentacarbonyl. The present findings shed light on the recent electron-induced chemistry of Fe(CO)4MA on a surface under ultrahigh vacuum.

A combined gas-phase dissociative ionization, dissociative electron attachment and deposition study on the potential FEBID precursor [Au(CH3)2Cl]2.

Motivated by the potential of focused-electron-beam-induced deposition (FEBID) in the fabrication of functional gold nanostructures for application in plasmonic and detector technology, we conducted a comprehensive study on [Au(CH3)2Cl]2 as a potential precursor for such depositions. Fundamental electron-induced dissociation processes were studied under single collision conditions, and the composition and morphology of FEBID deposits fabricated in an ultrahigh-vacuum (UHV) chamber were explored on different surfaces and at varied beam currents. In the gas phase, dissociative ionization was found to lead to significant carbon loss from this precursor, and about 50% of the chlorine was on average removed per dissociative ionization incident. On the other hand, in dissociative electron attachment, no chlorine was removed from the parent molecule. Contrary to these observations, FEBID in the UHV setup was found to yield a quantitative loss and desorption of the chlorine from the deposits, an effect that we attribute to electron-induced secondary and tertiary reactions in the deposition process. We find this precursor to be stable at ambient conditions and to have sufficient vapor pressure to be suitable for use in HV instruments. More importantly, in the UHV setup, FEBID with [Au(CH3)2Cl]2 yielded deposits with high gold content, ranging from 45 to 61 atom % depending on the beam current and on the cleanliness of the substrates surface.

Electrical, thermal and noise properties of platinum-carbon free-standing nanowires designed as nanoscale resistive thermal devices.

Platinum-carbon (PtC) composite nanowires were fabricated using focused electron beam induced deposition and postprocessed, and their performance as a nanoscale resistive thermal device (RTD) was evaluated. Nanowires were free-standing and deposited on a dedicated substrate to eliminate the influence of the substrate itself and of the halo effect on the results. The PtC free-standing nanowires were postprocessed to lower their electrical resistance using electron beam irradiation and thermal annealing using Joule heat both separately and combined. Postprocessed PtC free-standing nanowires were characterized to evaluate their noise figure (NF) and thermal coefficients at the temperature range from 30 K to 80 °C. The thermal sensitivity of RTD was lowered with the reduced resistance but simultaneously the NF improved, especially with electron-beam irradiation. The temperature measurement resolution achievable with the PtC free-standing nanowires was 0.1 K in 1 kHz bandwidth.

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.

3D Magnonic Conduits by Direct Write Nanofabrication.

Magnonics is a rapidly developing domain of nanomagnetism, with application potential in information processing systems. Realisation of this potential and miniaturisation of magnonic circuits requires their extension into the third dimension. However, so far, magnonic conduits are largely limited to thin films and 2D structures. Here, we introduce 3D magnonic nanoconduits fabricated by the direct write technique of focused-electron-beam induced deposition (FEBID). We use Brillouin light scattering (BLS) spectroscopy to demonstrate significant qualitative differences in spatially resolved spin-wave resonances of 2D and 3D nanostructures, which originates from the geometrically induced non-uniformity of the internal magnetic field. This work demonstrates the capability of FEBID as an additive manufacturing technique to produce magnetic 3D nanoarchitectures and presents the first report of BLS spectroscopy characterisation of FEBID conduits.

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.

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.

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.

A Core-Shell MWCNT-Pt Nanowire Electron Source with Anomalously Long-Term Stable Field Emission.

A hybrid core-shell structured nanowire is proposed for a long-term stable electron source based on an isolated platinum/multi-walled carbon nanotube (Pt/MWCNT). This hybrid nanowire is prepared by growing a Pt shell on a metallic MWCNT through a field-emission-induced deposition (FEID) method. An in situ field emission (FE) platform was constructed inside a scanning electron microscope (SEM) equipped with two nanorobotic manipulators (NRMs) for the preparation and testing of the hybrid nanowire. An in situ fatigue test was conducted with high current intensity (500 nA) to show the influence of the Pt shell. Compared with the pristine bare MWCNT, our hybrid-nanowire-based electron source has a lifetime of hundreds of times longer and can work continuously for up to 48 h under relatively high pressure (3.6×10-3 Pa) without having an apparent change in its structure or emission currents, demonstrating good stability and tolerance to poor working conditions. The anomalous long-term stability is attributed mainly to the shielding of oxygen by Pt from the carbon shells and less heating due to the work function lowering by Pt.

Site-Selective Chemical Vapor Deposition on Direct-Write 3D Nanoarchitectures.

Recent advancements in additive manufacturing have enabled the preparation of free-shaped 3D objects with feature sizes down to and below the micrometer scale. Among the fabrication methods, focused electron beam- and focused ion beam-induced deposition (FEBID and FIBID, respectively) associate a high flexibility and unmatched accuracy in 3D writing with a wide material portfolio, thereby allowing for the growth of metallic to insulating materials. The combination of the free-shaped 3D nanowriting with established chemical vapor deposition (CVD) techniques provides attractive opportunities to synthesize complex 3D core-shell heterostructures. Hence, this hybrid approach enables the fabrication of morphologically tunable layer-based nanostructures with the great potential of unlocking further functionalities. Here, the fundamentals of such a hybrid approach are demonstrated by preparing core-shell heterostructures using 3D FEBID scaffolds for site-selective CVD. In particular, 3D microbridges are printed by FEBID with the (CH3)3CH3C5H4Pt precursor and coated by thermal CVD using the Nb(NMe2)3(N-t-Bu) and HFeCo3(CO)12 precursors. Two model systems on the basis of CVD layers consisting of a superconducting NbC-based layer and a ferromagnetic Co3Fe layer are prepared and characterized with regard to their composition, microstructure, and magneto-transport properties.

Controlled evolution of three-dimensional magnetic states in strongly coupled cylindrical nanowire pairs.

Cylindrical magnetic nanowires are promising systems for the development of three-dimensional spintronic devices. Here, we simulate the evolution of magnetic states during fabrication of strongly-coupled cylindrical nanowires with varying degrees of overlap. By varying the separation between wires, the relative strength of exchange and magnetostatic coupling can be tuned. Hence, we observe the formation of six fundamental states as a function of both inter-wire separation and wire height. In particular, two complex three-dimensional magnetic states, a 3D Landau Pattern and a Helical domain wall, are observed to emerge for intermediate overlap. These two emergent states show complex spin configurations, including a modulated domain wall with both Néel and Bloch character. The competition of magnetic interactions and the parallel growth scheme we follow (growing both wires at the same time) favours the formation of these anti-parallel metastable states. This works shows how the engineering of strongly coupled 3D nanostructures with competing interactions can be used to create complex spin textures.

Controlled Morphological Bending of 3D-FEBID Structures via Electron Beam Curing.

Focused electron beam induced deposition (FEBID) is one of the few additive, direct-write manufacturing techniques capable of depositing complex 3D nanostructures. In this work, we explore post-growth electron beam curing (EBC) of such platinum-based FEBID deposits, where free-standing, sheet-like elements were deformed in a targeted manner by local irradiation without precursor gas present. This process diminishes the volumes of exposed regions and alters nano-grain sizes, which was comprehensively characterized by SEM, TEM and AFM and complemented by Monte Carlo simulations. For obtaining controlled and reproducible conditions for smooth, stable morphological bending, a wide range of parameters were varied, which will here be presented as a first step towards using local EBC as a tool to realize even more complex nano-architectures, beyond current 3D-FEBID capabilities, such as overhanging structures. We thereby open up a new prospect for future applications in research and development that could even be further developed towards functional imprinting.

Towards Improved Humidity Sensing Nanomaterials via Combined Electron and NH3 Treatment of Carbon-Rich FEBID Deposits.

Focused Electron Beam Induced Deposition (FEBID) is a unique tool to produce nanoscale materials. The resulting deposits can be used, for instance, as humidity or strain sensors. The humidity sensing concept relies on the fact that FEBID using organometallic precursors often yields deposits which consist of metal nanoparticles embedded in a carbonaceous matrix. The electrical conductivity of such materials is altered in the presence of polar molecules such as water. Herein, we provide evidence that the interaction with water can be enhanced by incorporating nitrogen in the deposit through post-deposition electron irradiation in presence of ammonia (NH3). This opens the perspective to improve and tune the properties of humidity sensors fabricated by FEBID. As a proof-of-concept experiment, we have prepared carbonaceous deposits by electron irradiation of adsorbed layers of three different precursors, namely, the aliphatic hydrocarbon n-pentane, a simple alkene (2-methyl-2-butene), and the potential Ru FEBID precursor bis(ethylcyclopentadienyl)ruthenium(II). In a subsequent processing step, we incorporated C-N bonds in the deposit by electron irradiation of adsorbed NH3. To test the resulting material with respect to its potential humidity sensing capabilities, we condensed sub-monolayer quantities of water (H2O) on the deposit and evaluated their thermal desorption behavior. The results confirm that the desorption temperature of H2O decisively depends on the degree of N incorporation into the carbonaceous residue which, in turn, depends on the chemical nature of the precursor used for deposition of the carbonaceous layer. We thus anticipate that the sensitivity of a FEBID-based humidity sensor can be tuned by a precisely timed post-deposition electron and NH3 processing step.

3D Nanoprinting of All-Metal Nanoprobes for Electric AFM Modes.

3D nanoprinting via focused electron beam induced deposition (FEBID) is applied for fabrication of all-metal nanoprobes for atomic force microscopy (AFM)-based electrical operation modes. The 3D tip concept is based on a hollow-cone (HC) design, with all-metal material properties and apex radii in the sub-10 nm regime to allow for high-resolution imaging during morphological imaging, conductive AFM (CAFM) and electrostatic force microscopy (EFM). The study starts with design aspects to motivate the proposed HC architecture, followed by detailed fabrication characterization to identify and optimize FEBID process parameters. To arrive at desired material properties, e-beam assisted purification in low-pressure water atmospheres was applied at room temperature, which enabled the removal of carbon impurities from as-deposited structures. The microstructure of final HCs was analyzed via scanning transmission electron microscopy-high-angle annular dark field (STEM-HAADF), whereas electrical and mechanical properties were investigated in situ using micromanipulators. Finally, AFM/EFM/CAFM measurements were performed in comparison to non-functional, high-resolution tips and commercially available electric probes. In essence, we demonstrate that the proposed all-metal HCs provide the resolution capabilities of the former, with the electric conductivity of the latter onboard, combining both assets in one design.

In Situ Time-of-Flight Mass Spectrometry of Ionic Fragments Induced by Focused Electron Beam Irradiation: Investigation of Electron Driven Surface Chemistry inside an SEM under High Vacuum.

Recent developments in nanoprinting using focused electron beams have created a need to develop analysis methods for the products of electron-induced fragmentation of different metalorganic compounds. The original approach used here is termed focused-electron-beam-induced mass spectrometry (FEBiMS). FEBiMS enables the investigation of the fragmentation of electron-sensitive materials during irradiation within the typical primary electron beam energy range of a scanning electron microscope (0.5 to 30 keV) and high vacuum range. The method combines a typical scanning electron microscope with an ion-extractor-coupled mass spectrometer setup collecting the charged fragments generated by the focused electron beam when impinging on the substrate material. The FEBiMS of fragments obtained during 10 keV electron irradiation of grains of silver and copper carboxylates and shows that the carboxylate ligand dissociates into many smaller volatile fragments. Furthermore, in situ FEBiMS was performed on carbonyls of ruthenium (solid) and during electron-beam-induced deposition, using tungsten carbonyl (inserted via a gas injection system). Loss of carbonyl ligands was identified as the main channel of dissociation for electron irradiation of these carbonyl compounds. The presented results clearly indicate that FEBiMS analysis can be expanded to organic, inorganic, and metal organic materials used in resist lithography, ice (cryo-)lithography, and focused-electron-beam-induced deposition and becomes, thus, a valuable versatile analysis tool to study both fundamental and process parameters in these nanotechnology fields.

On the Electron-Induced Reactions of (CH3)AuP(CH3)3: A Combined UHV Surface Science and Gas-Phase Study.

Focused-electron-beam-induced deposition (FEBID) is a powerful nanopatterning technique where electrons trigger the local dissociation of precursor molecules, leaving a deposit of non-volatile dissociation products. The fabrication of high-purity gold deposits via FEBID has significant potential to expand the scope of this method. For this, gold precursors that are stable under ambient conditions but fragment selectively under electron exposure are essential. Here, we investigated the potential gold precursor (CH3)AuP(CH3)3 using FEBID under ultra-high vacuum (UHV) and spectroscopic characterization of the corresponding metal-containing deposits. For a detailed insight into electron-induced fragmentation, the deposit's composition was compared with the fragmentation pathways of this compound through dissociative ionization (DI) under single-collision conditions using quantum chemical calculations to aid the interpretation of these data. Further comparison was made with a previous high-vacuum (HV) FEBID study of this precursor. The average loss of about 2 carbon and 0.8 phosphor per incident was found in DI, which agreed well with the carbon content of the UHV FEBID deposits. However, the UHV deposits were found to be as good as free of phosphor, indicating that the trimethyl phosphate is a good leaving group. Differently, the HV FEBID experiments showed significant phosphor content in the deposits.

Electron-Induced Decomposition of Different Silver(I) Complexes: Implications for the Design of Precursors for Focused Electron Beam Induced Deposition.

Focused electron beam induced deposition (FEBID) is a versatile tool to produce nanostructures through electron-induced decomposition of metal-containing precursor molecules. However, the metal content of the resulting materials is often low. Using different Ag(I) complexes, this study shows that the precursor performance depends critically on the molecular structure. This includes Ag(I) 2,2-dimethylbutanoate, which yields high Ag contents in FEBID, as well as similar aliphatic Ag(I) carboxylates, aromatic Ag(I) benzoate, and the acetylide Ag(I) 3,3-dimethylbutynyl. The compounds were sublimated on inert surfaces and their electron-induced decomposition was monitored by electron-stimulated desorption (ESD) experiments in ultrahigh vacuum and by reflection-absorption infrared spectroscopy (RAIRS). The results reveal that Ag(I) carboxylates with aliphatic side chains are particularly favourable for FEBID. Following electron impact ionization, they fragment by loss of volatile CO2. The remaining alkyl radical converts to a stable and equally volatile alkene. The lower decomposition efficiency of Ag(I) benzoate and Ag(I) 3,3-dimethylbutynyl is explained by calculated average local ionization energies (ALIE) which reveal that ionization from the unsaturated carbon units competes with ionization from the coordinate bond to Ag. This can stabilise the ionized complex with respect to fragmentation. This insight provides guidance with respect to the design of novel FEBID precursors.

Low-energy electron interaction and focused electron beam-induced deposition of molybdenum hexacarbonyl (Mo(CO)6).

Motivated by the potential role of molybdenum in semiconductor materials, we present a combined theoretical and experimental gas-phase study on dissociative electron attachment (DEA) and dissociative ionization (DI) of Mo(CO)6 in comparison to focused electron beam-induced deposition (FEBID) of this precursor. The DEA and DI experiments are compared to previous work, differences are addressed, and the nature of the underlying resonances leading to the observed DEA processes are discussed in relation to an earlier electron transmission study. Relative contributions of individual ionic species obtained through DEA and DI of Mo(CO)6 and the average CO loss per incident are calculated and compared to the composition of the FEBID deposits produced. These are also compared to gas phase, surface science and deposition studies on W(CO)6 and we hypothesize that reductive ligand loss through electron attachment may promote metal-metal bond formation in the deposition process, leading to further ligand loss and the high metal content observed in FEBID for both these compounds.

Low-resistivity, high-resolution W-C electrical contacts fabricated by direct-write focused electron beam induced deposition.

Background: The use of a focused ion beam to decompose a precursor gas and produce a metallic deposit is a widespread nanolithographic technique named focused ion beam induced deposition (FIBID). However, such an approach is unsuitable if the sample under study is sensitive to the somewhat aggressive exposure to the ion beam, which induces the effects of surface amorphization, local milling, and ion implantation, among others. An alternative strategy is that of focused electron beam induced deposition (FEBID), which makes use of a focused electron beam instead, and in general yields deposits with much lower metallic content than their FIBID counterparts. Methods: In this work, we optimize the deposition of tungsten-carbon (W-C) nanowires by FEBID to be used as electrical contacts by assessing the impact of the deposition parameters during growth, evaluating their chemical composition, and investigating their electrical response. Results: Under the optimized irradiation conditions, the samples exhibit a metallic content high enough for them to be utilized for this purpose, showing a room-temperature resistivity of 550 µΩ cm and maintaining their conducting properties down to 2 K. The lateral resolution of such FEBID W-C metallic nanowires is 45 nm. Conclusions: The presented optimized procedure may prove a valuable tool for the fabrication of contacts on samples where the FIBID approach is not advised.

Irradiation-driven molecular dynamics simulation of the FEBID process for Pt(PF3)4.

This paper presents a detailed computational protocol for the atomistic simulation of formation and growth of metal-containing nanostructures during focused electron beam-induced deposition (FEBID). The protocol is based upon irradiation-driven molecular dynamics (IDMD), a novel and general methodology for computer simulations of irradiation-driven transformations of complex molecular systems by means of the advanced software packages MBN Explorer and MBN Studio. Atomistic simulations performed following the formulated protocol provide valuable insights into the fundamental mechanisms of electron-induced precursor fragmentation and the related mechanism of nanostructure formation and growth using FEBID, which are essential for the further advancement of FEBID-based nanofabrication. The developed computational methodology is general and applicable to different precursor molecules, substrate types, and irradiation regimes. The methodology can also be adjusted to simulate the nanostructure formation by other nanofabrication techniques using electron beams, such as direct electron beam lithography. In the present study, the methodology is applied to the IDMD simulation of the FEBID of Pt(PF3)4, a widely studied precursor molecule, on a SiO2 surface. The simulations reveal the processes driving the initial phase of nanostructure formation during FEBID, including the nucleation of Pt atoms and the formation of small metal clusters on the surface, followed by their aggregation and the formation of dendritic platinum nanostructures. The analysis of the simulation results provides spatially resolved relative metal content, height, and growth rate of the deposits, which represents valuable reference data for the experimental characterization of the nanostructures grown by FEBID.