Area-Selective Chemical Vapor Deposition of Gold by Electron Beam Seeding.

Chemical vapor deposition (CVD) is an established method for producing high-purity thin films, but it typically necessitates the pre- and post-processing using a mask to produce structures. This study presents a novel maskless patterning technique that enables area-selective CVD of gold. A focused electron beam is used to decompose the metal-organic precursor Au(acac)Me2 locally, thereby creating an autocatalytically active seed layer for subsequent CVD with the same precursor. The procedure can be included in the same CVD process without the need for clean room lithographic processing. Moreover, it operates at low temperatures of 80 °C, over 200 K lower than standard CVD temperatures for this precursor, reducing thermal load on the specimen. Given that electron beam seeding operates on any even moderately conductive surface, the process does not constrain device design. This is demonstrated by the example of vertical nanostructures with high aspect ratios of ≈40:1 and more. Written using a focused electron beam and the same precursor, these nanopillars exhibit catalytically active nuclei on their surface. Furthermore, by using the onset of the autocatalytic CVD growth, for the first time the local temperature increase caused by the writing of nanostructures with an electron beam can be precisely determined.

Ligand Size and Carbon-Chain Length Study of Silver Carboxylates in Focused Electron-Beam-Induced Deposition.

Gas-assisted focused electron-beam-induced deposition is a versatile tool for the direct writing of complex-shaped nanostructures with unprecedented shape fidelity and resolution. While the technique is well-established for various materials, the direct electron beam writing of silver is still in its infancy. Here, we examine and compare five different silver carboxylates, three perfluorinated: [Ag2(µ-O2CCF3)2], [Ag2(µ-O2CC2F5)2], and [Ag2(µ-O2CC3F7)2], and two containing branched substituents: [Ag2(µ-O2CCMe2Et)2] and [Ag2(µ-O2CtBu)2], as potential precursors for focused electron-beam-induced deposition. All of the compounds show high sensitivity to electron dissociation and efficient dissociation of Ag-O bonds. The as-deposited materials have silver contents from 42 at.% to above 70 at.% and are composed of silver nano-crystals with impurities of carbon and fluorine between them. Precursors with the shortest carbon-fluorine chain ligands yield the highest silver contents. In addition, the deposited silver content depends on the balance of electron-induced ligand co-deposition and ligand desorption. For all of the tested compounds, low electron flux was related to high silver content. Our findings demonstrate that silver carboxylates constitute a promising group of precursors for gas-assisted focused electron beam writing of high silver content materials.

From metal nanowires to ultrathin crystalline ALD nanotubes: process development and mechanism revealed by in situ TEM heating experiments.

The creation of hollow nanomaterials based on metal oxides has become an important research topic, as they show potential in a broad range of technical applications. However, the controlled synthesis of long and at the same time thin nanotubes is still challenging. Here we present a universal approach to create ultrathin aluminum oxide nanotubes with a length/diameter ratio of >1200 and minimum wall thickness of ≤4 nm. We use a facile process based on defined heat treatment of specific core-shell nanowires. The metal nanowires act as a template, which is thermally removed during heat treatment until an empty tube is created. The core-shell nanowires are produced by Physical Vapour Deposition (PVD) with a subsequent coating via Atomic Layer Deposition (ALD). The custom-built PVD-ALD system enables a direct sample transfer without breaking the vacuum, which allows determining the effect of a native oxide layer on the metal-ALD bonding. In combination with correlative ex situ observations, in situ Transmission Electron Microscopy (TEM) heating experiments unravel the dynamical processes going on at small scales. Based on the microscopic analysis, the energetics of the core material is analyzed, giving insights about heat induced effects as well as the phase transition from the amorphous to the crystalline state.

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.

Structure, Morphology, Heat Capacity, and Electrical Transport Properties of Ti3(Al,Si)C2 Materials.

A study of Ti3Al1-xSixC2 (x = 0 to x = 1) MAX-phase alloys is reported. The materials were obtained from mixtures of Ti3AlC2 and Ti3SiC2 powders with hot pressing sintering technique. They were characterised with X-ray diffraction, heat capacity, electrical resistivity, and magnetoresistance measurements. The results show a good quality crystal structure and metallic properties with high residual resistivity. The resistivity weakly varies with Si doping and shows a small, positive magnetoresistance effect. The magnetoresistance exhibits a quadratic dependence on the magnetic field, which indicates a dominant contribution from open electronic orbits. The Debye temperatures and Sommerfeld coefficient values derived from specific heat data show slight variations with Si content, with decreasing tendency for the former and an increase for the latter. Experimental results were supported by band structure calculations whose results are consistent with the experiment concerning specific heat, resistivity, and magnetoresistance measurements. In particular, they reveal that of the s-electrons at the Fermi level, those of Al and Si have prevailing density of states and, thus predominantly contribute to the metallic conductivity. This also shows that the high residual resistivity of the materials studied is an intrinsic effect, not due to defects of the crystal structure.

Room Temperature Direct Electron Beam Lithography in a Condensed Copper Carboxylate.

High-resolution metallic nanostructures can be fabricated with multistep processes, such as electron beam lithography or ice lithography. The gas-assisted direct-write technique known as focused electron beam induced deposition (FEBID) is more versatile than the other candidates. However, it suffers from low throughput. This work presents the combined approach of FEBID and the above-mentioned lithography techniques: direct electron beam lithography (D-EBL). A low-volatility copper precursor is locally condensed onto a room temperature substrate and acts as a positive tone resist. A focused electron beam then directly irradiates the desired patterns, leading to local molecule dissociation. By rinsing or sublimation, the non-irradiated precursor is removed, leaving copper-containing structures. Deposits were formed with drastically enhanced growth rates than FEBID, and their composition was found to be comparable to gas-assisted FEBID structures. The influence of electron scattering within the substrate as well as implementing a post-purification protocol were studied. The latter led to the agglomeration of high-purity copper crystals. We present this as a new approach to electron beam-induced fabrication of metallic nanostructures without the need for cryogenic or hot substrates. D-EBL promises fast and easy fabrication results.

High Sensitivity of Fluorine Gas-Assisted FIB-TOF-SIMS for Chemical Characterization of Buried Sublayers in Thin Films.

In this work, we present the potential of high vacuum-compatible time-of-flight secondary ion mass spectrometry (TOF-SIMS) detectors, which can be integrated within focused ion beam (FIB) instruments for precise and fast chemical characterization of thin films buried deep under the sample surface. This is demonstrated on complex multilayer systems composed of alternating ceramic and metallic layers with thicknesses varying from several nanometers to hundreds of nanometers. The typical problems of the TOF-SIMS technique, that is, low secondary ion signals and mass interference between ions having similar masses, were solved using a novel approach of co-injecting fluorine gas during the sample surface sputtering. In the most extreme case of the Al/Al2O3/Al/Al2O3/.../Al sample, a <10 nm thick Al2O3 thin film buried under a 0.5 µm material was detected and spatially resolved using only 27Al+ signal distribution. This is an impressive achievement taking into account that Al and Al2O3 layers varied only by a small amount of oxygen content. Due to its high sensitivity, fluorine gas-assisted FIB-TOF-SIMS can be used for quality control of nano- and microdevices as well as for the failure analysis of fabrication processes. Therefore, it is expected to play an important role in the development of microelectronics and thin-film-based devices for energy applications.

Molecular layer deposited alucone thin films from long-chain organic precursors: from brittle to ductile mechanical characteristics.

Molecular layer deposition (MLD) is a strongly emerging thin-film technique for deposition of ultra-thin inorganic-organic hybrid ("metalcone") coatings directly from the gas phase, even on complex three-dimensional surfaces. In particular alucones (Al-based hybrids) have been found interesting e.g. for Li-ion battery and gas-barrier applications owing to the promise for enhanced mechanical performance provided by the organic fragments in the materials' structure. However, the metalcones based on short/small organic fragments are relatively brittle from the mechanical perspective. Here, we demonstrate an efficient approach for tailoring mechanical properties of MLD-fabricated hybrid inorganic-organic thin films through control over the organic precursor chain length. The proof-of-concept data is presented for alucones prepared using trimethyl aluminum together with 1,6-hexanediol or 1,10-decanediol as the precursors. Tensile testing coupled with in situ optical microscopy reveals a gradual increase in stretchability with the increasing chain length, such that the crack onset strain value of 9.9 ± 0.2% is obtained for the 1,10-decanediol-based 100 nm-thick film. Through the demonstration of substantially suppressed crack propagation-as a sign of brittle-to-ductile transition-and the decrease in the elastic modulus value down to 4.6 ± 2.1 GPa, the mechanical performance of the alucone family is extended to the polymeric regime. The substantial increase in the mechanical performance within the metalcone material family makes the results particularly interesting for high-capacity high-volume-change battery electrodes requiring mechanically highly robust coatings.

Metals by Micro-Scale Additive Manufacturing: Comparison of Microstructure and Mechanical Properties.

Many emerging applications in microscale engineering rely on the fabrication of 3D architectures in inorganic materials. Small-scale additive manufacturing (AM) aspires to provide flexible and facile access to these geometries. Yet, the synthesis of device-grade inorganic materials is still a key challenge toward the implementation of AM in microfabrication. Here, a comprehensive overview of the microstructural and mechanical properties of metals fabricated by most state-of-the-art AM methods that offer a spatial resolution ≤10 µm is presented. Standardized sets of samples are studied by cross-sectional electron microscopy, nanoindentation, and microcompression. It is shown that current microscale AM techniques synthesize metals with a wide range of microstructures and elastic and plastic properties, including materials of dense and crystalline microstructure with excellent mechanical properties that compare well to those of thin-film nanocrystalline materials. The large variation in materials' performance can be related to the individual microstructure, which in turn is coupled to the various physico-chemical principles exploited by the different printing methods. The study provides practical guidelines for users of small-scale additive methods and establishes a baseline for the future optimization of the properties of printed metallic objects-a significant step toward the potential establishment of AM techniques in microfabrication.

Flexible ε-Fe2O3-Terephthalate Thin-Film Magnets through ALD/MLD.

Pliable and lightweight thin-film magnets performing at room temperature are indispensable ingredients of the next-generation flexible electronics. However, conventional inorganic magnets based on f-block metals are rigid and heavy, whereas the emerging organic/molecular magnets are inferior regarding their magnetic characteristics. Here we fuse the best features of the two worlds, by tailoring ε-Fe2O3-terephthalate superlattice thin films with inbuilt flexibility due to the thin organic layers intimately embedded within the ferrimagnetic ε-Fe2O3 matrix; these films are also sustainable as they do not contain rare heavy metals. The films are grown with sub-nanometer-scale accuracy from gaseous precursors using the atomic/molecular layer deposition (ALD/MLD) technique. Tensile tests confirm the expected increased flexibility with increasing organic content reaching a 3-fold decrease in critical bending radius (2.4 ± 0.3 mm) as compared to ε-Fe2O3 thin film (7.7 ± 0.3 mm). Most remarkably, these hybrid ε-Fe2O3-terephthalate films do not compromise the exceptional intrinsic magnetic characteristics of the ε-Fe2O3 phase, in particular the ultrahigh coercive force (∼2 kOe) even at room temperature.

Mechanical Properties of 3D Nanostructures Obtained by Focused Electron/Ion Beam-Induced Deposition: A Review.

This article reviews the state-of-the -art of mechanical material properties and measurement methods of nanostructures obtained by two nanoscale additive manufacturing methods: gas-assisted focused electron and focused ion beam-induced deposition using volatile organic and organometallic precursors. Gas-assisted focused electron and ion beam-induced deposition-based additive manufacturing technologies enable the direct-write fabrication of complex 3D nanostructures with feature dimensions below 50 nm, pore-free and nanometer-smooth high-fidelity surfaces, and an increasing flexibility in choice of materials via novel precursors. We discuss the principles, possibilities, and literature proven examples related to the mechanical properties of such 3D nanoobjects. Most materials fabricated via these approaches reveal a metal matrix composition with metallic nanograins embedded in a carbonaceous matrix. By that, specific material functionalities, such as magnetic, electrical, or optical can be largely independently tuned with respect to mechanical properties governed mostly by the matrix. The carbonaceous matrix can be precisely tuned via electron and/or ion beam irradiation with respect to the carbon network, carbon hybridization, and volatile element content and thus take mechanical properties ranging from polymeric-like over amorphous-like toward diamond-like behavior. Such metal matrix nanostructures open up entirely new applications, which exploit their full potential in combination with the unique 3D additive manufacturing capabilities at the nanoscale.

Thin-Film Engineering of Mechanical Fragmentation Properties of Atomic-Layer-Deposited Metal Oxides.

Mechanical fracture properties were studied for the common atomic-layer-deposited Al2O3, ZnO, TiO2, ZrO2, and Y2O3 thin films, and selected multilayer combinations via uniaxial tensile testing and Weibull statistics. The crack onset strains and interfacial shear strains were studied, and for crack onset strain, TiO2/Al2O3 and ZrO2/Al2O3 bilayer films exhibited the highest values. The films adhered well to the polyimide carrier substrates, as delamination of the films was not observed. For Al2O3 films, higher deposition temperatures resulted in higher crack onset strain and cohesive strain values, which was explained by the temperature dependence of the residual strain. Doping Y2O3 with Al or nanolaminating it with Al2O3 enabled control over the crystal size of Y2O3, and provided us with means for improving the mechanical properties of the Y2O3 films. Tensile fracture toughness and fracture energy are reported for Al2O3 films grown at 135 °C, 155 °C, and 220 °C. We present thin-film engineering via multilayering and residual-strain control in order to tailor the mechanical properties of thin-film systems for applications requiring mechanical stretchability and flexibility.

Application of a Gas-Injection System during the FIB-TOF-SIMS Analysis-Influence of Water Vapor and Fluorine Gas on Secondary Ion Signals and Sputtering Rates.

Combining a Gas-Injection System (GIS) with the Focused Ion Beam (FIB) has a broad scope of applications in sample preparation such as protective layer deposition, increasing material sputtering rates, and reducing FIB-related artifacts. On the other hand, injecting certain specific gases during a Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) analysis can significantly increase element ionization probability and, therefore, improve the quality of 3D representation of a sample elemental structure. In this work, for the first time, the potential of GIS for enhancing secondary ion signals acquired using a TOF detector incorporated into a commercial Ga+ FIB-SEM (Focused Ion Beam combined with Scanning Electron Microscope) instrument is presented. The depth profiles of pure metals (thin films of Cu, Zr, Ag, and W with the thickness in the order of 100 nm) were acquired under ambient vacuum conditions as well as under an exposure to water and fluorine gases. The influence of supplementary gases on the ion yields and sputtering rates was studied. Simulations were performed to assess the local gas pressure at the location of FIB-TOF-SIMS analysis. The highest enhancement of ionization probability was achieved in the case of the Cu thin film (10 times during water vapor coinjection and 510 times when using a fluorine gas). Regarding the sputtering rates, the response of Zr to the effect of the gases was the strongest. Compared to standard background pressure measurements, this thin film was milled around 6 times faster under exposure to water vapor and over 2 times faster when fluorine gas was supplied.

Focused Electron Beam-Induced Deposition and Post-Growth Purification Using the Heteroleptic Ru Complex (η3-C3H5)Ru(CO)3Br.

Focused electron beam-induced deposition using the heteroleptic complex (η3-C3H5)Ru(CO)3Br as a precursor resulted in deposition of material with Ru content of 23 at. %. Transmission electron microscopy images indicated a nanogranular structure of pure Ru nanocrystals, embedded into a matrix containing carbon, oxygen, and bromine. The deposits were purified by annealing in a reactive 98% N2/2% H2 atmosphere at 300 °C, resulting in a reduction of contaminants and an increase of the Ru content to 83 at. %. Although a significant volume loss of 79% was found, the shrinkage was observed mostly for vertical thickness (around 75%). The lateral dimensions decreased much less significantly (around 9%). Deposition results, in conjunction with previous gas-phase and condensed-phase surface studies on the electron-induced reactions of (η3-C3H5)Ru(CO)3Br, provide insights into the behavior of allyl, carbonyl, and bromide ligands under identical electron beam irradiation.

Fracture Mechanics and Oxygen Gas Barrier Properties of Al2O3/ZnO Nanolaminates on PET Deposited by Atomic Layer Deposition.

Rapid progress in the performance of organic devices has increased the demand for advances in the technology of thin-film permeation barriers and understanding the failure mechanisms of these material systems. Herein, we report the extensive study of mechanical and gas barrier properties of Al2O3/ZnO nanolaminate films prepared on organic substrates by atomic layer deposition (ALD). Nanolaminates of Al2O3/ZnO and single compound films of around 250 nm thickness were deposited on polyethylene terephthalate (PET) foils by ALD at 90 °C using trimethylaluminium (TMA) and diethylzinc (DEZ) as precursors and H2O as the co-reactant. STEM analysis of the nanolaminate structure revealed that steady-state film growth on PET is achieved after about 60 ALD cycles. Uniaxial tensile strain experiments revealed superior fracture and adhesive properties of single ZnO films versus the single Al2O3 film, as well as versus their nanolaminates. The superior mechanical performance of ZnO was linked to the absence of a roughly 500 to 900 nm thick sub-surface growth observed for single Al2O3 films as well as for the nanolaminates starting with an Al2O3 initial layer on PET. In contrast, the gas permeability of the nanolaminate coatings on PET was measured to be 9.4 × 10-3 O2 cm³ m-2 day-1. This is an order of magnitude less than their constituting single oxides, which opens prospects for their applications as gas barrier layers for organic electronics and food and drug packaging industries. Direct interdependency between the gas barrier and the mechanical properties was not established enabling independent tailoring of these properties for mechanically rigid and impermeable thin film coatings.

Focused Electron Beam-Based 3D Nanoprinting for Scanning Probe Microscopy: A Review.

Scanning probe microscopy (SPM) has become an essential surface characterization technique in research and development. By concept, SPM performance crucially depends on the quality of the nano-probe element, in particular, the apex radius. Now, with the development of advanced SPM modes beyond morphology mapping, new challenges have emerged regarding the design, morphology, function, and reliability of nano-probes. To tackle these challenges, versatile fabrication methods for precise nano-fabrication are needed. Aside from well-established technologies for SPM nano-probe fabrication, focused electron beam-induced deposition (FEBID) has become increasingly relevant in recent years, with the demonstration of controlled 3D nanoscale deposition and tailored deposit chemistry. Moreover, FEBID is compatible with practically any given surface morphology. In this review article, we introduce the technology, with a focus on the most relevant demands (shapes, feature size, materials and functionalities, substrate demands, and scalability), discuss the opportunities and challenges, and rationalize how those can be useful for advanced SPM applications. As will be shown, FEBID is an ideal tool for fabrication / modification and rapid prototyping of SPM-tipswith the potential to scale up industrially relevant manufacturing.

A novel copper precursor for electron beam induced deposition.

A fluorine free copper precursor, Cu(tbaoac)2 with the chemical sum formula CuC16O6H26 is introduced for focused electron beam induced deposition (FEBID). FEBID with 15 keV and 7 nA results in deposits with an atomic composition of Cu:O:C of approximately 1:1:2. Transmission electron microscopy proved that pure copper nanocrystals with sizes of up to around 15 nm were dispersed inside the carbonaceous matrix. Raman investigations revealed a high degree of amorphization of the carbonaceous matrix and showed hints for partial copper oxidation taking place selectively on the surfaces of the deposits. Optical transmission/reflection measurements of deposited pads showed a dielectric behavior of the material in the optical spectral range. The general behavior of the permittivity could be described by applying the Maxwell-Garnett mixing model to amorphous carbon and copper. The dielectric function measured from deposited pads was used to simulate the optical response of tip arrays fabricated out of the same precursor and showed good agreement with measurements. This paves the way for future plasmonic applications with copper-FEBID.

Towards the third dimension in direct electron beam writing of silver.

Carboxylates constitute an extremely promising class of precursor compounds for the electron beam induced deposition of silver. In this work both silver 2,2-dimethylbutyrate and silver pentafluoropropionate were investigated with respect to their dwell-time-dependent deposition behavior and growth characteristics. While silver 2,2-dimethylbutyrate showed a strong depletion in the center of the impinging electron beam profile hindering any vertical growth, silver pentafluoropropionate indicated a pronounced dependency of the deposit height on the dwell time. Truly three-dimensional silver structures could be realized with silver pentafluoropropionate. The pillars were polycrystalline with silver contents of more than 50 atom % and exhibit strong Raman enhancement. This constitutes a promising route towards the direct electron beam writing of three-dimensional plasmonic device parts from the gas phase.

Comparative study of post-growth annealing of Cu(hfac)2, Co2(CO)8 and Me2Au(acac) metal precursors deposited by FEBID.

Non-noble metals, such as Cu and Co, as well as noble metals, such as Au, can be used in a number modern technological applications, which include advanced scanning-probe systems, magnetic memory and storage, ferroelectric tunnel junction memristors, metal interconnects for high performance integrated circuits in microelectronics and nano-optics applications, especially in the areas of plasmonics and metamaterials. Focused-electron-beam-induced deposition (FEBID) is a maskless direct-write tool capable of defining 3-dimensional metal deposits at nanometre scale for above applications. However, codeposition of organic ligands when using organometallic precursors is a typical problem that limits FEBID of pure metal nanostructures. In this work, we present a comparative study using a post-growth annealing protocol at 100, 200, and 300 °C under high vacuum on deposits obtained from Co2(CO)8, Cu(II)(hfac)2, and Me2Au(acac) to study improvements on composition and electrical conductivity. Although the as-deposited material was similar for all precursors, metal grains embedded in a carbonaceous matrix, the post-growth annealing results differed. Cu-containing deposits showed the formation of pure Cu nanocrystals at the outer surface of the initial deposit for temperatures above 100 °C, due to the migration of Cu atoms from the carbonaceous matrix containing carbon, oxygen, and fluorine atoms. The average size of the Cu crystals doubles between 100 and 300 °C of annealing temperature, while the composition remains constant. In contrast, for Co-containing deposits oxygen release was observed upon annealing, while the carbon content remained approximately constant; the cobalt atoms coalesced to form a metallic film. The as-deposited Au-containing material shows subnanometric grains that coalesce at 100 °C, maintaining the same average size at annealing temperatures up to 300 °C. Raman analysis suggests that the amorphous carbonaceous matrix of the as-written Co, Cu and Au deposits turned into nanocrystalline graphite with comparable crystal sizes of 12-14 nm at 300 °C annealing temperature. However, we observed a more effective formation of graphite clusters in Co- than in Cu- and Au-containing deposits. The graphitisation has a minor influence on the electrical conductivity improvements of Co-C deposits, which is attributed to the high as-deposited Co content and the related metal grain percolation. On the contrary, electrical conductivity improvements by factors of 30 and 12 for, respectively, Cu-C and Au-C deposits with low metal content are mainly attributed to the graphitisation. This relatively simple vacuum-based post-growth annealing protocol may be useful for other precursors as it proved to be efficient in reliably tuning the electrical properties of as-deposited FEBID materials. Finally, a H2-assisted gold purification protocol is demonstrated at temperatures around 300 °C by fully removing the carbon matrix and drastically reducing the electrical resistance of the deposit.

Gas-assisted silver deposition with a focused electron beam.

Focused electron beam induced deposition (FEBID) is a flexible direct-write method to obtain defined structures with a high lateral resolution. In order to use this technique in application fields such as plasmonics, suitable precursors which allow the deposition of desired materials have to be identified. Well known for its plasmonic properties, silver represents an interesting candidate for FEBID. For this purpose the carboxylate complex silver(I) pentafluoropropionate (AgO2CC2F5) was used for the first time in FEBID and resulted in deposits with high silver content of up to 76 atom %. As verified by TEM investigations, the deposited material is composed of pure silver crystallites in a carbon matrix. It showed good electrical properties and a strong Raman signal enhancement. Interestingly, silver crystal growth presents a strong dependency on electron dose and precursor refreshment.