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.

A new approach for fast field calculation in electrostatic electron lens design and optimization.

In electron optics, calculation of the electric field plays a major role in all computations and simulations. Accurate field calculation methods such as the finite element method (FEM), boundary element method and finite difference method, have been used for years. However, such methods are computationally very expensive and make the computer simulation challenging or even infeasible when trying to apply automated design of electrostatic lens systems with many free parameters. Hence, for years, electron optics scientists have been searching for a fast and accurate method of field calculation to tackle the aforementioned problem in the design and optimization of electrostatic electron lens systems. This paper presents a novel method for fast electric field calculation in electrostatic electron lens systems with reasonably high accuracy to enable the electron-optical designers to design and optimize an electrostatic lens system with many free parameters in a reasonably short time. The essence of the method is to express the off-axis potential in an axially symmetrical coordinate system in terms of derivatives of the axial potential up to the fourth order, and equate this to the potential of the electrode at that axial position. Doing this for a limited number of axial positions, we get a set of equations that can be solved to obtain the axial potential, necessary for calculating the lens properties. We name this method the fourth-order electrode method because we take the axial derivatives up to the fourth order. To solve the equations, a quintic spline approximation of the axial potential is calculated by solving three sets of linear equations simultaneously. The sets of equations are extracted from the Laplace equation and the fundamental equations that describe a quintic spline. The accuracy and speed of this method is compared with other field calculation methods, such as the FEM and second order electrode method (SOEM). The new field calculation method is implemented in design/optimization of electrostatic lens systems by using a genetic algorithm based optimization program for electrostatic lens systems developed by the authors. The effectiveness of this new field calculation method in optimizing optical parameters of electrostatic lens systems is compared with FEM and SOEM and the results are presented. It should be noted that the formulation is derived for general axis symmetrical electrostatic electron lens systems, however the examples shown in this paper are with cylindrical electrodes due to the simplicity of the implementation in the software.

Structured illumination microscopy with noise-controlled image reconstructions.

Super-resolution structured illumination microscopy (SIM) has become a widely used method for biological imaging. Standard reconstruction algorithms, however, are prone to generate noise-specific artifacts that limit their applicability for lower signal-to-noise data. Here we present a physically realistic noise model that explains the structured noise artifact, which we then use to motivate new complementary reconstruction approaches. True-Wiener-filtered SIM optimizes contrast given the available signal-to-noise ratio, and flat-noise SIM fully overcomes the structured noise artifact while maintaining resolving power. Both methods eliminate ad hoc user-adjustable reconstruction parameters in favor of physical parameters, enhancing objectivity. The new reconstructions point to a trade-off between contrast and a natural noise appearance. This trade-off can be partly overcome by further notch filtering but at the expense of a decrease in signal-to-noise ratio. The benefits of the proposed approaches are demonstrated on focal adhesion and tubulin samples in two and three dimensions, and on nanofabricated fluorescent test patterns.

Gold(I) N-heterocyclic carbene precursors for focused electron beam-induced deposition.

Seven gold(I) N-heterocyclic carbene (NHC) complexes were synthesized, characterized, and identified as suitable precursors for focused electron beam-induced deposition (FEBID). Several variations on the core Au(NHC)X moiety were introduced, that is, variations of the NHC ring (imidazole or triazole), of the alkyl N-substituents (Me, Et, or iPr), and of the ancillary ligand X (Cl, Br, I, or CF3). The seven complexes were tested as FEBID precursors in an on-substrate custom setup. The effect of the substitutions on deposit composition and growth rate indicates that the most suitable organic ligand for the gold precursor is triazole-based, with the best deposit composition of 15 atom % gold, while the most suitable anionic ligand is the trifluoromethyl group, leading to a growth rate of 1 × 10-2 nm3/e-.

Electron beam-induced deposition of platinum from Pt(CO)2Cl2 and Pt(CO)2Br2.

Two platinum precursors, Pt(CO)2Cl2 and Pt(CO)2Br2, were designed for focused electron beam-induced deposition (FEBID) with the aim of producing platinum deposits of higher purity than those deposited from commercially available precursors. In this work, we present the first deposition experiments in a scanning electron microscope (SEM), wherein series of pillars were successfully grown from both precursors. The growth of the pillars was studied as a function of the electron dose and compared to deposits grown from the commercially available precursor MeCpPtMe3. The composition of the deposits was determined using energy-dispersive X-ray spectroscopy (EDX) and compared to the composition of deposits from MeCpPtMe3, as well as deposits made in an ultrahigh-vacuum (UHV) environment. A slight increase in metal content and a higher growth rate are achieved in the SEM for deposits from Pt(CO)2Cl2 compared to MeCpPtMe3. However, deposits made from Pt(CO)2Br2 show slightly less metal content and a lower growth rate compared to MeCpPtMe3. With both Pt(CO)2Cl2 and Pt(CO)2Br2, a marked difference in composition was found between deposits made in the SEM and deposits made in UHV. In addition to Pt, the UHV deposits contained halogen species and little or no carbon, while the SEM deposits contained only small amounts of halogen species but high carbon content. Results from this study highlight the effect that deposition conditions can have on the composition of deposits created by FEBID.

Quantitative mechanics of 3D printed nanopillars interacting with bacterial cells.

One of the methods to create sub-10 nm resolution metal-composed 3D nanopillars is electron beam-induced deposition (EBID). Surface nanotopographies (e.g., nanopillars) could play an important role in the design and fabrication of implantable medical devices by preventing the infections that are caused by the bacterial colonization of the implant surface. The mechanical properties of such nanoscale structures can influence their bactericidal efficiency. In addition, these properties are key factors in determining the fate of stem cells. In this study, we quantified the relevant mechanical properties of EBID nanopillars interacting with Staphylococcus aureus (S. aureus) using atomic force microscopy (AFM). We first determined the elastic modulus (17.7 GPa) and the fracture stress (3.0 ± 0.3 GPa) of the nanopillars using the quantitative imaging (QI) mode and contact mode (CM) of AFM. The displacement of the nanopillars interacting with the bacteria cells was measured by scanning electron microscopy (50.3 ± 9.0 nm). Finite element method based simulations were then applied to obtain the force-displacement curve of the nanopillars (considering the specified dimensions and the measured value of the elastic modulus) based on which an interaction force of 88.7 ± 36.1 nN was determined. The maximum von Mises stress of the nanopillars subjected to these forces was also determined (3.2 ± 0.3 GPa). These values were close to the maximum (i.e., fracture) stress of the pillars as measured by AFM, indicating that the nanopillars were close to their breaking point while interacting with S. aureus. These findings reveal unique quantitative data regarding the mechanical properties of nanopillars interacting with bacterial cells and highlight the possibilities of enhancing the bactericidal activity of the investigated EBID nanopillars by adjusting both their geometry and mechanical properties.

Deciphering the Roles of Interspace and Controlled Disorder in the Bactericidal Properties of Nanopatterns against Staphylococcus aureus.

Recent progress in nano-/micro-fabrication techniques has paved the way for the emergence of synthetic bactericidal patterned surfaces that are capable of killing the bacteria via mechanical mechanisms. Different design parameters are known to affect the bactericidal activity of nanopatterns. Evaluating the effects of each parameter, isolated from the others, requires systematic studies. Here, we systematically assessed the effects of the interspacing and disordered arrangement of nanopillars on the bactericidal properties of nanopatterned surfaces. Electron beam induced deposition (EBID) was used to additively manufacture nanopatterns with precisely controlled dimensions (i.e., a height of 190 nm, a diameter of 80 nm, and interspaces of 100, 170, 300, and 500 nm) as well as disordered versions of them. The killing efficiency of the nanopatterns against Gram-positive Staphylococcus aureus bacteria increased by decreasing the interspace, achieving the highest efficiency of 62 ± 23% on the nanopatterns with 100 nm interspacing. By comparison, the disordered nanopatterns did not influence the killing efficiency significantly, as compared to their ordered correspondents. Direct penetration of nanopatterns into the bacterial cell wall was identified as the killing mechanism according to cross-sectional views, which is consistent with previous studies. The findings indicate that future studies aimed at optimizing the design of nanopatterns should focus on the interspacing as an important parameter affecting the bactericidal properties. In combination with controlled disorder, nanopatterns with contrary effects on bacterial and mammalian cells may be developed.

Towards osteogenic and bactericidal nanopatterns?

Recent discoveries have shown that nanopatterns with feature sizes ≤100 nm could direct stem cell fate or kill bacteria. These effects could be used to develop orthopedic implants with improved osseointegration and decreased chance of implant-associated infections. The quest for osteogenic and bactericidal nanopatterns is ongoing but no controlled nanopatterns with dual osteogenic and bactericidal functionalities have been found yet. In this study, electron beam induced deposition (EBID) was used for accurate and reproducible decoration of silicon surfaces with four different types of nanopatterns. The features used in the first two nanopatterns (OST1 and OST2) were derived from osteogenic nanopatterns known to induce osteogenic differentiation of stem cells in the absence of osteogenic supplements. Two modifications of these nanopatterns were also included (OST2-SQ, OST2-H90) to study the effects of controlled disorder and lower nanopillar heights. An E. coli K-12 strain was used for probing the response of bacteria to the nanopatterns. Three nanopatterns (OST2, OST2-SQ, and OST2-H90) exhibited clear bactericidal behavior as evidenced by severely damaged cells and disrupted formation of extracellular polymeric substance. These findings indicate that controlled nanopatterns with features derived from osteogenic ones can have bactericidal activity and that EBID represents an enabling nanotechnology to achieve (multi)functional nanopatterns for bone implants.

Charged particle single nanometre manufacturing.

Following a brief historical summary of the way in which electron beam lithography developed out of the scanning electron microscope, three state-of-the-art charged-particle beam nanopatterning technologies are considered. All three have been the subject of a recently completed European Union Project entitled "Single Nanometre Manufacturing: Beyond CMOS". Scanning helium ion beam lithography has the advantages of virtually zero proximity effect, nanoscale patterning capability and high sensitivity in combination with a novel fullerene resist based on the sub-nanometre C60 molecule. The shot noise-limited minimum linewidth achieved to date is 6 nm. The second technology, focused electron induced processing (FEBIP), uses a nozzle-dispensed precursor gas either to etch or to deposit patterns on the nanometre scale without the need for resist. The process has potential for high throughput enhancement using multiple electron beams and a system employing up to 196 beams is under development based on a commercial SEM platform. Among its potential applications is the manufacture of templates for nanoimprint lithography, NIL. This is also a target application for the third and final charged particle technology, viz. field emission electron scanning probe lithography, FE-eSPL. This has been developed out of scanning tunneling microscopy using lower-energy electrons (tens of electronvolts rather than the tens of kiloelectronvolts of the other techniques). It has the considerable advantage of being employed without the need for a vacuum system, in ambient air and is capable of sub-10 nm patterning using either developable resists or a self-developing mode applicable for many polymeric resists, which is preferred. Like FEBIP it is potentially capable of massive parallelization for applications requiring high throughput.

Origami lattices with free-form surface ornaments.

Lattice structures are used in the design of metamaterials to achieve unusual physical, mechanical, or biological properties. The properties of such metamaterials result from the topology of the lattice structures, which are usually three-dimensionally (3D) printed. To incorporate advanced functionalities into metamaterials, the surface of the lattice structures may need to be ornamented with functionality-inducing features, such as nanopatterns or electronic devices. Given our limited access to the internal surfaces of lattice structures, free-form ornamentation is currently impossible. We present lattice structures that are folded from initially flat states and show that they could bear arbitrarily complex surface ornaments at different scales. We identify three categories of space-filling polyhedra as the basic unit cells of the cellular structures and, for each of those, propose a folding pattern. We also demonstrate "sequential self-folding" of flat constructs to 3D lattices. Furthermore, we folded auxetic mechanical metamaterials from flat sheets and measured the deformation-driven change in their negative Poisson's ratio. Finally, we show how free-form 3D ornaments could be applied on the surface of flat sheets with nanometer resolution. Together, these folding patterns and experimental techniques present a unique platform for the fabrication of metamaterials with unprecedented combination of physical properties and surface-driven functionalities.

Electron beam induced deposition of silacyclohexane and dichlorosilacyclohexane: the role of dissociative ionization and dissociative electron attachment in the deposition process.

We present first experiments on electron beam induced deposition of silacyclohexane (SCH) and dichlorosilacyclohexane (DCSCH) under a focused high-energy electron beam (FEBID). We compare the deposition dynamics observed when growing pillars of high aspect ratio from these compounds and we compare the proximity effect observed for these compounds. The two precursors show similar behaviour with regards to fragmentation through dissociative ionization in the gas phase under single-collision conditions. However, while DCSCH shows appreciable cross sections with regards to dissociative electron attachment, SCH is inert with respect to this process. We discuss our deposition experiments in context of the efficiency of these different electron-induced fragmentation processes. With regards to the deposition dynamics, we observe a substantially faster growth from DCSCH and a higher saturation diameter when growing pillars with high aspect ratio. However, both compounds show similar behaviour with regards to the proximity effect. With regards to the composition of the deposits, we observe that the C/Si ratio is similar for both compounds and in both cases close to the initial molecular stoichiometry. The oxygen content in the DCSCH deposits is about double that of the SCH deposits. Only marginal chlorine is observed in the deposits of from DCSCH. We discuss these observations in context of potential approaches for Si deposition.

Nanofabrication of a gold fiducial array on specimen support for electron tomography.

Here we describe the production, using lithography and micro-engineering technologies, of patterned arrays of nanofabricated gold dots on a thin Si3N4 electron transparent layer, supported by silicon. We illustrate that the support with a patterned structure of nanosized gold can be exploited for (cryo) electron tomography application as a specimen support with predefined alignment markers. This nanogold patterned support has several advantages. The Si3N4 window provides a 50 nm thin, strong and flat support with a ~0.7 mm(2) large electron-beam transparent window. The nanogold pattern has a user-defined size and density, is highly regular and stable. This facilitates accurate tracking during tilt series acquisition, provides sufficient contrast for accurate alignment during the image reconstruction step and avoids an uneven lateral distribution and movement of individual fiducials. We showed that the support is suitable for electron tomography on plastic sections.

Focused electron-beam-induced deposition of 3 nm dots in a scanning electron microscope.

Electron-beam-induced deposition allows the creation of three-dimensional nanodevices within a scanning electron microscope. Typically the dimensions of the fabricated structure are from 20 nm to several micrometers. Until now the record for the smallest deposited feature in an SEM was 3.5 nm, measured by an indirect method. We have achieved a nanodot having a full width half-maximum of 2.8 +/- 0.3 nm, measured directly in the same microscope after deposition.

Approaching the resolution limit of nanometer-scale electron beam-induced deposition.

We report the writing of very high resolution tungsten containing dots in regular arrays by electron beam-induced deposition (EBID). The size averaged over 100 dots was 1.0 nm at fwhm. Because of the statistical spread in the dot size, large and small dots are present in the arrays, with the smallest having a diameter of only 0.7 nm at fwhm. To date these are the smallest features fabricated by EBID. We have also fabricated lines with the smallest having a width at fwhm of 1.9 nm and a spacing of 3.2 nm.