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.

The rational design of a Au(I) precursor for focused electron beam induced deposition.

Au(I) complexes are studied as precursors for focused electron beam induced processing (FEBIP). FEBIP is an advanced direct-write technique for nanometer-scale chemical synthesis. The stability and volatility of the complexes are characterized to design an improved precursor for pure Au deposition. Aurophilic interactions are found to play a key role. The short lifetime of ClAuCO in vacuum is explained by strong, destabilizing Au-Au interactions in the solid phase. While aurophilic interactions do not affect the stability of ClAuPMe3, they leave the complex non-volatile. Comparison of crystal structures of ClAuPMe3 and MeAuPMe3 shows that Au-Au interactions are much weaker or partially even absent for the latter structure. This explains its high volatility. However, MeAuPMe3 dissociates unfavorably during FEBIP, making it an unsuitable precursor. The study shows that Me groups reduce aurophilic interactions, compared to Cl groups, which we attribute to electronic rather than steric effects. Therefore we propose MeAuCO as a potential FEBIP precursor. It is expected to have weak Au-Au interactions, making it volatile. It is stable enough to act as a volatile source for Au deposition, being stabilized by 6.5 kcal/mol. Finally, MeAuCO is likely to dissociate in a single step to pure Au.

Acetone and the precursor ligand acetylacetone: distinctly different electron beam induced decomposition?

In focused electron beam induced deposition (FEBID) acetylacetone plays a role as a ligand in metal acetylacetonate complexes. As part of a larger effort to understand the chemical processes in FEBID, the electron-induced reactions of acetylacetone were studied both in condensed layers and in the gas phase and compared to those of acetone. X-ray photoelectron spectroscopy (XPS) shows that the electron-induced decomposition of condensed acetone layers yields a non-volatile hydrocarbon residue while electron irradiation of acetylacetone films produces a non-volatile residue that contains not only much larger amounts of carbon but also significant amounts of oxygen. Electron-stimulated desorption (ESD) and thermal desorption spectrometry (TDS) measurements reveal striking differences in the decay kinetics of the layers. In particular, intact acetylacetone suppresses the desorption of volatile products. Gas-phase studies of dissociative electron attachment and electron impact ionization suggest that this effect cannot be traced back to differences in the initial fragmentation reactions of the isolated molecules but is due to subsequent dissociation processes and to an efficient reaction of released methyl radicals with adjacent acetylacetone molecules. These results could explain the incorporation of large amounts of ligand material in deposits fabricated by FEBID processes using acetylacetonate complexes.

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

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

Microscopic characterisation of suspended graphene grown by chemical vapour deposition.

We present a multi-technique characterisation of graphene grown by chemical vapour deposition (CVD) and thereafter transferred to and suspended on a grid for transmission electron microscopy (TEM). The properties of the electronic band structure are investigated by angle-resolved photoelectron spectromicroscopy, while the structural and crystalline properties are studied by TEM and Raman spectroscopy. We demonstrate that the suspended graphene membrane locally shows electronic properties comparable with those of samples prepared by micromechanical cleaving of graphite. Measurements show that the area of high quality suspended graphene is limited by the folding of the graphene during the transfer.

The role of electron scattering in electron-induced surface chemistry.

Electron-induced chemistry on surfaces plays a key role in focused electron beam induced processing (FEBIP), a single-step lithography technique that has increasingly gained interest in the past decade. It is crucial for the understanding and modelling of this process to know the role of the surface in the electron-induced dissociation of an adsorbed precursor molecule. However, the electron scattering in the underlying solid makes it impossible to determine this directly. In this paper the contribution of electron scattering in the target on the measured deposition yield is calculated for the precursor MeCpPt(IV)Me(3), using the matrix inversion method. The calculation is based on experimental data for the dissociation yield and secondary electron emission. Two trends are observed in the analysis. Firstly, the contribution of electron scattering to the experimentally determined dissociation yield is not dominant for primary electron (PE) energies up to about 50 eV. Therefore, the role of the surface in this energy range can therefore reasonably be deduced from differences between electron-induced dissociation in the gas phase and the adsorbed phase. Secondly, at PE energies above 80 eV the electron scattering contributes significantly to the measured dissociation yield. The cross section that is calculated with the matrix inversion method peaks at 80-150 eV, which is typical for gas phase ionization. This suggests that surface interactions (other than electron scattering) do not dominate the chemistry for energies above PE energies of 80 eV. The obtained result can be used as input for Monte Carlo simulations for focused electron beam induced deposition.

Molecule-by-molecule writing using a focused electron beam.

The resolution of lithography techniques needs to be extended beyond their current limits to continue the trend of miniaturization and enable new applications. But what is the ultimate spatial resolution? It is known that single atoms can be imaged with a highly focused electron beam. Can single atoms also be written with an electron beam? We verify this with focused electron-beam-induced deposition (FEBID), a direct-write technique that has the current record for the smallest feature written by (electron) optical lithography. We show that the deposition of an organometallic precursor on graphene can be followed molecule-by-molecule with FEBID. The results show that mechanisms that are inherent to the process inhibit a further increase in control over the process. Hence, our results present the resolution limit of (electron) optical lithography techniques. The writing of isolated, subnanometer features with nanometer precision can be used, for instance, for the local modification of graphene and for catalysis.

Selective functionalization of tailored nanostructures.

The controlled positioning of nanostructures with active molecular components is of importance throughout nanoscience and nanotechnology. We present a novel three-step method to produce nanostructures that are selectively decorated with functional molecules. We use fluorophores and nanoparticles to functionalize SiO features with defined shapes and with sizes ranging from micrometers to 25 nm. The method is called MACE-ID: molecular assembly controlled by electron-beam-induced deposition. In the first step, SiO nanostructures are written with focused electron-beam-induced deposition, a direct-writing technique. In the second step, the deposits are selectively silanized. In the final step, the silanes are functionalized with fluorescent dyes, polystyrene spheres, or gold nanoparticles. This recipe gives exciting new possibilities for combining the highly accurate control of top-down patterning (e-beam direct writing) with the rich variety of the bottom-up approach (self-assembly), leading to active or responsive surfaces. An important advantage of MACE-ID is that it can be used on substrates that already contain complex features, such as plasmonic structures, nanoantennas, and cavities.

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.