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Energy-filtered backscattered electron imaging in a scanning electron microscope is performed on a blend of zinc-phthalocyanine (ZnPc) and fullerene (C60), whose morphology is characterized using a novel energy selective backscattered (EsB) electron detector in combination with low acceleration voltages for the primary electrons. Such blends are used as an active layer of organic solar cells in bulk heterojunction architectures. The key to optimizing the solar cell performance is understanding the morphology of the blend components. Comparing the results to TEM micrographs, the EsB detector allows for a simple and fast identification of the phases in the blend. The relevance of the findings for applying ZnPc–C60 blends in solar cells is also discussed.

The electron-induced decomposition of cisplatin (cis-Pt(NH3)(2)Cl-2) was investigated to reveal if ammine (NH3) ligands have a favorable effect on the purity of deposits produced from metal-containing precursor molecules by focused electron beam induced deposition (FEBID). Scanning electron microscopy showed that cisplatin particles of different sizes react violently during electron irradiation. In particular, faceted particles of a few mu m in size started to boil, became spherical and subsequently degraded. Energy-dispersive X-ray spectroscopy gave evidence for the formation of nearly pure platinum and a decrease of the chlorine content. Nitrogen, however, was not detected, pointing to an efficient and rapid removal of NH3. In contrast, PtCl2 particles do not degrade under comparable conditions, demonstrating that the ammine ligand plays an important role in the reduction of cisplatin to pure platinum. The fast release of NH3 ligands under electron exposure was confirmed by high resolution electron energy loss spectroscopy, focusing in particular on low-energy electrons as produced in high amounts during the FEBID process. Finally, FEBID experiments using cisplatin adsorbed from the gas phase onto a surface produced amorphous deposits. In contrast to the decomposed cisplatin particles, these deposits had a chlorine content of about 50 at. %. Only after extensive irradiation in a transmission electron microscope was this chlorine content reduced and were crystalline particles obtained. In conclusion, using NH3 as ligand in metal containing FEBID precursors can favor the formation of pure metal deposits, but its effectiveness depends on the precise experimental conditions.

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.

Area selectivity is an emerging sub-topic in the field of atomic layer deposition (ALD), which employs opposite nucleation phenomena to distinct heterogeneous starting materials on a surface. In this paper, we intend to grow Ru exclusively on locally pre-defined Pt patterns, while keeping a SiO

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.

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.

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.

The effect of 500 eV electrons on nanometer scale thick films of trimethyl(methylcyclopentadienyl)platinum(IV) (MeCpPtIVMe3), were studied in situ, under ultrahigh vacuum conditions using a combination of temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), mass spectrometry, and reflection absorption infrared spectroscopy. TPD results revealed the presence of a monolayer state, with a desorption energy >10 kJ mol−1 larger than the multilayer. XPS data indicate that electron beam induced decomposition of adsorbed MeCpPtIVMe3 produced a carbonaceous film that contained Pt atoms in an electronic state intermediate between metallic Pt and Pt(IV). In addition to Pt(IV) reduction, electron beam irradiation was also accompanied by the evolution of methane and hydrogen from the adsorbate layer and the loss of C−H groups. The rate of Pt(IV) reduction and methane production and the loss of C−H groups from the film were all proportional to the MeCpPtIVMe3 coverage and the incident electr...

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.

Area selectivity is an emerging sub-topic in the field of atomic layer deposition (ALD), which employs opposite nucleation phenomena to distinct heterogeneous starting materials on a surface. In this paper, we intend to grow Ru exclusively on locally pre-defined Pt patterns, while keeping a SiO2 substratum free from any deposition. In a first step, we study in detail the Ru ALD nucleation on SiO2 and clarify the impact of the set-point temperature. An initial incubation period with actually no growth was revealed before a formation of minor, isolated RuO x islands; clearly no continuous Ru layer formed on SiO2. A lower temperature was beneficial in facilitating a longer incubation and consequently a wider window for (inherent) selectivity. In a second step, we write C-rich Pt micro-patterns on SiO2 by focused electron-beam-induced deposition (FEBID), varying the number of FEBID scans at two electron beam acceleration voltages. Subsequently, the localized Pt(C) deposits are pre-cleaned in O2 and overgrown by Ru ALD. Already sub-nanometer-thin Pt(C) patterns, which were supposedly purified into some form of Pt(O x ), acted as very effective activation for the locally restricted, thus area-selective ALD growth of a pure, continuous Ru covering, whereas the SiO2 substratum sufficiently inhibited towards no growth. FEBID at lower electron energy reduced unwanted stray deposition and achieved well-resolved pattern features. We access the nucleation phenomena by utilizing a hybrid metrology approach, which uniquely combines in-situ real-time spectroscopic ellipsometry, in-vacuo x-ray photoelectron spectroscopy, ex-situ high-resolution scanning electron microscopy, and mapping energy-dispersive x-ray spectroscopy.

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 gas field ion microscope was used to investigate helium and neon ion beam induced etching of nickel as a candidate technique for extreme ultraviolet (EUV) lithography mask editing. No discernable nickel etching was observed for room temperature helium exposures at 16 and 30 keV in the dose range of 1 x 10(15)-1 x 10(18) He+/cm(2); however, transmission electron microscopy (TEM) revealed subsurface damage to the underlying Mo-Si multilayer EUV mirror. Subsequently, neon beam induced etching at 30 keV was investigated over a similar dose range and successfully removed the entire 50 nm nickel top absorber film at a dose of similar to 3 x 10(17) Ne+/cm(2). Similarly, TEM revealed subsurface damage in the underlying Mo-Si multilayer. To further understand the helium and neon damage, the authors simulated the ion-solid interactions with our EnvizION Monte-Carlo model, which reasonably correlated the observed damage and bubble formation to the nuclear energy loss and the implanted inert gas concentration, respectively. A critical nuclear energy density loss of similar to 80 eV/nm(3) and critical implant concentration of similar to 2.5 x 10(20) atoms/cm(3) have been estimated for damage generation in the multilayer structure. (C) 2014 American Vacuum Society.

This paper concentrates on focused electron beam induced deposition of silicon oxide. Silicon oxide pillars are written using 2, 4, 6, 8, 10-pentamethyl-cyclopenta-siloxane (PMCPS) as precursor. It is observed that branching of the pillar occurs above a minimum pillar height. The branching is attributed to charging of the deposit by the electron beam. The branching can be suppressed by introducing water into the chamber together with PMCPS. At the same time, the cointroduction of water results in a higher growth rate, which is found to be specific to PMCPS. (C) 2011 American Vacuum Society. [DOI: 10.1116/1.3659713]

Electron beam induced deposition of organometallic precursors has emerged as an effective and versatile method for creating two-dimensional and three-dimensional metal-containing nanostructures. However, to improve the properties and optimize the chemical composition of nanostructures deposited in this way, the electron stimulated decomposition of the organometallic precursors must be better understood. To address this issue, we have employed an ultrahigh vacuum-surface science approach to study the electron induced reactions of dimethyl-(acetylacetonate) gold(III) [AuIII(acac)Me2] adsorbed onto solid substrates. Using thin molecular films adsorbed onto cooled substrates, surface reactions, reaction kinetics, and gas phase products were studied in the incident energy regime between 40 and 1500 eV using a combination of x-ray photoelectron spectroscopy (XPS), reflection absorption infrared spectroscopy (RAIRS), and mass spectrometry (MS). XPS and RAIRS data indicate that electron irradiation of AuIII(acac)Me2 is accompanied by the reduction in AuIII to a metallic Au0 species embedded in a dehydrogenated carbon matrix, while MS reveals the concomitant evolution of methane, ethane, carbon monoxide, and hydrogen. The electron stimulated decomposition of AuIII(acac)Me2 is first-order with respect to the surface coverage of the organometallic precursor, and exhibits a rate constant that is proportional to the electron flux. At an incident electron energy of 520 eV, the total reaction cross section was ? 3.6×10?16?cm2. As a function of the incident electron energy, the maximum deposition yield was observed at ?175 eV. The structure of discrete Au-containing deposits formed at room temperature by rastering an electron beam across a highly ordered pyrolytic graphite substrate in the presence of a constant partial pressure of AuIII(acac)Me2 was also investigated by atomic force microscopy.