Marie-Madeleine Walz

Tetraphenylporphyrin picks up zinc atoms from a silver surface

We demonstrate that adsorbed meso-tetraphenylporphyrin molecules can coordinate Zn atoms that are pre-deposited on an Ag(111) surface, forming a complex that is identical to directly deposited tetraphenylporphyrinato-zinc(II); this reaction, which we studied with XPS, is the first example of an oxidative dissolution of a metal by a large organic ligand under ultrahigh vacuum conditions.

Electrons as “Invisible Ink”: Fabrication of Nanostructures by Local Electron Beam Induced Activation of SiOx

The injection or removal of electrons can be used to trigger chemical processes, such as bond formation or dissociation. In this regard, electrons are an excellent and “clean” tool to modify or engineer the properties of different materials. The availability of localized electron probes, for example, in scanning electron microscopy (SEM), has made it possible to apply electron-induced processes on the nanometer and subnanometer scale. This approach can be used to target the generation of extremely small, pure nanostructures with lithographic control, which is one of the main goals in nanotechnology. The starting point of our study was the electron beam induced deposition (EBID) technique. The principle of EBID is outlined in Scheme 1a–c. A highly focused electron beam locally decomposes adsorbed precursor molecules to leave a deposit of nonvolatile fragments. The importance of EBID recently increased since it superseded focused ion beam processing as a method to repair lithographic masks in the semiconductor industry. The underlying physical and chemical principles of electron-induced bond making and breaking are in general also of great interest for important technological applications such as electron beam lithography (EBL), which is the standard method of generating the masks for UV lithography. As there is a large variety of precursor molecules and there are nearly no restrictions in regard to the substrate, EBID allows almost every combination of deposit material and substrate to be targeted. As a prototype example for conductive structures on an insulating material, our aim here was to generate clean iron nanostructures on a SiOx layer on Si(001). Scheme 1a–c depicts a schematic representation of

Magnetotransport properties of iron microwires fabricated by focused electron beam induced autocatalytic growth

We have prepared iron microwires in a combination of focused electron beam induced deposition and autocatalytic growth from the iron pentacarbonyl, Fe(CO)5, precursor gas under ultra-high vacuum conditions. The electrical transport properties of the microwires were investigated and it was found that the temperature dependence of the longitudinal resistivity (?xx) shows a typical metallic behaviour with a room temperature value of about 88????cm. In order to investigate the magnetotransport properties we have measured the isothermal Hall-resistivities in the range between 4.2 and 260?K. From these measurements, positive values for the ordinary and the anomalous Hall coefficients were derived. The relation between anomalous Hall resistivity (?AN) and longitudinal resistivity is quadratic, , revealing an intrinsic origin of the anomalous Hall effect. Finally, at low temperature in the transversal geometry a negative magnetoresistance of about 0.2% was measured.

Electron Beam-Induced Writing of Nanoscale Iron Wires on a Functional Metal Oxide

Electron beam-induced surface activation (EBISA) has been used to grow wires of iron on rutile TiO2(110)-(1 × 1) in ultrahigh vacuum. The wires have a width down to ∼20 nm and hence have potential utility as interconnects on this dielectric substrate. Wire formation was achieved using an electron beam from a scanning electron microscope to activate the surface, which was subsequently exposed to Fe(CO)5. On the basis of scanning tunneling microscopy and Auger electron spectroscopy measurements, the activation mechanism involves electron beam-induced surface reduction and restructuring.

Defects in oxygen-depleted titanate nanostructures.

The identification of defects and their controlled generation in titanate nanostructures is a key to their successful application in photoelectronic devices. We comprehensively explored the effect of vacuum annealing on morphology and composition of Na(2)Ti(3)O(7) nanowires and protonated H(2)Ti(3)O(7) nanoscrolls using a combination of scanning electron microscopy, Auger and Fourier-transform infrared (FT-IR) spectroscopy, as well as ab initio density functional theory (DFT) calculations. The observation that H(2)Ti(3)O(7) nanoscrolls are more susceptible to electronic reduction and annealing-induced n-type doping than Na(2)Ti(3)O(7) nanowires is attributed to the position of the conduction band minimum. It is close to the vacuum level and, thus, favors the Fermi level-induced compensation of donor states by cation vacancies. In agreement with theoretical predictions that suggest similar formation energies for oxygen and sodium vacancies, we experimentally observed the annealing induced depletion of sodium from the surface of the nanowires.

Investigation of proximity effects in electron microscopy and lithography

A fundamental challenge in lithographic and microscopic techniques employing focused electron beams are so-called proximity effects due to unintended electron emission and scattering in the sample. Herein, we apply a method that allows for visualizing electron induced surface modifications on a SiN substrate covered with a thin native oxide layer by means of iron deposits. Conventional wisdom holds that by using thin membranes proximity effects can be effectively reduced. We demonstrate that, contrary to the expectation, these can be indeed larger on a 200 nm SiN-membrane than on the respective bulk substrate due to charging effects.

Electron-beam-induced deposition and post-treatment processes to locally generate clean titanium oxide nanostructures on Si(100)

We have investigated the lithographic generation of TiO(x) nanostructures on Si(100) via electron-beam-induced deposition (EBID) of titanium tetraisopropoxide (TTIP) in ultra-high vacuum (UHV) by scanning electron microscopy (SEM) and local Auger electron spectroscopy (AES). In addition, the fabricated nanostructures were also characterized ex situ via atomic force microscopy (AFM) under ambient conditions. In EBID, a highly focused electron beam is used to locally decompose precursor molecules and thereby to generate a deposit. A drawback of this nanofabrication technique is the unintended deposition of material in the vicinity of the impact position of the primary electron beam due to so-called proximity effects. Herein, we present a post-treatment procedure to deplete the unintended deposits by moderate sputtering after the deposition process. Moreover, we were able to observe the formation of pure titanium oxide nanocrystals (<100 nm) in situ upon heating the sample in a well-defined oxygen atmosphere. While the nanocrystal growth for the as-deposited structures also occurs in the surroundings of the irradiated area due to proximity effects, it is limited to the pre-defined regions, if the sample was sputtered before heating the sample under oxygen atmosphere. The described two-step post-treatment procedure after EBID presents a new pathway for the fabrication of clean localized nanostructures.

Electron beam induced surface activation of ultrathin porphyrin layers on Ag(111).

We demonstrate how a focused electron beam can be used to chemically activate porphyrin layers on Ag(111) such that they become locally reactive toward the decomposition of iron pentacarbonyl, Fe(CO)5. This finding considerably expands the scope of electron beam induced surface activation (EBISA) and also has implications for electron beam induced deposition (EBID). The influence of the porphyrin layer thickness on both processes is studied in detail using scanning tunneling microscopy (STM) and scanning electron microscopy (SEM) as well as Auger electron spectroscopy (AES) and scanning Auger microscopy (SAM). While a closed monolayer of porphyrin molecules does exhibit some activity toward Fe(CO)5 decomposition after electron irradiation, a growth enhancement is found for bi- and multilayer films. This is attributed to a partial quenching of activated centers in the first layer due to the close proximity of the silver substrate. In addition, we demonstrate that the catalytic decomposition of gaseous Fe(CO)5 on Ag(111) can be effectively inhibited by introducing a densely packed monolayer of 2H-tetraphenylporphyrin (2HTPP) molecules.

Fabrication of layered nanostructures by successive electron beam induced deposition with two precursors: protective capping of metallic iron structures.

We report on the stepwise generation of layered nanostructures via electron beam induced deposition (EBID) using organometallic precursor molecules in ultra-high vacuum (UHV). In a first step a metallic iron line structure was produced using iron pentacarbonyl; in a second step this nanostructure was then locally capped with a 2-3 nm thin titanium oxide-containing film fabricated from titanium tetraisopropoxide. The chemical composition of the deposited layers was analyzed by spatially resolved Auger electron spectroscopy. With spatially resolved x-ray absorption spectroscopy at the Fe L₃ edge, it was demonstrated that the thin capping layer prevents the iron structure from oxidation upon exposure to air.

Strong enrichment of atmospherically relevant organic ions at the aqueous interface: the role of ion pairing and cooperative effects

Surface affinity, orientation and ion pairing are investigated in mixed and single solute systems of aqueous sodium hexanoate and hexylammonium chloride. The surface sensitive X-ray photoelectron spectroscopy technique has been used to acquire the experimental results, while the computational data have been calculated using molecular dynamics simulations. By comparing the single solute solutions with the mixed one, we observe a non-linear surface enrichment and reorientation of the organic ions with their alkyl chains pointing out of the aqueous surface. We ascribe this effect to ion paring between the charged functional groups on the respective organic ion and hydrophobic expulsion of the alkyl chains from the surface in combination with van der Waals interactions between the alkyl chains. These cooperative effects lead to a substantial surface enrichment of organic ions, with consequences for aerosol surface properties.