Thomas Lukasczyk

Electron-Beam-Induced Deposition in Ultrahigh Vacuum: Lithographic Fabrication of Clean Iron Nanostructures

The generation of nanostructures with arbitrary shapes and well-defined chemical composition is still a challenge and targets the core of the fast-growing field of nanotechnology. One approach is the maskless nanofabrication technique of electron-beam-induced deposition (EBID). Up to now, the purity of these EBID structures has been rather poor. Here we demonstrate that by performing the EBID process solely under ultrahigh vacuum conditions, the lithographic generation of iron nanostructures on Si(100) with an unprecedented purity of higher than 95% is possible. One particular new aspect is the formation of EBID deposits with reduced size in a strain-induced diffusive process, resulting in deposits significantly smaller than 10 nm.

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 The importance of EBID recently increased since it superseded focused ion beam processing as a method to repair lithographic masks in the semiconductor industry.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

Generation of Clean Iron Structures by Electron-Beam-Induced Deposition and Selective Catalytic Decomposition of Iron Pentacarbonyl on Rh(110)

We explore the electron-beam-induced deposition (EBID) of iron pentacarbonyl, Fe(CO)5, in ultrahigh vacuum (UHV) on clean and modified Rh(110) surfaces by scanning electron microscopy (SEM), scanning Auger microscopy (SAM), and local Auger electron spectroscopy (AES). In EBID a highly focused electron beam is used to locally decompose the iron pentacarbonyl precursor molecules with the goal to generate pure iron nanostructures. It is demonstrated that the selectivity of the process strongly depends on the surface properties. On a perfect, clean Rh(110) surface almost no selectivity is observed; i.e., deposition of Fe is found on irradiated and nonirradiated surface regions due to catalytic decomposition of the Fe(CO)5. However, on a structurally nonperfect Rh(110) surface and on a Ti-precovered Rh(110) surface high selectivity is found; i.e., Fe deposits are primarily formed in irradiated regions. The role of catalytic and autocatalytic growth of iron on clean Rh respective iron deposits is discussed. The purity of the Fe deposits was always very high (>88%). It is demonstrated that the deposited Fe structures can be selectively oxidized to iron oxide by exposure to oxygen. Furthermore, attempts to write Fe line deposits were also successful, and line diameters smaller than 25 nm could be achieved.

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.

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.