Theodor Weiss

Bio: Theodor Weiss is an academic researcher from University of Bremen. The author has contributed to research in topics: Thin film & Chemical vapor deposition. The author has an hindex of 4, co-authored 5 publications receiving 71 citations.

Chemisorbed Oxygen on the Au(321) Surface Alloyed with Silver: A First-Principles Investigation

Abstract: The adsorption of oxygen on kinked Au(321) slabs is investigated theoretically on the basis of density functional theory. On-surface, subsurface, and surface-oxide forms of O are analyzed and compared on pure gold and on the surfaces containing silver atoms. At low O coverage (0.1 ML) subsurface O species are shown to be unstable both thermodynamically and kinetically due to a low barrier for conversion to stronger bound on-surface chemisorbed oxygen. The presence of Ag in the near-surface region was shown to increase the binding strength of on-surface as well as subsurface O, but the activation barrier for releasing subsurface O to the surface remains essentially unaffected by the presence of Ag. At oxygen coverage 0.2 ML or higher, the most stable surface arrangements of O atoms are chain-like structures consisting of linear −O–Au–O– fragments. Subsurface O atoms being a part of such chains are significantly stabilized. We examine phase transitions between the clean surface and possible stable oxidized ...

Influence of Water on Chemical Vapor Deposition of Ni and Co thin films from ethanol solutions of acetylacetonate precursors.

Abstract: In chemical vapor deposition experiments with pulsed spray evaporation (PSE-CVD) of liquid solutions of Ni and Co acetylacetonate in ethanol as precursors, the influence of water in the feedstock on the composition and growth kinetics of deposited Ni and Co metal films was systematically studied. Varying the water concentration in the precursor solutions, beneficial as well as detrimental effects of water on the metal film growth, strongly depending on the concentration of water and the β-diketonate in the precursor, were identified. For 2.5 mM Ni(acac)2 precursor solutions, addition of 0.5 vol% water improves growth of a metallic Ni film and reduces carbon contamination, while addition of 1.0 vol% water and more leads to significant oxidation of deposited Ni. By tuning the concentration of both, Ni(acac)2 and water in the precursor solution, the fraction of Ni metal and Ni oxide in the film or the film morphology can be adjusted. In the case of Co(acac)2, even smallest amounts of water promote complete oxidation of the deposited film. All deposited films were analyzed with respect to chemical composition quasi in situ by XPS, their morphology was evaluated after deposition by SEM.

XPS study of thermal and electron-induced decomposition of Ni and Co acetylacetonate thin films for metal deposition

Abstract: Optimizing thin metal film deposition techniques from metal-organic precursors such as atomic layer deposition, chemical vapor deposition (CVD), or electron beam-induced deposition (EBID) with the help of surface science analysis tools in ultrahigh vacuum requires a contamination-free precursor delivery technique, especially in the case of the less volatile precursors. For this purpose, the preparation of layers of undecomposed Ni(acac)2 and Co(acac)2 was tried via pulsed spray evaporation of a liquid solution of the precursors in ethanol into a flow of nitrogen on a CVD reactor. Solvent-free layers of intact precursor molecules were obtained when the substrate was held at a temperature of 115 °C. A qualitative comparison of thermally initiated and electron-induced precursor decomposition and metal center reduction was carried out. All deposited films were analyzed with respect to chemical composition quasi in situ by x-ray photoelectron spectroscopy. Thermally initiated decomposition yielded higher metal...

Investigation of the growth behaviour of cobalt thin films from chemical vapour deposition, using directly coupled X-ray photoelectron spectroscopy

Abstract: Abstract Thin films and coatings are a basis for many technological processes, including microelectronics, electrochemistry and catalysis. The successful deposition of metal films and nanoparticles by chemical vapour deposition (CVD) needs control over a number of physico-chemical processes such as precursor and substrate selection, delivery, temperature, pressure and flow conditions. Here, cobalt thin films were deposited by means of pulsed-spray evaporation chemical vapour deposition (PSE-CVD) from ethanol solutions of Co(acac)2 and Co(acac)3 on bare glass and silicon substrates. The physico-chemical properties of the grown films were characterised by XRD (X-ray diffraction), XPS (X-ray photoelectron spectroscopy) and HIM (helium ion microscopy). Co(acac)2 enabled the growth of cobalt metal at lower temperatures than Co(acac)3. The difference in deposition temperature was attributed to the ability of ethanol to reduce Co(acac)2 better than Co(acac)3. In addition, the film deposited from Co(acac)2 exhibited a higher metal content and a less porous structure than that deposited from Co(acac)3. Increasing the substrate temperature enhanced the carbon content because of the thermal decomposition of both precursors. Using a nickel seed layer improved the growth rate until a critical temperature of 360 ℃, at which the thermal decomposition of the precursor becomes predominant. A decrease in the deposition temperature when using the nickel seed layer was only observed with Co(acac)2 precursor; the growth behaviour under these conditions was monitored with a unique UHV-compatible PSE-CVD reactor directly attached to an XPS system and ascribed to an enhancement of its catalytic reduction by ethanol.

Design of a compact ultrahigh vacuum-compatible setup for the analysis of chemical vapor deposition processes.

Abstract: Optimizing thin film deposition techniques requires contamination-free transfer from the reactor into an ultrahigh vacuum (UHV) chamber for surface science analysis. A very compact, multifunctional Chemical Vapor Deposition (CVD) reactor for direct attachment to any typical UHV system for thin film analysis was designed and built. Besides compactness, fast, easy, and at the same time ultimately clean sample transfer between reactor and UHV was a major goal. It was achieved by a combination of sample manipulation parts, sample heater, and a shutter mechanism designed to fit all into a NW38 Conflat six-ways cross. The present reactor design is versatile to be employed for all commonly employed variants of CVD, including Atomic Layer Deposition. A demonstration of the functionality of the system is provided. First results of the setup (attached to an Omicron Multiprobe x-ray photoelectron spectroscopy system) on the temperature dependence of Pulsed Spray Evaporation-CVD of Ni films from Ni acetylacetonate as the precursor demonstrate the reactor performance and illustrate the importance of clean sample transfer without breaking vacuum in order to obtain unambiguous results on the quality of CVD-grown thin Ni films. The widely applicable design holds promise for future systematic studies of the fundamental processes during chemical vapor deposition or atomic layer deposition.

O2 Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

Abstract: The activation of O2 on metal surfaces is a critical process for heterogeneous catalysis and materials oxidation. Fundamental studies of well-defined metal surfaces using a variety of techniques have given crucial insight into the mechanisms, energetics, and dynamics of O2 adsorption and dissociation. Here, trends in the activation of O2 on transition metal surfaces are discussed, and various O2 adsorption states are described in terms of both electronic structure and geometry. The mechanism and dynamics of O2 dissociation are also reviewed, including the importance of the spin transition. The reactivity of O2 and O toward reactant molecules is also briefly discussed in the context of catalysis. The reactivity of a surface toward O2 generally correlates with the adsorption strength of O, the tendency to oxidize, and the heat of formation of the oxide. Periodic trends can be rationalized in terms of attractive and repulsive interactions with the d-band, such that inert metals tend to feature a full d band ...

Dynamic restructuring drives catalytic activity on nanoporous gold-silver alloy catalysts

Abstract: Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver-gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changes occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.

Nanoporous Gold: Understanding the Origin of the Reactivity of a 21st Century Catalyst Made by Pre-Columbian Technology

Abstract: Nanoporous gold (np-Au), a three-dimensional nanoporous bulk material, is made by selective corrosion of Ag from Ag–Au alloys, a technique already applied by the pre-Columbian cultures of South America. Nanoporous gold is actually a Au-rich Ag–Au alloy which, specifically the Ag0.03Au0.97 composition, combines high reactivity and selectivity for a wide variety of oxidation reactions, from simple CO oxidation to complex oxygen-assisted coupling reactions. Its catalytic reactivity is surprising because np-Au is a nonsupported Au catalyst with relatively large feature sizes on the order of tens of nanometers, thus breaking the generally accepted notion that gold must be in the form of small particles (about a few nanometers) to be an active catalyst. The ease of sample preparation in combination with high reactivity, selectivity, and long-term stability suggests that nanoporous gold has the potential to bring Au catalysis closer to practical applications. In this perspective, we provide a critical review of ...

How Does Nanoporous Gold Dissociate Molecular Oxygen

Abstract: Nanoporous Au and other dilute AgAu alloys are highly active and selective oxidation catalysts. Their ability to dissociate O2 is to a large extent unexplained, given that unsupported Au cannot generally dissociate O2, while large ensembles of Ag atoms (>4) are generally necessary to lower the O2 dissociation barrier significantly. Here, we identify a site on the surface of dilute AgAu alloys that is stable under reaction conditions and has a low O2 dissociation barrier, in agreement with experimental measurements. Although Ag generally prefers to disperse throughout Au, the presence of adsorbed O near surface steps creates sites of high local Ag concentration, where the Ag atoms sit in the rows next to the step Au atoms. O2 adsorbs on the Au step atoms, but the transition state involves significant Ag–O interaction, resulting in a barrier lower than expected from the adsorption energies of either the initial or final state.