High reflectivity and long-term stability in multilayer mirrors (MLMs) are crucial for extreme ultraviolet (EUV) photolithography. The conventional base stack to reflect 13.5 nm light is a Mo/Si... Show moreHigh reflectivity and long-term stability in multilayer mirrors (MLMs) are crucial for extreme ultraviolet (EUV) photolithography. The conventional base stack to reflect 13.5 nm light is a Mo/Si multilayer, which offers a maximum theoretical reflectivity of 75%. In practice, however, the efficiency of the mirror is strongly affected by intermixing between Mo and Si. Diffusion barriers have therefore been adopted, which nevertheless do not provide a perfect solution. In this work, we propose to suppress intermixing in Mo/Si MLMs by substituting the pure Si with a Si compound that can ensure higher thermodynamic stability, while simultaneously providing comparably high EUV theoretical reflectivity, with the net effect of increasing both reflectivity and lifetime. Our theoretical calculations show that rubidium silicide is the most promising material for this purpose. We estimate the optical and thermodynamic properties for each phase of rubidium silicide, and we show that Mo/Rb12Si17 provides the highest theoretical reflectivity, while Mo/RbSi is the most thermodynamically stable. The suppression of intermixing in Mo/RbSi MLMs should lead to a maximum reflectivity at least 2% higher than the best Mo/Si MLMs, integrated with diffusion barriers. The proposed Mo/RbSi MLM solution has the potential to increase the total EUV lithography throughput by similar to 50%. Show less
The hydrodesulfurization process is one of the cornerstones of the chemical industry, removing harmful sulfur from oil to produce clean hydrocarbons. The reaction is catalyzed by the edges of MoS2... Show moreThe hydrodesulfurization process is one of the cornerstones of the chemical industry, removing harmful sulfur from oil to produce clean hydrocarbons. The reaction is catalyzed by the edges of MoS2 nanoislands and is operated in hydrogen-oil mixtures at 5–160 bar and 260–380 °C. Until now, it has remained unclear how these harsh conditions affect the structure of the catalyst. Using a special-purpose high-pressure scanning tunneling microscope, we provide direct observations of an active MoS2 model catalyst under reaction conditions. We show that the active edge sites adapt their sulfur, hydrogen, and hydrocarbon coverages depending on the gas environment. By comparing these observations to density functional theory calculations, we propose that the dominant edge structure during the desulfurization of CH3SH contains a mixture of adsorbed sulfur and CH3SH. Show less
Functionalizing noble metal surfaces with (bio)organic molecules is a vibrant field of research, with key applications in medicine, catalysis, and molecular electronics. Control over the molecular... Show moreFunctionalizing noble metal surfaces with (bio)organic molecules is a vibrant field of research, with key applications in medicine, catalysis, and molecular electronics. Control over the molecular self-assembly is essential to creating functional devices. Here, we exploit our high-pressure, high-temperature scanning tunneling microscope (STM) to relate the effects of controllable parameters (temperature and pressure) to atomic-scale assembly mechanisms. Using methanethiol self-assembly on Au(111) as a model system, we monitor the formation and assembly of the ubiquitous (CH3S)2Au “staple” motif into row structures at pressures of up to 1 bar. We observe a pressure-induced transition from the usual 1/3 monolayer (ML) saturation coverage in vacuum to 3/8 ML at 1 bar, thus providing the first evidence for a pressure gap effect for thiol adsorption. Complementing our experiments, we employed dispersion-corrected density functional theory computations to model the formed surface adlayers, corresponding STM images, and underlying equilibrium thermodynamics. Show less
The effect of a sequential oxidation and resulfidation treatment on γ-Al2O3 supported (Ni/Co)MoS2 catalyst nanoparticles was investigated using (HR)TEM, XPS, and thiophene HDS catalytic performance... Show moreThe effect of a sequential oxidation and resulfidation treatment on γ-Al2O3 supported (Ni/Co)MoS2 catalyst nanoparticles was investigated using (HR)TEM, XPS, and thiophene HDS catalytic performance experiments. Analysis of the HRTEM images revealed that, after initial sulfidation and oxidation, the resulfidation treatment restored the original slab length or increased it. The chemical composition of the samples, as determined by XPS, also slightly changed: the concentration of oxidic species increased, especially for the Ni promoter atoms. Comparing the catalytic HDS activity of the samples before and after the oxidation-resulfidation treatment showed that the catalysts were more than 20% more active after resulfidation. This increase in HDS activity is ascribed to a redistribution of the (Ni/Co)MoS2 slabs during the second sulfidation treatment, indicating a size effect. Show less
This paper reports on the preparation and characterization of nanostructured Re and Co–Re/Al2O3/NiAl(110) surfaces designed as model catalysts for operando studies of Fischer–Tropsch synthesis.... Show moreThis paper reports on the preparation and characterization of nanostructured Re and Co–Re/Al2O3/NiAl(110) surfaces designed as model catalysts for operando studies of Fischer–Tropsch synthesis. Scanning tunneling microscopy on pure Re particles identified strong Re–Al2O3 support interaction, resulting in uniform nucleation and growth on random point defects. X-ray photoelectron spectroscopy confirmed the strong interaction through a shift in the binding energy, in addition to size-dependent final state effects. Co–Re particles were prepared by sequential deposition of the two metals, resulting in core–shell structures in which the shell was (strongly) enriched with the metal deposited second. Annealing of bimetallic particles allowed for elemental redistribution, as was concluded from the XPS data and supported by modeling. The annealing also resulted in sintering of bimetallic clusters. Interestingly, the thermal stability of the Co–Re surfaces prepared by sequential deposition of Co, followed by Re, was better than that of both pure Co and pure Re. Show less
Scanning tunneling microscopy (STM) is an excellent technique to image the surfaces of materials with extreme spatial resolution. However, it is difficult to maintain its imaging quality when... Show moreScanning tunneling microscopy (STM) is an excellent technique to image the surfaces of materials with extreme spatial resolution. However, it is difficult to maintain its imaging quality when applying the technique under the conditions used in many practical processes, such as chemical vapor deposition and catalysis. In this article, we describe two special classes of STM instruments that are capable of maintaining good imaging quality under “difficult” conditions, namely, one for high and variable temperatures and the other for the combination of high temperatures and high gas pressures. In both cases, we discuss the special design features that make these instruments robust with respect to the challenging imaging conditions and provide examples to illustrate how they are applied. Show less
Spronsen, M.A. van; Frenken, J.W.M.; Groot, I.M.N. 2017