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TiOx/Pt3Ti(111) surface-directed formation of electronically responsive supramolecular assemblies of tungsten oxide clusters

2021, Moors, Marco, An, Yun, Kuc, Agnieszka, Monakhov, Kirill Yu

Highly ordered titanium oxide films grown on a Pt3Ti(111) alloy surface were utilized for the controlled immobilization and tip-induced electric field-triggered electronic manipulation of nanoscopic W3O9 clusters. Depending on the operating conditions, two different stable oxide phases, z'-TiO x and w'-TiO x , were produced. These phases show a strong effect on the adsorption characteristics and reactivity of W3O9 clusters, which are formed as a result of thermal evaporation of WO3 powder on the complex TiO x /Pt3Ti(111) surfaces under ultra-high vacuum conditions. The physisorbed tritungsten nano-oxides were found as isolated single units located on the metallic attraction points or as supramolecular self-assemblies with a W3O9-capped hexagonal scaffold of W3O9 units. By applying scanning tunneling microscopy to the W3O9-(W3O9)6 structures, individual units underwent a tip-induced reduction to W3O8. At elevated temperatures, agglomeration and growth of large WO3 islands, which thickness is strongly limited to a maximum of two unit cells, were observed. The findings boost progress toward template-directed nucleation, growth, networking, and charge state manipulation of functional molecular nanostructures on surfaces using operando techniques.

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Thin film deposition using energetic ions

2010, Manova, D., Gerlach, J.W., Mändl, S.

One important recent trend in deposition technology is the continuous expansion of available processes towards higher ion assistance with the subsequent beneficial effects to film properties. Nowadays, a multitude of processes, including laser ablation and deposition, vacuum arc deposition, ion assisted deposition, high power impulse magnetron sputtering and plasma immersion ion implantation, are available. However, there are obstacles to overcome in all technologies, including line-of-sight processes, particle contaminations and low growth rates, which lead to ongoing process refinements and development of new methods. Concerning the deposited thin films, control of energetic ion bombardment leads to improved adhesion, reduced substrate temperatures, control of intrinsic stress within the films as well as adjustment of surface texture, phase formation and nanotopography. This review illustrates recent trends for both areas; plasma process and solid state surface processes. © 2010 by the authors.

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Laser-induced backside wet etching of transparent materials with organic and metallic absorbers

2008, Zimmer, K., Böhme, R.

Laser-induced backside wet etching (LIBWE) allows the high-quality etching of transparent materials for micro- and nanopatterning. Recent own results of LIBWE with hydrocarbon and metallic absorbers (H- and M-LIBWE) are summarized and compared with selected results of other groups regarding the etching process and the etched surface. Significant results on the impact of the liquid absorber, the material and the wavelength, and the pulse length of the laser to the etching are selected for this comparison. The etching of submicron-sized periodic structures in sapphire and fused silica with interference techniques and the selection of the preferred method in dependence on the material and the processing goal discussed. The experimental results are discussed on a thermal model considering both interface and volume absorption of the laser beam. These results have the conclusion that the etching at M-LIBWE is mainly due to material melting and evaporation whereas at H-LIBWE, a modified near-surface region with a very high absorption is ablated.

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Laser Embossing of Micro-and Submicrometer Surface Structures in Copper

2012, Ehrhardt, M., Lorenz, P., Frost, F., Zimmer, K.

Micro- and submicrometer structures have been transferred from nickel foils into solid copper surfaces by laser microembossing. The developed arrangement for laser microembossing allows a large-area replication using multi- pulse laser scanning scheme, guaranties a low contamination of the embossed surface and enables the utilization of thick workpieces. In the micrometer range the replicated patterns feature a high accuracy regarding the shape. A significant difference between the master and the replication pattern could be observed for the laser embossing of submicrometer patterns. In conclusion, the results show that the proposed laser embossing process is a promising method with a number of applications in microengineering.

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Comparative study of sculptured metallic thin films deposited by oblique angle deposition at different temperatures

2018, Liedtke, Susann, Grüner, Christoph, Gerlach, Jürgen W., Rauschenbach, Bernd

Metals with a wide range of melting points are deposited by electron beam evaporation under oblique deposition geometry on thermally oxidized Si substrates. During deposition the sample holder is cooled down to 77 K. It is observed that all obliquely deposited metals grow as tilted, high aspect ratio columns and hence with a similar morphology. A comparison of such columns with those deposited at room temperature (300 K) reveals that shadowing dominates the growth process for columns deposited at 77 K, while the impact of surface diffusion is significantly increased at elevated substrate temperatures. Furthermore, it is discussed how the incidence angle of the incoming particle flux and the substrate temperature affect the columnar tilt angles and the porosity of the sculptured thin films. Exemplarily for tilted Al columns deposited at 77 K and at 300 K, in-plane pole figure measurements are carried out. A tendency to form a biaxial texture as well as a change in the crystalline structure depending on the substrate temperature is found for those films.

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Increased biocompatibility and bioactivity after energetic PVD surface treatments

2009, Mändl, S.

Ion implantation, a common technology in semiconductor processing, has been applied to biomaterials since the 1960s. Using energetic ion bombardment, a general term which includes conventional ion implantation plasma immersion ion implantation (PIII) and ion beam assisted thin film deposition, functionalization of surfaces is possible. By varying and adjusting the process parameters, several surface properties can be attuned simultaneously. Extensive research details improvements in the biocompatibility, mainly by reducing corrosion rates and increasing wear resistance after surface modification. Recently, enhanced bioactivity strongly correlated with the surface topography and less with the surface chemistry has been reported, with an increased roughness on the nanometer scale induced by self-organisation processes during ion bombardment leading to faster cellular adhesion processes. © 2009 by the authors;.

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Laser-Induced front Side Etching: An Easy and Fast Method for Sub-μm Structuring of Dielectrics

2012, Lorenz, P., Ehrhardt, M., Zimmer, K.

Laser-induced front side etching (LIFE) is a method for the nanometer-precision structuring of dielectrics, e.g. fused silica, using thin metallic as well as organic absorber layer attached to the laser-irradiated front side of the sample. As laser source an excimer laser with a wavelength of 248 nm and an pulse duration of 25 ns was used. For sub-μm patterning a phase mask illuminated by the top hat laser beam was projected by a Schwarzschild objective. The LIFE process allows the fabrication of well-defined and smooth surface structures with sub-μm lateral etching regions (Δx < 350 nm) and vertical etching depths from 1 nm to sub-mm.

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Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands

2017, Börner, Martin, Blömer, Laura, Kischel, Marcus, Richter, Peter, Salvan, Georgeta, Zahn, Dietrich R. T., Siles, Pablo F., Fuentes, Maria E. N., Bufon, Carlos C. B., Grimm, Daniel, Schmidt, Oliver G., Breite, Daniel, Abel, Bernd, Kersting, Berthold

The chemisorption of magnetically bistable transition metal complexes on planar surfaces has recently attracted increased scientific interest due to its potential application in various fields, including molecular spintronics. In this work, the synthesis of mixed-ligand complexes of the type [NiII2L(L’)](ClO4), where L represents a 24-membered macrocyclic hexaazadithiophenolate ligand and L’ is a ω-mercapto-carboxylato ligand (L’ = HS(CH2)5CO2− (6), HS(CH2)10CO2− (7), or HS(C6H4)2CO2− (8)), and their ability to adsorb on gold surfaces is reported. Besides elemental analysis, IR spectroscopy, electrospray ionization mass spectrometry (ESIMS), UV–vis spectroscopy, and X-ray crystallography (for 6 and 7), the compounds were also studied by temperature-dependent magnetic susceptibility measurements (for 7 and 8) and (broken symmetry) density functional theory (DFT) calculations. An S = 2 ground state is demonstrated by temperature-dependent susceptibility and magnetization measurements, achieved by ferromagnetic coupling between the spins of the Ni(II) ions in 7 (J = +22.3 cm−1) and 8 (J = +20.8 cm−1; H = −2JS1S2). The reactivity of complexes 6–8 is reminiscent of that of pure thiolato ligands, which readily chemisorb on Au surfaces as verified by contact angle, atomic force microscopy (AFM) and spectroscopic ellipsometry measurements. The large [Ni2L] tail groups, however, prevent the packing and self-assembly of the hydrocarbon chains. The smaller film thickness of 7 is attributed to the specific coordination mode of the coligand. Results of preliminary transport measurements utilizing rolled-up devices are also reported.

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Heterobimetallic conducting polymers based on salophen complexes via electrosynthesis

2023, Bia, Francesca, Gualandi, Isacco, Griebel, Jan, Rasmussen, Leon, Hallak, Bassam, Tonelli, Domenica, Kersting, Berthold

In this work, we report the first electrochemical synthesis of two copolymeric bimetallic conducting polymers by a simple anodic electropolymerization method. The adopted precursors are electroactive transition metal (M = Ni, Cu and Fe) salophen complexes, which can be easily obtained by direct chemical synthesis. The resulting films, labeled poly-NiCu and poly-CuFe, were characterized by cyclic voltammetry in both organic and aqueous media, attenuated total reflectance Fourier transform infrared spectroscopy, UV-vis spectroscopy, scanning electron microscopy, and coupled energy dispersive X-ray spectroscopy. The films are conductive and exhibit great electrochemical stability in both organic and aqueous media (resistant over 100 cycles without significant loss in current response or changes in electrochemical behavior), which makes them good candidates for an array of potential applications. Electrochemical detection of ascorbic acid was performed using both materials.

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Pattern transfer of sub-micrometre-scaled structures into solid copper by laser embossing

2014, Ehrhardt, M., Lorenz, P., Lotnyk, A., Romanus, H., Thelander, E., Zimmer, K.

Laser embossing allows the micron and submicron patterning of metal substrates that is of great interest in a wide range of applications. This replication process enables low-cost patterning of metallic materials by non-thermal, high-speed forming which is driven by laser-induced shock waves. In this study the surface topography characteristics as well as the material structure at laser embossing of sub-micrometre gratings into solid copper is presented. The topography of the laser-embossed copper pattern is analysed with atomic force microscopy (AFM) in comparison to the master surface. The height of the embossed structures and the replicated pattern fidelity increases up to a laser fluence of F ∼ 10 J/cm2. For higher laser fluences the height of the embossed structures saturates at 75% of the master pattern height and the shape is adequate to the master. Structural modifications in the copper mono crystals after the laser embossing process were investigated with transmission electron microscopy (TEM) and electron backscatter diffraction (EBSD). Almost no modifications were detected. The residual stress after laser embossing of 32 MPa (F = 30 J/cm2) has only a limited influence on the surface pattern formation.