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Thin indium tin oxide (ITO) layers are essential in optoelectronics due to their good electrical conductivity, optical transparency in the visible and near infrared regions, substrate adherence and chemical stability. They are widely used in photovoltaic cells, displays, and organic LEDs, and as low emissivity coatings in smart windows and energy-efficient buildings. For nanophotonic devices, understanding the interplay of ITO’s optical and electrical properties is crucial. Electrical resistivity can be tuned by modifying deposition conditions and layer thickness. However, measuring these properties, especially on microstructured surfaces, remains challenging due to the issues like homogeneity and instability during etching.
Spectroscopic ellipsometry (SE), a non-destructive and phase-sensitive optical technique, offers precise measurement of thin film thickness and dielectric properties. In this study, we investigated the layer thickness, optical constants, and sheet resistance of unstructured and microstructured ITO thin layers using SE. Unstructured layers were deposited via DC-magnetron sputtering on silicon (Si) substrates in argon (Ar) atmospheres with varying oxygen (O2) flows.
This multi-technique approach enhances the understanding of ITO layer structuring and provides robust methodologies for correlating optical and electrical properties, advancing metrology for nanotechnology applications and material science. It also opens the pathway to new reference samples and calibration methods for electrical properties involving device-like structured samples.
Indium tin oxide (ITO), a transparent conductive oxide, is widely used in optoelectronic applications due to its electrical conductivity, optical transparency, and chemical stability. This study employs spectroscopic ellipsometry (SE) to analyze ITO layers, enabling nondestructive determination of film thickness, dielectric functions, and bulk conductivity. Electrical properties derived from SE are compared with those obtained using the four‐point probe method (4PM) to improve metrological tools for nanotechnology applications and optimize deposition process monitoring for better control of film properties. This work also investigates the chemical stability of ITO layers under etching conditions and explores the development of new sheet resistance standards for scanning microwave microscopy (SMM). The results show that ITO resistivity, calculated from fitted SE data, increases with oxygen flow rate up to 5 cm3(STP) min−1. Good agreement is observed between sheet resistance values obtained by SE and 4PM up to 3 cm3(STP) min−1. Additionally, the sheet resistance values of a distinct set of microstructured ITO samples with different ITO layer thicknesses are determined by SMM, which are highly consistent with those obtained by the 4PM.
Polydopamine – a bio-inspired polymer for X-ray mirror coatings and other technical applications
(2025)
Although the organic molecule dopamine (3,4-dihydroxyphenethylamine) is commonly known as one of the “hormones of happiness”, thin polymer films of polydopamine (PDA) also have interesting technical properties. PDA is a very strong glue that sticks on almost everything, even under water. In nature, PDA is found in the byssal thread cuticles of mussels. When produced by dip-coating, the self-organizing PDA layers grow in a reproducible thickness of single or multiple molecule monolayers of a few nanometres thickness only. Here we present an optimized preparation regime as derived from polymerization analysis through absorption spectroscopy. One application is the use of thin PDA overcoatings to increase the soft X-ray reflectivity of astronomical X-ray mirrors. Furthermore, we give an outlook to other technical applications for this interesting material, presenting this bio-inspired organic polymer as an innovative technical solution for the future, with applications such as PDA-based super-capacitors and its promising role in enhancing separator materials for batteries.
Polydopamine (PDA) recently came into focus as an innovative material for applications in various technical fields. It is a very strong glue that sticks on almost everything, even under water: In nature, PDA is found in the byssal thread cuticles of mussels. In 2007, Lee et al. first showed that dipping substrates into a solution of dopamine results in the formation of thin PDA films on numerous materials. The simple preparation and the high durability of these coatings have stimulated growing research interest and a wide variety of applications in energy, biomedical and environmental science, and other fields.
We have investigated thin layers of PDA with different methods including ellipsometry, tactile measurements of the layer thickness and in situ absorption measurements during the polymerization process. During polymerization the dopamine solution shows a progressive colour change from transparent to brown that has been monitored by spectrometric measurements. The increasing absorption of the cuvette with dopamine solution can be seen in figure 1. The absorption levels off after approximately 2,5 h of polymerization time, thus indicating termination of the primary formation of the PDA film. This data shows that for homogeneous layer growth it is advantageous to interrupt the process after two hours. To generate a higher layer thickness, the samples need to be cleaned and immersed in a fresh dopamine solution subsequently. In addition, ellipsometry measurements on polydopamine layers could determine the corresponding coating thickness as well as its complex refractive index over a broad wavelength range.
Laser materials processing is an important tool for creating and shaping new materials. Laser machining, especially with ultrashort pulses offers the modification of surfaces, thin coatings, and bulk materials with an unprecedented precision and control. The most desired feature of pulsed laser processing in the femtosecond range is that the heat-affected zone in the irradiated material will be extremely small. To better understand the mechanisms involved during laser irradiation, it is important to analyse the outcome of light-matter interaction with spectroscopic methods. Ellipsometry, especially spectroscopic imaging ellipsometry (SIE), has become an important tool for this in recent times, as it gives access to local layer thicknesses, materials dielectric functions, and features like changes in surface roughness.
This work includes an overview over our recent studies examining near-infrared fs-laser surface processing of different group IV materials. The superficial phase change of silicon from crystalline to amorphous has been investigated in the past as the result of laser processing strongly depends on the crystal orientation. Moreover, SIE is capable of determining the
properties of buried a-Si interfaces with micrometer lateral and sub-nanoneter vertical precision. Additionally, the growth of native and laser-induced oxides can be revealed.
This work studies the influence of the adsorbed layer on the glass transition of thin films of polysulfone. Therefore, the growth kinetics of the irreversibly adsorbed layer of polysulfone on silicon substrates was first investigated using the solvent leaching approach, and the thickness of the remaining layer was measured with atomic force microscopy. Annealing conditions before leaching were varied in temperature and time (0–336 h). The growth kinetics showed three distinct regions: a pre-growth step where it was assumed that phenyl rings align parallel to the substrate at the shortest annealing times, a linear growth region, and a crossover from linear to logarithmic growth observed at higher temperatures for the longest annealing times. No signs of desorption were observed, pointing to the formation of a strongly adsorbed layer.
Second, the glass transition of thin polysulfone films was studied in dependence on the film thickness using spectroscopic ellipsometry. Three annealing conditions were compared: two with only a tightly bound layer formed in the linear growth regime and one with both tightly bound and loosely adsorbed layers formed in the logarithmic growth regime. The onset thickness and increase in the glass transition temperature increases with annealing time and temperature. These differences were attributed to the distinct conformations of the formed adsorbed layers.
The molecular dynamics of thin films and the adsorbed layer of poly(2-vinylpyridine) (P2VP) were investigated using broadband dielectric spectroscopy (BDS) and spectroscopic ellipsometry. Thin films of P2VP were prepared on silicon substrates and characterized to understand the influence of film thickness on the thermal glass transition temperature (Tg) and molecular mobility. The ellipsometric study revealed a decrease in Tg with decreasing film thickness, attributed to the enhanced mobility at the polymer/air interface. The adsorbed layer, prepared via the solvent leaching approach, exhibited a higher Tg compared to the bulk, indicating reduced molecular mobility due to strong polymer substrate interactions. The dielectric measurements were carried out in two different electrode configurations, crossed electrode capacitors (CEC) and nanostructured electrodes (NSE), where the latter allows for a free surface layer at the polymer/air interface. The relaxation rates of the α-relaxation measured in the CEC geometry collapse into one chart independent from the film thickness. For the thin films measured in the NSE arrangement the relaxation rates slow down with decreasing film thickness which was discussed as related to a stronger interaction of the P2VP segments with the native SiO2 at the surface of the silicon substrate compared to aluminum. It is worth to note that the effect of the enhanced mobility at the polymer/air interface is not observed in the dielectric measurements. BDS measurements in NSE geometry identified an additional relaxation process (α*-relaxation) in thin films, which was more pronounced in the adsorbed layer. This process is hypothesized to be related to molecular fluctuations within the adsorbed layer including the adsorption/desorption dynamics of segments or to a Slow Arrhenius Process (SAP) related to the equilibration dynamics deep in the glassy state.
Electrochemical methods offer great promise in meeting the demand for user-friendly on-site devices for Monitoring important parameters. The food industry often runs own lab procedures, for example, for mycotoxin analysis, but it is a major goal to simplify analysis, linking analytical methods with smart technologies. Enzyme-linked immunosorbent assays, with photometric detection of 3,3’,5,5’-tetramethylbenzidine (TMB),form a good basis for sensitive detection. To provide a straightforward approach for the miniaturization of the detectionstep, we have studied the pitfalls of the electrochemical TMB detection. By cyclic voltammetry it was found that the TMB electrochemistry is strongly dependent on the pH and the electrode material. A stable electrode response to TMB could be achieved at pH 1 on gold electrodes. We created a smartphonebased, electrochemical, immunomagnetic assay for the detection of ochratoxin A in real samples, providing a solid basis forsensing of further analytes.
CS particles show unique properties by merging individual characteristics of the core and the shell materials. An alteration particularly in their surface roughness affects the final performance of the particles in the targeted application. Quantitative evaluation of the roughness of CS microparticles is, however, a challenging task employing microscopic techniques being scarce and showing large differences in terms of methodology and results.
In our previous work, we have reported a systematic study with a reliable analysis tool, which evaluates profile roughness quantitatively, for individual core-shell microparticles using electron microscopy (EM) images of both types, Scanning Electron Microscopy (SEM) and transmission mode SEM (or TSEM). The SEM images contain two-dimensional (2D) information, therefore, provide profile roughness data only from the projection in the horizontal plane (in other words, from the “belly”) of a spherical particle. The present study offers a practical procedure to give access to more information by tilting the sample holder and hence allowing images of a single particle to be recorded at different orientations under the same view angle. From the analysis of these images, extended information on surface roughness of the particle can be extracted. Thus, instead of obtaining 2D information from a single SEM image, three-dimensional (3D) information is obtained from 2D projections recorded at different particle orientations.
This dataset accompanies the following publication:
Hülagü, D., Tobias, C., Dao, R., Komarov, P., Rurack, K., Hodoroaba, V.-D., Towards 3D determination of the surface roughness of core-shell microparticles as a routine quality control procedure by scanning electron microscopy. Sci.Rep, 14, 17936 (2024), https://doi.org/10.1038/s41598-024-68797-7.
It contains SEM and AFM-in-SEM images of polystyrene (PS) core particles, polystyrene-iron oxide (PS/Fe3O4) core-shell particles, and polystyrene-iron oxide-silica (PS/Fe3O4/SiO2) core-shell-shell particles. Please refer to the publication and its supporting information for more details on the acquisition and contents of the dataset, as well as the GitHub repository at https://github.Com/denizhulagu/roughness-analysis-by-electron-microscopy.
The investigated particles were produced at BAM laboratories as previously described in:
Hülagü, D. et al. Generalized analysis approach of the profile roughness by electron microscopy with the example of hierarchically grown polystyrene–iron oxide–silica core–shell–shell particles. Adv. Eng. Mater. 24, 2101344, https://doi.org/10.1002/adem.202101344 (2022).
Tobias, C., Climent, E., Gawlitza, K. & Rurack, K. Polystyrene microparticles with convergently grown mesoporous silica shells as a promising tool for multiplexed bioanalytical assays. ACS Appl. Mater. Interfaces 13, 207, https://dx.doi.org/10.1021/acsami.0c17940 (2020).