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Paper des Monats
- ja (1)
We compare standard and inverted bulk heterojunction solar cells composed of PCPDTBT:PC70BM
blends. Inverted devices comprising 100 nm thick active layers exhibited short circuit currents of
15 mA/cm², 10% larger than in corresponding standard devices. Modeling of the optical field distribution
in the different device stacks proved that this enhancement originates from an increased absorption of
incident light in the active layer. Internal quantum efficiencies (IQEs) were obtained from the direct
comparison of experimentally derived and modeled currents for different layer thicknesses, yielding IQEs
of ~70% for a layer thickness of 100 nm. Simulations predict a significant increase of the light harvesting
efficiency upon increasing the layer thickness to 270 nm. However, a continuous deterioration of the
photovoltaic properties with layer thickness was measured for both device architectures, attributed to
incomplete charge extraction. On the other hand, our optical modeling suggests that inverted devices
based on PCPDTBT should be able to deliver high power conversion efficiencies (PCEs) of more than
7% provided that recombination losses can be reduced.
The aim of this study is to develop nanometer-thin epoxy-based films on aluminium alloy AA2024-T3 as a model coating system for high resolution corrosion studies. Spin coating was used for the layer-by-layer (LbL) deposition of poly-(ethylenimine) (PEI) and poly([o-cresyl glycidyl ether]-co-formaldehyde) (CNER) bilayers. The film chemistry and the cross-linking process were characterized by means of Fourier-transform infrared spectroscopy (FTIR).
Ellipsometric data confirmed the linear increase of film thickness. The potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) results indicate the improvement of the film barrier properties with increasing film thickness. Mapping of the topography and the volta potential was performed by means of scanning Kelvin probe force microscopy (SKPFM).
The results indicate the presence of a homogeneous film structure, while the intermetallic phases can still be identified below the coating. The SKPFM Analysis confirmed that the model films are suitable for investigation of corrosion processes at the coating/metal interface.
In this work, thin iron doped tin oxide layers (3–6 nm) were investigated with regard to gas sensitivity by means of surface plasmon resonance (SPR) effect with ellipsometric readout. The experimental set-up was a Kretschmann configuration with gold as metal layer. The sensor system was exposed to different concentrations of methane in the low ppm range and the sensor response of an uncoated gold layer compared to a gold layer coated with iron doped tin oxide. The additional layer effects stability with regard to drift behavior of the sensor and an increase in sensitivity. Furthermore, the sensor is able to detect the toxic gas carbon monoxide in low concentration range (down to 0.5 ppm). The thin layers were investigated by X-ray photoelectron spectroscopy, secondary electron microscopy and spectroscopic ellipsometry. The possible mechanisms taking place on the surface are discussed.
The irradiation of ~0.9-µm-thick hydrogenated amorphous carbon (a-C:H) layers deposited on silicon substrates with single femtosecond (fs) laser pulses (35 fs pulse duration, 790 nm centre wavelength) in air is studied experimentally. Irradiation spots have been generated with different peak fluences and subsequently investigated by optical topometry, micro Raman spectroscopy and microscale mechanical indentation in order to evaluate their microscopic, topographical, structural and mechanical properties (e.g. elastic modulus). By this multi-method approach, a clear separation of different effects (delamination and graphitisation) becomes possible. The joint application of mechanical and spectroscopic techniques provides unique insights into the effects of the fs-laser radiation on the carbon layer.
The thickness measurement of transparent layers with optical techniques is very problematic. The observed deviations can easily reach 100% of the layer thickness to be measured. In order to analyse these deviations, tactile reference measurements have been developed. The proposed method is based on contact mode measurements with low contact pressure. With stylus instruments, this can be realized either by using the recommended tip radius of 2 µm and very small probing forces in the micronewton range (and low scanning speeds of 50 µm s-1) or by using the recommended probing force of 750 µN, but a large probing tip radius. Three metal layers on silicon or silicon dioxide and two polymer resist materials on a thin chromium adhesive layer on silicon are used as artefacts. The comparison of the optical measurements with the tactile reference values disclosed deviations of the optical measurements of up to 195% of the layer thickness. Layer thicknesses were between 200 nm and 4 µm. This paper analyses the deviations of two white light interference microscopes, one phase shift interference microscope, one confocal microscope, one autofocus sensor, a chromatic sensor, an interferometric film thickness sensor and one spectroscopic ellipsometer. Simple and well-known expressions for the description of the observed deviations are presented and discussed. The order of magnitude of the observed deviations can be described well by these correction formulas but further investigations are necessary in order to better understand the systematic deviations of optical surface measuring instruments on non-cooperating surfaces.
Critical defects, also known as device killers, in wide bandgap semiconductors significantly affect the performance of power electronic devices. We used the methods imaging ellipsometry (IE) and white light interference microscopy (WLIM) in a hybrid optical metrology study for fast and non-destructive detection, classification, and characterisation of defects in 4H–SiC homoepitaxial layers on 4H–SiC substrates. Ellipsometry measurement results are confirmed by WLIM. They can be successfully applied for wafer characterisation already during production of SiC epilayers and for subsequent industrial quality control.
Background: Gas sensors are very important in several fields like gas monitoring, safety and environmental applications. In this approach, a new gas sensing concept is investigated which combines the powerful adsorption probability of metal oxide conductive sensors (MOS) with an optical ellipsometric readout. This concept Shows promising results to solve the problems of cross sensitivity of the MOS concept.
Results: Undoped tin oxide (SnOx) and iron doped tin oxide (Fe:SnOx) thin add-on films were prepared by magnetron sputtering on the top of the actual surface plasmon resonance (SPR) sensing gold layer. The films were tested for their sensitivity to several gas species in the surface plasmon resonance enhanced (SPREE) gas measurement. It was found that the undoped tin oxide (SnOx) shows higher sensitivities to propane (C3H8) then to carbon monoxide (CO). By using Fe:SnOx, this relation is inverted. This behavior was explained by a change of the amount of binding sites for CO in the layer due to this iron doping. For hydrogen (H2) no such relation was found but the sensing ability was identical for both layer materials. This observation was related to a different sensing mechanism for H2 which is driven by the Diffusion into the layer instead of adsorption on the surface.
Conclusion: The gas sensing selectivity can be enhanced by tuning the properties of the thin film overcoating. A relation of the binding sites in the doped and undoped SnOx films and the gas sensing abilities for CO and C3H8 was found. This could open the path for optimized gas sensing devices with different coated SPREE sensors.
In this study, thickness related changes of the optical properties of doped tin oxide were studied. Two different sets of samples were prepared. The first set was doped with iron or nickel on silicon substrate with thicknesses of 29–56 nm, the second was iron doped on gold/glass substrate with 1.6–6.3 nm. The optical constants were determined by using spectral ellipsometry (SE) followed by modelling of the dielectric function with an oscillator model using Gaussian peaks. The analysis of the optical constants shows a dependence of the refraction and the absorption on the thickness of the doped tin oxide coating. In addition to the tin oxide absorption in the UV, one additional absorption peak was found in the near-IR/red which is related to plasmonic effects due to the doping. This peak shifts from the near-IR to the red part of the visible spectrum and becomes stronger by reducing the thickness, probably due to the formation of metal nanoparticles in this layer. These results were found for two different sets of samples by using the same optical model. Afterwards the second sample set was tested in the Surface Plasmon Resonance Enhanced Ellipsometric (SPREE) gas measurement with CO gas. It was found that the thickness has significant influence on the sensitivity and thus the adsorption of the CO gas. By increasing the thickness from 1.6 nm to 5.1 nm, the sensing ability is enhanced due to a higher coverage of the surface with the over coating. This is explained by the high affinity of CO molecules to the incorporated Fe-nanoparticles in the tin oxide coating. By increasing the thickness further to 6.3 nm, the sensing ability drops because the layer disturbs the SPR sensing effect too much.
Single Femtosecond Laser-Pulse-Induced Superficial Amorphization and Re-Crystallization of Silicon
(2021)
Superficial amorphization and re-crystallization of silicon in <111> and <100> orientation after irradiation by femtosecond laser pulses (790 nm, 30 fs) are studied using optical imaging and transmission electron microscopy. Spectroscopic imaging ellipsometry (SIE) allows fast data acquisition at multiple wavelengths and provides experimental data for calculating nanometric amorphous layer thickness profiles with micrometric lateral resolution based on a thin-film layer model. For a radially Gaussian laser beam and at moderate peak fluences above the melting and below the ablation thresholds, laterally parabolic amorphous layer profiles with maximum thicknesses of several tens of nanometers were quantitatively attained. The accuracy of the calculations is verified experimentally by high-resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (STEM-EDX). Along with topographic information obtained by atomic force microscopy (AFM), a comprehensive picture of the superficial re-solidification of silicon after local melting by femtosecond laser pulses is drawn.
The 7th International Conference on Spectroscopic Ellipsometry (ICSE-7) was held in Berlin in June 2016, jointly organised by ICSE and BAM. The publication of the proceedings special issue in Applied Surface Science follows this event. In the special issue, about 100 articles on current topics of optics and surface science related to ellipsometry, polarimetry, and similar techniques are presented, underpinning the high significance of these techniques for many fields of materials science.
Hydrogen-Containing Amorphous Carbon Layers as Optical Materials in the Near-IR Spectral Range
(2007)
Hydrogenated amorphous carbon layers were deposited on various substrates by means of a plasma CVD process with a RF substrate bias as well as an ECR plasma source. The optical properties of the a-C:H layers were obtained via spectroscopic ellipsometry and correlated with their mechanical and chemical properties. The layers from pure RF plasma exhibit a higher absorption constant in the visible spectral range and a higher refractive index. All layers are nearly transparent in the NIR spectral range making them candidates for optical thin layer systems. The laser damage behaviour of the a-C:H layers was investigated with ultrashort pulses. The damage thresholds were consistent with the absorption constants of the layers. Interesting damage morphologies were observed indicating a sensitivity of this experiment to sub-structures in the layer.
The laser ablation behaviour of ion-doped glass filter materials under irradiation with femtosecond laser pulses was investigated with respect to spot size and repetition rate. The damage threshold fluence of Schott BG18 depends on the size of the irradiated area. The effect is discussed in terms of a defect-site model.
Surface damage and color centers generated by femtosecond pulses in borosilicate glass and silica
(2004)
Color center generation by femtosecond laser pulses (30 fs) is observed in a fluence range below the damage threshold in an alkali-free barium borosilicate (BBS) glass, and in a thin layer of SiO2 on a fused silica substrate. The color centers are characterized spectroscopically. The optical density of the color centers in BBS glass is by two orders of magnitude higher than that in silica. A healing process with a time constant of about 30 h can be found.
Ellipsometry is a useful tool for studying the optical properties of thin films such as photovoltaic devices. We employ Müller matrix ellipsometry to study the thin film photovoltaic material copper indium gallium selenide Cu(In,Ga) Se2 (CIGS), a commercially relevant material with high energy conversion efficiency. Confocal microscopy reveals an rms roughness of 68 nm, which greatly affects the ellipsometry data. Rayleigh-Rice theory is employed to account for the optical properties of the surface roughness in the ellipsometry experiment, and a library search method is used to compare Müller parameters calculated for various CIGS compositions, to the measured data. The Müller parameters calculated with the Rayleigh-Rice model are found to correspond well with the measured data, and a surface roughness of 37nm and a correlation length of 125nm are extracted.
Commercial grade-1 titanium samples (Ti, 99.6%) were treated using three alternative methods, (i) femtosecond laser processing, (ii) thermal heat treatment, and (iii) electrochemical anodization, respectively, resulting in the formation of differently conditioned superficial titanium oxide layers. The laser processing (i) was carried out by a Ti:sapphire laser (pulse duration 30 fs, central wavelength 790 nm, pulse repetition rate 1 kHz) in a regime of generating laser-induced periodic surface structures (LIPSS). The experimental conditions (laser fluence, spatial spot overlap) were optimized in a sample-scanning setup for the processing of several square-millimeters large surface areas covered homogeneously by these nanostructures. The differently oxidized titanium surfaces were characterized by optical microscopy, micro Raman spectroscopy, variable angle spectroscopic ellipsometry, and instrumented indentation testing. The tribological performance was characterized in the regime of mixed friction by reciprocating sliding tests against a sphere of hardened steel in fully formulated engine oil as lubricant. The specific tribological performance of the differently treated surfaces is discussed with respect to possible physical and chemical mechanisms.
Iron-doped SnO2 coatings were deposited in a 50 kHz DC-pulsed magnetron sputtering discharge. The pulses had a duration of 4 µs in selected gas mixtures from pure argon up to
60% of oxygen at a constant total pressure of 0.2 Pa. A single target of SnO2 with Fe inset was used. The mass spectrometry study detected the gas-related ions Ar+, O2+ and O+, where the last one becomes the dominant positive ion at higher oxygen contents. Atomic oxygen ions had a higher energy as it resulted from the collision-caused dissociation on the target surface. The tin-related species were detected as Sn+ and SnO+. SnO2+ species were not detected. The deposition rate decreased by using gas mixtures with oxygen as well as the corresponding amount of Sn-related species in the plasma. The increase of oxygen also increased significantly the sheet resistance of the films. The XPS study showed that the iron concentration decreased by using additional oxygen. But the O/Sn ratio in the coatings was constant, contrary to the increased FeO/Fe ratio in the films. An additional analysis of the coatings by spectroscopic ellipsometry has shown a dependence of the polarizability and the permittivity on the amount of oxygen used during the deposition. In contrast, the study has found no such dependence for the absorption of the layers.
Coatings deposited by magnetron co-sputtering from a single RF magnetron with a ceramic SnO2 target with iron inset in argon plasma were studied. The mass spectra of the process identified Sn+ and SnO+ species as the dominant species sputtered from the target, but no SnO2+ species were detected. The dominant positive ions in argon plasma are Ar+ species. The only detected negative ions were O-. Sputtered neutral tin related species were not detected. Iron related species were also not detected because their concentration is below the detection limit.
The concentration of iron dopant in the tin oxide coatings was controlled by the RF bias applied on the substrate holder while the discharge pressure also has some influence. The iron concentration was in the range from 0.9 at.% up to 19 at.% increasing with the substrate bias while the sheet resistivity decreases. The stoichiometry ratio of O/(Sn + Fe) in the coatings increased from 1.7 up to 2 in dependence on the substrate bias from floating bias (- 5 V) up to - 120 V of RF self-bias, respectively. The tin in the coatings was mainly bonded in Sn4 + state and iron was mainly in Fe2 + state when other tin bonding states were detected only in a small amounts. Iron bonding states in contrary to elemental compositions of the coatings were not influenced by the RF bias applied on the substrate.
The coatings showed high transparency in the visible spectral range. However, an increased metallic behavior could be detected by using a higher RF bias for the deposition. The X-ray diffraction patterns and electron microscopy pictures made on the coatings confirmed the presence of an amorphous phase.
Hydrogenated amorphous carbon layers were deposited on BK7 glass in a plasma-assisted chemical vapor deposition
process. Low and high refracting films with thicknesses d ranging from 11 nm to 5.8 µm were produced having refractive
indices n between 1.68 and 2.41 and linear absorption coefficients of α~100 cm-1 and α~20000 cm-1 at 800 nm wavelength as a result of different plasma modes. Laser ablation thresholds Fth in dependence on d were determined using 30-fs laser pulses. Low absorbing layers show a constant Fth while Fth increases with rising d up to the optical penetration depth of light α-1 for high absorbing films.
MgF2 and TiO2 single layers and layer stacks were produced by a spin-coating sol-gel process. The final temperature treatment was carried out at 100 °C. The layers were deposited onto silicon and fused silica substrates and were analysed by means of atomic force microscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, ellipsometry, and UV-vis transmission spectroscopy. MgF2 and TiO2 single layers have morphological and optical properties comparable with physical vapour deposited layers. By using spectroscopic mapping ellipsometry, a good inter- and intra-sample homogeneity was confirmed. Multiple deposition steps result in a linear increase of layer thickness. Various films were deposited with thicknesses between 25 nm and 350 nm.
It was shown that the low temperature sol-gel process results in films of optical quality. Anti-reflective and high reflective layer stacks consisting of MgF2 and TiO2 were designed and can be produced now by a sol-gel process, whereas the MgF2 layers in the layer stacks contains also traces of MgF2-2xOx.
Dielectric, anti-reflective or high reflective systems consist of low and high refractive index layers. Common systems are oxides. The preparation of low refractive index MgF2-films of optical quality by means of an anhydrous low temperature solgel synthesis is presented. The MgF2-sol is prepared by spin-coating on silicon and glass substrates. Various film thicknesses between 20 nm and 435 nm have been deposited. It has been shown that the thickness increase is proportional to the number of coating steps. The deposited MgF2-films consist of 10 nm to 20 nm large nanoparticles and have smooth surfaces with an average roughness (Ra) of (1.7 ± 0.3) nm. The optical constants n and k of the films are in agreement with the literature data of bulk-MgF2.
Thin films of MgF2 have been deposited on silicon wafers in optical quality with a novel sol-gel deposition process at temperatures as low as 100 °C. The properties of the fluoride layers are compared to bulk MgF2 with respect to the optical constants. By employing spectroscopic mapping ellipsometry, the uniformity of the thickness of fluoride layers is confirmed to be within acceptable limits for optical applications. The optical constants are close to the bulk data. High-quality low-index films of suitable and homogeneous thickness have already been produced on a laboratory scale.
Single- and multi-shot ablation thresholds of gold films in the thickness range of 311400 nm were determined employing a Ti:sapphire laser delivering pulses of 28 fs duration, 793 nm center wavelength at 1 kHz repetition rate. The gold layers were deposited on BK7 glass by an electron beam evaporation process and characterized by atomic force microscopy and ellipsometry. A linear dependence of the ablation threshold fluence Fth on the layer thickness d was found for d ≤ 180 nm. If a film thickness of about 180 nm was reached, the damage threshold remained constant at its bulk value. For different numbers of pulses per spot (N-on-1), bulk damage thresholds of ~0.7 J cm-2 (1-on-1), 0.5 J cm-2 (10-on-1), 0.4 J cm-2 (100-on-1), 0.25 J cm-2 (1000-on-1), and 0.2 J cm-2 (10000-on-1) were obtained experimentally indicating an incubation behavior. A characteristic layer thickness of Lc 180 nm can be defined which is a measure for the heat penetration depth within the electron gas before electronphonon relaxation occurs. Lc is by more than an order of magnitude larger than the optical absorption length of α-1 12 nm at 793 nm wavelength.
Fluid-assisted mass transport reactions by dissolution-precipitation, where a precursor mineral reacts with a fluid, play an important role in metamorphism and metasomatism. We investigated titanite growth on rutile in time series experiments between one and 107 days at constant P-T conditions of 600 °C and 400 MPa in the system TiO2-CaO-SiO2-Na2O-HCl-H2O. A two-capsule assemblage allows for transport of Ca and Si from dissolving wollastonite to dissolving rutile, the Ti-source, in a NaCl-bearing aqueous fluid, according to the general reaction CaSiO3 + TiO2 = CaTiSiO5. Complete overgrowth of rutile by titanite occurred after just one day of experiment. Fine-grained lozenge-shaped titanite crystals of short-time runs (up to 14 days) reorganize to larger predominantly prismatic crystals after >14 days.
After investigation by scanning electron microscopy, the titanite overgrowth was removed from the rutile by hydrofluoric acid, to provide a three-dimensional view of the dissolution-reaction front on the rutile surface. The morphology of the rutile surface is dominated by humps or ridges beneath the central region of a titanite crystal and valleys at the grain boundaries between adjacent titanite crystals. The dissolution pattern on the rutile surface mimics the titanite overgrowth and changes with changing grain size and shape of the titanite with longer run times. The preferred dissolution of rutile in the valleys is clearly linked to the position of the titanite grain boundaries, which served as pathways for fluid-assisted element transport. Rutile-titanite and titanite-titanite boundaries show a significant porosity in transmission electron microscopy images of foils prepared by focused ion beam milling. The large-scale dissolution pattern on the rutile surface is independent of the crystallographic orientation of the rutile and entirely dominated by the arrangement of titanite crystals in the overgrowth. Dissolution features on a scale smaller than ~1 µm are dominated by stepwise dissolution and etch-pits following the crystallographic orientation of the rutile. Similar observations were made in experiments with an additional Al-source, although these experiments result in a different overgrowth pattern; i.e., an exposed rutile surface is always present and solitary titanite crystals are accompanied by partial overgrowths. Quantitative characterization of the surface morphology by white-light interference microscopy demonstrates that, with increasing grain size of titanite, dissolution of rutile is strongly enhanced at the titanite grain boundaries.
Natural examples of titanite overgrowths on rutile show the same relations between element pathways, arrangement of titanite crystals and 3D dissolution pattern on rutile as in the experimental systems. We conclude that the transport of Ti away from the rutile and of Ca + Si into the reaction rim occurred in a grain boundary fluid, the composition of which must have been strongly different from the composition of the bulk fluid in the experiment, as well as in the natural system. The reaction progress depends on the availability of a fluid, and relicts of rutile in titanite indicate restricted availability of fluid in the natural system (e.g., a fluid pulse that was consumed by the reactions). The reaction examined here can serve as a proxy for other reactions of the conversion of oxide minerals (e.g., spinel or corundum) into silicates.
The thermodynamic behavior of thin PVME films including the irreversible adsorbed layer on the substrate is investigated. In a first step, the growth kinetics of the adsorbed layer was studied combining a leaching technique and atomic force microscopy. Further, it was shown that there is a critical initial film thickness for the formation of a surface-filling adsorbed layer. Additionally, spectroscopic ellipsometry measurements were carried out to investigate the influence of the adsorbed layer on the glass transition temperature of the thin films. For 30 nm films and below, the influence of the adsorbed layer percolates strongly to the bulk-like layer of the film. Finally, the molecular dynamics of the adsorbed layer was studied by broadband dielectric spectroscopy, employing nanostructured-electrode systems. One process was revealed, which was assigned either to molecular fluctuations taking place in a loosely-bounded the part of the adsorbed layer, or to the desorption/adsorption of segments at the substrate.
The discussions on the nanoconfinement effect on the glass transition and glassy dynamics phenomena have yielded many open questions. Here, the thickness dependence of the thermal glass transition temperature of thin films of a PVME/PS blend is investigated by ellipsometry. Its thickness dependence was compared to that of the dynamic glass transition (measured by specific heat spectroscopy), and the deduced Vogel temperature (T0). While and T0 showed a monotonous increase, with decreasing the film thickness, the dynamic glass transition temperature () measured at a finite frequency showed a non-monotonous dependence that peaks at 30 nm. This was discussed by assuming different cooperativity length scales at these temperatures, which have different sensitivities to composition and thickness. This non-monotonous thickness dependence of disappears for frequencies characteristic for T0. Further analysis of the fragility parameter, showed a change in the glassy dynamics from strong to fragile, with decreasing film thickness.
The multi-pulse ablation threshold of barium borosilicate glass was measured using 30-fs pulses of a high repetition rate (1 kHz) laser system. The threshold fluence was found to decrease with increasing beam radius ranging from 20 to 400 m. Two existing models are applied by considering thermal accumulation and point defects, respectively .
Textile, aluminium and polyethylene used as components in laser protection curtains were investigated with respect to their ablation behaviour. Employing 33-fs pulses (800 nm wavelength, 1 kHz repetition rate), ex situ geometrical measurements of the ablation cavities and in situ acoustic investigations with a microphone were performed to determine the ablation thresholds in the single- and multi-pulse cases. The acoustical method proved advantageous for complex surface morphologies and/or single laser pulse interactions. Incubation phenomena can be observed for all the materials studied. Technically relevant multi-pulse ablation thresholds are presented and are compared with the single-pulse (1-on-1) irradiation.
Hierarchical micro/-nanostructures were produced on polycarbonate polymer surfaces by employing a two-step UV-laser processing strategy based on the combination of Direct Laser Interference Patterning (DLIP) of gratings and pillars on the microscale (3 ns, 266 nm, 2 kHz) and subsequently superimposing Laser-induced Periodic Surface Structures (LIPSS; 7–10 ps, 350 nm, 100 kHz) which adds nanoscale surface features. Particular emphasis was laid on the influence of the direction of the laser beam polarization on the morphology of resulting hierarchical surfaces. Scanning electron and atomic force microscopy methods were used for the characterization of the hybrid surface structures. Finite-difference time-domain (FDTD) calculations of the laser intensity distribution on the DLIP structures allowed to address the specific polarization dependence of the LIPSS formation observed in the second processing step. Complementary chemical analyzes by micro-Raman spectroscopy and attenuated total reflection Fourier-transform infrared spectroscopy provided in-depth information on the chemical and structural material modifications and material degradation imposed by the laser processing. It was found that when the linear laser polarization was set perpendicular to the DLIP ridges, LIPSS could be formed on top of various DLIP structures. FDTD calculations showed enhanced optical intensity at the topographic maxima, which can explain the dependency of the morphology of LIPSS on the polarization with respect to the orientation of the DLIP structures. It was also found that the degradation of the polymer was enhanced for increasing accumulated fluence levels.
Transparent conductive oxides such as indium tin oxide (ITO) are standards for thin film electrodes, providing a synergy of high optical transparency and electrical conductivity. In an electrolytic environment, the determination of an inert electrochemical potential window is crucial to maintain a stable material performance during device operation. We introduce operando ellipsometry, combining cyclic voltammetry (CV) with spectroscopic ellipsometry, as a versatile tool to monitor the evolution of both complete optical (i.e., complex refractive index) and electrical properties under wet electrochemical operational conditions. In particular, we trace the degradation of ITO electrodes caused by electrochemical reduction in a pH-neutral, water-based electrolyte environment during electrochemical cycling. With the onset of hydrogen evolution at negative bias voltages, indium and tin are irreversibly reduced to the metallic state, causing an advancing darkening, i.e., a gradual loss of transparency, with every CV cycle, while the conductivity is mostly conserved over multiple CV cycles. Post-operando analysis reveals the reductive (loss of oxygen) formation of metallic nanodroplets on the surface. The reductive disruption of the ITO electrode happens at the solid–liquid interface and proceeds gradually from the surface to the bottom of the layer, which is evidenced by cross-sectional transmission electron microscopy imaging and complemented by energy-dispersive X-ray spectroscopy mapping. As long as a continuous part of the ITO layer remains at the bottom, the conductivity is largely retained, allowing repeated CV cycling. We consider operando ellipsometry a sensitive and nondestructive tool to monitor early stage material and property changes, either by tracing failure points, controlling intentional processes, or for sensing purposes, making it suitable for various research fields involving solid–liquid interfaces and electrochemical activity.
A gas sensor system based on the surface plasmon resonance (SPR) effect in a 44 nm Au layer was studied. The usability of this sensor system was investigated for several analyte gases and gas mixtures which are interesting due to their flammability, toxicity or greenhouse effect. The SPR effect of gold was measured in nitrogen and compared with the gaseous alkane series which caused a shift of the position of the SPR effect. For in situ measurements, the phase shift Δ at the SPR angle (ψ minimum) in the analyte gas mixtures was measured for investigated gases in comparison with nitrogen. With this method, detection limits of different gases could be determined, which lie in a range interesting for safety engineering. Furthermore the aging effect of the gold layers which leads to loss in sensitivity of the sensor was investigated.
An ellipsometric gas sensor based on the surface Plasmon resonance (SPR) effect of ~ 43 nm thick gold layers was investigated. To protect the gold layer from contamination and to improve the detection limits, the gold layers were top-coated with 5–6 nm thick layers of organic a-C:H or with inorganic metal oxides TiO2 or ZrO2. The additional layers increased the long-term stability, whereas the metal oxide layers protect better than a-C:H. Furthermore, the additional layers decreased the detection limits by one order of magnitude in case of a-C:H and two orders of magnitude in case of the oxides. It could be shown that the detection limits also depend on the kind of preparation (sol–gel process or physical vapour deposition) of the additional layers.
The glass transition behavior of thin films of poly(bisphenol A carbonate) (PBAC) was studied employing ellipsometry. The glass transition temperature increases with the reduction of the film thickness. This result is attributed to the formation of an adsorbed layer with a reduced mobility compared to bulk PBAC. Therefore, for the first time, the growth kinetics of the adsorbed layer of PBAC was investigated, prepared by leaching samples from a 200 nm thin film which were annealed for several times at three different temperatures. The thickness of each prepared adsorbed layer was measured by multiple scans using atomic force microscopy (AFM). Additionally, an unannealed sample was measured. Comparison of the measurements of the unannealed and the annealed samples provides proof of a pre-growth regime for all annealing temperatures which was not observed for other polymers. For the lowest annealing temperature after the pre-growth stage only a growth regime with a linear time dependence is observed. For higher annealing temperatures the growth kinetics changes from a linear to a logarithmic growth regime at a critical time. At the longest annealing times the films showed signs of dewetting where segments of the adsorbed film were removed from the substrate (dewetting by desorption). The dependence of the surface roughness of the PBAC surface on annealing time also confirmed that the films annealed at highest temperatures for the longest times desorbed from the substrate.
One of the crucial characteristics of functionalized thin films is their porosity (i.e., the ratio between the pore volume and the volume of the whole film). Due to the very low amount of material per coated area corresponding to thin films, it is a challenge for analytics to measure the film porosity. In this work, we present an Approach to determine the porosity of thin films by means of electron probe microanalysis (EPMA) either by wavelength-dispersive X-ray spectrometry (WDX) or by energy-dispersive X-ray spectrometry (EDX) with a scanning electron microscope (SEM). The procedure is based on the calculation of the film mass deposition from electron-excited X-ray spectra. The
mass deposition is converted into film density by division of measured film thickness.
Finally, the film porosity is calculated from the measured film density and the density of bulk, nonporous film material. The general applicability of the procedure to determine the
porosity is demonstrated on thin templated mesoporous TiO₂
films, dip-coated on silicon
wafer, with controlled porosity in the range of 15 to 50%. The high accuracy of the mass deposition as determined from X-ray spectra was validated with independent methods (ICP-OES and weighing). Furthermore, for the validation of the porosity results, ellipsometry, interference fringes method (IFM), and focused ion beam (FIB) cross sectioning were employed as independent techniques. Hence, the approach proposed
in the present study is proven to be suited as a new analytical tool for accurate and relatively fast determination of the porosity of thin films.
Analysis methods and instrumentation for obtaining optical parameters and thickness profiles of thin-film samples from spectrophotometric and ellipsometric measurements are presented. Measured samples include thermally grown and evaporated SiO2 on a silicon substrate and a polymer photoresist layer on silicon. Experimental results at multiple sample positions give the thickness uniformity and optical constants of thin films. The thickness results obtained with spectrophotometry and ellipsometry agree within 1 nm for the 300 nm thick layer of SiO2 on silicon. For the 1600 nm thick resist sample the agreement of the measurement methods is within 8 nm. For the sample with a nominally 6000 nm thick layer of SiO2 on silicon, there is a deviation of ~100 nm between the spectrophotometry and ellipsometry results. As an application, the optical parameters of a SiO2 layer on an induced junction silicon photodiode are determined by spectrophotometry and are used to confirm earlier values and uncertainties of the SiO2 refractive index and layer thickness non-uniformity.
Spatial Period of Laser-Induced Surface Nanoripples on PET Determines Escherichia coli Repellence
(2021)
Bacterial adhesion and biofilm formation on surfaces are associated with persistent microbial contamination, biofouling, and the emergence of resistance, thus, calling for new strategies to impede bacterial surface colonization. Using ns-UV laser treatment (wavelength 248 nm and a pulse duration of 20 ns), laser-induced periodic surface structures (LIPSS) featuring different submicrometric periods ranging from ~210 to ~610 nm were processed on commercial poly(ethylene terephthalate) (PET) foils. Bacterial adhesion tests revealed that these nanorippled surfaces exhibit a repellence for E. coli that decisively depends on the spatial periods of the LIPSS with the strongest reduction (~91%) in cell adhesion observed for LIPSS periods of 214 nm. Although chemical and structural analyses indicated a moderate laser-induced surface oxidation, a significant influence on the bacterial adhesion was ruled out. Scanning electron microscopy and additional biofilm studies
using a pili-deficient E. coli TG1 strain revealed the role of extracellular appendages in the bacterial repellence observed here.
The present study investigates the use of imaging and mapping ellipsometry to determine the properties of non-ideal and patterned thin film samples. Samples which are candidates for future references and standards were prepared for this purpose. The samples investigated were lithographically patterned SiO2 and photoresist layers. The thickness and the optical constants of the two materials were determined using spectroscopic ellipsometry in the visible spectral range. On a larger lateral scale of several mm lateral resolution, the homogeneity was investigated using a goniospectral rotating compensator ellipsometer. A nulling imaging ellipsometer was used to determine the properties of the sample on a smaller scale of 25–150 µm.
The practical performance of surface coatings in applications like catalysis, water splitting or batteries depends critically on the coating materials’ porosity. Determining the porosity in a fast and nondestructive way is still an unsolved problem for industrial thin-films technology. As a contribution to calibrated, non-destructive, optical layer characterisation, we present a multi-method comparison study on porous TiO2 films deposited by sol-gel synthesis on Si wafers. The ellipsometric data were collected on a range of samples with different TiO2 layer thickness and different porosity values. These samples were produced by templated sol-gel synthesis resulting in layers with a well-defined pore size and pore density. The ellipsometry measurement data were analysed by means of a Bruggeman effective medium approximation (BEMA), with the aim to determine the mixture ratio of void and matrix material by a multi-sample analysis strategy. This analysis yielded porosities and layer thicknesses for all samples as well as the dielectric function for the matrix material. Following the idea of multi-method techniques in metrology, the data was referenced to imaging by electron microscopy (SEM) and to a new EPMA (electron probe microanalysis) porosity approach for thin film analysis. This work might lead to a better metrological understanding of optical porosimetry and also to better-qualified characterisation methods for nano-porous layer systems.
1. IntroductionPorous materials, especially porous thin films play an importantrole in chemical and physical technology in every case where thecontact area between two media has to be maximised. From cataly-sis to photochemistry and photovoltaics, the applications of porouslayer materials are diverse and numerous [1–6].The accurate and non-destructive characterisation of porousfilms for layered systems poses a challenge. This applies especiallyfor the key parameter of porous films, their porosity, i.e. the mix-ing ratio between the Matrix of the film (host material) and thepore volume which is empty or filled with a fluid medium (inclu-sions). This parameter influences most of the physical and chemicalproperties of a porous thin film and is therefore essential for theunderstanding as well as the optimisation of this class of materials.
The synthesis of polymerlike amorphous carbon (a-C:H) thin-films by microwave excited collisional hydrocarbon plasma process is reported. Stable and highly aromatic a-C:H were obtained containing significant inclusions of poly(p-phenylene vinylene) (PPV). PPV confers universal optoelectronic properties to the synthesized material. That is a-C:H with tailor-made refractive index are capable of becoming absorption-free in visible (red)-near infrared wavelength range. Production of large aromatic hydrocarbon including phenyl clusters and/or particles is attributed to enhanced coagulation of elemental plasma species under collisional plasma conditions. Detailed structural and morphological changes that occur in a-C:H during the plasma synthesis are also described.
Hydrogen features a very high specific energy density and is therefore a promising candidate for clean fuel from renewable resources. Water electrolysis can convert electrical energy into storable and transportable hydrogen gas. Under acidic conditions, platinum is the most active and stable monometallic catalyst for the hydrogen evolution reaction (HER). Yet, platinum is rare and needs to be used efficiently. Here, we report a synthesis concept for colloidal bimetallic platinum–ruthenium and rhodium–ruthenium nanoparticles (PtRuNP, RhRuNP) and their incorporation into ordered mesoporous carbon (OMC) films. The films exhibit high surface area, good electrical conductivity and well-dispersed nanoparticles inside the mesopores. The nanoparticles retain their size, crystallinity and composition during carbonization. In the hydrogen evolution reaction (HER), PtRuNP/OMC catalyst films show up to five times higher activity per Pt than Pt/C/Nafion® and PtRu/C/Nafion® reference catalysts.
Catalysts are important components in chemical processes because they lower the activation energy and thus determine the rate, efficiency and selectivity of a chemical reaction. This property plays an important role in many of today’s processes, including the electrochemical splitting of water. Due to the continuous development of catalyst materials, they are becoming more complex, which makes a reliable evaluation of physicochemical properties challenging even for modern analytical measurement techniques and industrial manufacturing.
We present a fast, vacuum-free and non-destructive analytical approach using multi-sample spectroscopic ellipsometry to determine relevant material parameters such as film thickness, porosity and composition of mesoporous IrOx–TiOy films. Mesoporous IrOx–TiOy films were deposited on Si wafers by sol–gel synthesis, varying the composition of the mixed oxide films between 0 and 100 wt%Ir. The ellipsometric modeling is based on an anisotropic Bruggeman effective medium approximation (a-BEMA) to determine the film thickness and volume fraction of the material and pores. The volume fraction of the material was again modeled using a Bruggeman EMA to determine the chemical composition of the materials. The ellipsometric fitting results were compared with complementary methods, such as scanning electron microscopy (SEM), electron probe microanalysis (EPMA) as well as environmental ellipsometric porosimetry (EEP).
Ellipsometry-based approach for the characterization of mesoporous thin films for H2 technologies
(2021)
Porous thin layer materials are gaining importance in different fields of technology and pose a challenge to the accurate determination of materials properties important for their function. In this work, we demonstrate a hybrid measurement technique using ellipsometry together with other independent methods for validation. Ellipsometry provides information about the porosity of different mesoporous films (PtRuNP/OMC = 45%; IrOx = 46%) as well as about the pore size (pore radius of ca. 5 nm for PtRuNP/OMC). In addition, the electronic structure of a material, such as intraband transitions of a mesoporous IrOx film, can be identified, which can be used to better understand the mechanisms of chemical processes. In addition, we show that ellipsometry can be used as a scalable imaging and visualization method for quality assurance in production. These require accurate and traceable measurements, with reference materials playing an important role that include porosity and other related properties. We show that our novel analytical methods are useful for improving analytical work in this entire field.
Efficient water electrolysis requires highly active electrodes. The activity of corresponding catalytic coatings strongly depends on material properties such as film thickness, crystallinity, electrical conductivity, and chemical surface speciation. Measuring these properties with high accuracy in vacuum-free and nondestructive methods facilitates the elucidation of structure−activity relationships in realistic environments. Here, we report a novel approach to analyze the optical and electrical properties of highly active oxygen evolution reaction (OER) catalysts via spectroscopic ellipsometry (SE). Using a series of differently calcined, mesoporous, templated iridium oxide films as an example, we assess the film thickness, porosity, electrical resistivity, electron concentration, electron mobility, and interband and intraband transition energies by modeling of the optical spectra. Independently performed analyses using scanning electron microscopy, energy-dispersive X-ray spectroscopy, ellipsometric porosimetry, X-ray reflectometry, and absorption spectroscopy indicate a high accuracy of the deduced material properties. A comparison of the derived analytical data from SE, resonant photoemission spectroscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy with activity measurements of the OER suggests that the intrinsic activity of iridium oxides scales with a shift of the Ir 5d t2g sub-level and an increase of p−d interband transition energies caused by a transition of μ1-OH to μ3-O species.
Vibrational cooling in the liquid phase studied by ultrafast investigations of cycloheptatriene
(2009)
Solvent-mediated vibrational relaxation in UV pump-probe experiments has been studied using cycloheptatriene (CHT) and its perdeuterated counterpart (CHTd8) as model systems. Transient spectra containing absolute e(t) values are obtained by a modified Sulzer-Wieland ansatz and a global fit function for vibrational relaxation is proposed.
Most of the polymeric materials used are easy to ignite and show extensive flame spread along their surfaces. Apart from extensive heat release rates, their short time to ignition (tig), in particular, is a key fire hazard. Preventing ignition eliminates fire hazards completely. Protection layers that shift tig by more than an order of magnitude are powerful flame retardancy approaches presenting an alternative to the usual flame retardancy concepts.
Coatings are proposed that consist of a three-layer system to ensure adhesion to the substrate, acting as an infrared (IR) mirror and protecting against oxidation. The IR-mirror layer stack is realised by physical vapour deposition in the sub-micrometre (<1 µm) range, reducing heat absorption by up to an order of magnitude. Not only is the ease of ignition diminished (tig is increased by several minutes), the flame spread and fire growth indices are also remarkably reduced to as little as 1/10 of the values of the uncoated polymers open for further optimization. Sub-micrometre thin IR-mirror coatings yielding surface absorptivity <0.1 are proposed as a novel and innovative flame retardancy approach.
Ellipsometry is a matured experimental method, whose roots reach back into the early phase of modern optics itself. It is often attributed to be invented by Paul Drude in the last decade of the 19th century, but similar techniques had already been applied for years before Drude started his work. With this Special Issue about ellipsometry and related techniques, we hope to bring more attention to this method and advance and propagate it to be used by a broader community. We have collected a good mixture of articles: some texts are more in the line of users’ tutorial and best practice guides; others are intended to show recent developments of the method. With this collection, we also hope to show the generally rapidly expanding possibilities of ellipsometry and polarimetry to draw attention of new users and previously unrelated communities to this valuable tool.
Visualization of surface modifications may be very challenging for coating/substrate systems of either almost identical optical constants, e.g. transparent films on substrates of the same material, or minor film thickness, substance quantity and affected area, e.g. ultra-thin or island films. Methods for visualization are optical microscopy (OM), imaging ellipsometry (IE), and referenced spectroscopic ellipsometry (RSE). Imaging ellipsometry operates at oblique incidence near Brewster angle of the bare, clean or unmodified substrate. In this configuration, reflected intensities are rather weak. However, the contrast to add-on and sub-off features may be superior. Referenced spectroscopic ellipsometry operates in a two-sample configuration but with much higher intensities. In many cases, both ellipsometric techniques reveal and visualize thin films, printed-pattern, laser-induced changes, and impurities better than optical microscopy. In particular for stratified homogeneous modifications, ellipsometric techniques give access to modelling and hence thickness determination. Modifications under investigation are polymer foil residue on silicon, laser-induced changes of ta-C:H coatings on 100Cr6 steel, imperfections of ta-C:H on thermal silicon oxide, degradation of glass, thin film tin oxide pattern on silicon, printed and dried pattern of liquids such as deionized water, cleaning agents, and dissolved silicone. © 2016 Elsevier B.V. All rights reserved.
Time-of-flight secondary ion mass spectrometry (TOF-SIMS) mappings provide a visualization of the distribution of chemical elements and phases on polished duplex steel surfaces as element and fragment secondary ion signals. The advantage of TOF-SIMS, compared to optical microscopy, is its potential to analyze the chemical composition with a lateral resolution at a submicrometer scale. TOF-SIMS mappings allow distinguishing between ferritic and austenitic phases because of the phase selective detection method without any requirement of etching or other processing.
Bulk metallic glasses (BMG) are amorphous metal alloys known for their unique physical and mechanical properties. In the present study, the formation of femtosecond (fs) laser-induced periodic surface structures (LIPSS) on the Zr-based BMGs Zr46Cu46Al8, Zr61Cu25Al12Ti2, Zr52.5Cu17.9Al10Ni14.6Ti5 (Vit105) and Zr57Cu15.4Al10Ni12.6Nb5 (Vit106) was investigated as a function of their different chemical composition. For this purpose, LIPSS were generated on the sample surfaces in an air environment by fs-laser irradiation (λ = 1025 nm, τ = 300 fs, frep = 100 kHz). The surface topography was characterized by scanning electron microscopy and atomic force microscopy. Moreover, the impact of LIPSS formation on the structure and chemical surface composition was analyzed before and after fs-laser irradiation by X-ray diffraction and X-ray photoelectron spectroscopy as well as by transmission electron microscopy in combination with energy dispersive X-ray spectroscopy. Despite the different chemical composition of the investigated BMGs, the fs-laser irradiation resulted in almost similar properties of the generated LIPSS patterns. In the case of Zr61Cu25Al12Ti2, Vit105 and Vit106, the surface analysis revealed the preservation of the amorphous state of the materials during fs-laser irradiation. The study demonstrated the presence of a native oxide layer on all pristine BMGs. In addition, fs-laser irradiation results in the formation of laser-induced oxide layers of larger thickness consisting of an amorphous ZrAlCu-oxide. The precise laser-structuring of BMG surfaces on the nanoscale provides a versatile alternative to thermoplastic forming of BMG surfaces and is of particular interest for the engineering of functional material surfaces.