Investigations of the adsorbed layer of polysulfone: Influence of the thickness of the adsorbed layer on the glass transition of thin films.

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.

Monitoring the Electrochemical Failure of Indium Tin Oxide Electrodes via Operando Ellipsometry Complemented by Electron Microscopy and Spectroscopy.

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.

Influence of nanoparticle encapsulation and encoding on the surface chemistry of polymer carrier beads.

Surface-functionalized polymer beads encoded with molecular luminophores and nanocrystalline emitters such as semiconductor nanocrystals, often referred to as quantum dots (QDs), or magnetic nanoparticles are broadly used in the life sciences as reporters and carrier beads. Many of these applications require a profound knowledge of the chemical nature and total number of their surface functional groups (FGs), that control bead charge, colloidal stability, hydrophobicity, and the interaction with the environment and biological systems. For bioanalytical applications, also the number of groups accessible for the subsequent functionalization with, e.g., biomolecules or targeting ligands is relevant. In this study, we explore the influence of QD encoding on the amount of carboxylic acid (COOH) surface FGs of 2 µm polystyrene microparticles (PSMPs). This is done for frequently employed oleic acid and oleylamine stabilized, luminescent core/shell CdSe QDs and two commonly used encoding procedures. This included QD addition during bead formation by a thermally induced polymerization reaction and a post synthetic swelling procedure. The accessible number of COOH groups on the surface of QD-encoded and pristine beads was quantified by two colorimetric assays, utilizing differently sized reporters and electrostatic and covalent interactions. The results were compared to the total number of FGs obtained by a conductometric titration and Fourier transform infrared spectroscopy (FTIR). In addition, a comparison of the impact of QD and dye encoding on the bead surface chemistry was performed. Our results demonstrate the influence of QD encoding and the QD-encoding strategy on the number of surface FG that is ascribed to an interaction of the QDs with the carboxylic acid groups on the bead surface. These findings are of considerable relevance for applications of nanoparticle-encoded beads and safe-by-design concepts for nanomaterials.

Growth kinetics of the adsorbed layer of poly(bisphenol A carbonate) and its effect on the glass transition behavior in thin films.

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.

Spatial Period of Laser-Induced Surface Nanoripples on PET Determines Escherichia coli Repellence.

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 sub-micrometric 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.

Oxygen isotope systematics of chondrules in the Paris CM2 chondrite: indication for a single large formation region across snow line.

In-situ oxygen three-isotope analyses of chondrules and isolated olivine grains in the Paris (CM) chondrite were conducted by secondary ion mass spectrometry (SIMS). Multiple analyses of olivine and/or pyroxene in each chondrule show indistinguishable Δ17O values, except for minor occurrences of relict olivine grains (and one low-Ca pyroxene). A mean Δ17O value of these homogeneous multiple analyses was obtained for each chondrule, which represent oxygen isotope ratios of the chondrule melt. The Δ17O values of individual chondrules range from -7‰ to -2‰ and generally increase with decreasing Mg# of olivine and pyroxene in individual chondrules. Most type I (FeO-poor) chondrules have high Mg# (~99) and variable Δ17O values from -7.0‰ to -3.3‰. Other type I chondrules (Mg# ≤97), type II (FeO-rich) chondrules, and two isolated FeO-rich olivine grains have host Δ17O values from -3‰ to -2‰. Eight chondrules contain relict grains that are either 16O-rich or 16O-poor relative to their host chondrule and show a wide range of Δ17O values from -13‰ to 0‰. The results from chondrules in the Paris meteorite are similar to those in Murchison (CM). Collectively, the Δ17O values of chondrules in CM chondrites continuously increase from -7‰ to -2‰ with decreasing Mg# from 99 to 37. The majority of type I chondrules (Mg# >98) show Δ17O values from -6‰ to -4‰, while the majority of and type II chondrules (Mg# 60-70) show Δ17O values of -2.5‰. The covariation of Δ17O versus Mg# observed among chondrules in CM chondrites may suggest that most chondrules in carbonaceous chondrites formed in a single large region across the snow line where the contribution of 16O-poor ice to chondrule precursors and dust enrichment factors varied significantly.

Single Femtosecond Laser-Pulse-Induced Superficial Amorphization and Re-Crystallization of Silicon.

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.

Hierarchical Micro-/Nano-Structures on Polycarbonate via UV Pulsed Laser Processing.

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.

A Coordinated Microstructural and Isotopic Study of a Wark-Lovering Rim on a Vigarano CAI.

We carried out a coordinated mineralogical and isotopic study of a Wark-Lovering (WL) rim on a Ca,Al-rich inclusion (CAI) from the reduced CV3 chondrite Vigarano. The outermost edge of the CAI mantle is mineralogically and texturally distinct compared to the underlying mantle that is composed of coarse, zoned melilite (Åk~10-60) grains. The mantle edge contains fine-grained gehlenite with hibonite and rare grossite that likely formed by rapid crystallization from a melt enriched in Ca and Al. These gehlenite and hibonite layers are surrounded by successive layers of spinel, zoned melilite (Åk~0-10), zoned diopside that grades outwards from Al,Ti-rich to Al,Ti-poor, and forsteritic olivine intergrown with diopside. These layered textures are indicative of sequential condensation of spinel, melilite, diopside, and forsterite onto hibonite. Anorthite occurs as a discontinuous layer that corrodes adjacent melilite and Al-diopside, and appears to have replaced them, probably even later than the forsterite layer formation. Based on these observations, we conclude that the WL rim formation was initiated by flash melting and extensive evaporation of the original inclusion edge, followed by subsequent gas-solid reactions under highly dynamic conditions. All the WL rim minerals are 16O-rich (Δ17O = ~-23‰), indicating their formation in an 16O-rich nebular reservoir. Our Al-Mg measurements of hibonite, spinel, and diopside from the WL rim, as well as spinel and Al,Ti-diopside in the core, define a single, well-correlated isochron with an inferred initial 26Al/27Al ratio of (4.94 ± 0.12) × 10-5. This indicates that the WL rim formed shortly after the host CAI. In contrast, the lack of 26Mg excesses in the WL rim anorthite suggest its later formation or later isotopic disturbance in the solar nebula, after 26Al had decayed.

The 26Al-26Mg systematics of FeO-rich chondrules from Acfer 094: two chondrule generations distinct in age and oxygen isotope ratios.

The 26Al-26Mg ages of FeO-rich (type II) chondrules from Acfer 094, one of the least thermally metamorphosed carbonaceous chondrites, were determined by SIMS analysis of plagioclase and olivine/pyroxene using a radio frequency (RF) plasma oxygen ion source. In combination with preexisting 26Al-26Mg ages of FeO-poor (type I) chondrules, the maximum range of formation ages recorded in chondrules from a single meteorite is determined to help provide constraints on models of material transport in the proto-planetary disk. We also report new SIMS oxygen three-isotope analyses of type II chondrules in Acfer 094. All but one of the plagioclase analyses show resolvable excesses in 26Mg and isochron regressions yield initial 26Al/27Al ratios of type II chondrules that range from (3.62 ± 0.86) × 10-6 to (9.3 ± 1.1) × 10-6, which translates to formation ages between 2.71 -0.22/+0.28 Ma and 1.75 -0.11/+0.12 Ma after CAI. This overall range is indistinguishable from that determined for type I chondrules in Acfer 094. The initial 26Al/27Al ratio of the oldest type II chondrule is resolved from that of all other type II chondrules in Acfer 094. Importantly, the oldest type I chondrule and the oldest type II chondrule in Acfer 094 possess within analytical error indistinguishable initial 26Al/27Al ratios and Δ17O values of ~0‰. Ages and oxygen isotope ratios clearly set these two chondrules apart from all other chondrules in Acfer 094. It is therefore conceivable that the formation region of these two chondrules differs from that of other chondrules and in turn suggests that Acfer 094 contains two distinct chondrule generations.

Oxygen isotope systematics of chondrule olivine, pyroxene, and plagioclase in one of the most pristine CV3Red chondrites (Northwest Africa 8613).

We performed in situ oxygen three-isotope measurements of chondrule olivine, pyroxenes, and plagioclase from the newly described CVRed chondrite NWA 8613. Additionally, oxygen isotope ratios of plagioclase in chondrules from the Kaba CV3OxB chondrite were determined to enable comparisons of isotope ratios and degree of alteration of chondrules in both CV lithologies. NWA 8613 was affected by only mild thermal metamorphism. The majority of oxygen isotope ratios of olivine and pyroxenes plot along a slope-1 line in the oxygen three-isotope diagram, except for a type II and a remolten barred olivine chondrule. When isotopic relict olivine is excluded, olivine, low- and high-Ca pyroxenes are indistinguishable regarding Δ17O values. Conversely, plagioclase in chondrules from NWA 8613 and Kaba plot along mass-dependent fractionation lines. Oxygen isotopic disequilibrium between phenocrysts and plagioclase was caused probably by exchange of plagioclase with 16O-poor fluids on the CV parent body. Based on an existing oxygen isotope mass balance model, possible dust enrichment and ice enhancement factors were estimated. Type I chondrules from NWA 8613 possibly formed at moderately high dust enrichment factors (50× to 150× CI dust relative to Solar abundances); estimates for water ice in the chondrule precursors range from 0.2 to 0.6× the nominal amount of ice in dust of CI composition. Findings agree with results from an earlier study on oxygen isotopes in chondrules of the Kaba CV chondrite, providing further evidence for a relatively dry and only moderately high dust-enriched disk in the CV chondrule-forming region.

Formation of chondrules in a moderately high dust enriched disk: evidence from oxygen isotopes of chondrules from the Kaba CV3 chondrite.

Oxygen three-isotope analysis by secondary ion mass spectrometry of chondrule olivine and pyroxene in combination with electron microprobe analysis were carried out to investigate 24 FeO-poor (type I) and 2 FeO-rich (type II) chondrules from the Kaba (CV) chondrite. The Mg#'s of olivine and pyroxene in individual chondrules are uniform, which confirms that Kaba is one of the least thermally metamorphosed CV3 chondrites. The majority of chondrules in Kaba contain olivine and pyroxene that show indistinguishable Δ17O values (= δ17O - 0.52 × Î´18O) within analytical uncertainties, as revealed by multiple spot analyses of individual chondrules. One third of chondrules contain olivine relict grains that are either 16O-rich or 16O-poor relative to other indistinguishable olivine and/or pyroxene analyses in the same chondrules. Excluding those isotopically recognized relicts, the mean oxygen isotope ratios (δ18O, δ17O, and Δ17O) of individual chondrules are calculated, which are interpreted to represent those of the final chondrule melt. Most of these isotope ratios plot on or slightly below the primitive chondrule mineral (PCM) line on the oxygen three-isotope diagram, except for the pyroxene-rich type II chondrule that plots above the PCM and on the terrestrial fractionation line. The Δ17O values of type I chondrules range from ~ -8‰ to ~ -4‰; the pyroxene-rich type II chondrule yields ~0‰, the olivine-rich type II chondrule ~ -2‰. In contrast to the ungrouped carbonaceous chondrite Acfer 094, the Yamato 81020 CO3, and the Allende CV3 chondrite, type I chondrules in Kaba only possess Δ17O values below -3‰ and a pronounced bimodal distribution of Δ17O values, as evident for those other chondrites, was not observed for Kaba. Investigation of the Mg#-Δ17O relationship revealed that Δ17O values tend to increase with decreasing Mg#'s, similar to those observed for CR chondrites though data from Kaba cluster at the high Mg# (>98) and the low Δ17O end (-6‰ and -4‰). A mass balance model involving 16O-rich anhydrous dust (Δ17O = -8‰) and 16O-poor water ice (Δ17O = +2‰) in the chondrule precursors suggests that type I chondrules in Kaba would have formed in a moderately high dust enriched protoplanetary disk at relatively dry conditions (~50-100× dust enrichment compared to Solar abundance gas and less than 0.6× ice enhancement relative to CI chondritic dust). The olivine-rich type II chondrule probably formed in a disk with higher dust enrichment (~2000× Solar).

Thin SnOx films for surface plasmon resonance enhanced ellipsometric gas sensing (SPREE).

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.

Decoupling of Dynamic and Thermal Glass Transition in Thin Films of a PVME/PS Blend.

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 Tgtherm 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 Tgtherm and T0 showed a monotonous increase, with decreasing film thickness, the dynamic glass transition temperature (Tgdyn) measured at a finite frequency showed a nonmonotonous 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 nonmonotonous thickness dependence of Tgdyn 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.

New Approach on Quantification of Porosity of Thin Films via Electron-Excited X-ray Spectra.

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.

Ultrafast lattice response of photoexcited thin films studied by X-ray diffraction.

Using ultrafast X-ray diffraction, we study the coherent picosecond lattice dynamics of photoexcited thin films in the two limiting cases, where the photoinduced stress profile decays on a length scale larger and smaller than the film thickness. We solve a unifying analytical model of the strain propagation for acoustic impedance-matched opaque films on a semi-infinite transparent substrate, showing that the lattice dynamics essentially depend on two parameters: One for the spatial profile and one for the amplitude of the strain. We illustrate the results by comparison with high-quality ultrafast X-ray diffraction data of SrRuO3 films on SrTiO3 substrates.