Dominating loss mechanisms were identified at hole-selective buried interfaces engineered with carbazole-based self-assembled monolayers between a metal halide perovskite absorber and a conductive metal oxide. The analysis of surface photovoltage transients with a minimalistic kinetic model allowed for the extraction of interfacial electron trap densities and hole transfer rates and their correlation with open-circuit voltages and fill factors of the corresponding highefficiency solar cells is demonstrated.

The irradiation-induced reduction of electrochemically grafted nitrobenzene films on Si(111) was monitored by high-resolution photoelectron spectroscopy. The experiments were performed using synchrotron soft X-ray irradiation at the BESSY II synchrotron facility. The evolution of different chemical species was monitored as a function of time. Careful fitting of the Si2p, C1s, N1s, and O1s core level spectra allowed us to follow this process in detail and to determine the constants of growth and decay of the specific components. The chemical changes were caused by the X-ray irradiation-induced secondary electron current through the aryl layer. A minor fraction (approximately 25%) of the initial nitro groups was split off and desorbed. The bulk of the NO2 groups was reduced to species in an amino-like chemical environment. A desorption of carbon fragments was not observed, and benzene ring specific shakeup satellites indicated that the aromatic ring structure remained intact. Irradiation-induced line-shape changes suggest a polymerization via -NH- bridges, which were formed after the irradiation-induced N-O bond splitting. A significant part of the released oxygen appeared to contribute to an oxidation of the silicon substrate at the Si(111)/benzene interface. The irradiation-induced aryl layer modification can be exploited for chemical lithography (i.e., a lateral structuring of functionalized silicon surfaces).

Molecular self-assembly, the function of biomembranes and the performance of organic solar cells rely on nanoscale molecular interactions. Understanding and control of such materials have been impeded by difficulties in imaging their properties with the desired nanometre spatial resolution, attomolar sensitivity and intermolecular spectroscopic specificity. Here we implement vibrational scattering-scanning near-field optical microscopy with high spectral precision to investigate the structure–function relationship in nano-phase separated block copolymers. A vibrational resonance is used as a sensitive reporter of the local chemical environment and we image, with few nanometre spatial resolution and 0.2 cm−1 spectral precision, solvatochromic Stark shifts and line broadening correlated with molecular-scale morphologies. We discriminate local variations in electric fields between nano-domains with quantitative agreement with dielectric continuum models. This ability to directly resolve nanoscale morphology and associated intermolecular interactions can form a basis for the systematic control of functionality in multicomponent soft matter systems.

The pH-dependent switching of a poly(acrylic acid) (PAA) polyelectrolyte brush was investigated in situ using infrared spectroscopic ellipsometry (IRSE). The brush was synthesized by a "grafting to" procedure on silicon substrate with a native oxide layer. The overall thickness of the PAA brush in the dry state was approximately 5 nm. Reversible switching of the polymer brush was studied at titration from pH 2 to 10 and back in steps of 1 pH unit. The switching process was observed by monitoring the characteristic vibrational bands of the carboxylic groups of the PAA molecules. Decreasing of the C=O vibrational band amplitude and arising of a COO(-) vibrational band proved the chemical changes in the molecular structure of the brushes due to changes of the pH value in the aqueous solution. Due to the strong absorption of these bands in the IR region, the switching process could be monitored clearly. Switching the brush in several cycles with increasing and decreasing pH value showed a hysteresis-like behavior. For the first time, such hysteresis is observed in titration experiments of polyelectrolyte brushes. This behavior is attributed to the complex mechanisms of the ion's mobility in the brush layer which is explained with a suggested simplifying model describing the influence of ions inside the brush layer. In addition to the IRSE measurements, X-ray standing waves (XSW), in situ visible ellipsometry, and contact angle measurements have been performed and were in good agreement with the results from IRSE. Repetition of the in situ measurement cycles proved the good reversibility of the switching process which is highly important for practical applications of polymer brushes.

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The ability to vary, adjust, and control hydrophobic interactions is crucial in manipulating interactions between biological objects and the surface of synthetic materials in aqueous environment. To this end a grafted polymer layer (multi‐component mixed polymer brush) is synthesized that is capable of reversibly exposing nanometer‐sized hydrophobic fragments at its hydrophilic surface and of tuning, turning on, and turning off the hydrophobic interactions. The reversible switching occurs in response to changes in the environment and alters the strength and range of attractive interactions between the layer and hydrophobic or amphiphilic probes in water. The grafted layer retains its overall hydrophilicity, while local hydrophobic forces enable the grafted layer to sense and attract the hydrophobic domains of protein molecules dissolved in the aqueous environment. The hydrophobic interactions between the material and a hydrophobic probe are investigated using atomic force microscopy measurements and a long‐range attractive and contact‐adhesive interaction between the material and the probe is observed, which is controlled by environmental conditions. Switching of the layer exterior is also confirmed via protein adsorption measurements.

Nanodomains formed by microphase separation in thin films of the diblock copolymers poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) and poly(styrene-b-ethyleneoxide) (PS-b-PEO) were imaged by means of infrared scattering-type near-field microscopy. When probing at 3.39 mum (2950 cm(-1)), contrast is obtained due to spectral differences between the C--H stretching vibrational resonances of the respective polymer constituents. An all-optical spatial resolution better than 10 nm was achieved, which corresponds to a sensitivity of just several thousand C--H groups facilitated by the local-field enhancement at the sharp metallic probe tips. The results demonstrate that infrared spectroscopy with access to intramolecular dimensions is within reach.

Infrared spectroscopic ellipsometry (IRSE), reflection absorption IR spectroscopy (RAIRS), IR transmission spectroscopy, and best-fit calculations are applied in a cooperative study to determine the anisotropic optical properties of a thin polyimide layer in the spectral range 4000–500 cm−1. The employed anisotropic uniaxial optical layer model afforded very good agreement between the calculated and the experimental spectra obtained by the different complementary IR methods. The main advantage of IRSE is that it is possible to obtain data for the optical constants and the thickness ( d = 1.81 μm) of the polyimide layer simultaneously within one experiment. From the ellipsometric spectra it was concluded that the layer structure can be regarded as possessing uniaxial symmetry where the layer is isotropic in directions (x, y) parallel to the sample surface. A qualitative determination of the anisotropic parameters of vibrational bands is possible by calculation of the ellipsometric spectra. The evaluation procedure can be improved by evaluation of polarized reflection spectra, provided the reference standard has been calibrated by ellipsometry. The oscillator parameters are then derived more accurately from the separate s- and p-polarized reflection spectra rather than from their ratio, which is measured in ellipsometry.