Polymer electrodes made of poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) are used in many applications but are also sensitive to humidity. We study humidity-induced changes of PEDOT:PSS electrodes as monitored with in situ time-of-flight neutron reflectivity (TOF-NR) measurements under high humidity conditions. The influence of the solvent additive Zonyl and a post-treatment of PEDOT:PSS films with ethylene glycol (EG) serving as electrodes are analyzed with respect to the swelling ratio and water uptake. Depending on the applied PEDOT:PSS treatment, PEDOT and PSS enrichment layers are clearly identified with TOF-NR at the substrate-polymer and polymer-air interface, respectively. The additive Zonyl reduces the water uptake and limits film swelling. EG post-treatment further increases hydrophobicity and thereby water incorporation into the PEDOT:PSS film is strongly suppressed. The characteristic time constants and effective interaction parameters extracted from the kinetic NR data show that additive and post-treatment reduce the sensitivity of the PEDOT:PSS electrodes to humidity.

The origin of high conductivity in polymer electrodes based on poly(3,4‐ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is investigated and the resilience against water exposure is tested. Post‐treatment with weak and strong acids, namely, hydrochloric acid (HCl), formic acid (HCOOH), nitric acid (HNO3), and sulfuric acid (H2SO4), is performed and compared to the commonly used ethylene glycol treatment. PEDOT:PSS electrodes with electrical conductivities of up to ≈3000 S cm−1 and high transmittance are obtained. The underlying mechanisms for enhanced conductivity are elucidated by means of electrical (4‐point probe), optical (UV‐Vis spectroscopy), compositional (X‐ray photo‐electron spectroscopy), and structural (grazing‐incidence wide‐angle X‐ray scattering, GIWAXS) characterizations. Selective PSS removal and structural rearrangement of PEDOT‐rich domains due to an enhanced lamellar stacking is identified as major influence on the improvement in electrical conductivity. This beneficial high order is evidenced via additional signals in the GIWAXS patterns, which are altered by subsequent H2O treatment. The PSS removal and structural rearrangement is linked to the acids' strength and dielectric constant. High conductivities are reached by efficient PSS removal via HNO3 or H2SO4 treatment with the drawback of high sensitivity against H2O. By contrast, HCl and HCOOH treatment obtaining a medium enhanced conductivity differ in the amount of PSS removal but show higher H2O resistance.

The swelling and phase transition behavior upon increasing temperature of a doubly thermoresponsive diblock copolymer thin film in steps above the characteristic cloud points (CPs) of the blocks is studied. An upper critical solution temperature (UCST)-type zwitterionic poly-(sulfobetaine), poly(N,N-dimethyl-N-(3-methacrylamidopropyl)-ammoniopropane sulfonate) (PSPP, CP UCST = 31.5 °C), is combined with a lower critical solution temperature (LCST)-type nonionic poly(N-isopropyl-/ methacrylamide) (PNIPMAM, CP LCST = 49.5 °C) block. Using time-offlight neutron reflectivity (ToF-NR), we observe the swelling in D 2 O vapor at a constant temperature of 20 °C, followed by two subsequent temperature jumps, from 20 to 40 °C (above CP UCST ) and from 40 to 60 °C (above CP LCST ). The observed response of the diblock copolymer films deviates from the aqueous solution behavior, which is mainly attributed to the increased polymer concentration. Temperature-induced changes in the thin-film nanostructure are investigated with ToF grazing-incidence small-angle neutron scattering (GISANS). Alterations in the chain conformation and hydrogen bonding are probed by Fourier transform infrared (FTIR) spectroscopy. The ionic SO 3 − groups (in the PSPP block) and the nonionic hydrophilic amide groups (in both blocks) are found to affect the mechanisms of D 2 O uptake and release significantly.

The humidity-induced swelling and exchange behavior of a block copolymer thin film, which consists of a zwitterionic poly­(sulfobetaine) [poly­(N,N-dimethyl-N-(3-(methacrylamido)­propyl)­ammoniopropanesulfonate) (PSPP)] block and a nonionic poly­(N-isopropylacrylamide) (PNIPAM) block, are investigated by time-of-flight neutron reflectometry (TOF-NR). We monitor in situ the swelling in the H2O atmosphere, followed by an exchange with D2O. In the reverse experiment, swelling in the D2O atmosphere and the subsequent exchange with H2O are studied. Both, static and kinetic TOF-NR measurements indicate significant differences in the interactions between the PSPP80-b-PNIPAM130 thin film and H2O or D2O, which we attribute to the different H- and D-bonds between water and the polymer. Changes in the chain conformation and hydrogen bonding are probed with Fourier transform infrared spectroscopy during the kinetics of the swelling and exchange processes, which reveals the key roles of the ionic SO3 – group in the PSPP block and of the polar amide groups of both blocks during water uptake and exchange.

To increase the moisture stability of hybrid perovskite photovoltaics, a combination of three-dimensional (3D) and a thin layer of two-dimensional (2D) perovskite incorporating long-chained organic cations is often employed as photoabsorber. However, the detailed interaction between water and 3D/2D perovskite heterojunctions has not been elucidated yet. Using in situ neutron and X-ray scattering techniques, we reveal surprisingly strong water uptake into 3D/2D perovskite films despite the presence of hydrophobic bulky cations. Our results show rapid disproportionation of the initial 2D phase (number of layers, m = 5) in methylammonium lead iodide (MAPI)/2D films into lower m phases under humidity. Nevertheless, the 2D perovskite inhibits the irreversible PbI 2 formation, which suggests that the suppression of I − and MA + ion migration and consequently of MAI escape is related to the improved moisture stability of MAPI/2D perovskite films. In comparison, quadruple-cation perovskites including Rb + exhibit poor stability toward phase segregation upon exposure to moisture regardless of the 2D perovskite layer.