Ionic Liquid-Induced Inversion of the Humidity-Dependent Conductivity of Thin PEDOT:PSS Films.

The humidity influence on the electronic and ionic resistance properties of thin post-treated poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films is investigated. In particular, the resistance of these PEDOT:PSS films post-treated with three different concentrations (0, 0.05, and 0.35 M) of ethyl-3-methylimidazolium dicyanamide (EMIM DCA) is measured while being exposed to a defined humidity protocol. A resistance increase upon elevated humidity is observed for the 0 M reference sample, while the EMIM DCA post-treated samples demonstrate a reverse behavior. Simultaneously performed in situ grazing-incidence small-angle X-ray scattering (GISAXS) measurements evidence changes in the film morphology upon varying the humidity, namely, an increase in the PEDOT domain distances. This leads to a detriment in the interdomain hole transport, which causes a rise in the resistance, as observed for the 0 M reference sample. Finally, electrochemical impedance spectroscopy (EIS) measurements at different humidities reveal additional contributions of ionic charge carriers in the EMIM DCA post-treated PEDOT:PSS films. Therefrom, a model is proposed, which describes the hole and cation transport in different post-treated PEDOT:PSS films dependent on the ambient humidity.

In Situ Observation of Morphological and Oxidation Level Degradation Processes within Ionic Liquid Post-treated PEDOT:PSS Thin Films upon Operation at High Temperatures.

Organic thermoelectric thin films are investigated in terms of their stability at elevated operating temperatures. Therefore, the electrical conductivity of ethyl-3-methylimidazolium dicyanamide (EMIM DCA) post-treated poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) thin films is measured over 4.5 h of heating at 50 or 100 °C for different EMIM DCA concentrations. The changes in the electrical performance are correlated with changes in the film morphology, as evidenced with in situ grazing-incidence small-angle X-ray scattering (GISAXS). Due to the overall increased PEDOT domain distances, the resulting impairment of the interdomain charge carrier transport directly correlates with the observed electrical conductivity decay. With in situ ultraviolet-visible (UV-Vis) measurements, a simultaneously occurring reduction of the PEDOT oxidation level is found to have an additional electrical conductivity lowering contribution due to the decrease of the charge carrier density. Finally, the observed morphology and oxidation level degradation is associated with the deterioration of the thermoelectric properties and hence a favorable operating temperature range is suggested for EMIM DCA post-treated PEDOT:PSS-based thermoelectrics.

Correlation of Thermoelectric Performance, Domain Morphology and Doping Level in PEDOT:PSS Thin Films Post-Treated with Ionic Liquids.

Ionic liquid (IL) post-treatment of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) thin films with ethyl-3-methylimidazolium dicyanamide (EMIM DCA), allyl-3-methylimidazolium dicyanamide (AMIM DCA), and 1-ethyl-3-methylimidazolium tetracyanoborate (EMIM TCB) is compared. Doping level modifications of PEDOT are characterized using UV-Vis spectroscopy and directly correlate with the observed Seebeck coefficient enhancement. With conductive atomic force microscopy (c-AFM) the authors investigate changes in the topographic-current features of the PEDOT:PSS thin film surface due to IL treatment. Grazing incidence small-angle X-ray scattering (GISAXS) demonstrates the morphological rearrangement towards an optimized PEDOT domain distribution upon IL post-treatment, directly facilitating the interconductivity and causing an increased film conductivity. Based on these improvements in Seebeck coefficient and conductivity, the power factor is increased up to 236 µW m-1 K- 2 . Subsequently, a model is developed indicating that ILs, which contain small, sterically unhindered ions with a strong localized charge, appear beneficial to boost the thermoelectric performance of post-treated PEDOT:PSS films.

Increasing Photostability of Inverted Nonfullerene Organic Solar Cells by Using Fullerene Derivative Additives.

Organic solar cells (OSCs) recently achieved efficiencies of over 18% and are well on their way to practical applications, but still considerable stability issues need to be overcome. One major problem emerges from the electron transport material zinc oxide (ZnO), which is mainly used in the inverted device architecture and decomposes many high-performance nonfullerene acceptors due to its photocatalytic activity. In this work, we add three different fullerene derivatives-PC71BM, ICMA, and BisPCBM-to an inverted binary PBDB-TF:IT-4F system in order to suppress the photocatalytic degradation of IT-4F on ZnO via the radical scavenging abilities of the fullerenes. We demonstrate that the addition of 5% fullerene not only increases the performance of the binary PBDB-TF:IT-4F system but also significantly improves the device lifetime under UV illumination in an inert atmosphere. While the binary devices lose 20% of their initial efficiency after only 3 h, this time is increased fivefold for the most promising ternary devices with ICMA. We attribute this improvement to a reduced photocatalytic decomposition of IT-4F in the ternary system, which results in a decreased recombination. We propose that the added fullerenes protect the IT-4F by acting as a sacrificial reagent, thereby suppressing the trap state formation. Furthermore, we show that the protective effect of the most promising fullerene ICMA is transferable to two other binary systems PBDB-TF:BTP-4F and PTB7-Th:IT-4F. Importantly, this effect can also increase the air stability of PBDB-TF:IT-4F. This work demonstrates that the addition of fullerene derivatives is a transferable and straightforward strategy to improve the stability of OSCs.