Lorenz Bießmann

Abstract 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 (HNO 3 ), and sulfuric acid (H 2 SO 4 ), 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 H 2 O 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 HNO 3 or H 2 SO 4 treatment with the drawback of high sensitivity against H 2 O. By contrast, HCl and HCOOH treatment obtaining a medium enhanced conductivity differ in the amount of PSS removal but show higher H 2 O resistance.

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.

Recently, hybrid perovskites have gathered much interest as alternative materials for the fabrication of highly efficient and cost-competitive solar cells; however, many questions regarding perovskite crystal formation and deposition methods remain. Here we have applied a two-step protocol where a crystalline PbI2 precursor film is converted to MAPbI3-xClx perovskite upon immersion in a mixed solution of methylammonium iodide and methylammonium chloride. We have investigated both films with grazing incidence small-angle X-ray scattering to probe the inner film morphology. Our results demonstrate a strong link between lateral crystal sizes in the films before and after conversion, which we attribute to laterally confined crystal growth. Additionally, we observe an accumulation of smaller grains within the bulk in contrast with the surface. Thus, our results help to elucidate the crystallization process of perovskite films deposited via a two-step technique that is crucial for controlled film formation, improved reproducibility, and high photovoltaic performance.

Ionic liquid (IL) post-treatment for thin films of poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is employed for the simultaneous enhancement of Seebeck coefficients and electrical conductivities. Through systematic variation of the ILs, by changing the anions while keeping the cation unchanged, changes in thermoelectric, spectroscopic, and morphological properties are investigated by means of UV-vis spectroscopy and grazing-incidence wide-angle X-ray scattering (GIWAXS) as a function of the IL concentration. The simultaneous enhancement in the two important thermoelectric properties is ascribed to the binary nature of the ILs, which complements that of PEDOT:PSS. The anions of the ILs primarily interact with the positively charged, conducting PEDOT, while the cations interact with negatively charged insulating PSS. Therefore, post-treatment with ILs allows for primary and secondary doping of PEDOT:PSS at the same time. Differences in the obtained Seebeck coefficients for the investigated ILs are ascribed to the chemical properties of the anions. Additionally, the choice of the latter has implications on the morphology of the treated PEDOT:PSS films regarding average π-π-stacking distances of PEDOT chains, PEDOT-to-PSS ratios, and edge-on-to-face-on ratios, influencing charge transport properties macroscopically. A morphological model is presented, highlighting the influence of each IL in comparison with pristine PEDOT:PSS films.

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 PbI2 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.