Session V4: Where Morphology Meets Functionality: Light and Electron Transporting Polymeric Complexes

From Morphology to Interfaces to Tandem Geometries: Enhancing the Performance of Perovskite/Polymer Solar Cells

We have taken a new approach to develop mesoporous lead iodide scaffolds, using the nucleation and growth of lead iodide crystallites in a wet film. A simple time-dependent growth control enabled the manipulation of the mesoporous lead iodide layer quality in a continuous manner. The morphology of lead iodide is shown to influence the subsequent crystallization of methyamoniumleadiodide film by using angle-dependent grazing incidence x-ray scattering. The morphology of lead iodide film can be fine-tuned, and thus the methyamoniumleadiodide film quality can be effectively controlled, leading to an optimization of the perovskite active layer. Using this strategy, perovskite solar cells with inverted PHJ structure showed a \textit{PCE} of 15.7 per cent with little hysteresis. Interface engineering is critical for achieving efficient solar cells, yet a comprehensive understanding of the interface between metal electrode and electron transport layer (ETL) is lacking. A significant power conversion efficiency (PCE) improvement of fullerene/perovskite planar heterojunction solar cells was achieved by inserting a fulleropyrrolidine interlayer between the silver electrode and electron transport layer. The interlayer was found to enhance recombination resistance, increases electron extraction rate and prolongs free carrier lifetime. We also uncovered a facile solution-based fabrication of high performance tandem perovskite/polymer solar cells where the front sub-cell consists of perovskite and the back sub-cell is a polymer-based layer. A record maximum PCE of 15.96 per cent was achieved, demonstrating the synergy between the perovskite and semiconducting polymers. This design balances the absorption of the perovskite and the polymer, eliminates the adverse impact of thermal annealing during perovskite fabrication, and affords devices with no hysteresis.   

Microwave absorption of free carriers in doped conjugated polymer films

Flash photolysis time-resolved microwave conductivity (\textit{fp-}TRMC) is a powerful spectroscopic tool for the detection of mobile charges in organic systems, such as conjugated polymers. We will report on a study of charge carrier generation in a number of polymer systems where the solid-state microstructure (SSM) of the thin films can be controlled using both molecular structure and processing conditions. By incorporating a low concentration of molecular acceptors, such as metallo-phthalocyanines, as well as substituted fullerenes and perylenes, the driving force for photoinduced electron transfer can be controlled through the excited state energy and the reduction potential. Our results indicate the importance of the crystalline phase of the polymer to stabilise and reduce the rate of recombination of the holes with the electrons that remain trapped on the acceptor. In addition, the role that the SSM plays on the stabilization of bound electron-hole pairs, or charge-transfer (CT) states will be examined.   

Making Glasses Conduct: Electrochemical Doping of Redox-Active Polymer Thin Films

Optoelectronically-active macromolecules have been established as promising materials in myriad organic electronic applications (e.g., organic field-effect transistors (OFETs) and organic photovoltaic (OPV) devices). To date, however, the majority of the work surrounding these materials has focused on materials with a great deal of conjugation along their macromolecular backbones and with varying degrees of crystalline structure. Here, we describe an emerging class of macromolecular charge conductors, radical polymers, that: (1) do not contain conjugation and (2) are completely amorphous glasses. Radical polymers contain non-conjugated macromolecular backbones and stable radical sites along the side chains of the electronically-active materials. In contrast to conjugated polymer systems, these materials conduct charge in the solid state through oxidation-reduction (redox) reactions along these pendant groups. Specifically, we demonstrate that controlling the chemical functionality of the pendant groups and the molecular mobility of the macromolecular backbones significantly impacts the charge transport ability of the pristine (i.e., not doped) radical polymers species. Through proper control of these crucial parameters, we show that radical polymers can have electrical conductivity and charge mobility values on par with commonly-used conjugated polymers. Importantly, we also highlight the ability to dope radical polymers with redox-active small molecule species. This doping, in turn, increases the electrical conductivity of the glassy radical polymer thin films in a manner akin to what is observed in traditional conjugated polymer systems. In this way, we establish a means by which to fabricate optically-transparent and colorless thin film glasses capable of conducting charge in a rather rapid manner. We anticipate that these fundamental insights will prove crucial in developing new transparent conducting layers for future electronic applications.   

Nanoparticle Polymer Hybrids for Solar Cells

Polymer-based solar cells are unique since their processing is extremely cost effective compared to silicon-based solar cells. They are also much less energy intensive to manufacture. However, their power conversion efficiency is low. Discussion of what affects this property in the context of the morphology characterized through thermal analysis as well as x-ray and neutron scattering will be given.