Institute of Fundamental Technological Research

Development and step-by-step characterizations of a novel cationic thiophene based copolymer (P1buP), including ionic phosphonium salt and dye-tetraphenylporphyrin (TPP) moiety in side chains, with an iconic property of solubility in a wide range of polar solvents is reported. Synthesized by using simple, low-cost, and straightforward procedures, the material is used to fabricate completely halogen-free (i.e., from ethanol) ternary organic solar cells (OSCs), in the presence of an alcohol-soluble ionic 3,4-dialkoxythiophene based homopolymer (P2buP) and a serinol-fullerene derivative (C60-Ser). Indeed, thanks to co-sensitization techniques, where multiple dyes harvest different parts of the solar spectrum, the power conversion efficiency of the best final device dramatically increases up to nearly 5.0%, as the light absorption is usually optimized. Additionally, since the use of a cathode interlayer in OSCs also plays a pivotal role in electron extraction and device stability, a possible application of the ionic TPP material as the interfacial layer is also investigated. Furthermore, to improve and optimize the best performing device, a successful post-metalation with Zn of the porphyrin core is carried out, and a ternary OSC (P1buP:P2buP:C60-Ser = 0.33:0.67:1 w/w) is fabricated, resulting in a photoconversion efficiency (PCE) of ∼6.0%.

Ionic dye-tetraphenylporphyrin, Co-sensitization, Ternary OSCs, Cathode interlayers, Halogen-free deposition

Three new ionic polythiophene derivatives, soluble in polar solvents, are synthesized with good yields using simple, low-cost, and straightforward procedures. They are investigated as interfacial cationic conjugated
polyelectrolyte (CPE) layers for halogen-free bulk heterojunction polymeric solar cells, based on a water-soluble electron-donor polymer
(poly[3-(6-diethanolaminohexyl)thiophene]) and a water-soluble electron-acceptor fullerene derivative (malonodiserinolamide fullerene). The simple insertion of the CPE interlayer between the active layer and the aluminum cathode dramatically increases the power conversion efficiency of the final device up to nearly 5%, resulting from a decrease of the electrode work function, improved electron extraction, and optimization of the morphology of the layers. The obtained results demonstrate that the incorporation of CPE layer is a powerful and convenient methodology for the
development of highly efficient and eco-friendly processable polymeric solar cells.

conjugated polyelectrolyte,electron transport layers,polythiophene

Four new conjugated polymers alternating benzothiadiazole units and thiophene moieties functionalized with ionic phosphonium or sulfonic acid salts in the side chains were synthesized by a postfunctionalization approach of polymeric precursors. The introduction of ionic groups makes the conjugated polymers soluble in water and/or polar solvents, allowing for the fabrication of bulk heterojunction (BHJ) solar cells using environmentally friendly conditions. All polymers were fully characterized by spectroscopic, thermal, electrochemical, X-ray diffraction, scanning electron, and atomic force techniques. BHJ solar cells were obtained from halogen-free solvents (i.e., ethanol and/or anisole) by blending the synthesized ionic push–pull polymers with a serinol-fullerene derivative or an ionic homopolymer acting as electron-acceptor (EA) or electron-donor (ED) counterparts, respectively. The device with the highest optical density and the smoothest surface of the active layer was the best-performing, showing a 4.76% photoconversion efficiency.

donor–acceptor systems, bifunctional materials, phosphonium salts, eco-friendly BHJ solar cells, anisole

A new side-chain C60-fullerene functionalized thiophene copolymer bearing tributylphosphine-substituted hexylic lateral groups was successfully synthesized by means of a fast and effective post-polymerization reaction on a regioregular ω-alkylbrominated polymeric precursor. The growth of the polymeric intermediate was followed by NMR spectrometry in order to determine the most convenient reaction time. The obtained copolymer was soluble in water and polar solvents and was used as a photoactive layer in single-material organic photovoltaic (OPV) solar cells. The copolymer photovoltaic efficiency was compared with that of an OPV cell containing a water-soluble polythiophenic homopolymer, functionalized with the same tributylphosphine-substituted hexylic side chains, in a blend with a water-soluble C60-fullerene derivative. The use of a water-soluble double-cable copolymer made it possible to enhance the control on the nanomorphology of the active blend, thus reducing phase-segregation phenomena, as well as the macroscale separation between the electron acceptor and donor components. Indeed, the power conversion efficiency of OPV cells based on a single material was higher than that obtained with the classical architecture, involving the presence of two distinct ED and EA materials (PCE: 3.11% vs. 2.29%, respectively). Moreover, the synthetic procedure adopted to obtain single material-based cells is more straightforward and easier than that used for the preparation of the homopolymer-based BHJ solar cell, thus making it possible to completely avoid the long synthetic pathway which is required to prepare water-soluble fullerene derivatives.

water-soluble polymers, double-cable copolymers, polythiophenes, GRIM polymerization, tributylphosphine, water-soluble fullerenes, OPVs