A Double Compatibilization Strategy To Boost the Performance of -- Solar Cells Based on Perovskite Deposited in Humid Ambient Air.

Formamidinium lead iodide (FAPI) represents the most promising perovskite for single junction solar cells, exhibiting an impressive performance when deposited in a controlled nitrogen environment. In order to foster the real-world application of this technology, the deposition of FAPI in ambient air is a highly desirable prospect, as it would reduce fabrication costs. This study demonstrates that the wettability of FAPI precursors on the hole transporting layers (HTL) used to fabricate inverted -- solar cells is extremely poor in ambient air, hampering the realization of a perovskite active layer with good optoelectronic quality.

-Symmetrical 3,4-Ethylenedioxythiophene Monomers through a Divergent Approach.

We present a divergent synthetic approach to -symmetrical 3,4-Ethylenedioxythiophene (EDOT) monomers in which functionalities can be introduced as pendant chains from the ethylene bridge. The key synthon, obtained through a high yielding -etherification, is the chiral EDOT with bromomethyl pendant groups and is prone to substitution reactions with oxygen-based nucleophiles. Elimination of the key precursor affords a diene that can be elaborated into unprecedented PhEDOT monomers using the Diels-Alder reaction.

Formamidinium Perovskite Deposition in Ambient Air Environment for Inverted p-i-n Solar Cells.

In order to move towards large-scale fabrication, perovskite solar cells need to detach themselves from strictly controlled environmental conditions and, to this end, fabrication in ambient air is highly desirable. Formamidinium iodide perovskite (FAPI) is one of the most promising perovskites but is also unstable at room temperature, which may make the ambient air deposition more difficult. Herein, we investigated different formulations of pure FAPI for the fabrication of perovskite solar cells (PSCs) in air.

3D Printing of Layered Structures of Metal-Ionic Polymers: Recent Progress, Challenges and Opportunities.

Layered Structures of Metal Ionic Polymers, or Ionic Polymer-Metal Composites (IPMCs) are formed by a membrane of an ionic electroactive materials flanked by two metal electrodes on both surfaces; they are devices able to change their shape upon application of an electrical external stimulus. This class of materials is used in various fields such as biomedicine, soft robotics, and sensor technology because of their favorable properties (light weight, biocompatibility, fast response to stimulus and good flexibility). With additive manufacturing, actuators can be customized and tailored to specific applications, allowing for the optimization of performance, size, and weight, thus reducing costs and time of fabrication and enhancing functionality and efficiency in various applications.

Regioselectivity Control in Spirobifluorene Nitration under Mild Conditions: Explaining the Crivello's Reagent Mechanism.

The regioselective nitration of 9,9'-spirobifluorene under mild conditions is reported for the first time by operating under Menke's and Crivello's conditions. The optimized protocol allows obtaining 2-nitro and 2,2'-dinitro-9,9'-spirobifluorene in yields of 79 and 95% and, for the first time, 2,2',7-trinitro-9,9'-spirobifluorene with 66% yield. Besides, the role of dinitrate salt in Crivello's protocol has been now clarified, which opens novel scenarios in the preparation of functional materials.

Supramolecular Weaving by Halogen-Bonding in Functionality-Rich Hexasubstituted Aromatic Synthons.

Hexasubstituted benzenes are interesting platforms for the generation of functional materials, whose applications span from supramolecular recognition to organic electronics. Their synthesis is difficult to achieve by controlling multiple substitution steps of all hydrogen atoms on the aromatic benzene skeleton, so, often, cycloaddition reactions from disubsituted alkynes are used. In this work, we report a novel, straightforward route to -symmetrical hexasubstituted aromatic synthons with a diverse and rich pattern of functionalities, and we report about their packing mode in the crystals, in which, unprecedentedly, directional, strong halogen bonding interactions are capable of forming bidimensional supramolecular weaving.

Polymer Solar Cells with Active Layer Thickness Compatible with Scalable Fabrication Processes: A Meta-Analysis.

Organic photovoltaics (OPV) has been considered for a long time a promising emerging solar technology. Currently, however, market shares of OPV are practically non-existent. A detailed meta-analysis of the literature published until mid-2021 is presented, focusing on one of the remaining issues that need to be addressed to translate the recent remarkable progress, obtained in devices' performance at lab-scale level, into the requirements able to boost the manufacturing-scale production.

Amphiphilic PTB7-Based Rod-Coil Block Copolymer for Water-Processable Nanoparticles as an Active Layer for Sustainable Organic Photovoltaic: A Case Study.

We synthetized a new rod-coil block copolymer (BCP) based on the semiconducting polymerpoly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-:4,5-]dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-]thiophenediyl}) (PTB7) and poly-4-vinylpyridine (P4VP), tailored to produce water-processable nanoparticles (WPNPs) in blend with phenyl-C71-butyric acid methyl ester (PCBM). The copolymer PTB7--P4VP was completely characterized by means of two-dimensional nuclear magnetic resonance (2D-NMR), matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry (MS), size-exclusion chromatography (SEC), and differential scanning calorimetry (DSC) to confirm the molecular structure. The WPNPs were prepared through an adapted miniemulsion approach without any surfactants.

Polymer-Assisted Single-Step Slot-Die Coating of Flexible Perovskite Solar Cells at Mild Temperature from Dimethyl Sulfoxide.

The industrialization of perovskite solar cells relies on solving intrinsic-to-material issues. To reach record efficiencies perovskite deposition needs to be finely adjusted by multi-step processes, in a humidity free glove-box environment and by means of hardly scalable techniques often associated with toxic solvents and anti-solvent dripping/bath. Herein, the use of polymeric material is proposed to deposit perovskite layers with easy processability.

Recent Advances in Non-Fullerene Acceptors of the IDIC/ITIC Families for Bulk-Heterojunction Organic Solar Cells.

The introduction of the IDIC/ITIC families of non-fullerene acceptors has boosted the photovoltaic performances of bulk-heterojunction organic solar cells. The fine tuning of the photophysical, morphological and processability properties with the aim of reaching higher and higher photocurrent efficiencies has prompted uninterrupted worldwide research on these peculiar families of organic compounds. The main strategies for the modification of IDIC/ITIC compounds, described in several contributions published in the past few years, can be summarized and classified into core modification strategies and end-capping group modification strategies.

One-Pot Regiodirected Annulations for the Rapid Synthesis of π-Extended Oligomers.

We demonstrate the broad applicability of the annulation protocol combining, in one pot, a direct arylation and cross aldol condensation for the straightforward synthesis at gram-scale of π-extended thiophene-based scaffolds. The regiospecific direct arylation drives the subsequent cross-aldol condensation proceed under the same basic conditions, and the overall protocol has broad applicability in the synthesis of extended aromatics wherein the thiophene ring is annulated with furans, pyridines, indoles, benzothiophenes, and benzofurans. These scaffolds can be further elaborated into π-extended, highly fluorescent oligomers with a central deficient benzothiadiazole unit with up to nine aromatic rings through coupling reactions.

A relatively wide-bandgap and air-stable donor polymer for fabrication of efficient semitransparent and tandem organic photovoltaics.

Organic photovoltaics (OPVs) have attracted tremendous attention in the field of thin-film solar cells due to their wide range of applications, especially for semitransparent devices. Here, we synthesize a dithiaindacenone-thiophene-benzothiadiazole-thiophene alternating donor copolymer named poly{[2,7-(5,5-didecyl-5H-1,8-dithia-as-indacenone)]-alt-[5,5-(5',6'-dioctyloxy-4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]} (PDTIDTBT), which shows a relatively wide bandgap of 1.82 eV, good mobility, and high transmittance and ambient stability.

Light Management in Organic Photovoltaics Processed in Ambient Conditions Using ZnO Nanowire and Antireflection Layer with Nanocone Array.

Low carrier mobility and lifetime in semiconductor polymers are some of the main challenges facing the field of organic photovoltaics (OPV) in the quest for efficient devices with high current density. Finding novel strategies such as device structure engineering is a key pathway toward addressing this issue. In this work, the light absorption and carrier collection of OPV devices are improved by employment of ZnO nanowire (NW) arrays with an optimum NW length (50 nm) and antireflection (AR) film with nanocone structure.

Effect of the Electron Transport Layer on the Interfacial Energy Barriers and Lifetime of R2R Printed Organic Solar Cell Modules.

Understanding the phenomena at interfaces is crucial for producing efficient and stable flexible organic solar cell modules. Minimized energy barriers enable efficient charge transfer, and good adhesion allows mechanical and environmental stability and thus increased lifetime. We utilize here the inverted organic solar module stack and standard photoactive materials (a blend of poly(3-hexylthiophene) and [6,6]-phenyl C61 butyric acid methyl ester) to study the interfaces in a pilot scale large-area roll-to-roll (R2R) process.

Atomistic modelling of entropy driven phase transitions between different crystal modifications in polymers: the case of poly(3-alkylthiophenes).

Polymorphism and related solid-state phase transitions affect the structure and morphology and hence the properties of materials, but they are not-so-well understood. Atomistic computational methods can provide molecular-level insights, but they have rarely proven successful for transitions between polymorphic forms of crystalline polymers. In this work, we report atomistic molecular dynamics (MD) simulations of poly(3-alkylthiophenes) (P3ATs), widely used organic semiconductors to explore the experimentally observed, entropy-driven transition from form II to more common form I type polymorphs, or, more precisely, to form I mesophases.

Synthesis of Dithienocyclohexanones (DTCHs) as a Family of Building Blocks for π-Conjugated Compounds in Organic Electronics.

The development and widespread application of organic electronic devices require the availability of simple and cost-effective suitable materials. In this study, the preparation of a new class of conjugated compounds on the basis of a dithienocyclohexanone (DTCH) core is reported. Several synthetic strategies for the preparation of dialkyl DTCH derivatives are explored, with special emphasis on the establishment of a sustainable synthetic access.

Domino Direct Arylation and Cross-Aldol for Rapid Construction of Extended Polycyclic π-Scaffolds.

Five-membered aromatic heterocycles are a ubiquitous skeleton of π-conjugated organic compounds, and their incorporation requires synthetic protocols that are not easily industrially sustainable or scalable. Improved methodologies for their insertion into π-scaffolds are therefore necessary. We report an efficient and scalable protocol involving a one-pot cross-Aldol direct arylation reaction protocol for the rapid construction of thiophene- and furan-based π-extended organic materials.

Direct Arylation Strategies in the Synthesis of π-Extended Monomers for Organic Polymeric Solar Cells.

π-conjugated macromolecules for organic polymeric solar cells can be rationally engineered at the molecular level in order to tune the optical, electrochemical and solid-state morphology characteristics, and thus to address requirements for the efficient solid state device implementation. The synthetic accessibility of monomers and polymers required for the device is getting increasing attention. Direct arylation reactions for the production of the π-extended scaffolds are gaining importance, bearing clear advantages over traditional carbon-carbon forming methodologies.

Conjugated Thiophene-Fused Isatin Dyes through Intramolecular Direct Arylation.

We report on the design, synthesis, and properties of innovative, planar, π-conjugated compounds in which a thiophene ring is fused with the skeleton of the naturally occurring dye isatin. The synthesis is achieved in high yields making use of an intramolecular direct arylation reaction as the key step, making the overall process potentially scalable. The synthetic sequence has been demonstrated also for an isatin bearing fluorine substituents on the aromatic ring.

The effect of donor content on the efficiency of P3HT:PCBM bilayers: optical and photocurrent spectral data analyses.

State-of-the-art organic solar cells mostly rely on bulk-heterojunction architectures, where the photoactive layer is cast from a solution containing both the electron donor and acceptor components and subsequently annealed. An alternative route for device preparation is the sequential deposition of the two components using "orthogonal" solvents. The morphology of sequentially deposited bilayers has been extensively studied, but the interplay between optical and electrical properties and its influence on device efficiency is still unclear.

Neat C₇₀-based bulk-heterojunction polymer solar cells with excellent acceptor dispersion.

The replacement of common fullerene derivatives with neat-C70 could be an effective approach to restrain the costs of organic photovoltaics and increase their sustainability. In this study, bulk-heterojunction solar cells made of neat-C70 and low energy-gap conjugated polymers, PTB7 and PCDTBT, are thoroughly investigated and compared. Upon replacing PC70BM with C70, the mobility of positive carriers in the donor phase is roughly reduced by 1 order of magnitude, while that of electrons is only slightly modified.

Pushing the Envelope of the Intrinsic Limitation of Organic Solar Cells.

The photogeneration of Frenkel-type excitons, instead of pairs of free charges, is one of the main drawbacks of organic photovoltaics, when compared with the inorganic counterpart. The strong Coulomb interaction of charge carriers of opposite sign in organic materials is responsible for the complexity of the process of generation of unbound charges, affecting the photogenerated current and still not clearly understood, as well as for the free energy loss of electrons resulting in a diminished open circuit voltage. Despite this practical limitation, record power conversion efficiencies approaching 10% are currently reported for lab-scale single-junction structures made of low-bandgap electron-donating conjugated small molecules or polymers blended with electron-accepting fullerene derivatives.

Solvent-free phenyl-C61-butyric acid methyl ester (PCBM) from clathrates: insights for organic photovoltaics from crystal structures and molecular dynamics.

The first solvent-free crystal structure of PCBM, an organic semiconductor widely used in solvent-free nanocrystalline films in plastic solar cells, is reported and its relevance to structure-property relationships discussed. The PCBM structure, obtained from o-dichlorobenzene solvates by solvent abstraction, was solved using powder diffraction, demonstrating this possibility for functionalized fullerenes.

A solid state density functional study of crystalline thiophene-based oligomers and polymers.

We present the results of a molecular modeling study of several thiophene-based oligomers and polymers by solid state density functional theory (DFT) calculations. In particular, we consider two polymers for which limit-ordered crystal structures have been reported by our group, on the basis of powder X-ray data analysis: poly(3-(S)-2-methylbutylthiophene) (P3MBT) and forms I' and II of poly(3-butylthiophene) (P3BT). The calculations employing the functional by Perdew and Wang (PWC) in conjunction with the double-ζ polarized numerical basis set (DNP) demonstrate that a standard quantum mechanical (QM) approach for solid phases can provide a balanced description of the overall structure and energetics of thiophene-based oligomers and polymers maintaining a moderate computational cost.