Photo-Cross-Linked Fullerene-Based Hole Transport Material for Moisture-Resistant Regular Fullerene Sandwich Perovskite Solar Cells.

Despite the high efficiencies currently achieved with perovskite solar cells (PSCs), the need to develop stable devices, particularly in humid conditions, still remains. This study presents the synthesis of a novel photo-cross-linkable fullerene-based hole transport material named FT12. For the first time, the photo-cross-linking process is applied to PSCs, resulting in the preparation of photo-cross-linked FT12 (PCL FT12). Regular PSCs based on C60-sandwich architectures were fabricated using FT12 and PCL FT12 as dopant-free hole transport layers (HTLs) and compared to the reference spiro-OMeTAD. The photovoltaic results demonstrate that both FT12 and PCL FT12 significantly outperform pristine spiro-OMeTAD regarding device performance and stability. The comparison between devices based on FT12 and PCL FT12 demonstrates that the photo-cross-linking process enhances device efficiency. This improvement is primarily attributed to enhanced charge extraction, partial oxidation of the HTL, increased hole mobility, and improved layer morphology. PCL FT12-based devices exhibit improved stability compared to FT12 devices, primarily due to the superior moisture resistance achieved through photo-cross-linking.

p-Type Functionalized Carbon Nanohorns and Nanotubes in Perovskite Solar Cells.

The incorporation of p-type functionalized carbon nanohorns (CNHs) in perovskite solar cells (PSCs) and their comparison with p-type functionalized single- and double-walled carbon nanotubes (SWCNTs and DWCNTs) are reported in this study for the first time. These p-type functionalized carbon nanomaterial (CNM) derivatives were successfully synthesized by [2 + 1] cycloaddition reaction with nitrenes formed from triphenylamine (TPA) and 9-phenyl carbazole (Cz)-based azides, yielding CNHs-TPA, CNHs-Cz, SWCNTs-Cz, SWCNTs-TPA, DWCNTs-TPA, and DWCNTs-Cz. These six novel CNMs were incorporated into the spiro-OMeTAD-based hole transport layer (HTL) to evaluate their impact on regular mesoporous PSCs. The photovoltaic results indicate that all p-type functionalized CNMs significantly improve the power conversion efficiency (PCE), mainly by enhancing the short-circuit current density (Jsc) and fill factor (FF). TPA-functionalized derivatives increased the PCE by 12-17% compared to the control device without CNMs, while Cz-functionalized derivatives resulted in a PCE increase of 4-8%. Devices prepared with p-type functionalized CNHs exhibited a slightly better PCE compared with those based on SWCNTs and DWCNTs derivatives. The increase in hole mobility of spiro-OMeTAD, additional p-type doping, better energy alignment with the perovskite layer, and enhanced morphology and contact interface play important roles in enhancing the performance of the device. Furthermore, the incorporation of p-type functionalized CNMs into the spiro-OMeTAD layer increased device stability by improving the hydrophobicity of the layer and enhancing the hole transport across the MAPI/spiro-OMeTAD interface. After 28 days under ambient conditions and darkness, TPA-functionalized CNMs maintained the performance of the device by over 90%, while Cz-functionalized CNMs preserved it between 75 and 85%.

Efficient and Stable Perovskite Solar Cells based on Nitrogen-Doped Carbon Nanodots.

The role of graphitic and amorphous nitrogen-doped carbon dots (N-CDs) as additives for perovskite solar cells (PSCs) is investigated. A detailed study of N-CDs: perovskite (PVSK) blends through X-ray diffraction, nuclear magnetic resonance, field emission scanning electron microscopy, UV-vis, and photoluminescence spectroscopy reveals the existence of interactions between N-CDs and PVSK. The amorphous or graphitic nature of these carbon nanoforms, as well as the interactions between CDs and PVSK, clearly determines the photovoltaic outcome of the PSCs. Thus, a small amount of graphitic carbon dots (g-N-CDs) leads to more-stable PSCs, while maintaining and even improving the power conversion efficiency (PCE). In addition, the long-term evaluation of the g-N-CDs-containing cells shows improvement of the PCE over time, up to 109% of the initial efficiency after 40 days while the reference performance is dropped to 86%.

Triarylamine Enriched Organostannoxane Drums: Synthesis, Optoelectrochemical Properties, Association Studies, and Gelation Behavior.

The straightforward synthesis of three organotin clusters endowed with six triarylamine-based moieties is reported herein. The optoelectronic properties of the molecules, as well as their ability to form gels, were investigated. The association ability of the compounds was studied as well by means of variable temperature nuclear magnetic resonance (NMR) and ultraviolet-visible (UV-vis) spectroscopy. The optimization of the geometry of the compounds has been performed and compared to the X-ray diffraction of the crystals. The results obtained through this comparison are useful for the explanation of their different gelation behaviors. In fact, organostannoxane drum 1 exhibits a strong ability to form organized supramolecular structures by means of a number of noncovalent short contacts that finally yield luminescent organogels in aromatic solvents.

Dendritic-Like Molecules Built on a Pillar[5]arene Core as Hole Transporting Materials for Perovskite Solar Cells.

Invited for the cover of this issue are the groups of S. Seki (Kyoto), G. Reginato (Sesto Fiorentino), J.-F. Nierengarten (Strasbourg), A. Abate (Berlin) and J. L. Delgado (San Sebastian). The image depicts an artistic view of a dendrimer-like hole transporting material at work in a perovskite solar cell. Read the full text of the article at 10.1002/chem.202101110.

Dendritic-Like Molecules Built on a Pillar[5]arene Core as Hole Transporting Materials for Perovskite Solar Cells.

Multi-branched molecules have recently demonstrated interesting behaviour as charge-transporting materials within the fields of perovskite solar cells (PSCs). For this reason, extended triarylamine dendrons have been grafted onto a pillar[5]arene core to generate dendrimer-like compounds, which have been used as hole-transporting materials (HTMs) for PSCs. The performances of the solar cells containing these novel compounds have been extensively investigated. Interestingly, a positive dendritic effect has been evidenced as the hole transporting properties are improved when going from the first to the second-generation compound. The stability of the devices based on the best performing pillar[5]arene material has been also evaluated in a high-throughput ageing setup for 500 h at high temperature. When compared to reference devices prepared from spiro-OMeTAD, the behaviour is similar. An analysis of the economic advantages arising from the use of the pillar[5]arene-based material revealed however that our pillar[5]arene-based material is cheaper than the reference.

Characterization of New Cationic N,N-Dimethyl[70]fulleropyrrolidinium Iodide Derivatives as Potent HIV-1 Maturation Inhibitors.

HIV-1 maturation can be impaired by altering protease (PR) activity, the structure of the Gag-Pol substrate, or the molecular interactions of viral structural proteins. Here we report the synthesis and characterization of new cationic N,N-dimethyl[70]fulleropyrrolidinium iodide derivatives that inhibit more than 99% of HIV-1 infectivity at low micromolar concentrations. Analysis of the HIV-1 life cycle indicated that these compounds inhibit viral maturation by impairing Gag and Gag-Pol processing. Importantly, fullerene derivatives 2a-c did not inhibit in vitro PR activity and strongly interacted with HIV immature capsid protein in pull-down experiments. Furthermore, these compounds potently blocked infectivity of viruses harboring mutant PR that are resistant to multiple PR inhibitors or mutant Gag proteins that confer resistance to the maturation inhibitor Bevirimat. Collectively, our studies indicate fullerene derivatives 2a-c as potent and novel HIV-1 maturation inhibitors.

Synthesis and characterization of (6-{[2-(pyridin-2-yl)hydrazinylidene]methyl}pyridin-2-yl)methanol: a supramolecular and topological study.

Hydrazones exhibit a versatile chemistry and are of interest for their potential use as functional molecular systems capable of undergoing reversible changes of configuration, i.e. E/Z isomerization. The title compound, C12H12N4O, has an E configuration with respect to the hydrazone C=N bond. The crystal packing is formed by N-H...N and O-H...N hydrogen bonds that give a two-dimensional layer structure and C-H...C interactions associated with layer stacking to produce the three-dimensional supramolecular structure. These intermolecular interactions were analyzed and quantified by the Hirshfeld surface method and the two-dimensional supramolecular arrangement was topologically simplified as a hcb network.