Herein, we demonstrate that the dimerization behavior of amine-substituted dicyanomethyl radicals can be switched from σ- to π-dimerization simply by varying the electron-donating substituents. For dicyanomethyl radicals with a 4,4'-ditolylamine (DT ) or a phenothiazine (PT ) substituent, the monomeric radical form and the corresponding dimer connected by a reversible C-C bond (σ-dimer) are in equilibrium in solution. On the other hand, the radical with the julolidine skeleton (JD ) does not undergo σ-dimerization and was isolated as a stable radical in spite of the absence of bulky protecting groups. X-ray single-crystal analysis revealed that JD forms the π-dimer in the crystalline state, and variable-temperature spectroscopy showed that JD is in equilibrium with the π-dimer in toluene solution. DFT calculations point to the importance of electrostatic interactions as a driving force for the π-dimerization of JD because of its polarized structure.

Hole-collecting monolayers have drawn attention in perovskite solar cell research due to their ease of processing, high performance, and good durability. Since molecules in the hole-collecting monolayer are typically composed of functionalized π-conjugated structures, hole extraction is expected to be more efficient when the π-cores are oriented face-on with respect to the adjacent surfaces. However, strategies for reliably controlling the molecular orientation in monolayers remain elusive. In this work, multiple phosphonic acid anchoring groups were used to control the molecular orientation of a series of triazatruxene derivatives chemisorbed on a transparent conducting oxide electrode surface. Using infrared reflection absorption spectroscopy and metastable atom electron spectroscopy, we found that multipodal derivatives align face-on to the electrode surface, while the monopodal counterpart adopts a more tilted configuration. The face-on orientation was found to facilitate hole extraction, leading to inverted perovskite solar cells with enhanced stability and high-power conversion efficiencies up to 23.0%.

Perovskite interfaces critically influence the final performance of the photovoltaic devices. Optimizing them by reducing the defect densities or improving the contact with the charge transporting material is key to further enhance the efficiency and stability of perovskite solar cells. Inverted (p–i–n) devices can particularly benefit here, as evident from various successful attempts. However, every reported strategy is adapted to specific cell structures and compositions, affecting their robustness and applicability by other researchers. In this work, we present the universality of perovskite top surface post-treatment with ethylene­diammonium diiodide (EDAI2) for p–i–n devices. To prove it, we compare devices bearing perovskite films of different composition, i.e., Sn-, Pb-, and mixed Sn–Pb-based devices, achieving efficiencies of up to 11.4, 22.0, and 22.9%, respectively. A careful optimization of the EDAI2 thickness indicates a different tolerance for Pb- and Sn-based devices. The main benefit of this treatment is evident in the open-circuit voltage, with enhancements of up to 200 mV for some compositions. In addition, we prove that this treatment can be successfully applied by both wet (spin-coating) and dry (thermal evaporation) methods, regardless of the composition. The versatility of this treatment makes it highly appealing for industrial application, as it can be easily adapted to specific processing requirements. We present a detailed experimental protocol, aiming to provide the community with an easy, universal perovskite post-treatment method for reliably improving the device efficiency, highlighting the potential of interfaces for the field.

Herein, we demonstrate that the dimerization behavior of amine‐substituted dicyanomethyl radicals can be switched from σ‐ to π‐dimerization simply by varying the electron‐donating substituents. For dicyanomethyl radicals with a 4,4′‐ditolylamine (DT.) or a phenothiazine (PT.) substituent, the monomeric radical form and the corresponding dimer connected by a reversible C−C bond (σ‐dimer) are in equilibrium in solution. On the other hand, the radical with the julolidine skeleton (JD.) does not undergo σ‐dimerization and was isolated as a stable radical in spite of the absence of bulky protecting groups. X‐ray single‐crystal analysis revealed that JD. forms the π‐dimer in the crystalline state, and variable‐temperature spectroscopy showed that JD. is in equilibrium with the π‐dimer in toluene solution. DFT calculations point to the importance of electrostatic interactions as a driving force for the π‐dimerization of JD. because of its polarized structure.