The low power conversion efficiency (PCE) of tin‐based hybrid perovskite solar cells (HPSCs) is mainly attributed to the high background carrier density due to a high density of intrinsic defects such as Sn vacancies and oxidized species (Sn4+) that characterize Sn‐based HPSCs. Herein, this study reports on the successful reduction of the background carrier density by more than one order of magnitude by depositing near‐single‐crystalline formamidinium tin iodide (FASnI3) films with the orthorhombic a‐axis in the out‐of‐plane direction. Using these highly crystalline films, obtained by mixing a very small amount (0.08 m) of layered (2D) Sn perovskite with 0.92 m (3D) FASnI3, for the first time a PCE as high as 9.0% in a planar p–i–n device structure is achieved. These devices display negligible hysteresis and light soaking, as they benefit from very low trap‐assisted recombination, low shunt losses, and more efficient charge collection. This represents a 50% improvement in PCE compared to the best reference cell based on a pure FASnI3 film using SnF2 as a reducing agent. Moreover, the 2D/3D‐based HPSCs show considerable improved stability due to the enhanced robustness of the perovskite film compared to the reference cell.

A few aspects of the nano‐morphology of hydrated Nafion and other ionomers and polyelectrolytes in their acid form are revisited by examining the evolution of small angle X‐ray scattering (SAXS) data which are recorded for a wide range of water volume fractions (Φwater ≈ 7–56 vol%). A consistency check with the recent “parallel cylinder model” discloses that this is most likely biased by a large uncertainty of the experimentally determined water content. We rather find our data to be consistent with locally flat and narrow (around 1 nm) water domains. The formation of relatively thin water “films” is suggested to be a common feature of many ionomers and polyelectrolytes, and the underlying driving force is most likely electrostatics within these highly dissociated systems. The water films may act as a charged (e.g., with positive protonic charge carriers) “glue”, keeping together the oppositely charged polymer structures. While this interaction tends to produce flat morphologies, the formation process is suggested to be constraint by limited conformational degrees of freedom of the corresponding polymer and the interactions between polymer backbones. This may leave severe tortuosities on larger scales which depend on the sample history (including swelling, de‐swelling, aging, stretching, and pressing).

In this contribution, for the first time, the molecular n-doping of a donor-acceptor (D-A) copolymer achieving 200-fold enhancement of electrical conductivity by rationally tailoring the side chains without changing its D-A backbone is successfully improved. Instead of the traditional alkyl side chains for poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl](NDI)-alt-5,5'-(2,2'-bithiophene)} (N2200), polar triethylene glycol type side chains is utilized and a high electrical conductivity of 0.17 S cm after doping with (4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)phenyl)dimethylamine is achieved, which is the highest reported value for n-type D-A copolymers. Coarse-grained molecular dynamics simulations indicate that the polar side chains can significantly reduce the clustering of dopant molecules and favor the dispersion of the dopant in the host matrix as compared to the traditional alkyl side chains. Accordingly, intimate contact between the host and dopant molecules in the NDI-based copolymer with polar side chains facilitates molecular doping with increased doping efficiency and electrical conductivity. For the first time, a heterogeneous thermoelectric transport model for such a material is proposed, that is the percolation of charge carriers from conducting ordered regions through poorly conductive disordered regions, which provides pointers for further increase in the themoelectric properties of n-type D-A copolymers.

Small angle X-ray scattering (SAXS), electrospray ionization charge detection mass spectrometry (CD-MS), dynamic light scattering (DLS), and transmission electron microscopy (TEM) are used to characterize poly(glycerol monomethacrylate)55-poly(2-hydroxypropyl methacrylate)x (G55-Hx) vesicles prepared by polymerization-induced self-assembly (PISA) using a reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization formulation. A G55 chain transfer agent is utilized to prepare a series of G55-Hx diblock copolymers, where the mean degree of polymerization (DP) of the membrane-forming block (x) is varied from 200 to 2000. TEM confirms that vesicles with progressively thicker membranes are produced for x = 200–1000, while SAXS indicates a gradual reduction in mean aggregation number for higher x values, which is consistent with CD-MS studies. Both DLS and SAXS studies indicate minimal change in the overall vesicle diameter between x = 400 and 800. Fitting SAXS patterns to a vesicle model enables calculation of the membrane thickness, degree of hydration of the membrane, and the mean vesicle aggregation number. The membrane thickness increases at higher x values, hence the vesicle lumen must become smaller if the external vesicle dimensions remain constant. Geometric considerations indicate that this growth mechanism lowers the total vesicle interfacial area and hence reduces the free energy of the system. However, it also inevitably leads to gradual ingress of the encapsulated water molecules into the vesicle membrane, as confirmed by SAXS analysis. Ultimately, the highly plasticized membranes become insufficiently hydrophobic to stabilize the vesicle morphology when x exceeds 1000, thus this PISA growth mechanism ultimately leads to vesicle “death”.

In this contribution, for the first time, the polarity of fullerene derivatives is tailored to enhance the miscibility between the host and dopant molecules. A fullerene derivative with a hydrophilic triethylene glycol type side chain (PTEG-1) is used as the host and (4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)phenyl)dimethylamine n-DMBI) as the dopant. Thereby, the doping efficiency can be greatly improved to around 18% (<1% for a nonpolar reference sample) with optimized electrical conductivity of 2.05 S cm , which represents the best result for solution-processed fullerene derivatives. An in-depth microstructural study indicates that the PTEG-1 molecules readily form layered structures parallel to the substrate after solution processing. The fullerene cage plane is alternated by the triethylene glycol side chain plane; the n-DMBI dopants are mainly incorporated in the side chain plane without disturbing the π-π packing of PTEG-1. This new microstructure, which is rarely observed for codeposited thin films from solution, formed by PTEG-1 and n-DMBI molecules explains the increased miscibility of the host/dopant system at a nanoscale level and the high electrical conductivity. Finally, a power factor of 16.7 µW m K is achieved at 40% dopant concentration. This work introduces a new strategy for improving the conductivity of solution-processed n-type organic thermoelectrics.