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The design principles of acceptor1–acceptor2 copolymers featuring alternating diketopyrrolopyrrole (DPP) and thienopyrrolodione (TPD) moieties are investigated. The investigated series of polymers is obtained by varying the aromatic linker between the two acceptor motifs between thiophene, thiazole, pyridine, and benzene. High electron affinities between 3.96 and 4.42 eV, facilitated by the synergy of the acceptor motifs are determined with optical gaps between 1.37 and 2.02 eV. Grazing incidence wide-angle X-ray scattering studies reveal a range of film morphologies after thermal annealing, including face-on, end-on and superstructure edge-on-like crystallites. Conversely, all materials form thin edge-on layers on the polymer–air interface, as demonstrated by multi-elemental near-edge X-ray absorption fine-structure spectroscopy. The benefit of the electron-deficient linkers thiazole and pyridine is evident: In organic field effect transistors, electron mobilities of up to 4.6 × 10−2 cm2 V−1 s−1 are obtained with outstanding on/off current ratios of 5 × 105, facilitated by the absence of detectable hole transport in these materials. Viability for all-polymer solar cells is assessed in active layer blends with the donor polymer PM6, yielding a maximum average power conversion efficiency of 4.8% and an open circuit voltage above 1 V.

Preparing halide perovskite films by solvent-free, powder-based processing approaches currently attracts more and more attention. However, working solar cells employing dry, powder-based halide perovskite thin films, have not been demonstrated so far. Herein, perovskite solar cells are presented where the absorber layer is prepared by transferring readily synthesized perovskite powders into a compact thin film using a fully dry-powder-processing concept. Compact thin films are deposited via an optimized powder aerosol deposition (PAD) process. Pressing at 120 °C further improves the morphology and the optoelectronic film properties. Integrating the perovskite films in a solar cell configuration results in fully working devices, with champion power conversion efficiencies of >6%. While the (optoelectronic) properties of the PAD-processed films are found to be comparable with their solution-processed counterparts, investigations of the solar cell stack suggest deterioration of the electron-transport layer properties due to the PAD process, and the presence of hydrates at the perovskite surface to be important factors that contribute to the limited solar cell efficiency. Herein, perspectives to overcome the identified limitations are outlined, emphasizing the high potential and realizability of efficient perovskite solar cells based on dry-powder-processing approaches in the future.

The development of an environmentally friendly fabrication process for non-fullerene acceptor organic solar cells is an essential condition for their commercialization. However, devices fabricated by processing the active layer with green solvents still struggle to reach, in terms of efficiency, the same performance as those fabricated with halogenated solvents. The reason behind this is the non-optimal nanostructure of the active layer obtained with green solvents. Additives in solution have been used to fine-tune the nanostructure and improve the performance of organic solar cells. Therefore, the identification of non-halogenated additives and the study of their effects on the device performance and stability are of primary importance. In this work, we propose the use of diphenyl ether (DPE) as additive, in combination with the non-halogenated solvent o-xylene, to fabricate organic solar cells with a completely halogen-free process. Thanks to the addition of DPE, a best efficiency of 11.7% have been obtained for the system TPD-3F:IT-4F, an increase over 15% with respect to the efficiency of devices fabricated without additive. Remarkably, the stability under illumination of the solar cells is also improved when DPE is used. The addition of DPE has effects on the molecular organization in the active layer, with an enhancement in the donor polymer ordering, showing a higher domain purity. The resulting structure improves the charge carrier collection, leading to a superior short-circuit current and fill factor. Furthermore, a reduction of the non-radiative recombination losses and an improved exciton diffusion, are the results of the superior molecular ordering. With a comprehensive insight of the effects of DPE when used in combination with a non-halogenated solvent, our study provides an approach to make the fabrication of organic solar cell environmentally friendlier and more suitable for large scale production.

Stability is one of the most important challenges facing material research for organic solar cells (OSC) on their path to further commercialization. In the high-performance material system PM6:Y6 studied here, we investigate degradation mechanisms of inverted photovoltaic devices. We have identified two distinct degradation pathways: one requires the presence of both illumination and oxygen and features a short-circuit current reduction, the other one is induced thermally and marked by severe losses of open-circuit voltage and fill factor. We focus our investigation on the thermally accelerated degradation. Our findings show that bulk material properties and interfaces remain remarkably stable, however, aging-induced defect state formation in the active layer remains the primary cause of thermal degradation. The increased trap density leads to higher non-radiative recombination, which limits the open-circuit voltage and lowers the charge carrier mobility in the photoactive layer. Furthermore, we find the trap-induced transport resistance to be the major reason for the drop in fill factor. Our results suggest that device lifetimes could be significantly increased by marginally suppressing trap formation, leading to a bright future for OSC.

The design principles of acceptor1–acceptor2 copolymers featuring alternating diketopyrrolopyrrole (DPP) and thienopyrrolodione (TPD) moieties are investigated. The investigated series of polymers is obtained by varying the aromatic linker between the two acceptor motifs between thiophene, thiazole, pyridine, and benzene. High electron affinities between 3.96 and 4.42 eV, facilitated by the synergy of the acceptor motifs are determined with optical gaps between 1.37 and 2.02 eV. Grazing incidence wide‐angle X‐ray scattering studies reveal a range of film morphologies after thermal annealing, including face‐on, end‐on and superstructure edge‐on‐like crystallites. Conversely, all materials form thin edge‐on layers on the polymer–air interface, as demonstrated by multi‐elemental near‐edge X‐ray absorption fine‐structure spectroscopy. The benefit of the electron‐deficient linkers thiazole and pyridine is evident: In organic field effect transistors, electron mobilities of up to 4.6 × 10−2 cm2 V−1 s−1 are obtained with outstanding on/off current ratios of 5 × 105, facilitated by the absence of detectable hole transport in these materials. Viability for all‐polymer solar cells is assessed in active layer blends with the donor polymer PM6, yielding a maximum average power conversion efficiency of 4.8% and an open circuit voltage above 1 V. [ABSTRACT FROM AUTHOR]

Polymer and small molecule blend thin films are of strong interest for organic electronics and particularly organic solar cells. The high miscibility in blends of ordinary P3HT and state‐of‐the‐art Y‐series non‐fullerene acceptors (NFAs) suppresses phase separation and aggregation challenging successful charge separation and transport. In a recent work, current‐induced doping (CID) is introduced, a method to precisely control the aggregation of Poly(3‐hexylthiophene) (P3HT) in solution. The highly ordered pre‐aggregation in solution is used here to control the P3HT aggregation in neat films and blends with Y12 (BTP‐4F‐12). This results in a 25‐fold increase in hole mobility in P3HT organic field‐effect transistor (OFET) devices and tunability of the P3HT aggregate quality in the presence of Y12 over large ranges. At the same time, particularly the Y12 long‐range ordering is heavily suppressed by increasing P3HT aggregation. However, solvent vapor annealing (SVA) leads to an extraordinarily high Y12 ordering, changes in the crystal orientation of Y12, and a further improvement of P3HT aggregation. A broad range of different degrees of aggregation of both materials can therefore be obtained in the final thin films solely by changing processing parameters without changing the composition of the material system. [ABSTRACT FROM AUTHOR]

In order to tailor the assembling of polymers and organic molecules, a deeper understanding of the kinetics involved in thin film production is necessary. While post-production characterization only provides insight on the final film structure, more sophisticated experimental setups are needed to probe the structure formation processes in situ during deposition. The drying kinetics of a deposited organic thin film strongly influences the assembling process on the nanometer scale. This work presents an experimental setup that enables fine control of the atmosphere composition surrounding the sample during slot die coating, while simultaneously probing the film formation kinetics using in situ grazing incidence X-ray scattering and spectroscopy.

PDIF-CN2 (N,N′-bis(1H,1H-perfluorobutyl)-dicyanoperylene-3,4:9,10-bis(dicarboximide)) is one of the benchmark molecules for n-type organic semiconductors and part of the large perylene diimide (PDI) family. PDIs are known for their rich polymorphism and strong links between molecular packing order and their electrical and optical properties. Here, meniscus-guided zone-casting is used to selectively deposit aligned crystalline films of two different polymorphs of PDIF-CN2 from solution. The two polymorphs can be identified by their characteristic low-wavenumber Raman modes and distinctive photoluminescence spectra that reflect different intermolecular coupling (J- and H-aggregates). One polymorph corresponds to the common single-crystal structure of PDIF-CN2, while for the other previously unidentified thin film polymorph we propose a likely crystal structure based on polarization-dependent UV-Vis absorption spectra, IR scattering near-field microscopy (IR-SNOM) and grazing incidence wide angle scattering (GIWAXS) data, further supported by quantum mechanical calculations. Despite different crystalline structures, field-effect transistors based on thin films of both polymorphs show similar electron mobilities. [ABSTRACT FROM AUTHOR]

Electron transporting (n‐type) polymers are the coveted complementary counterpart to more thoroughly studied hole transporting (p‐type) semiconducting polymers. Besides intrinsic stability issues of the doped form of n‐type polymer toward ubiquitous oxidizing agents (H2O and O2), the choice of suitable n‐dopants and underlying mechanism of doping is an open research field. Using a low LUMO, n‐type unipolar acceptor1‐acceptor2 copolymer poly(DPP‐TPD) in conjunction with bulk n‐doping using Cs2CO3 these issues can be addressed. A solid‐state acid‐base interaction between polymer and basic carbonate increases the backbone electron density by deprotonation of the thiophene comonomer while forming bicarbonate, as revealed by NMR and optical spectroscopy. Comparable to N‐DMBI hydride/electron transfer, Cs2CO3 proton abstraction doping shifts the poly(DPP‐TPD) work function toward the LUMO. Thereby, the anionic doped state is resilient against O2 but is susceptible toward H2O. Based on GIWAXS, Cs2CO3 is mostly incorporated into the amorphous regions of poly(DPP‐TPD) with the help of hydrophilic side chains and has minor impact on the short‐range order of the polymer. Cs2CO3 proton abstraction doping and the acceptor1‐acceptor2 copolymer architecture creates a synergistic n‐doped system with promising properties for thermoelectric energy conversion, as evidenced by a remarkable power factor of (5.59 ± 0.39) × µW m−1 K−2. [ABSTRACT FROM AUTHOR]

We present a comparative study of the nanomorphology of spray and spin coated films of a blend of thieno[3,4-b]thiophene/benzodithiophene (PTB7) semiconducting polymer and [6,6]-phenyl-[C.sub.71]-butyric acid methyl ester (P[C.sub.71]BM). The surface morphology and inner structure of these films are investigated with optical microscopy, atomic force microscopy (AFM), and grazing incidence wide-angle X-ray scattering (GIWAXS). The spray coated PTB7:P[C.sub.71]BM films exhibit significant differences in the molecular packing compared with their spin-coated counterparts. Only very weak order is observed in the spraycoated films as compared to well-defined ordered periodic lamellar structure and π-π stacking of the PTB7 polymer of the spin-coated systems. This difference in the resulting nanomorphology is related to the different structural formation mechanisms in the two deposition techniques., INTRODUCTION Semiconducting polymers and their blends with fullerene derivatives are enabling many emerging advanced technologies such as organic solar cells, organic transistors, and organic light emitting diodes [1-17]. The structure [...]

To develop a detailed understanding about halide perovskite processing from solution, the crystallization processes are investigated during spin coating and slot‐die coating of MAPbI3 at different evaporation rates by simultaneous in situ photoluminescence, light scattering, and absorption measurements. Based on the time evolution of the optical parameters it is found that for both processing methods initially solvent‐complex‐structures form, followed by perovskite crystallization. The latter proceeds in two stages for spin coating, while for slot‐die coating only one perovskite crystallization phase occurs. For both processing methods, it is found that with increasing evaporation rates, the crystallization kinetics of the solvent‐complex structure and the perovskite crystallization remain constant on a relative time scale, whereas the duration of the second perovskite crystallization in spin coating increases. This second perovskite crystallization appears restricted due to differences in solvent‐complex phase morphologies from which the perovskite forms. The work emphasizes the importance of the exact precursor state properties on the perovskite formation. It further demonstrates that detailed analyses of multimodal optical in situ spectroscopy allows gaining a fundamental understanding of the crystallization processes that take place during solution processing of halide perovskites, independent from the specific processing method. [ABSTRACT FROM AUTHOR]