Conjugated polymers belong to a class of organic semiconductors that are used in a broad range of optoelectronic applications such as organic solar cells and organic light-emitting diodes. Thin films of two or more conjugated polymers or small molecules are coated from a solution that undergoes phase separation during drying and forms multiscale structures. In state-of-the-art bulk heterojunction organic solar cells, electron-donating and electron-accepting molecules form a network of donor-rich and acceptor-rich phases, whose domain sizes, composition, and interconnectivity play an important role in their power conversion efficiency. While these mesoscale structures formed in bulk heterojunction blend films under some circumstances can be observed by conventional scanning probe microscopy techniques, the task of mapping the film morphology becomes increasingly difficult when the donor and acceptor molecules are more chemically similar. Here we use AFM-IR, a combination of AFM (atomic force microscopy) and IR (infrared) spectroscopy, to image, with nanometer resolution, the morphology of a blend film of a donor polymer, TQ1, and an acceptor polymer, N2200, by using their distinct chemical composition contrast. These composition maps expose an interpenetrating network of the polymers that could not be distinguished by topography or phase imaging. Moreover, the dependence of the film structures, visualized by AFM-IR, on the molecular weight of the N2200 acceptor and the donor:acceptor blend ratio could be rationalized using Hansen solubility parameters (HSP).

The limited operational lifetime of organic solar cells remains an obstacle to their commercial development and is largely due to the poor intrinsic photostability of the conjugated molecules that constitute the photoactive layer. Here, we selected a series of state-of-the-art donor and acceptor materials including PBDB-T, Y5, PF5-Y5, and PYT to study their photostability under AM1.5 simulated sunlight in ambient conditions. Their properties are monitored over time, using various spectroscopy techniques, including UV-Vis absorption, Fourier-transform infrared (FTIR), and X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS). We found that the absorption spectra of Y5 and PYT films remain almost intact even after 30 hours of light exposure in air, while the PF5-Y5 and PBDB-T films undergo rapid photobleaching. The absorption losses observed in blend films of PBDB-T with Y5 and with PF5-Y5 can be understood as composed of contributions from the separate blend components that are similar to the absorption losses in neat films. The new peaks emerging in the FTIR spectra of PBDB-T, PF5-Y5, and their blend films witness the formation of new carbonyl groups, while these are absent in the spectra of the Y5 and PYT films. The XPS C 1s spectra of the PF5-Y5 and PBDB-T films confirm this carbonyl formation and the S 2p spectra reveal that sulphone groups are formed after 30 hours of exposure of these films. These results confirm that films of Y5 and the copolymer PYT are significantly more resistant to photooxidation, compared to the copolymer PF5-Y5. The comparison of these results suggests that the benzo[1,2-b:4,5-b ']dithiophene moiety with alkylated thiophenes as side chains (BDT-T) accelerates the photodegradation of PBDB-T and PF5-Y5. The replacement of the BDT-T unit by thiophene contributes to the enhanced stability of PYT, demonstrating that the nature of the co-monomer has a significant effect on the intrinsic photostability of Y5-based copolymers. These new insights are expected to stimulate the design of stable donors and acceptor polymers for the development of long-lived OPV devices. Absorption spectra show the photobleaching of acceptor copolymer PF5-Y5. The replacement of BDT-T by thiophene strongly improves the photostability.

The lifetime of organic solar cells critically depends on the photochemical stability of the materials. To shed light on the photostability of novel Y-series electron acceptors, we investigate the evolution of optical properties and composition during one-sun illumination in ambient atmosphere of thin films of the small-molecule acceptor Y5 and its copolymers PF5-Y5 and PYT. We employ UV-vis, Fourier-transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS), to assess changes in these properties as a function of illumination time. UV-Vis spectra show that PF5-Y5 undergoes rapid photobleaching, while the Y5 spectrum remains essentially unaffected even after 30 hours of exposure. The absorption spectrum of PYT, which contains a different co-mer than PF5-Y5, is only weakly affected. XPS C1s spectra of the PF5- Y5 film show a decreasing main peak and the development of a new component after 30 hours exposure, while the Y5 film surface composition remained intact. The photodegradation products of PF5-Y5 are characterized by the presence of new carbonyl groups, emerging as absorption bands in the FTIR spectra, while such spectral changes are absent for the Y5 film, indicating that Y5 is resistant to photooxidation, while PF5-Y5 undergoes photochemical reactions. The faster photodegradation of PF5-Y5 compared to Y5 and PYT raises the question about the role of the copolymer’s BDT moiety in the photooxidation. These new insights on the dependence of the photostability of acceptor molecules on their molecular structure are expected to contribute to the design of stable acceptor copolymers for organic solar cells with long operational lifetimes. 

In the quest towards more durable solution-processed solar cells, the stability of the active layer materials under operation conditions is important. While lifetimes of several years have been demonstrated for encapsulated organic solar cells, it is generally known that degradation events can be accounted for by air components (O₂ and/or water vapour) leaking into the cell through a non-ideal sealing. Here we present a fundamental study of intentional photo-degradation of the electron-acceptor PC₆₀BM ([6,6]-phenyl-C₆₁-butyric acid methyl ester) in air, with the purpose of improving the understanding of the electronic effects of fullerene photo-oxidation. We have studied spincoated thin films of PC₆₀BM by X-ray Photoelectron Spectroscopy, Near-edge X-ray Absorption Fine Structure spectroscopy, and Fourier Transform Infrared Spectroscopy, before and after exposing them to simulated sunlight in air. The changes observed in the spectra obtained by these complementary methods were compared with calculated spectra of a large set of possible oxidation products of PC₆₀BM where oxygen atoms have been attached to the C₆₀ cage. The best fit with experimental IR spectra of photodegraded PC₆₀BM films was obtained for a linear combination of calculated spectra for two degradation products, a dicarbonyl and an anhydride, both with open cages with 58 carbon atoms, and the pristine PC₆₀BM molecule. From this comparison, we conclude that the conjugation of the fullerene cage is disturbed by the formation of several carbonyl-based derivatives on the C₆₀ cage, accompanied by a transition from sp² to sp³-hybridized carbon. The π* resonance in the C1s NEXAFS spectrum was found to be a very sensitive probe for small changes to the fullerene cage, and FT-IR was needed in combination with O1s NEXAFS, to identify the oxidation products.

We report the design and testing of a custom-built experimental setup for dip-coating from volatile solutions under microgravity conditionsonboard an aircraft. Function and safety considerations for the equipment are described. The equipment proved to work well, both concerningthe safety and the preparation of thin films. No leakage of the solvents, nor the solvent vapors, was detected, not even in a situation with afluctuating gravitational field due to bad weather conditions. We have shown that the equipment can be used to prepare thin films of polymerblends, relevant for organic solar cells, from solution in a feasible procedure under microgravity conditions. The prepared films are similar tothe corresponding films prepared under 1 g conditions, but with differences that can be related to the absence of a gravitational field duringdrying of the applied liquid coating. We report on some introductory results from the characterization of the thin films that show differencesin film morphology and structure sizes.

Optimizing the nanostructure of the active layer of polymer solar cells (PSCs) is one of the main challenges to achieve high device performances. The phase separation of the donor polymer and molecular acceptor within the bulk heterojunction (BHJ) layer is often driven by the crystallisation of the acceptor molecules. Hence, a suitable crystallisation tendency of the chosen acceptor is ultimately important. In this work, we identified melting temperature as an indicator for the crystallisation tendency and introduced extended fused-aromatic rings to the end groups of the nonfullerene acceptor molecule to enhance the intermolecular binding energy as well as its crystallisation tendency. The crystallinity, crystal regularity and average crystal size were significantly increased for those molecules with larger fused end groups. The devices containing molecule IDTTC with two fused thiophene rings, which displayed intermediate crystallisation tendency, were found to possess an optimized phase separation scale, balanced hole/electron mobility and highest device performances with the fill factor as high as 73.2% and a power conversion efficiency of 13.49%. With the above observations, we established a new route and paradigm to adjust the crystallisation tendency and BHJ nanostructure of nonfullerene acceptor molecules, thus enhancing the device performances through molecular engineering.

While photovoltaic blends based on non-fullerene acceptors are touted for their thermal stability, this type of acceptor tends to crystallize, which can result in a gradual decrease in photovoltaic performance and affects the reproducibility of the devices. Two halogenated indacenodithienothiophene-based acceptors that readily co-crystallize upon mixing are studied, which indicates that the use of an acceptor mixture alone does not guarantee the formation of a disordered mixture. The addition of the donor polymer to the acceptor mixture readily suppresses the crystallization, which results in a fine-grained ternary blend with nanometer-sized domains that do not coarsen due to a highT(g)approximate to 200 degrees C. As a result, annealing at temperatures of up to 170 degrees C does not markedly affect the photovoltaic performance of ternary devices, in contrast to binary devices that suffer from acceptor crystallization in the active layer. The results indicate that the ternary approach enables the use of high-temperature processing protocols, which are needed for upscaling and high-throughput fabrication of organic solar cells. Further, ternary devices display a stable photovoltaic performance at 130 degrees C for at least 205 h, which indicates that the use of acceptor mixtures allows to fabricate devices with excellent thermal stability.

A short lifetime is the main factor hindering the wider implementation of low-cost organic photovoltaics in large-area and outdoor applications. Ingress of oxygen and water vapour through non-ideal encapsulation layers is a known cause of degradation for polymer/fullerene based solar cells. To better understand the origin of this performance degradation, we study the effect of intentional exposure of the photo-active layer to simulated sunlight (AM1.5) in air both on the solar cell performance and on the molecular semiconductor materials. Cathode-free thin films of a blend of the electron donor polymer poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1) and the electron acceptor fullerene derivative [6,6]-phenyl-C₇₀-butyric acid methyl ester (PC₇₀BM) were exposed to simulated sunlight in air. Fourier-transform infrared spectra demonstrate the formation of carbonyl photo-oxidation products in the blend films, as well as in the pristine polymer and fullerene films. Solar cells prepared with photo-oxidized active layers show increasingly degraded electrical performance (lower short circuit current, open circuit voltage and fill factor) with increasing exposure time. The increased diode ideality factor indicates that trap-assisted recombination hinders device operation after exposure. The external quantum efficiency decreases drastically with increasing exposure time over the whole photon energy range, while the UV-vis absorption spectra of the blend films only show a mild photo-induced bleaching. This demonstrates that not only the photo-induced degradation of the solar cell performance is not predominantly caused by the loss in light absorption, but charge transport and collection are also hampered. This is explained by the fact that photo-oxidation of PC₇₀BM causes bonds in its conjugated cage to break, as evidenced by the decreased ∏* intensity in C1s-NEXAFS spectra of PC₇₀BM films. This degradation of unoccupied states of PC₇₀BM will hinder the transport of photo-generated electrons to the electrode. Surface photovoltage spectroscopy gives direct evidence for gap states at the surface of a PC₇₀BM film, formed after 2 hours of exposure and resulting in upward band bending at the PC₇₀BM/air surface. These observations indicate that the photo-oxidation of PC₇₀BM is likely to be the main cause of the performance degradation observed when the photoactive layer of a TQ1:PC₇₀BM solar cell is intentionally exposed to light in air.