skip to main content


Title: The hole in the bucky: structure-property mapping of closed- vs. open-cage fullerene solar-cell blends via temperature/composition phase diagrams
The morphology development of polymer-based blends, such as those used in organic photovoltaic (OPV) systems, typically arrests in a state away from equilibrium – how far from equilibrium this is will depend on the materials chemistry and the selected assembly parameters/environment. As a consequence, small changes during the blend assembly alters the solid-structure development from solution and, in turn, the final device performance. Comparing an open-cage ketolactam fullerene with the prototypical [6,6]-phenyl-C₆₁-butyric acid methyl ester in blends with poly[2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene (PBTTT), we demonstrate that experimentally established, non-equilibrium temperature/composition phase diagrams can be useful beyond rationalization of optimum blend composition for OPV device performance. Indeed, they can be exploited as tools for rapid, qualitative structure-property mapping, providing insights into why apparent similar donor:acceptor blends display different optoelectronic processes resulting from changes in the phase-morphology formation induced by the different chemistries of the fullerenes.  more » « less
Award ID(s):
1729737 1905901
NSF-PAR ID:
10296337
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Journal of Materials Chemistry C
ISSN:
2050-7526
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Understanding the correlation between polymer aggregation, miscibility, and device performance is important to establish a set of chemistry design rules for donor polymers with nonfullerene acceptors (NFAs). Employing a donor polymer with strong temperature‐dependent aggregation, namely PffBT4T‐2OD [poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3″′‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2″′‐quaterthiophen‐5,5‐diyl)], also known as PCE‐11 as a base polymer, five copolymer derivatives having a different thiophene linker composition are blended with the common NFA O‐IDTBR to investigate their photovoltaic performance. While the donor polymers have similar optoelectronic properties, it is found that the device power conversion efficiency changes drastically from 1.8% to 8.7% as a function of thiophene content in the donor polymer. Results of structural characterization show that polymer aggregation and miscibility with O‐IDTBR are a strong function of the chemical composition, leading to different donor–acceptor blend morphology. Polymers having a strong tendency to aggregate are found to undergo fast aggregation prior to liquid–liquid phase separation and have a higher miscibility with NFA. These properties result in smaller mixed donor–acceptor domains, stronger PL quenching, and more efficient exciton dissociation in the resulting cells. This work indicates the importance of both polymer aggregation and donor–acceptor interaction on the formation of bulk heterojunctions in polymer:NFA blends.

     
    more » « less
  2. Abstract

    The relation of phase morphology and solid‐state microstructure with organic photovoltaic (OPV) device performance has intensely been investigated over the last twenty years. While it has been established that a combination of donor:acceptor intermixing and presence of relatively phase‐pure donor and acceptor domains is needed to get an optimum compromise between charge generation and charge transport/charge extraction, a quantitative picture of how much intermixing is needed is still lacking. This is mainly due to the difficulty in quantitatively analyzing the intermixed phase, which generally is amorphous. Here, fast scanning calorimetry, which allows measurement of device‐relevant thin films (<200 nm thickness), is exploited to deduce the precise composition of the intermixed phase in bulk‐heterojunction structures. The power of fast scanning calorimetry is illustrated by considering two polymer:fullerene model systems. Somewhat surprisingly, it is found that a relatively small fraction (<15 wt%) of an acceptor in the intermixed amorphous phase leads to efficient charge generation. In contrast, charge transport can only be sustained in blends with a significant amount of the acceptor in the intermixed phase (in this case: ≈58 wt%). This example shows that fast scanning calorimetry is an important tool for establishing a complete compositional characterization of organic bulk heterojunctions. Hence, it will be critical in advancing quantitative morphology–function models that allow for the rational design of these devices, and in delivering insights in, for example, solar cell degradation mechanisms via phase separation, especially for more complex high‐performing systems such as nonfullerene acceptor:polymer bulk heterojunctions.

     
    more » « less
  3. Spin casting has become an attractive method to fabricate polymer thin films found in organic electronic devices such as field-effect transistors, and light emitting diodes. Many studies have shown that altering spin casting parameters can improve device performance, which has been directly correlated to the degree of polymer alignment, crystallinity, and morphology of the thin film. To provide a thorough understanding of the balance of thermodynamic and kinetic factors that influence the stratification of polymer blend thin films, we monitor stratified polymer blend thin films developed from poly(3-hexylthiophene-2,5-diyl) and poly(methyl methacrylate) blends at controlled loading ratios, relative molecular weights, and casting speed. The structures of these thin films were characterized via neutron reflectivity, and the results show that at the fastest casting speed, polymer–polymer interactions and surface energy of the polymers in the blend dictate the final film structure, and at the slowest casting speed, there is less control over the film layering due to the polymer–polymer interactions, surface energy, and entropy simultaneously driving stratification. As well, the relative solubility limits of the polymers in the pre-deposition solution play a role in the stratification process at the slowest casting speed. These results broaden the current understanding of the relationship between spin casting conditions and vertical phase separation in polymer blend thin films and provide a foundation for improved rational design of polymer thin film fabrication processes to attain targeted stratification, and thus performance. 
    more » « less
  4. Abstract

    Designed multiblock copolymers with complex architectures offer unlimited opportunities to obtain novel nanostructured phases, however, their synthesis could be challenging and expensive. An alternative approach to access desired nanostructures is to use blends of block copolymers with simple chain architectures and designed block‐block interactions. We use binary blends composed of AB and CD diblock copolymers as a model system to establish design principles of polymeric blends containing block copolymers. Specifically, we explore the phase behavior of AB/CD blends by using the polymeric self‐consistent field theory to construct phase diagrams of the blends focusing on the sphere‐forming regions in the phase space. We predict the formation of various spherical packing phases composed of either core‐shell‐structured spheres or binary spheres resembling metallic alloys. We demonstrate that the equilibrium morphology can be regulated by adjusting the blend composition and molecular parameters such as block fractions, conformational asymmetry, and segment‐segment interactions. The strategy of using secondary interaction in polymeric blends to control the phase behavior explored in the current study can also be generalized to other soft matter systems.

     
    more » « less
  5. Abstract

    The development of nonfullerene acceptors has brought polymer solar cells into a new era. Maximizing the performance of nonfullerene solar cells needs appropriate polymer donors that match with the acceptors in both electrical and morphological properties. So far, the design rationales for polymer donors are mainly borrowed from fullerene‐based solar cells, which are not necessarily applicable to nonfullerene solar cells. In this work, the influence of side chain length of polymer donors based on a set of random terpolymers PTAZ‐TPD10‐Cnon the device performance of polymer solar cells is investigated with three different acceptor materials, i.e., a fullerene acceptor [70]PCBM, a polymer acceptor N2200, and a fused‐ring molecular acceptor ITIC. Shortening the side chains of polymer donors improves the device performance of [70]PCBM‐based devices, but deteriorates the N2200‐ and ITIC‐based devices. Morphology studies unveil that the miscibility between donor and acceptor in blend films depends on the side chain length of polymer donors. Upon shortening the side chains of the polymer donors, the miscibility between the donor and acceptor increases for the [70]PCBM‐based blends, but decreases for the N2200‐ and ITIC‐based blends. These findings provide new guidelines for the development of polymer donors to match with emerging nonfullerene acceptors.

     
    more » « less