Morphology Control for Efficient Nonfused Acceptor-Based Organic Photovoltaic Cells.

Non-fused electron acceptors have huge advantages in fabricating low-cost organic photovoltaic (OPV) cells. However, morphology control is a challenge as non-fused C─C single bonds bring more molecular conformations. Here, by selecting two typical polymer donors, PBDB-TF and PBQx-TF, the blend morphologies and its impacts on the power conversion efficiencies (PCEs) of non-fused acceptor-based OPV cells are studied. A selenium-containing non-fused acceptor named ASe-5 is designed. The results suggest that PBQx-TF has a lower miscibility with ASe-5 when compared with PBDB-TF. Additionally, the polymer networks may form earlier in the PBQx-TF:ASe-5 blend film due to stronger preaggregation performance, leading to a more obvious phase separation. The PBQx-TF:ASe-5 blend film shows faster charge transfer and suppressed charge recombination. As a result, the PBQx-TF:ASe-5-based device records a good PCE of 14.7% with a higher fill factor (FF) of 0.744, while the PBDB-TF:ASe-5-based device only obtains a moderate PCE of 12.3% with a relatively low FF of 0.662. The work demonstrates that the selection of donors plays a crucial role in controlling the blend morphology and thus improving the PCEs of non-fused acceptor-based OPV cells.

Influence of Asphaltene Modification on Structure of P3HT/Asphaltene Blends: Molecular Dynamics Simulations.

Further development and commercialization of bulk heterojunction (BHJ) solar cells require the search for novel low-cost materials. The present study addresses the relations between the asphaltenes' chemical structure and the morphology of the poly(3-hexylthiohene) (P3HT)/asphaltene blends as potential materials for the design of BHJ solar cells. By means of all-atom molecular dynamics simulations, the formation of heterophase morphology is observed for the P3HT-based blends with carboxyl-containing asphaltenes, as well as the aggregation of the asphaltenes into highly ordered stacks. Although the π-π interactions between the polyaromatic cores of the asphaltenes in solutions are sufficient for the molecules to aggregate into ordered stacks, in a blend with a conjugated polymer, additional stabilizing factors are required, such as hydrogen bonding between carboxyl groups. It is found that the asphaltenes' aliphatic side groups may improve significantly the miscibility between the polymer and the asphaltenes, thereby preventing the formation of heterophase morphology. The results also demonstrate that the carboxyl-containing asphaltenes/P3HT ratio should be at least 1:1, as a decrease in concentration of the asphaltenes leads to the folding of the polymer chains, lower ordering in the polymer phase and the destruction of the interpenetrating 3D structure formed by P3HT and the asphaltene phases. Overall, the results of the present study for the first time reveal the aggregation behavior of the asphaltenes of varying chemical structures in P3HT, as well the influence of their presence and concentration on the polymer phase structure and blend morphology, paving the way for future development of BHJ solar cells based on the conjugated polymer/asphaltene blends.

A Top-Down Strategy to Engineer ActiveLayer Morphology for Highly Efficient and Stable All-Polymer Solar Cells.

A major challenge hindering the further development of all-polymer solar cells (all-PSCs) employing polymerized small-molecule acceptors is the relatively low fill factor (FF) due to the difficulty in controlling the active-layer morphology. The issues typically arise from oversized phase separation resulting from the thermodynamically unfavorable mixing between two macromolecular species, and disordered molecular orientation/packing of highly anisotropic polymer chains. Herein, a facile top-down controlling strategy to engineer the morphology of all-polymer blends is developed by leveraging the layer-by-layer (LBL) deposition. Optimal intermixing of polymer components can be achieved in the two-step process by tuning the bottom-layer polymer swelling during top-layer deposition. Consequently, both the molecular orientation/packing of the bottom layer and the molecular ordering of the top layer can be optimized with a suitable top-layer processing solvent. A favorable morphology with gradient vertical composition distribution for efficient charge transport and extraction is therefore realized, affording a high all-PSC efficiency of 17.0% with a FF of 76.1%. The derived devices also possess excellent long-term thermal stability and can retain >90% of their initial efficiencies after being annealed at 65 °C for 1300 h. These results validate the distinct advantages of employing an LBL processing protocol to fabricate high-performance all-PSCs.

The Effects of Copolymer Compatibilizers on the Phase Structure Evolution in Polymer Blends-A Review.

This paper summarizes the results of studies describing the effect of block and graft copolymers on the phase structure formation and evolution in immiscible polymer blends. The main phenomenological rules for prediction of the copolymer compatibilization efficiency are briefly described and compared with selected experimental data. The results of the theories of equilibrium distribution of a copolymer between the blend interface and the bulk phases and its effect on the blend interfacial tension are summarized. The theories of the compatibilizer effect on the droplet breakup in flow are analyzed. The mechanisms of the copolymer effect on the coalescence of droplets in flow are compared and their effect on the droplet size is shown. The problems of reliable description of the effect of a copolymer on the coalescence in quiescent state are presented. Obstacles to derivation of a realistic theory of the copolymer effect on the competition between the droplet breakup and coalescence are discussed. Selected experimental data are compared with the theoretical results.

Impact of Chlorination Patterns of Naphthalenediimide-Based Polymers on Aggregated Structure, Crystallinity, and Device Performance of All-Polymer Solar Cells and Organic Transistors.

The aggregation properties of conjugated polymers can play a crucial role in their thin film structures and performance of electronic devices. Control of these aggregated structures is particularly important in producing efficient all-polymer solar cells (all-PSCs), considering that strong demixing of the polymer donor and polymer acceptor typically occurs during film formation because of the low entropic contribution to the thermodynamics of the system. Here, three naphthalenediimide (NDI)-based polymer acceptors with different backbone chlorination patterns are developed to investigate the effect of the chlorination patterns on the aggregation tendencies of the polymer acceptors, which greatly influence their crystalline structures, electrical properties, and device performances of the resultant all-PSCs and organic field-effect transistors (OFETs). The counterparts of NDI units, dichlorinated bithiophene (Cl2T2), monochlorinated bithiophene (ClT2), and dichlorinated thienylene-vinylene-thienylene (Cl2TVT), are employed to synthesize a series of P(NDIOD-Cl2T2), P(NDIOD-ClT2), and P(NDIOD-Cl2TVT) polymers. The P(NDIOD-Cl2T2) polymer takes advantage of strong noncovalent bonding induced by its chlorine substituents, resulting in the formation of optimal face-on oriented crystalline structures which are suitable for efficient all-PSC devices. In comparison, the P(NDIOD-Cl2TVT) polymer forms bimodal crystalline structures in thin films to yield optimal performances in the resultant OFETs. When the three chlorinated polymers are applied to all-PSCs with the PBDTTTPD polymer donor, P(NDIOD-Cl2T2) achieves a maximum power conversion efficiency (PCE) of 7.22% with an appropriate blend morphology and high fill factor, outperforming P(NDIOD-ClT2) (PCE = 4.80%) and P(NDIOD-Cl2TVT) (PCE = 5.78%). Our observations highlight the effectiveness of the chlorination strategy for developing efficient polymer acceptors and demonstrate the important role of polymer aggregation in modulating the blend morphology and all-PSC performance.

Effects of a Fluorinated Donor Polymer on the Morphology, Photophysics, and Performance of All-Polymer Solar Cells Based on Naphthalene Diimide-Arylene Copolymer Acceptors.

Naphthalene diimide (NDI)-biselenophene copolymer (PNDIBS), NDI-selenophene copolymer (PNDIS), and the fluorinated donor polymer PM6 were used to investigate how a fluorinated polymer component affects the morphology and performance of all-polymer solar cells (all-PSCs). Although the PM6:PNDIBS blend system exhibits a high open-circuit voltage (Voc = 0.925 V) and a desired low optical bandgap energy loss (Eloss = 0.475 eV), the overall power conversion efficiency (PCE) was 3.1%. In contrast, PM6:PNDIS blends combine a high Voc (0.967 V) with a high fill factor (FF = 0.70) to produce efficient all-PSCs with 9.1% PCE. Furthermore, the high-performance PM6:PNDIS all-PSCs could be fabricated by various solution processing approaches and at active layer thickness as high as 300 nm without compromising photovoltaic efficiency. The divergent photovoltaic properties of PNDIS and PNDIBS when paired respectively with PM6 are shown to originate from the starkly different blend morphologies and blend photophysics. Efficient PM6:PNDIS blend films were found to exhibit a vertical phase stratification along with lateral phase separation, while the molecular packing had a predominant face-on orientation. Bulk lateral phase separation with both face-on and edge-on molecular orientations featured in the poor-performing PM6:PNDIBS blend films. Enhanced charge photogeneration and suppressed geminate and bimolecular recombinations with 99% charge collection probability found in PM6:PNDIS blends strongly differ from the poor charge collection probability (66%) and high electron-hole pair recombination seen in PM6:PNDIBS. Our findings demonstrate that beyond the generally expected enhancement of Voc, a fluorinated polymer component in all-PSCs can also exert a positive or negative influence on photovoltaic performance via the blend morphology and blend photophysics.

Phase Morphology of NR/SBR Blends: Effect of Curing Temperature and Curing Time.

The morphology of natural rubber/styrene⁻butadiene rubber blends (NR/SBR) was characterized by atomic force microscopy (AFM), with regard to curing temperature and curing time. The changes in blend morphology were directly visualized by AFM which confirmed the results of indirect experiments like differential scanning calorimetry (DSC). Comparing the phase morphologies at different curing temperatures indicated that the domain size of SBR increases with temperature at lower curing temperatures, but domain growing stops at the latest scorch time. This effect is explained by longer scorch times at low curing temperatures which facilitate phase separation, while the short scorch times at higher temperatures meant that the coalescence of SBR phases was hindered by cross-linking between polymer chains.

Alkenyl Carboxylic Acid: Engineering the Nanomorphology in Polymer-Polymer Solar Cells as Solvent Additive.

We have investigated a series of commercially available alkenyl carboxylic acids with different alkenyl chain lengths (trans-2-hexenoic acid (CA-6), trans-2-decenoic acid (CA-10), 9-tetradecenoic acid (CA-14)) for use as solvent additives in polymer-polymer non-fullerene solar cells. We systematically investigated their effect on the film absorption, morphology, carrier generation, transport, and recombination in all-polymer solar cells. We revealed that these additives have a significant impact on the aggregation of polymer acceptor, leading to improved phase segregation in the blend film. This in-depth understanding of the additives effect on the nanomorphology in all-polymer solar cell can help further boost the device performance. By using CA-10 with the optimal alkenyl chain length, we achieved fine phase separation, balanced charge transport, and suppressed recombination in all-polymer solar cells. As a result, an optimal power conversion efficiency (PCE) of 5.71% was demonstrated which is over 50% higher than that of the as-cast device (PCE = 3.71%) and slightly higher than that of devices with DIO treatment (PCE = 5.68%). Compared with widely used DIO, these halogen-free alkenyl carboxylic acids have a more sustainable processing as well as better performance, which may make them more promising candidates for use as processing additives in organic non-fullerene solar cells.

Morphology Formation in PC/ABS Blends during Thermal Processing and the Effect of the Viscosity Ratio of Blend Partners.

Morphology formation during compounding, as well as injection molding of blends containing 60 wt % polycarbonate (PC) and 40 wt % polybutadiene rubber-modified styrene-acrylonitrile copolymers (ABS), has been investigated by transmission electron microscopy (TEM). Profiles of the blend morphology have been recorded in injection-molded specimens and significant morphology gradients observed between their skin and core. A <10 µm thick surface layer with strongly dispersed and elongated nano-scale (streak-like) styrene acrylonitrile (SAN) phases and well-dispersed, isolated SAN-grafted polybutadiene rubber particles is followed by a 50-150 µm thick skin layer in which polymer morphology is characterized by lamellar SAN/ABS phases. Thickness of these lamellae increases with the distance from the specimen's surface. In the core of the specimens the SAN-grafted polybutadiene rubber particles are exclusively present within the SAN phases, which exhibit a much coarser and less oriented, dispersed morphology compared to the skin. The effects of the viscosity of the SAN in the PC/ABS blends on phase morphologies and correlations with fracture mechanics in tensile and impact tests were investigated, including scanning electron microscopy (SEM) assessment of the fracture surfaces. A model explaining the mechanisms of morphology formation during injection molding of PC/ABS blends is discussed.

All-polymer bulk heterojuction solar cells with 4.8% efficiency achieved by solution processing from a co-solvent.

All-polymer solar cells with 4.8% power conversion efficiency are achieved via solution processing from a co-solvent. The observed short-circuit current density of 10.5 mA cm(-2) and external quantum efficiency of 61.3% are also the best reported in all-polymer solar cells so far. The results demonstrate that processing the active layer from a co-solvent is an important strategy in achieving highly efficient all-polymer solar cells.