Naphthalene Diimide-Based Terpolymers with Controlled Crystalline Properties for Producing High Electron Mobility and Optimal Blend Morphology in All-Polymer Solar Cells

摘要： We report a series of new n-type random copolymers (P(NDI2OD-Se-Th x) where x = 0, 0.5, 0.7, 0.8, 0.9, 1.0) consisting of naphthalene diimide (NDI), selenophene-2,2’-thiophene (Se-Th), and seleno[3,2-b]thiophene (SeTh) to demonstrate their use in producing efficient all-polymer solar cells (all-PSCs) and organic field-effect transistors (OFETs). To investigate the effect of polymer crystallinity on the performance of all-PSCs and OFETs, we tuned the composition of the Se-Th and SeTh moieties in the P(NDI2OD-Se-Th x) polymers, resulting in enhanced crystalline properties with higher Se-Th ratio. Thus, the OFET electron mobility was increased with higher Se-Th ratio, exhibiting the highest value of 1.38×10?1 cm2 V?1 s?1 with P(NDI2OD-Se-Th 1.0). However, the performance of all-PSCs based on PBDB-T:P(NDI2OD-Se-Th x) showed a non-linear trend relative to the Se-Th ratio and the performance was optimized with P(NDI2OD-Se-Th 0.8) exhibiting the highest power coversion efficiency of 8.30%. This is attributed to the stronger crystallization-driven phase separation in all-polymer blends for higher Se-Th ratio. At the optimal crystallinity of P(NDI2OD-Se-Th 0.8) in all-PSCs, the degree of phase separation, domain purity and the electron mobility were optimized, resulting in enhanced charge generation and transport. Our works describe structure-property-performance relationships to design effective n-type polymers in terms of crystalline and electrical properties suitable for both efficient OFETs and all-PSCs.

Decoding Charge Recombination through Charge Generation in Organic Solar Cells

摘要： The in-depth understanding of charge carrier photogeneration and recombination mechanisms in organic solar cells is still an ongoing effort. In donor:acceptor (bulk) heterojunction organic solar cells, charge photogeneration and recombination are inter-related via the kinetics of charge transfer states—being singlet or triplet states. Although high-charge-photogeneration quantum yields are achieved in many donor:acceptor systems, only very few systems show significantly reduced bimolecular recombination relative to the rate of free carrier encounters, in low-mobility systems. This is a serious limitation for the industrialization of organic solar cells, in particular when aiming at thick active layers. Herein, a meta-analysis of the device performance of numerous bulk heterojunction organic solar cells is presented for which field-dependent photogeneration, charge carrier mobility, and fill factor are determined. Herein, a “spin-related factor” that is dependent on the ratio of back electron transfer of the triplet charge transfer (CT) states to the decay rate of the singlet CT states is introduced. It is shown that this factor links the recombination reduction factor to charge-generation efficiency. As a consequence, it is only in the systems with very efficient charge generation and very fast CT dissociation that free carrier recombination is strongly suppressed, regardless of the spin-related factor.

Corrigendum: Impact of Polymer Backbone Fluorination on the Charge Generation/Recombination Patterns and Vertical Phase Segregation in Bulk Heterojunction Organic Solar Cells

Critical Role of Polymer Aggregation and Miscibility in Nonfullerenea??Based Organic Photovoltaics

摘要： 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.

Charge photogeneration and recombination in single-material organic solar cells and photodetectors based on conjugated star-shaped donor-acceptor oligomers

摘要： Single-material organic solar cells (SMOSC) are attracted by their simple structure and ease of fabrication so that they are virtually free from a number of drawbacks of heterojunction organic solar cells. However, the performance of SMOSC is still low, first of all because of poor understanding of losses on the way of energy conversion from light to electricity. In this work, we present solution-processed SMOSC based on star-shaped π-conjugated donor-acceptor oligomers with triphenylamine donor (N-Ph3) and alkyl- or phenyl dicyanovinyl acceptor (DCV-R) of general formulae N(Ph-nT-DCV-R)3, where nT stands for n-oligothiophene, and study charge photogeneration and recombination in them. SMOSC demonstrate small energy losses resulting in high open-circuit voltage of 1.08 – 1.19 V and the power conversion efficiency up to 1.22% under illumination intensity of 0.45 sun (1.13% under one sun) with the maximum external quantum efficiency up to 24% for N(Ph-2T-DCV-Ethyl)3, which are among the highest for SMOSC based on conjugated donor-acceptor small molecules or oligomers. It was found that monomolecular recombination dominates at the short-circuit condition and the maximum power point, but at the open-circuit condition the photoinduced charges recombine nearly bimolecularly. The bottleneck in the SMOSC performance was shown to be the field-assisted charge generation perfectly described by the Onsager model in the limit of weak electric fields. The results obtained suggest that intermolecular charge delocalization in conjugated donor-acceptor molecules would be beneficial for further progress in SMOSC.

Subtle Molecular Tailoring Induces Significant Morphology Optimization Enabling over 16% Efficiency Organic Solar Cells with Efficient Charge Generation

摘要： Manipulating charge generation in a broad spectral region has proved to be crucial for nonfullerene-electron-acceptor-based organic solar cells (OSCs). 16.64% high efficiency binary OSCs are achieved through the use of a novel electron acceptor AQx-2 with quinoxaline-containing fused core and PBDB-TF as donor. The significant increase in photovoltaic performance of AQx-2 based devices is obtained merely by a subtle tailoring in molecular structure of its analogue AQx-1. Combining the detailed morphology and transient absorption spectroscopy analyses, a good structure–morphology–property relationship is established. The stronger π–π interaction results in efficient electron hopping and balanced electron and hole mobilities attributed to good charge transport. Moreover, the reduced phase separation morphology of AQx-2-based bulk heterojunction blend boosts hole transfer and suppresses geminate recombination. Such success in molecule design and precise morphology optimization may lead to next-generation high-performance OSCs.