Sang Myeon Lee

Ternary solar cells with a mixed face-on and edge-on orientation enable an unprecedented efficiency of 12.1%

Ternary organic solar cells (OSCs), with a simple structure, can be easily adopted as sub-cells in a tandem design, thereby further enhancing the power conversion efficiency (PCE). Considering the potential to surpass the theoretical PCE limit in OSCs, we incorporated a benzo[1,2-b;4,5-b′]dithiophene-based small molecule into a poly(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b′]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl):[6,6]-phenyl-C71-butyric acid methyl ester host system. A hitherto unrealized PCE of 12.1% was achieved at the optimized composition of the ternary blend. The ternary blend surprisingly had a face-on and edge-on co-existent texture, which is far better than that of the face-on orientated host film. To the best of our knowledge, this intriguing result refutes for the first time a general paradigm that high-performance OSCs are unambiguously linked to face-on structures. Therefore, our study provides a new platform for refining the theoretical underpinning of multiple blending OSCs.

Synthesis of PCDTBT-based fluorinated polymers for high open-circuit voltage in organic photovoltaics: towards an understanding of relationships between polymer energy levels engineering and ideal morphology control.

The introduction of fluorine (F) atoms onto conjugated polymer backbone has verified to be an effective way to enhance the overall performance of polymer-based bulk-heterojunction (BHJ) solar cells, but the underlying working principles are not yet fully uncovered. As our attempt to further understand the impact of F, herein we have reported two novel fluorinated analogues of PCDTBT, namely, PCDTFBT (1F) and PCDT2FBT (2F), through inclusion of either one or two F atoms into the benzothiadiazole (BT) unit of the polymer backbone and the characterization of their physical properties, especially their performance in solar cells. Together with a profound effect of fluorination on the optical property, nature of charge transport, and molecular organization, F atoms are effective in lowering both the HOMO and LUMO levels of the polymers without a large change in the energy bandgaps. PCDTFBT-based BHJ solar cell shows a power conversion efficiency (PCE) of 3.96 % with high open-circuit voltage (VOC) of 0.95 V, mainly due to the deep HOMO level (-5.54 eV). To the best of our knowledge, the resulting VOC is comparable to the record VOC values in single junction devices. Furthermore, to our delight, the best PCDTFBT-based device, prepared using 2 % v/v diphenyl ether (DPE) additive, reaches the PCE of 4.29 %. On the other hand, doubly-fluorinated polymer PCDT2FBT shows the only moderate PCE of 2.07 % with a decrease in VOC (0.88 V), in spite of the further lowering of the HOMO level (-5.67 eV) with raising the number of F atoms. Thus, our results highlight that an improvement in efficiency by tuning the energy levels of the polymers by means of molecular design can be expected only if their truly optimized morphologies with fullerene in BHJ systems are materialized.

Fluorinated Benzothiadiazole (BT) Groups as a Powerful Unit for High-Performance Electron-Transporting Polymers

Over the past few years, one of the most remarkable advances in the field of polymer solar cells (PSCs) has been the development of fluorinated 2,1,3-benzothiadiazole (BT)-based polymers that lack the solid working principles of previous designs, but boost the power conversion efficiency. To assess a rich data set for the influence of the fluorinated BT units on the charge-transport characteristics in organic field-effect transistors (OFETs), we synthesized two new polymers (PDPP-FBT and PDPP-2FBT) incorporating diketopyrrolopyrrole (DPP) and either single- or double-fluorinated BT and thoroughly investigated them via a range of techniques. Unlike the small differences in the absorption properties of PDPP-FBT and its nonfluorinated analogue (PDPP-BT), the introduction of doubly fluorinated BT into the polymer backbone induces a noticeable change in its optical profiles and energy levels, which results in a slightly wider bandgap and deeper HOMO for PDPP-2FBT, relative to the others. Grazing incidence X-ray diffraction (GIXD) analysis reveals that both fluorinated polymer films have long-range orders along the out-of-plane direction, and π-π stacking in the in-plane direction, implying semicrystalline lamellar structures with edge-on orientations in the solid state. Thanks to the strong intermolecular interactions and highly electron-deficient π-systems driven by the inclusion of F atoms, the polymers exhibit electron mobilities of up to 0.42 and 0.30 cm2 V(-1) s(-1) for PDPP-FBT and PDPP-2FBT, respectively, while maintaining hole mobilities higher than 0.1 cm2 V(-1) s(-1). Our results highlight that the use of fluorinated BT blocks in the polymers is a promising molecular design strategy for improving electron transporting performance without sacrificing their original hole mobility values.

High-Performance Furan-Containing Conjugated Polymer for Environmentally Benign Solution Processing

Developing semiconducting polymers that exhibit both strong charge transport capability via highly ordered structures and good processability in environmentally benign solvents remains a challenge. Given that furan-based materials have better solubility in various solvents than analogous thiophene-based materials, we have synthesized and characterized furanyl-diketopyrrolopyrrole polymer (PFDPPTT-Si) together with its thienyl-diketopyrrolopyrrole-based analogue (PTDPPTT-Si) to understand subtle changes induced by the use of furan instead of thiophene units. PTDPPTT-Si films processed in common chlorinated solvent exhibit a higher hole mobility (3.57 cm2 V-1 s-1) than PFDPPTT-Si films (2.40 cm2 V-1 s-1) under the same conditions; this greater hole mobility is a result of tightly aggregated π-stacking structures in PTDPPTT-Si. By contrast, because of its enhanced solubility, PFDPPTT-Si using chlorine-free solution processing results in a device with higher mobility (as high as 1.87 cm2 V-1 s-1) compared to that of the corresponding device fabricated using PTDPPTT-Si. This mobility of 1.87 cm2 V-1 s-1 represents the highest performances among furan-containing polymers reported to the best of our knowledge for nonchlorinated solvents. Our study demonstrates an important step toward environmentally compatible electronics, and we expect the results of our study to reinvigorate the furan-containing semiconductors field.

Siloxane-Based Hybrid Semiconducting Polymers Prepared by Fluoride-Mediated Suzuki Polymerization†

Siloxane-containing materials are a large and important class of organic-inorganic hybrids. In this report, a practical variation of the Suzuki polymerization to generate semiconducting polymeric hybrids based on siloxane units, which proceeds under essentially nonbasic conditions, is presented. This method generates solution-processable poly(diketopyrrolopyrrole-alt-benzothiadiazole) (PDPPBT-Si) consisting of the hybrid siloxane substituents, which could not be made using conventional methods. PDPPBT-Si exhibits excellent ambipolar transistor performance with well-balanced hole and electron FET mobilities. The siloxane-containing DPP-thiophene polymer classes (PDPP3T-Si and PDPP4T-Si), synthesized by this method, exhibit high hole mobility of up to 1.29 cm(2)  V(-1)  s(-1) . This synthetic approach should provide access to a variety of novel siloxane-containing conjugated semiconductor classes by using a variety of aryldihalides and aryldiboronic acids/esters.

Amphiphilic Graft Copolymers as a Versatile Binder for Various Electrodes of High‐Performance Lithium‐Ion Batteries

It is known that grafting one polymer onto another polymer backbone is a powerful strategy capable of combining dual benefits from each parent polymer. Thus amphiphilic graft copolymer precursors (poly(vinylidene difluoride)-graft-poly(tert-butylacrylate) (PVDF-g-PtBA)) have been developed via atom transfer radical polymerization, and demonstrated its outstanding properties as a promising binder for high-performance lithium-ion battery (LIB) by using in situ pyrolytic transformation of PtBA to poly(acrylic acid) segments. In addition to its superior mechanical properties and accommodation capability of volume expansion, the Si anode with PVDF-g-PtBA exhibits the excellent charge and discharge capacities of 2672 and 2958 mAh g(-1) with the capacity retention of 84% after 50 cycles. More meaningfully, the graft copolymer binder shows good operating characteristics in both LiN0.5 M1.5 O4 cathode and neural graphite anode, respectively. By containing such diverse features, a graft copolymer-loaded LiN0.5 M1.5 O4 /Si-NG full cell has been successfully achieved, which delivers energy density as high as 546 Wh kg(-1) with cycle retention of ≈70% after 50 cycles (1 C). For the first time, this work sheds new light on the unique nature of the graft copolymer binders in LIB application, which will provide a practical solution for volume expansion and low efficiency problems, leading to a high-energy-density lithium-ion chemistry.

Effects of incorporating different chalcogenophene comonomers into random acceptor terpolymers on the morphology and performance of all-polymer solar cells

A new family of naphthalenediimide (NDI)-bithiophene-based random terpolymers (PNDI-Fu10, PNDI-Th10, and PNDI-Se10) was prepared by incorporating a small amount (10 mol%) of different chalcogenophene units, namely furan (Fu), thiophene (Th), and selenophene (Se), into a poly((N,N’-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl)-alt-5,5′-(2,2′-bithiophene)) (P(NDI2OD-T2)) backbone. The terpolymers all exhibited negligible optical property and frontier energy level differences. Interestingly, the blend film morphology and photovoltaic performance of all-polymer solar cells (all-PSCs), comprising a random terpolymer series as an acceptor and poly(6-fluoro-2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-dyl-alt-thiophene-2,5-diyl) (FTQ) as a donor, were strongly dependent on the type of chalcogenophene. Consequently, the all-PSCs revealed a clear variation in short-circuit current density (JSC) and fill factor (FF) while retaining identical open-circuit voltages (VOC). The greatest power-conversion efficiency of 5.88% with a high JSC of 10.77 mA cm−2 was observed for PNDI-Th10:FTQ because of a synergistic contribution from a more preferential π-face-on orientation and suppression of bimolecular/geminate recombination. This was confirmed by a detailed investigation on the morphology and charge dynamic structural properties. In addition to understanding their effects on photovoltaic characteristics, this study demonstrates that introducing a small amount of the chalcogenophenes into a well-performing polymer is a simple and effective method to improve JSC values while maintaining VOCs of the parent polymers.

Influence of Simultaneous Tuning of Molecular Weights and Alkyl Substituents of Poly(thienoisoindigo-alt-naphthalene)s on Morphology and Change Transport Properties

To simultaneously assess the impact of molecular weight (Mn) and alkyl substituent variations of polymers on the structural and optoelectronic properties, herein, we conduct a systematic study of a series of poly(thienoisoindigo-alt-naphthalene) (PTIIG-Np)-based polymers containing different alkyl substituents (2-hexyldecyl (HD), 2-octyldodecyl (OD), and 2-decyltetradecyl (DT) chains) and Mns (low (L) and high (H)). All of the polymers produce almost identical energy levels, whereas their optical spectra show a clear dependence on Mns and the alkyl substituents. Interestingly, increasing the alkyl substituent sizes of the polymers steadily increases the lamellar d-spacings (d100), ultimately leading to a densely packed lamellar structure for PTIIGHD-Np. In addition, both H-PTIIGOD-Np and H-PTIIGDT-Np exhibit larger π-stacking crystallites than the corresponding low-Mn polymers, while for PTIIGHD-Np, their size increases in the low-Mn batch. Ultimately, L-PTIIGHD-Np shows the best hole mobility of 1.87 cm2 V-1 s-1 in top-gate and bottom-contact organic field-effect transistors (OFETs) with a poly(methyl methacrylate), which is nearly 1 order of magnitude higher than other polymers tested in this study. Our results demonstrate that the simultaneous Mn and alkyl substituent engineering of the polymers can optimize their film morphology to produce high-performance OFETs.

A dithienodisilacyclohexadiene (DTDS)-based conjugated model semiconductor: understanding unique features and monitoring structural transition

To enable a superior σ*–π* conjugation, we present a dithienodisilacyclohexadiene (DTS) analogue of DTS(FBTTh2)2 – namely, DTDS(FBTTh2)2 – by replacing dithienosilole (DTS) with a dithienodisilacyclohexadiene (DTDS) ring in the main backbone, where DTDS possesses a double silicon-bridged bithiophene (Si–Si). With this replacement, a blue shift of the absorption and a high-lying LUMO are observed. Disclosed herein is a structural change of DTDS(FBTTh2)2 (DTDS to ox-DTDS skeleton as the corresponding oxidation structure) occurring under ambient conditions, which is monitored by real-time 1H NMR and UV absorption methods. This work not only provides a full understanding of the nature of DTDS, but also uses unique DTDS chemistry as a new toolbox to develop systems as novel functionality materials.

Ultrafast Channel II process induced by a 3-D texture with enhanced acceptor order ranges for high-performance non-fullerene polymer solar cells

To achieve efficient non-fullerene polymer solar cells (NF-PSCs), an in-depth understanding of the key properties that govern the power output is necessary. Herein, three trialkylsilyl substituted benzodithiophene-based polymer donors (PJ1, PJ2, and PJ3) were synthesized with fine-tuning of the highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) and optical absorption. Using the polymer series paired with absorption-complementary small molecular acceptors (SMAs), namely, m-ITIC, IDIC, and AIDIC, we systematically studied the performance of a 3 × 3 matrix of NF-PSCs. An increasing open-circuit voltage with deepening HOMOs of the polymer donors, and the enhanced short-circuit current (JSC) and fill factor (FF) were ascribed to the well-intermixed blend morphology containing enhanced SMA order ranges with mixed face-on and edge-on orientations, the so-called 3-D texture. Such an optimal microstructure is best exemplified in the PJ2:IDIC combination, affording a highest efficiency of 12.01% with a simultaneously high JSC of 17.0 mA cm−2 and FF of 75.3%. The devices with an active layer thickness of 300 nm still maintain an impressive efficiency approaching 10% with a decent FF of 60.0%. Moreover, the Channel II process, i.e., photoinduced hole transfer through acceptor excitation, was demonstrated to be crucially important for photocurrent generation. This study highlights the importance of optimizing the trade-off between charge separation/transport and domain size to achieve high-performance NF-PSCs.