Subtle Side Chain Triggers Unexpected Two-Channel Charge Transport Property Enabling 80% Fill Factors and Efficient Thick-Film Organic Photovoltaics.

To clearly show how important the impact of side chains on organic solar cells (OSCs) is, we designed three acceptors IDIC-CxPh (x = 4, 5, or 6) via subtle side-chain regulation. Despite this small change, significant distinctions were detected. IDIC-C4Ph devices achieve an optimal efficiency of 13.94% under thermal annealing, but thermal-assistant solvent-vapor annealing hugely suppresses the efficiencies to 10%. However, the C6Ph side chain endows extremely disordered stacking orientations, generating moderate efficiencies of ~12.50%. Excitingly, the IDIC-C5Ph affords an unexpected two-channel π-π charge transport (TCCT) property, boosting the fill factor (FF) by up to 80.02% and efficiency to 14.56%, ranking the best among five-ring fused-ladder-type acceptors. Impressively, the special TCCT behavior of IDIC-C5Ph enables 470 nm thick-film OSC with a high FF of up to 70.12% and efficiency of 13.01%, demonstrating the great promise in fabricating large-scale OSCs.

Appropriate Molecular Interaction Enabling Perfect Balance Between Induced Crystallinity and Phase Separation for Efficient Photovoltaic Blends.

Fluorination is a promising modification method to adjust the photophysical profiles of organic semiconductors. Notably, the fluorine modification on donor or acceptor materials could impact the molecular interaction, which is strongly related to the morphology of bulk heterojunction (BHJ) blends and the resultant device performance. Therefore, it is essential to investigate how the molecular interaction affects the morphology of BHJ films. In this study, a new fluorinated polymer PBDB-PSF is synthesized to investigate the molecular interaction in both nonfluorinated (ITIC) and fluorinated (IT-4F) systems. The results reveal that the F-F interaction in the PBDB-PSF:IT-4F system could effectively induce the crystallization of IT-4F while retaining the ideal phase separation scale, resulting in outstanding charge transport. On the contrary, poor morphology can be observed in the PBDB-PSF:ITIC system because of the unbalanced molecular interaction. As a consequence, the PBDB-PSF:IT-4F device delivers an excellent power conversion efficiency of 13.63%, which greatly exceeds that of the PBDB-PSF:ITIC device (9.84%). These results highlight manipulating the micromorphology with regard to molecular interaction.

Significantly Enhanced Molecular Stacking in Ternary Bulk Heterojunctions Enabled by an Appropriate Side Group on Donor Polymer.

Ternary strategy is a promising approach to broaden the photoresponse of polymer solar cells (PSCs) by adopting combinatory photoactive blends. However, it could lead to a more complicated situation in manipulating the bulk morphology. Achieving an ideal morphology that enhances the charge transport and light absorption simultaneously is an essential avenue to promote the device performance. Herein, two polymers with different lengths of side groups (P1 is based on phenyl side group and P2 is based on biphenyl side group) are adopted in the dual-acceptor ternary systems to evaluate the relationship between conjugated side group and crystalline behavior in the ternary system. The P1 ternary system delivers a greatly improved power conversion efficiency (PCE) of 13.06%, which could be attributed to the intense and broad photoresponse and improved charge transport originating from the improved crystallinity. Inversely, the P2 ternary device only exhibits a poor PCE of 8.97%, where the decreased device performance could mainly be ascribed to the disturbed molecular stacking of the components originating from the overlong conjugated side group. The results demonstrate a conjugated side group could greatly determine the device performance by tuning the crystallinity of components in ternary systems.

Size Effect of Two-Dimensional Conjugated Space in Photovoltaic Polymers' Side Chain: Balancing Phase Separation and Charge Transport.

Various two-dimensional (2D) side-chain-substituted benzo(1,2-b:4,5-b')dithiophene (BDT) blocks have been used to construct donor polymers, whereas the size effect of the side chains on the photovoltaic performance was overlooked in the past few years. In this work, three size-varied conjugated spaces (benzene, naphthalene, and biphenyl) were introduced into the corresponding polymers PBDB-Ph, PBDB-Na, and PBDB-BPh. This space engineering has a significant impact on the extent of phase separation in the active layer which blended with the polymer and the acceptor ITCPTC and preserved the desired morphology. The varied space size in the side chains lead to distinct balance mobility ratios of holes to electrons (benzene, 0.21; naphthalene, 0.75; and biphenyl, 0.57). Finally, PBDB-Na-based polymer solar cells (PSCs) delivered the highest power conversion efficiency of 12.52% when compared to the PSC performances of PBDB-Ph (8.48%) and PBDB-BPh (11.35%). The method in tailoring the side chain structures could fabricate a balance between phase separation and charge transport, providing an enlightenment for the development of photovoltaic devices.

Regulation of Molecular Packing and Blend Morphology by Finely Tuning Molecular Conformation for High-Performance Nonfullerene Polymer Solar Cells.

The asymmetric thienobenzodithiophene (TBD) structure is first systematically compared with the benzo[1,2-b:4,5-b']dithiophene (BDT) and dithieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene (DTBDT) units in donor-acceptor (D-A) copolymers and applied as the central core in small molecule acceptors (SMAs). Specific polymers including PBDT-BZ, PTBD-BZ, and PDTBDT-BZ with different macromolecular conformations are synthesized and then matched with four elaborately designed acceptor-donor-acceptor (A-D-A) SMAs with structures comparable to their donor counterparts. The resulting polymer solar cell performance trends are dramatically different from each other and highly material-dependent, and the active layer morphology is largely governed by polymer conformation. Because of its more linear backbone, the PTBD-BZ film has higher crystallinity and more ordered and denser π-π stacking than those of the PBDT-BZ and PDTBDT-BZ films. Thus, PTBD-BZ shows excellent compatibility with and strong independence on the SMAs with varied structures, and PTBD-BZ-based cells deliver high power conversion efficiency (PCE) of 10-12.5%, whereas low PCE is obtained by cells based on PDTBDT-BZ because of its zigzag conformation. Overall, this study reveals control of molecular conformation as a useful approach to modulate the photovoltaic properties of conjugated polymers.

Revealing the Position Effect of an Alkylthio Side Chain in Phenyl-Substituted Benzodithiophene-Based Donor Polymers on the Photovoltaic Performance of Non-Fullerene Organic Solar Cells.

In this work, position effects of an alkylthio side chain were investigated by designing and synthesizing two copolymers based on a phenyl-substituted benzo[1,2-b:4,5-b']dithiophene (BDTP) and difluorobenzotriazole (FTAZ). The polymer based on the meta-position-alkylthiolated BDTP, named m-PBDTPS-FTAZ, showed a relatively broader bandgap (2.00 vs 1.96 eV) and lower highest occupied molecular orbital (HOMO) energy level (-5.40 vs -5.32 eV) than its para-positioned structural isomeric analogue polymer (named p-PBDTPS-FTAZ), that is, m- and p-PBDTPS-FTAZ with the side chain structured as ethylhexyl- in the phenyl unit and hexyldecyl- in the FTAZ moiety. When blended with ITIC, m-PBDTPS-FTAZ showed a comparable crystallinity but more uniform morphology compared to that of p-PBDTPS-FTAZ. A high power conversion efficiency of 13.16% was achieved for m-PBDTPS-FTAZ:ITIC devices with a high open circuit voltage (VOC) of 0.95 V, which is higher than that of p-PBDTPS-FTAZ:ITIC devices (10.86%) with a VOC of 0.89 V. Therefore, m-BDTPS could be an effective donor unit to construct high-efficiency polymers due to its effectively decreased HOMO energy level of polymers while still maintaining good molecular stacking.

Steady Enhancement in Photovoltaic Properties of Fluorine Functionalized Quinoxaline-Based Narrow Bandgap Polymer.

To investigate the influence of fluoride phenyl side-chains onto a quinoxaline (Qx) unit on the photovoltaic performance of the narrow bandgap (NBG) photovoltaic polymers, herein, two novel NBG copolymers, PBDTT-DTQx and PBDTT-DTmFQx, were synthesized and characterized. 2-ethylhexylthiothiophene-substituted benzodithiophene (BDTT), 2,3-diphenylquinoxaline (DQx) [or 2,3-bis(3-fluorophenyl)quinoxaline (DmFQx)] and 2-ethylhexylthiophene (T) were used as the electron donor (D) unit, electron-withdrawing acceptor (A) unit and π-bridge, respectively. Compared to non-fluorine substituted PBDTT-DTQx, fluoride PBDTT-DTmFQx exhibited a wide UV-Vis absorption spectrum and high hole mobility. An enhanced short-circuit current (Jsc) and fill factor (FF) simultaneously gave rise to favorable efficiencies in the polymer/PC71BM-based polymer solar cells (PSCs). Under the illumination of AM 1.5G (100 mW cm-2), a maximum power conversion efficiency (PCE) of 6.40% was achieved with an open-circuit voltage (Voc) of 0.87 V, a Jsc of 12.0 mA cm-2 and a FF of 61.45% in PBDTT-DTmFQx/PC71BM-based PSCs, while PBDTT-DTQx-based devices also exhibited a PCE of 5.43%. The excellent results obtained demonstrate that PBDTT-DTmFQx by fluorine atom engineering could be a promising candidate for organic photovoltaics.

Side-Chain-Promoted Benzodithiophene-based Conjugated Polymers toward Striking Enhancement of Photovoltaic Properties for Polymer Solar Cells.

In this work, we have reported a highly efficient photovoltaic material, PBDTTz-SBP, by fine-tuning the side chains of the benzodithiophene (BDT) unit. With the replacement of alkoxy chains with alkylthio chains, a large increase in power conversion efficiency (PCE) was realized. Non-fullerene polymer solar cells (PSCs) without any post-treatment generate an optimal PCE of up to 12.09%, with a high VOC of 0.914 V, JSC of 18.52 mA cm-2, and fill factor of 71.43%. Notably, the efficiency of a PBDTTz-SBP-based solar cell was about 1.31-fold of the PCE (9.20%) of its counterpart based on the polymer, PBDTTz-BP, with alkoxy chains, indicating the striking modulation effect of side-chain engineering. Although VOC and JSC were lower than those of non-fullerene devices, the PSCs with PC71BM as the acceptor exhibited a fairly high fill factor of up to 76.69%, affording a moderate PCE. Our work reported a highly efficient polymer solar cell with a PCE of 12.09% and clearly demonstrated the great tuning effect of alkylthio chains on photovoltaic performance.

Pyran-Bridged Indacenodithiophene as a Building Block for Constructing Efficient A-D-A-Type Nonfullerene Acceptors for Polymer Solar Cells.

In recent years, nonfullerene acceptors have attracted much attention, owing to their great potential for use in high-performance polymer solar cells.The ladder-type building block, pyran-bridged indacenodithiophene (PDT), was used for constructing A-D-A nonfullerene acceptors through introduction of oxygen atoms into an indacenodithiophene (IDT) unit. The synthesis of PDT is accomplished by a BBr3 -mediated tandem cyclization-deprotection reaction to construct the pyran ring. Hence, molecular acceptor PTIC was synthesized and used in a polymer solar cell device. Compared to the IDT-based acceptor, PTIC exhibits higher HOMO levels and wider optical band gap at 550-800 nm. Devices fabricated with poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene)-co-(1,3-di(5-thiophene-2-yl)-5,7-bis(2-ethylhexyl)-benzo[1,2-c:4,5-c']dithiophene-4,8-dione)] (PBDB-T):PTIC as the active layer give a power conversion efficiency (PCE) of 7.66 %.

Unsubstituted Benzodithiophene-Based Conjugated Polymers for High-Performance Organic Field-Effect Transistors and Organic Solar Cells.

Unsubstituted benzo[1,2-b:4,5-b']dithiophene (BDT) was used to construct a high-performance conjugated polymer with 5,6-difluoro-4,7-bis[4-(2-octyldodecyl)thiophene-2-yl]benzo[c][1,2,5] thiadiazole (DTFFBT), named PBDT-DTFFBT. The polymer shows the low-lying highest occupied molecular orbital (HOMO) energy level (-5.40 eV) and a broad absorption spectra with strong vibronic absorption peak. Pure polymer films exhibit good crystallinity and edge-on orientation, partially attributed to the BDT units without any side chains, and as a result, the corresponding thin-film transistor showed excellent hole mobility over 1 cm(2) V(-1) s(-1). Interestingly, a well-distributed nanofibrillar polymer aggregation with face-on orientation was obviously formed when blending with PC71BM, which was in favor of the charge transportation. Consequently, the bulk heterojunction polymer solar cells based on the blends showed high power conversion efficiency of 9.29% with large short-current density (14.56 mA cm(-2)) and high fill factor (0.751) without any process additives or thermal annealing.