All-Polymer Solar Cells with 3.3% Efficiency Based on Naphthalene Diimide-Selenophene Copolymer Acceptor

The lack of suitable acceptor (n-type) polymers has limited the photocurrent and efficiency of polymer/polymer bulk heterojunction (BHJ) solar cells. Here, we report an evaluation of three naphthalene diimide (NDI) copolymers as electron acceptors in BHJ solar cells which finds that all-polymer solar cells based on an NDI-selenophene copolymer (PNDIS-HD) acceptor and a thiazolothiazole copolymer (PSEHTT) donor exhibit a record 3.3% power conversion efficiency. The observed short circuit current density of 7.78 mA/cm² and external quantum efficiency of 47% are also the best such photovoltaic parameters seen in all-polymer solar cells so far. This efficiency is comparable to the performance of similarly evaluated [6,6]-Phenyl-C₆₁-butyric acid methyl ester (PC₆₀BM)/PSEHTT devices. The lamellar crystalline morphology of PNDIS-HD, leading to balanced electron and hole transport in the polymer/polymer blend solar cells accounts for its good photovoltaic properties

n‑Type Semiconducting Naphthalene Diimide-Perylene Diimide Copolymers: Controlling Crystallinity, Blend Morphology, and Compatibility Toward High-Performance All-Polymer Solar Cells

Knowledge of the critical factors that determine compatibility, blend morphology, and performance of bulk heterojunction (BHJ) solar cells composed of an electron-accepting polymer and an electron-donating polymer remains limited. To test the idea that bulk crystallinity is such a critical factor, we have designed a series of new semiconducting naphthalene diimide (NDI)-selenophene/perylene diimide (PDI)-selenophene random copolymers, <i>x</i>PDI (10PDI, 30PDI, 50PDI), whose crystallinity varies with composition, and investigated them as electron acceptors in BHJ solar cells. Pairing of the reference crystalline (crystalline domain size <i>L</i>_c = 10.22 nm) NDI-selenophene copolymer (PNDIS-HD) with crystalline (<i>L</i>_c = 9.15 nm) benzodithiophene-thieno­[3,4-<i>b</i>]­thiophene copolymer (PBDTTT-CT) donor yields incompatible blends, whose BHJ solar cells have a power conversion efficiency (PCE) of 1.4%. However, pairing of the new 30PDI with optimal crystallinity (<i>L</i>_c = 5.11 nm) as acceptor with the same PBDTTT-CT donor yields compatible blends and all-polymer solar cells with enhanced performance (PCE = 6.3%, <i>J</i>_sc = 18.6 mA/cm², external quantum efficiency = 91%). These photovoltaic parameters observed in 30PDI:PBDTTT-CT devices are the best so far for all-polymer solar cells, while the short-circuit current (<i>J</i>_sc) and external quantum efficiency are even higher than reported values for [70]-fullerene:PBDTTT-CT solar cells. The morphology and bulk carrier mobilities of the polymer/polymer blends varied substantially with crystallinity of the acceptor polymer component and thus with the NDI/PDI copolymer composition. These results demonstrate that the crystallinity of a polymer component and thus compatibility, blend morphology, and efficiency of polymer/polymer blend solar cells can be controlled by molecular design

Polymer/Polymer Blend Solar Cells Using Tetraazabenzodifluoranthene Diimide Conjugated Polymers as Electron Acceptors

Two n-type semiconducting polymers with alternating arylene (thiophene or selenophene)–tetraazabenzodifluoranthene diimide (BFI) donor–acceptor architecture have been investigated as new electron acceptors in polymer/polymer blend solar cells. The new selenophene-linked polymer, PBFI-S, has a significantly smaller optical band gap (1.13 eV) than the thiophene-linked PBFI-T (1.38 eV); however, both polymers have similar HOMO/LUMO energy levels determined from cyclic voltammetry. Blends of PBFI-T with the thiazolothiazole–dithienylsilole donor polymer (PSEHTT) gave a 2.60% power conversion efficiency (PCE) with a 7.34 mA/cm² short-circuit current. In contrast, PBFI-S:PSEHTT blends had a 0.75% PCE with similarly reduced photocurrent and external quantum efficiency. Reduced free energy for charge transfer and reduced bulk electron mobility in PBFI-S:PSEHTT blends compared to PBFI-T:PSEHTT blends as well as significant differences in bulk film morphology are among the reasons for the large loss in efficiency in PBFI-S:PSEHTT blend solar cells

Beyond Fullerenes: Design of Nonfullerene Acceptors for Efficient Organic Photovoltaics

New electron-acceptor materials are long sought to overcome the small photovoltage, high-cost, poor photochemical stability, and other limitations of fullerene-based organic photovoltaics. However, all known nonfullerene acceptors have so far shown inferior photovoltaic properties compared to fullerene benchmark [6,6]-phenyl-C₆₀-butyric acid methyl ester (PC₆₀BM), and there are as yet no established design principles for realizing improved materials. Herein we report a design strategy that has produced a novel multichromophoric, large size, nonplanar three-dimensional (3D) organic molecule, DBFI-T, whose π-conjugated framework occupies space comparable to an aggregate of 9 [C₆₀]-fullerene molecules. Comparative studies of DBFI-T with its planar monomeric analogue (BFI-P2) and PC₆₀BM in bulk heterojunction (BHJ) solar cells, by using a common thiazolothiazole-dithienosilole copolymer donor (PSEHTT), showed that DBFI-T has superior charge photogeneration and photovoltaic properties; PSEHTT:DBFI-T solar cells combined a high short-circuit current (10.14 mA/cm²) with a high open-circuit voltage (0.86 V) to give a power conversion efficiency of 5.0%. The external quantum efficiency spectrum of PSEHTT:DBFI-T devices had peaks of 60–65% in the 380–620 nm range, demonstrating that both hole transfer from photoexcited DBFI-T to PSEHTT and electron transfer from photoexcited PSEHTT to DBFI-T contribute substantially to charge photogeneration. The superior charge photogeneration and electron-accepting properties of DBFI-T were further confirmed by independent Xenon-flash time-resolved microwave conductivity measurements, which correctly predict the relative magnitudes of the conversion efficiencies of the BHJ solar cells: PSEHTT:DBFI-T > PSEHTT:PC₆₀BM > PSEHTT:BFI-P2. The results demonstrate that the large size, multichromophoric, nonplanar 3D molecular design is a promising approach to more efficient organic photovoltaic materials