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      Artificial light-harvesting n-type porphyrin for panchromatic organic photovoltaic devices†

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          We developed a novel NIR-harvesting n-type porphyrin derivative, PDI–P Zn–PDI, that shows a low bandgap of 1.27 eV. Panchromatic absorption was extended to the NIR area with a significantly low energy loss of 0.54 eV which led to promising photovoltaic performance.


          A near-infrared-harvesting n-type porphyrin-based acceptor for organic photovoltaics (OPVs) was developed. The n-type acceptor, PDI–P Zn–PDI, was designed by connecting a zinc porphyrin (P Zn) core to two perylenediimide (PDI) wings through ethyne bridges. A narrow bandgap of 1.27 eV was achieved through the extended π-conjugation and intramolecular charge transfer between the strongly electron-donating P Zn core and the electron-accepting PDI wings. A bulk heterojunction (BHJ) structured photovoltaic device fabricated from PDI–P Zn–PDI with PTB7-Th exhibited panchromatic photon-to-current conversion from 350 to 900 nm. A power conversion efficiency of 5.25% with a remarkably low E loss of 0.54 eV was achieved by optimizing the nanomorphology of the BHJ films by adding pyridine and by controlling the ZnO/BHJ interfacial properties.

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          Most cited references 35

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          Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers.

          Dye-sensitized solar cells have gained widespread attention in recent years because of their low production costs, ease of fabrication and tunable optical properties, such as colour and transparency. Here, we report a molecularly engineered porphyrin dye, coded SM315, which features the prototypical structure of a donor-π-bridge-acceptor and both maximizes electrolyte compatibility and improves light-harvesting properties. Linear-response, time-dependent density functional theory was used to investigate the perturbations in the electronic structure that lead to improved light harvesting. Using SM315 with the cobalt(II/III) redox shuttle resulted in dye-sensitized solar cells that exhibit a high open-circuit voltage VOC of 0.91 V, short-circuit current density JSC of 18.1 mA cm(-2), fill factor of 0.78 and a power conversion efficiency of 13%.
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            Lessons from nature about solar light harvesting.

            Solar fuel production often starts with the energy from light being absorbed by an assembly of molecules; this electronic excitation is subsequently transferred to a suitable acceptor. For example, in photosynthesis, antenna complexes capture sunlight and direct the energy to reaction centres that then carry out the associated chemistry. In this Review, we describe the principles learned from studies of various natural antenna complexes and suggest how to elucidate strategies for designing light-harvesting systems. We envisage that such systems will be used for solar fuel production, to direct and regulate excitation energy flow using molecular organizations that facilitate feedback and control, or to transfer excitons over long distances. Also described are the notable properties of light-harvesting chromophores, spatial-energetic landscapes, the roles of excitonic states and quantum coherence, as well as how antennas are regulated and photoprotected.
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              Integrated molecular, interfacial, and device engineering towards high-performance non-fullerene based organic solar cells.

              High-performance non-fullerene OSCs with PCEs of up to ca. 6.0% are demonstrated based on PBDTT-F-TT polymer and a molecular di-PBI acceptor through comprehensive molecular, interfacial, and device engineering. Impressive PCEs can also be retained in devices with relatively thick BHJ layer and processed through non-halogenated solvents, indicating these high-performance non-fullerene OSCs are promising for large-area printing applications.

                Author and article information

                Chem Sci
                Chem Sci
                Chemical Science
                Royal Society of Chemistry
                1 July 2017
                16 May 2017
                : 8
                : 7
                : 5095-5100
                [a ] Department of Chemistry , Kookmin University , 77 Jeongneung-ro, Seongbuk-gu , Seoul 02707 , Republic of Korea . Email: ihjung@ ; Email: syjang@
                [b ] Department of Chemistry , Yonsei University , 50 Yonsei-ro, Seodaemun-gu , Seoul , Republic of Korea . Email: wdjang@
                [c ] UNIST Central Research Facilities , School of Natural Science , Ulsan National Institute of Science and Technology (UNIST) , 50 UNIST-gil, Eonyang-eup, Ulju-gun , Ulsan , Republic of Korea
                [d ] Center for Molecular Modeling and Simulation , Korea Research Institute of Chemical Technology (KRICT) , 141 Gajeong-ro, Yuseong-gu , Daejeon , Republic of Korea
                Author notes

                ‡These authors contributed equally.

                This journal is © The Royal Society of Chemistry 2017

                This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License ( which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.



                †Electronic supplementary information (ESI) available: 1H and 13C NMR, MALDI-TOF-MS, TGA and PL spectra, SCLC graph and photovoltaic properties are provided in detail. See DOI: 10.1039/c7sc01275f


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