Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 141, Issue 7, Pages 3274-3287Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b13653
Keywords
-
Categories
Funding
- Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0001059]
- U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences [DE-FG02-08ER46.536]
- AFOSR [FA9550-18-1-0320]
- Northwestern University Materials Research Science and Engineering Center under NSF [DMR-1720139]
- U.S. Department of Commerce, National Institute of Standards and Technology as part of the Center for Hierarchical Materials Design (CHiMaD) [70NANB14H012]
- Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource [NSF ECCS-1542205, NSF NNCI-1542205]
- National Science Foundation (NSF) [NSF CHE-1048773]
- State of Illinois
- International Institute for Nano technology (IIN)
- U.S. DOE [DE-AC02-06CH11357]
- NSF
- Northwestern University
Ask authors/readers for more resources
Indacenodithienothiophene (IDTT)-based postfullerene electron acceptors, such as ITIC (2,2'-[[6,6,12,12-tetrakis (4-hexylphenyl)-6,12-dihydrodithie no [2,3-d:2',3'-d']-s-indaceno [1,2-b:5,6-b']dithiophene-2,8-diyl]-bis-[methylidyne(3-oxo-1H-indene-2,1 (3H)-diylidene) This[propanedinitrile]), have become synonymous with high power conversion efficiencies (PCEs) in bulk heterojunction (BHJ) polymer solar cells (PSCs). Here we systematically investigate the influence of end-group fluorination density and positioning on the physicochemical properties, single-crystal packing, end-group redistribution propensity, and BHJ photovoltaic performance of a series of ITIC variants, ITIC-nF (n = 0, 2, 3, 4, and 6). Increasing n from 0 -> 6 contracts the optical bandgap, but only marginally lowers the LUMO for n > 4. This yields enhanced photovoltaic short-circuit current density and good open-circuit voltage, so that ITIC-6F achieves the highest PCE of the series, approaching 12% in blends with the PBDB-TF donor polymer. Single-crystal diffraction reveals that the ITIC-nF molecules cofacially interleave with ITIC-6F having the shortest pi-pi distance of 3.28 angstrom. This feature together with ZINDO-level computed intermolecular electronic coupling integrals as high as 57 meV, and B3LYP/DZP-level reorganization energies as low as 147 meV, rival or surpass the corresponding values for fullerenes, ITIC-OF, and ITIC-4F, and track a positive correlation between the ITIC-nF space-charge limited electron mobility and n. Finally, a heretofore unrecognized solution-phase redistribution process between the 2-(3-oxoindan-1-ylidene)-malononitrile-derived end-groups (EGs) of IDTT-based NFAs, i.e., EG(1)-IDTT-EG(1) + EG(2)-IDTT-EG(2) reversible arrow 2 EG(1)-IDTT-EG(2), with implications for the entire ITIC PSC field, is identified and mechanistically characterized, and the effects on PSC performance are assessed.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available