skip to main content


This content will become publicly available on March 2, 2019

Title: Intra-molecular Charge Transfer and Electron Delocalization in Non-fullerene Organic Solar Cells

Two types of electron acceptors were synthesized by coupling two kinds of electron-rich cores with four equivalent perylene diimides (PDIs) at the a position. With fully aromatic cores, TPB and TPSe have pi-orbitals spread continuously over the whole aromatic conjugated backbone, unlike TPC and TPSi, which contain isolated PDI units due to the use of a tetrahedron carbon or silicon linker. Density functional theory calculations of the projected density of states showed that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) for TPB are localized in separate regions of space. Further, the LUMO of TPB shows a greater contribution from the orbitals belonging to the connective core of the molecules than that of TPC. Overall, the properties of the HOMO and LUMO point at increased intra-molecular delocalization of negative charge carriers for TPB and TPSe than for TPC and TPSi and hence at a more facile intra-molecular charge transfer for the former. The film absorption and emission spectra showed evidences for the inter -molecular electron delocalization in TPB and TPSe, which is consistent with the network structure revealed by X-ray diffraction studies on single crystals of TPB. These features benefit the formation of charge transfer statesmore » and/or facilitate charge transport. Thus, higher electron mobility and higher charge dissociation probabilities under J sc condition were observed in blend films of TPB:PTB7-Th and TPSe:PTB7-Th than those in TPC:PTB7Th and TPSi:PTB7-Th blend films. As a result, the J sc and fill factor values of 15.02 mA/cm 2, 0.58 and 14.36 mA/cm 2, 0.55 for TPB- and TPSe-based solar cell are observed, whereas those for TPC and TPSi are 11.55 mA/cm 2, 0.47 and 10.35 mA/cm 2, 0.42, respectively.« less
ORCiD logo [1] ;  [2] ; ORCiD logo [3] ; ORCiD logo [2] ; ORCiD logo [2] ;  [4] ; ORCiD logo [2] ; ORCiD logo [4] ; ORCiD logo [4] ;  [4] ;  [2]
  1. Shantou Univ., Guangdong (China). Dept. of Chemistry, Key Lab. for Preparation and Application of Ordered Structural Materials of Guangdong Province
  2. Univ. of Chicago, IL (United States). Dept. of Chemistry, The James Franck Inst.
  3. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division, Inst. for Molecular Engineering; Univ. of Chicago, IL (United States). Inst. for Molecular Engineering
Publication Date:
Grant/Contract Number:
AC02-06CH11357; SC0001059; DMR-1263006; CHE-1346572
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 12; Journal ID: ISSN 1944-8244
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Country of Publication:
United States
25 ENERGY STORAGE; 14 SOLAR ENERGY; electron delocalization; intra-molecular charge transfer; non-fullerene electron acceptor; organic solar cell; perylene diimide
OSTI Identifier: