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Charge transfer properties of diphenyl substituted cyclopentadithiophene organic semiconductors: The role of fluorine and malononitrile substitutions and crystal ordering

Journal Article · · Organic Electronics
 [1];  [2];  [3]
  1. Hubei Univ., Wuhan (China). Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials. Ministry-of-Education Key Lab. for the Synthesis and Application of Organic Functional Molecules. College of Chemistry and Chemical Engineering; Univ. of Massachusetts, Amherst, MA (United States). Dept. of Polymer Science and Engineering; DOE/OSTI
  2. Univ. of Massachusetts, Amherst, MA (United States). Dept. of Polymer Science and Engineering. Dept. of Chemistry
  3. Univ. of Massachusetts, Amherst, MA (United States). Dept. of Chemical Engineering
+ Show Author Affiliations
The geometry and electronic structures of four cyclopentadithiophene (CPD) derivatives in their crystals are systematically studied through density functional theory (DFT) calculations. The factors influencing the CPDs' semiconductor nature and charge carrier mobility are analyzed in detail, revealing the different roles of fluorine and dicyanomethylene in the CPDs examined in this study. Malononitrile substitutions show a large effect in lowering the molecular LUMO energy level but induce a smaller charge transfer integral due to the resulting reduced crystal order caused by the resulting steric hindrance. In comparison, although F substitution lowers the LUMO level more weakly than C(CN)2 substitution, it allows the molecule to retain a more planar configuration with more orbital delocalization, and the crystals of the F substituted compounds are more ordered than those of the C(CN)2 substituted compounds. Overall, this comparison can explain why F substitution is a more effective method to cause a transition of a p-type semiconductor to n-type. Crystal ordering plays a significant role in determining the charge transfer mobility in devices. In spite of the advantage offered by dicyanomethylene substitution in terms of charge injection barrier compared to fluorine substitution, the reduced crystal order caused by C(CN)2 limits the charge transfer in CPDs with C(CN)2 substitution. The validity of these findings can be generalized, which is expected to contribute to the rational design of n-type semiconductors based on CPDs.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Polymer-Based Materials for Harvesting Solar Energy (PHaSE); Univ. of Massachusetts, Amherst, MA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001087
OSTI ID:
1538697
Alternate ID(s):
OSTI ID: 1549628
Journal Information:
Organic Electronics, Journal Name: Organic Electronics Vol. 50; ISSN 1566-1199
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
HOMO-LUMO control
charge transfer
cyclopentadithiophene
density functional theory
random-walk charge transfer simulation