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Controlled n–Doping of Naphthalene Diimide–Based Two–Dimensional Polymers

Journal Article · · Advanced Materials
 [1];  [1];  [2];  [3];  [4];  [1];  [5];  [1];  [1];  [1];  [6];  [7];  [8];  [1];  [1];  [6];  [9];  [5];  [1];  [10] more »;  [4];  [7];  [10];  [4];  [1] « less
  1. Northwestern University, Evanston, IL (United States)
  2. Georgia Institute of Technology, Atlanta, GA (United States); Hunan Univ., Changsha (China)
  3. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
  4. Georgia Institute of Technology, Atlanta, GA (United States)
  5. Princeton University, NJ (United States)
  6. Argonne National Laboratory (ANL), Lemont, IL (United States)
  7. National Renewable Energy Laboratory (NREL), Golden, CO (United States); University of Colorado, Boulder, CO (United States)
  8. University of Arizona, Tucson, AZ (United States); CY Cergy Paris Univ. (France)
  9. Northwestern University, Evanston, IL (United States); Simpson Querrey Institute, and Chemistry of Life Processes Institute, Evanston, IL (United States)
  10. University of Arizona, Tucson, AZ (United States)
+ Show Author Affiliations

Two-dimensional polymers (2DPs) are promising as structurally well-defined, permanently porous, organic semiconductors. However, 2DPs are nearly always isolated as closed shell organic species with limited charge carriers, which leads to low bulk conductivities. Here, we enhance the bulk conductivity of two naphthalene diimide (NDI)-containing 2DP semiconductors by controllably n-doping the NDI units using cobaltocene (CoCp2). Optical and transient microwave spectroscopy reveals that both as-prepared NDI-containing 2DPs are semiconducting with sub-2 eV optical bandgaps and photoexcited charge-carrier lifetimes of tens of nanoseconds. Following reduction with CoCp2, both 2DPs largely retain their periodic structures and exhibit optical and electron-spin resonance spectroscopic features consistent with the presence of NDI-radical anions. Here, while the native NDI-based 2DPs are electronically insulating, maximum bulk conductivities of >10–4 S cm–1 are achieved by substoichiometric levels of n-doping. Density functional theory calculations show that the strongest electronic couplings in these 2DPs exist in the out-of-plane (π-stacking) crystallographic directions, which indicates that cross-plane electronic transport through NDI stacks is primarily responsible for the observed electronic conductivity. Taken together, this study underlines that controlled molecular doping is a useful approach to access structurally well-defined, paramagnetic, 2DP n-type semiconductors with measurable bulk electronic conductivities of interest for electronic or spintronic devices.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
Grant/Contract Number:
AC36-08GO28308; SC0019356; AC02-06CH11357; AC02-05CH11231
OSTI ID:
1836031
Alternate ID(s):
OSTI ID: 1845176
OSTI ID: 1905580
OSTI ID: 1923071
Report Number(s):
NREL/JA-5900-79759; MainId:36979; UUID:a3759a70-4481-4f2f-9c99-3195beb728aa; MainAdminID:63418
Journal Information:
Advanced Materials, Journal Name: Advanced Materials Journal Issue: 22 Vol. 34; ISSN 0935-9648
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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36 MATERIALS SCIENCE
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
conductive polymers
covalent organic frameworks
molecular doping
organic semiconductor
solar-photochemistry
time-resolved microwave conductivity
two-dimensional polymers