Spectroscopic Investigation into P(NDI2OD-T2) Charge Localization
- University of Colorado Boulder
- National Renewable Energy Lab., Golden, CO (United States)
- University of Arizona
- Stanford University
- Diamond Light Source
P(NDI2OD-T2), commonly referred to as N2200, stands out as a promising electron-transporting (n-type) polymer for low-cost, flexible (photo)electrochemical applications due to its reversible two-electron reduction and high electron mobility. UV-vis spectroelectrochemistry in the tetrabutyl ammonium hexafluorophosphate/acetonitrile electrolyte shows two sets of chemically reversible redox signals in the cyclic voltammetry corresponding to the reduction of the neutral polymer film to polaronic and bipolaronic species. These electrochemical signatures suggest a distinct electronic reorganization upon reduction (polaron/bipolaron formation), highlighting the need for molecular-level insights into how charges are accommodated within the polymer backbone. While it has been previously hypothesized that charge predominantly localizes on the naphthalene diimide (NDI) unit during reductive charging, specific changes in atomic environments that confirm this localization have not been characterized in n-type polymers. Herein, we use near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to probe electronic transitions in an electrochemically charged polymer to deduce charge localization. The O K-edge (1s) spectra exhibit two distinct pi* peaks; the intensity of the lower-energy pi*a peak that corresponds to an excitation to a largely localized carbonyl state decreases with reductive potentials relative to the higher-energy pi*b peak. We corroborate this with Raman spectroscopy at different potentials, which shows a decrease in intensity on the C-C/C==C and C==O stretching bands of NDI as well as a red shift of the carbonyl band due to the formation of a polaron on the NDI. Additionally, new Raman active NDI signals associated with elongated C==O and C==C bonds are observed at lower energy during the formation of charged states. Together with theoretical calculations, these findings show that the injected charge spatially localizes on the NDI units and is dominantly distributed on the carbonyl groups. The combination of NEXAFS, optical and vibrational spectroscopies, and theoretical calculations is generalizable to other pi-conjugated polymers and can identify charge localization for the further development of organic semiconductors.
- Research Organization:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- DOE Contract Number:
- AC36-08GO28308
- OSTI ID:
- 3011907
- Report Number(s):
- NREL/JA-5900-93731
- Journal Information:
- Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 19 Vol. 37
- Country of Publication:
- United States
- Language:
- English
Similar Records
Polymorphs of the n–Type Polymer P(NDI2OD–T2): A Comprehensive Description of the Impact of Processing on Crystalline Morphology and Charge Transport