ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Figure 1Loading Img

Structural Characterization of Highly Oriented Naphthalene-Diimide-Bithiophene Copolymer Films via Vibrational Spectroscopy

View Author Information
Center for NanoScience and Technology CNST, [email protected], via Pascoli 70/3, 20133 Milano, Italy
Dipartimento di Chimica, Materiali e Ing. Chimica, CMIC, “G. Natta”, Politecnico di Milano, p.zza Leonardo da Vinci, 20133 Milano, Italy
§ Max-Planck-Institut für Kohlenforschung (MPI-KOFO), Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
Institute for Macromolecular Chemistry, University of Freiburg, Stefan-Meier-Strasse 31, 79104 Freiburg, Germany
Institut Charles Sadron, CNRS − Université de Strasbourg, 23 Rue du Loess, 67034 Strasbourg, France
Cite this: J. Phys. Chem. B 2015, 119, 5, 2062–2073
Publication Date (Web):January 7, 2015
Copyright © 2015 American Chemical Society

Article Views





Read OnlinePDF (5 MB)
Supporting Info (1)»


Abstract Image

Epitaxially grown highly oriented crystalline films, named form I and form II, and spin-coated films of poly{[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)}, P(NDI2OD-T2), have been investigated through infrared vibrational spectroscopy techniques (infrared absorption in double transmission at normal incidence (IRA-TR) and reflection absorption infrared spectroscopy at grazing angle incidence (RAIRS)) to get access to polymer chain orientation and structure. An analytic model to correlate the experimental intensities of the IR bands with structural parameters has been developed and applied for the three film morphologies. While spin-coated and form I films show P(NDI2OD-T2) chains lying parallel to the substrate in the face-on arrangement, form II films feature a structure with chains tilted out from the surface. The combined experimental and theoretical methodology gives insights into the local molecular orientations of naphthalene diimide (NDI2OD) and bithiophene (T2) counits. This approach can be easily extended to a variety of organic polymer semiconductors, allowing one to directly correlate molecular structure to properties such as charge transport, which is of fundamental relevance for developing quantitative models for applications in organic electronics and photovoltaics.

Supporting Information

Jump To

Derivation of the analytical expressions of relative infrared absorption intensities of C═O stretchings (a and b bands) (S1) and of OPLA (c band) (S2) in IRA-TR and RAIRS experiments; sketches of regular polymer structures (S3). This material is available free of charge via the Internet at

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

Cited By

This article is cited by 17 publications.

  1. Sichun Wang, Hongxiang Li, Kefeng Zhao, Lu Zhang, Qiang Zhang, Xinhong Yu, Hongkun Tian, Yanchun Han. Increasing the Charge Transport of P(NDI2OD-T2) by Improving the Polarization of the NDI2OD Unit along the Backbone Direction and Preaggregation via H-Bonding. Macromolecules 2022, 55 (7) , 2497-2508.
  2. Ilaria Denti, Simone Cimò, Luigi Brambilla, Alberto Milani, Chiara Bertarelli, Matteo Tommasini, Chiara Castiglioni. Polaron Confinement in n-Doped P(NDI2OD-T2) Unveiled by Vibrational Spectroscopy. Chemistry of Materials 2019, 31 (17) , 6726-6739.
  3. Yannic M. Gross, Daniel Trefz, Carsten Dingler, Daniel Bauer, Vishnu Vijayakumar, Viktoriia Untilova, Laure Biniek, Martin Brinkmann, Sabine Ludwigs. From Isotropic to Anisotropic Conductivities in P(NDI2OD-T2) by (Electro-)Chemical Doping Strategies. Chemistry of Materials 2019, 31 (9) , 3542-3555.
  4. Jack T. Ly, Edmund K. Burnett, Simil Thomas, Areej Aljarb, Yao Liu, Soohyung Park, Stephen Rosa, Yeonjin Yi, Hyunbok Lee, Todd Emrick, Thomas P. Russell, Jean-Luc Brédas, Alejandro L. Briseno. Efficient Electron Mobility in an All-Acceptor Napthalenediimide-Bithiazole Polymer Semiconductor with Large Backbone Torsion. ACS Applied Materials & Interfaces 2018, 10 (46) , 40070-40077.
  5. Mohammad Al Kobaisi , Sidhanath V. Bhosale , Kay Latham , Aaron M. Raynor , and Sheshanath V. Bhosale . Functional Naphthalene Diimides: Synthesis, Properties, and Applications. Chemical Reviews 2016, 116 (19) , 11685-11796.
  6. Chi-Feng Huang, San-Lien Wu, Yi-Fan Huang, Ying-Cheng Chen, Shu-Ting Chang, Tzu-Yi Wu, Kuan-Yi Wu, Wei-Tsung Chuang, and Chien-Lung Wang . Packing Principles for Donor–Acceptor Oligomers from Analysis of Single Crystals. Chemistry of Materials 2016, 28 (15) , 5175-5190.
  7. Arthur Markus Anton, Robert Steyrleuthner, Wilhelm Kossack, Dieter Neher, and Friedrich Kremer . Spatial Orientation and Order of Structure-Defining Subunits in Thin Films of a High Mobility n-Type Copolymer. Macromolecules 2016, 49 (5) , 1798-1806.
  8. Jun Yin, Zilong Wang, Daniele Fazzi, Zexiang Shen, and Cesare Soci . First-Principles Study of the Nuclear Dynamics of Doped Conjugated Polymers. The Journal of Physical Chemistry C 2016, 120 (3) , 1994-2001.
  9. Clemens Matt, Rukiya Matsidik, Deborah L. Meyer, Mirjam Schröder, Michael Sommer, Till Biskup. Know your building blocks: Time-resolved EPR spectroscopy reveals NDI-T2 and not T-NDI-T to resemble the electronic structure of PNDIT2. Organic Electronics 2023, 117 , 106790.
  10. Xuhao Luo, Yingying Xue, Juntao Wu, Wanzhu Cai, Daniela Täuber, Ivan Malovicho, Bogdan Sava, Guobiao Cen, Xing Lu, Chuanxi Zhao, Ivan G. Scheblykin, Jianhui Yu, Wenjie Mai, Feng Liu, Ergang Wang, Lintao Hou. Intrinsic polarization-sensitive organic photodetector with self-assembled all-polymer heterojunction. Applied Physics Letters 2022, 121 (23) , 233301.
  11. Yannic M. Gross, Sabine Ludwigs. P(NDI2OD-T2) revisited – Aggregation control as key for high performance n-type applications. Synthetic Metals 2019, 253 , 73-87.
  12. Jana Zaumseil. Semiconducting Single-Walled Carbon Nanotubes or Very Rigid Conjugated Polymers: A Comparison. Advanced Electronic Materials 2019, 5 (2) , 1800514.
  13. Dongyoon Khim, Alessandro Luzio, Giorgio Ernesto Bonacchini, Giuseppina Pace, Mi-Jung Lee, Yong-Young Noh, Mario Caironi. Uniaxial Alignment of Conjugated Polymer Films for High-Performance Organic Field-Effect Transistors. Advanced Materials 2018, 30 (20) , 1705463.
  14. Deborah L. Meyer, Rukiya Matsidik, Michael Sommer, Till Biskup. Electronic Structure Trumps Planarity: Unexpected Narrow Exciton Delocalization in PNDIT2 Revealed by Time-Resolved Electron Paramagnetic Resonance (EPR) Spectroscopy. Advanced Electronic Materials 2018, 4 (3) , 1700385.
  15. Steven J. Brown, Ruth A. Schlitz, Michael L. Chabinyc, Jon A. Schuller. Morphology-dependent optical anisotropies in the n -type polymer P(NDI2OD-T2). Physical Review B 2016, 94 (16)
  16. Daniele Fazzi, Mario Caironi. Multi-length-scale relationships between the polymer molecular structure and charge transport: the case of poly-naphthalene diimide bithiophene. Physical Chemistry Chemical Physics 2015, 17 (14) , 8573-8590.
  17. Rui Xin, Jie Zhang, Xiaoli Sun, Huihui Li, Zhaobin Qiu, Shouke Yan. Epitaxial Effects on Polymer Crystallization. 2015, 55-94.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Your Mendeley pairing has expired. Please reconnect