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Title: Quasi one-dimensional band dispersion and surface metallization in long-range ordered polymeric wires

Journal Article · · Nature Communications
DOI:https://doi.org/10.1038/ncomms10235· OSTI ID:1237642
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [4];  [5];  [6];  [6];  [7];  [7];  [8];  [9];  [10]
  1. Univ. de Lorraine/CNRS, Nancy (France)
  2. Institut National de la Recherche Scientifique (INRS), Varennes, QC (Canada); Institut de Recherches sur la Catalyse et l'Environnement de Lyon, Villeurbanne (France)
  3. Institut National de la Recherche Scientifique (INRS), Varennes, QC (Canada)
  4. Institut National de la Recherche Scientifique (INRS), Varennes, QC (Canada); Queensland Univ. of Technology, Queensland (Australia)
  5. Institut National de la Recherche Scientifique (INRS), Varennes, QC (Canada); Univ. of Electronic Science and Technology of China, Chengdu (China)
  6. Instituto di Struttura della Materia, Roma (Italy)
  7. L'Orme des Merisiers, Gif sur Yvette (France)
  8. Rensselaer Polytechnic Inst., Troy, NY (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  9. Rensselaer Polytechnic Inst., Troy, NY (United States)
  10. McGill Univ., Montreal QC (Canada)
+ Show Author Affiliations

We study the electronic structure of an ordered array of poly(para-phenylene) chains produced by surface-catalyzed dehalogenative polymerization of 1,4-dibromobenzene on copper (110). The quantization of unoccupied molecular states is measured as a function of oligomer length by scanning tunnelling spectroscopy, with Fermi level crossings observed for chains longer than ten phenyl rings. Angle-resolved photoelectron spectroscopy reveals a quasi-one-dimensional valence band as well as a direct gap of 1.15 eV, as the conduction band is partially filled through adsorption on the surface. Tight-binding modelling and ab initio density functional theory calculations lead to a full description of the organic band-structure, including the k-dispersion, the gap size and electron charge transfer mechanisms, highlighting a strong substrate-molecule interaction that drives the system into a metallic behaviour. In summary, we have fully characterized the band structure of a carbon-based conducting wire. This model system may be considered as a fingerprint of -conjugation of surface organic frameworks.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1237642
Journal Information:
Nature Communications, Vol. 7, Issue 26; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 81 works
Citation information provided by
Web of Science

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Cited By (16)

Photochemistry Highlights on On‐Surface Synthesis journal June 2019
Functionalized Graphdiyne Nanowires: On-Surface Synthesis and Assessment of Band Structure, Flexibility, and Information Storage Potential journal February 2018
Bloch Oscillations in Fibonacci lattices: polaron formation journal March 2019
On-surface synthesis of aligned functional nanoribbons monitored by scanning tunnelling microscopy and vibrational spectroscopy journal April 2017
Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures journal March 2017
Strain-induced skeletal rearrangement of a polycyclic aromatic hydrocarbon on a copper surface journal July 2017
Covalent on-surface polymerization journal January 2020
The role of halogens in on-surface Ullmann polymerization journal January 2017
Surface-mediated assembly, polymerization and degradation of thiophene-based monomers journal January 2019
An unexpected organometallic intermediate in surface-confined Ullmann coupling journal January 2019
Reversibility and intermediate steps as key tools for the growth of extended ordered polymers via on-surface synthesis journal February 2018
Finding the hidden valence band of N  =  7 armchair graphene nanoribbons with angle-resolved photoemission spectroscopy journal April 2018
Diacetylene Linked Anthracene Oligomers Synthesized by One-Shot Homocoupling of Trimethylsilyl on Cu(111) journal July 2018
Controlling a Chemical Coupling Reaction on a Surface: Tools and Strategies for On-Surface Synthesis journal March 2019
Π Band Dispersion along Conjugated Organic Nanowires Synthesized on a Metal Oxide Semiconductor journal April 2016
Tunable Band Alignment with Unperturbed Carrier Mobility of On-Surface Synthesized Organic Semiconducting Wires text January 2016

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