Electronic Structure of a Polydiacetylene Nanowire Fabricated on Highly Ordered Pyrolytic Graphite

Akai‐Kasaya, Megumi; Shimizu, Katsuya; Watanabe, Yu; Saitô, Akira; Aono, Masakazu; Kuwahara, Yuji

doi:10.1103/physrevlett.91.255501

Cited by 73 publications

(85 citation statements)

References 20 publications

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“…Chains up to 14 units long are formed and define a pð1 × 2Þ lattice, as shown by the green rectangle (see also SI Text). The average distance between EDOT-EDOT elements along the [1][2][3][4][5][6][7][8][9][10] direction is measured to be 3.57 AE 0.04 Å, which is consistent with the Cu(110) lattice constant (3.61 Å). These distances are ∼10% smaller than the gas-phase EDOT-EDOT separation of 3.963 Å (21) expected for the free polymer (which adopts an all-anti conformation in the gas phase).…”

Section: Resultssupporting

confidence: 61%

“…This binding leads to an adsorption energy of 5.38 eV, which is much larger than the adsorption energy of the thiophene C 4 H 4 S on Cu (110) (0.50 eV), which adsorbs in a virtually planar orientation (28). This strong binding to the surface and the large separation between the monomers (5.12 Å) prevents polymerization along the [1][2][3][4][5][6][7][8][9][10] …”

Section: Resultsmentioning

confidence: 96%

“…Dosing DIEDOT on a Cu(110) surface held at 200°C produces a sparse array of lines oriented along the [1][2][3][4][5][6][7][8][9][10] direction of the Cu lattice, separated by the Cuð110Þ-ð1 × 1Þ lattice, as shown in the STM micrograph displayed in Fig. 1A.…”

Section: Resultsmentioning

confidence: 99%

“…As was observed in the experimental data, the molecules reside above the long bridge sites of the Cu(110) lattice, because this corresponds to the lowest energy adsorption site identified by DFT. The model shows that each molecule is tilted by approximately 18°away from the surface normal toward the [1][2][3][4][5][6][7][8][9][10] direction. The mostly upright orientation is somewhat surprising for thiophene-derived units.…”

Section: Resultsmentioning

confidence: 99%

“…However, these polymers are not good conductors due to a very large bond length alternation in their conjugated acetylene structures. (8). Conductive ordered polythiophene wires have been prepared by pulsed electrooxidative polymerization of substituted thiophenes (9,10).…”

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confidence: 99%

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Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction

Lipton‐Duffin

Miwa

Kondratenko

et al. 2010

Proc. Natl. Acad. Sci. U.S.A.

116

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One of the great challenges in surface chemistry is to assemble aromatic building blocks into ordered structures that are mechanically robust and electronically interlinked-i.e., are held together by covalent bonds. We demonstrate the surface-confined growth of ordered arrays of poly(3,4-ethylenedioxythiophene) (PEDOT) chains, by using the substrate (the 110 facet of copper) simultaneously as template and catalyst for polymerization. Copper acts as promoter for the Ullmann coupling reaction, whereas the inherent anisotropy of the fcc 110 facet confines growth to a single dimension. High resolution scanning tunneling microscopy performed under ultrahigh vacuum conditions allows us to simultaneously image PEDOT oligomers and the copper lattice with atomic resolution. Density functional theory calculations confirm an unexpected adsorption geometry of the PEDOToligomers, which stand on the sulfur atom of the thiophene ring rather than lying flat. This polymerization approach can be extended to many other halogen-terminated molecules to produce epitaxially aligned conjugated polymers. Such systems might be of central importance to develop future electronic and optoelectronic devices with high quality active materials, besides representing model systems for basic science investigations.metal-catalyzed coupling reaction | molecular wires | cis-polythiophene | scanning probe microscopy | polymerization mechanism T he tunability and diversity of the structural and electronic properties of π-conjugated organic polymers have spurred a wide interest in these materials as wires and semiconductors for future electronic devices (1, 2), although significant optimization is required for real breakthrough performance. Conventional organic synthesis can create conjugated polymers of practically any length and structure (3), yet their controlled positioning and ordering on a surface remains nontrivial. This supramolecular ordering ultimately controls properties such as the charge mobility and recombination, which are critical for any application, including nanoelectronics and light harvesting. The approach presented here proposes a way to precisely control the long-range order in conducting polymers by performing synthesis of these materials, in an epitaxial way, directly on crystalline substrates. Although electrochemical polymerization on conducting surfaces has long been used to prepare films of conjugated polymers such as polythiophene (4), the techniques for preparation and characterization of aligned arrays of polymers have only recently been developed. Promising results were obtained by using UV irradiation (5) or scanning probe microscope tip pulsing (6) to form polydiacetylenes and surface-catalyzed coupling to form polyphenylene (7). However, these polymers are not good conductors due to a very large bond length alternation in their conjugated acetylene structures. (8). Conductive ordered polythiophene wires have been prepared by pulsed electrooxidative polymerization of substituted thiophenes (9, 10). The symmetry of the...

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Section: Resultssupporting

confidence: 61%

Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

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Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction

Lipton‐Duffin

Miwa

Kondratenko

et al. 2010

Proc. Natl. Acad. Sci. U.S.A.

116

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Two‐Dimensional Polymers

Sakamoto

Schlüter

2012

Materials Science and Technology

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The sections in this article are Introduction Why 2‐ D Polymers? What Is Not Considered a 2‐ D Polymer? General Considerations on Rational 2‐ D Polymer Synthesis Approaches to 2‐ D Polymers and Related Structures Thermolytic Synthesis Synthesis in the Flask Synthesis in 2‐ D Confinement Polymerization at Gas/Liquid and Liquid/Liquid Interfaces Polymerization in Layered Templates Polymerization in Layered Monomer Assemblies Polymerization on Solid Substrates Miscellaneous Conclusions and Outlook

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An Effective Approach to Achieve a Spin Gapless Semiconductor–Half‐Metal–Metal Transition in Zigzag Graphene Nanoribbons: Attaching A Floating Induced Dipole Field via π–π Interactions

Guan

Chen

et al. 2012

Adv Funct Materials

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Under fi rst-principles computations, a simple strategy is identifi ed to modulate the electronic and magnetic properties of zigzag graphene nanoribbons (zGNRs). This strategy takes advantage of the effect of the fl oating dipole fi eld attached to zGNRs via π -π interactions. This dipole fi eld is induced by the acceptor/donor functional groups, which decorate the ladder-structure polydiacetylene derivatives with an excellent delocalized π -conjugated backbone. By tuning the acceptor/donor groups, -C≡C-number, and zGNR width, greatly enriched electronic and magnetic properties, e.g., spin gapless semiconducting, half-metallic, and metallic behaviors, with the antiferromagnetic − ferromagnetic conversion can be achieved in zGNRs with perfect, 57-reconstructed, and partially hydrogenated edge patterns. can produce potential differences between the edges of zGNRs and drive zGNRs into half-metal, even provide other appealing electronic features, e.g., spin gapless semiconductor, by changing the -C≡C-number of the PDA bridges. Note that PDA and its -C≡C-bridged ladder-structure derivatives have been synthesized experimentally, [71][72][73][74][75] and a PDA layer adhered on the graphene surface has been fabricated recently as a bimorph actuator with compelling advantages to the traditional electromechanical actuation technology, [ 76 ] and the electronic couplings of PDA nanowires on graphite have also been experimentally studied. [77][78][79] Moreover, the NO 2 /NH 2 decorated ladder-structure PDA derivatives linked with one -C≡C-bond were predicted to exhibit signifi cantly enhanced nonlinear optical (NLO) responses due to the excellent π -conjugated delocalization of the PDA backbone. [ 80 ] Here, we perform comprehensive density functional theory (DFT) computations to investigate the electronic and magnetic properties of the joint systems of zGNR and the decorated PDA derivatives, emphasizing the effects of different pairs of acceptor/donor groups, number of -C≡C-bonds in the PDA derivatives and the zGNR width, even the existence of edge 57-reconstruction in zGNRs. Our studies revealed that depositing the decorated PDA derivatives on perfect H-terminated zGNRs renders the joint systems the transition of SGS-halfmetal-metal, accompanied by the magnetic conversion from AFM to FM. Even with the existence of 57-reconstruction at the zGNR edges, abundant electronic and magnetic transitions of AFM SGS-FM half-metal-AFM metal-NM metal can also be observed in the joint systems. Moreover, through partially hydrogenating zGNRs at the 57-reconstructed edges, the effect of the edge reconstruction can be eliminated, and more fascinatingly, the electronic and magnetic properties of the joint systems based on edge-reconstructed wide zGNRs can be generally recovered to those of the corresponding joint systems with perfect narrow H-terminated zGNRs representing the remaining pristine zGNRs inside. DOIThese provide immensely valuable insights for facilitating the spintronic applications and effectively modulating the electronic an...

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Electronic Structure of a Polydiacetylene Nanowire Fabricated on Highly Ordered Pyrolytic Graphite

Cited by 73 publications

References 20 publications

Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction

Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction

Two‐Dimensional Polymers

An Effective Approach to Achieve a Spin Gapless Semiconductor–Half‐Metal–Metal Transition in Zigzag Graphene Nanoribbons: Attaching A Floating Induced Dipole Field via π–π Interactions

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