Electronic Structure Modification of Ion Implanted Graphene: The Spectroscopic Signatures of p- and n-Type Doping

Kepaptsoglou, Demie; Hardcastle, Trevor; Seabourne, Che R.; Bangert, U.; Zan, Recep; Amani, Julian Alexander; Hofsäß, H.; Nicholls, Rebecca J.; Brydson, Rik; Scott, A. J.; Ramasse, Quentin M.

doi:10.1021/acsnano.5b05305

Cited by 87 publications

(106 citation statements)

References 70 publications

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“…These are the movement of the trivalent Si substitution via an out-of-plane bond inversion process 34 , the rotation of a Si trimer in a divacancy 52 , the atomic motions in a Si 6 cluster in a pore 53 , and the jumping of a bivalent N between two equivalent bonding sites across a single vacancy 54 . Although not previously discussed, we have observed both B and N substitutions to also undergo lattice jumps similar to Si (data from published experiments 32,54,55 ). Fig.…”

Section: Atom-scale Dynamics: State-of-the-artsupporting

confidence: 62%

Towards atomically precise manipulation of 2D nanostructures in the electron microscope

et al. 2017

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Despite decades of research, the ultimate goal of nanotechnology-top-down manipulation of individual atoms-has been directly achieved with only one technique: scanning probe microscopy. In this Review, we demonstrate that scanning transmission electron microscopy (STEM) is emerging as an alternative method for the direct assembly of nanostructures, with possible applications in plasmonics, quantum technologies, and materials science. Atomically precise manipulation with STEM relies on recent advances in instrumentation that have enabled non-destructive atomic-resolution imaging at lower electron energies. While momentum transfer from highly energetic electrons often leads to atom ejection, interesting dynamics can be induced when the transferable kinetic energies are comparable to bond strengths in the material. Operating in this regime, very recent experiments have revealed the potential for single-atom manipulation using theÅngström-sized electron beam. To truly enable control, however, it is vital to understand the relevant atomic-scale phenomena through accurate dynamical simulations. Although excellent agreement between experiment and theory for the specific case of atomic displacements from graphene has been recently achieved using density functional theory molecular dynamics, in many other cases quantitative accuracy remains a challenge. We provide a comprehensive reanalysis of available experimental data on beam-driven dynamics in light of the state-of-the-art in simulations, and identify important targets for improvement. Overall, the modern electron microscope has great potential to become an atom-scale fabrication platform, especially for covalently bonded 2D nanostructures. We review the developments that have made this possible, argue that graphene is an ideal starting material, and assess the main challenges moving forward. arXiv:1708.08780v1 [cond-mat.mtrl-sci]

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Section: Atom-scale Dynamics: State-of-the-artsupporting

confidence: 62%

Towards atomically precise manipulation of 2D nanostructures in the electron microscope

et al. 2017

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“…Indeed a p and n character has recently been verified in suspended graphene containing single substitutional B and N atom dopants. 29 Under certain circumstances, boron and nitrogen doping is also expected to induce a band gap in graphene. 24,25 .…”

Section: Introductionmentioning

confidence: 99%

“…31 Due to the ideal STEM 32 combination of ultra-high vacuum conditions and low acceleration voltage (which minimises any beam-induced damage to the samples), individual B 23,29 and N 23, 29,33,34 atom dopants in graphene can be identified directly in an ADF image. So-called "core" EEL spectra (EEL > 50 eV) contain information about the local electronic structure and bonding in graphene, 28,29,[33][34][35] while "valence" EEL spectra (EEL < 50 eV) contain information about the graphene dielectric response 18,19,[36][37][38][39][40][41] . In combination with simultaneous (STEM) ADF imaging, EEL spectra allow for a direct correlation of defect-induced modifications of the graphene electronic structure 28,29,[33][34][35] and dielectric response 18,19 with atomic scale structure.…”

Section: Introductionmentioning

confidence: 99%

Local Plasmon Engineering in Doped Graphene

et al. 2018

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Single-atom B or N substitutional doping in single-layer suspended graphene, realized by low-energy ion implantation, is shown to induce a dampening or enhancement of the characteristic interband π plasmon of graphene through a high-resolution electron energy loss spectroscopy study using scanning transmission electron microscopy. A relative 16% decrease or 20% increase in the π plasmon quality factor is attributed to the presence of a single substitutional B or N atom dopant, respectively. This modification is in both cases shown to be relatively localized, with data suggesting the plasmonic response tailoring can no longer be detected within experimental uncertainties beyond a distance of approximately 1 nm from the dopant. Ab initio calculations confirm the trends observed experimentally. Our results directly confirm the possibility of tailoring the plasmonic properties of graphene in the ultraviolet waveband at the atomic scale, a crucial step in the quest for utilizing graphene's properties toward the development of plasmonic and optoelectronic devices operating at ultraviolet frequencies.

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“…heavier (atomic number 32 as compared to 14) and larger (covalent atomic radius of 122 pm as compared to 111 pm for Si and 77 pm for C). This raises the question whether it could also be incorporated into graphene similar to the lighter boron and nitrogen, 13,16 the often observed silicon, [17][18][19] and the recently implanted phosphorus, 20 all of which are able to directly substitute for single C atoms. Due to its greater size, a significant increase of bond length resulting in threefold Ge buckling out of the plane is predicted.…”

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confidence: 99%

Implanting Germanium into Graphene

et al. 2018

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Incorporating heteroatoms into the graphene lattice may be used to tailor its electronic, mechanical and chemical properties, although directly observed substitutions have thus far been limited to incidental Si impurities and P, N and B dopants introduced using low-energy ion implantation. We present here the heaviest impurity to date, namely Ge ions implanted into monolayer graphene. Although sample contamination remains an issue, atomic resolution scanning transmission electron microscopy imaging and quantitative image simulations show that Ge can either directly substitute single atoms, bonding to three carbon neighbors in a buckled out-of-plane configuration, or occupy an in-plane position in a divacancy. First-principles molecular dynamics provides further atomistic insight into the implantation process, revealing a strong chemical effect that enables implantation below the graphene displacement threshold energy. Our results demonstrate that heavy atoms can be implanted into the graphene lattice, pointing a way toward advanced applications such as single-atom catalysis with graphene as the template.

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Electronic Structure Modification of Ion Implanted Graphene: The Spectroscopic Signatures of p- and n-Type Doping

Cited by 87 publications

References 70 publications

Towards atomically precise manipulation of 2D nanostructures in the electron microscope

Towards atomically precise manipulation of 2D nanostructures in the electron microscope

Local Plasmon Engineering in Doped Graphene

Implanting Germanium into Graphene

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