Site-selective local fluorination of graphene induced by focused ion beam irradiation

Li, Hu; Daukiya, Lakshya; Haldar, Soumyajyoti; Lindblad, Andreas; Sanyal, Biplab; Eriksson, Olle; Aubel, Dominique; Hajjar‐Garreau, Samar; Simon, Laurent; Leifer, Klaus

doi:10.1038/srep19719

Cited by 41 publications

(32 citation statements)

References 39 publications

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“…This effect has been successfully exploited e.g., for graphene patterning with high precision using the focused ion beam (FIB) from a helium ion microscope [ 75 , 78 , 79 ]. Note that also conventional FIBs based on Ga ions have successfully been used for patterning and functionalization of graphene [ 80 , 81 ] as well as for thinning of MoS

[ 82 ], however the main drawback here is that with these ions typically unwanted collateral damage occurs. For example, in graphene edges are amorphized by the beam, probably due to the presence of residual gases [ 83 ] and tails of the focused ion beam.…”

Section: Defect Engineering By Particle Irradiation: State Of the mentioning

confidence: 99%

2D Material Science: Defect Engineering by Particle Irradiation

Schleberger

Kotakoski

2018

Materials

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Two-dimensional (2D) materials are at the heart of many novel devices due to their unique and often superior properties. For simplicity, 2D materials are often assumed to exist in their text-book form, i.e., as an ideal solid with no imperfections. However, defects are ubiquitous in macroscopic samples and play an important – if not imperative – role for the performance of any device. Thus, many independent studies have targeted the artificial introduction of defects into 2D materials by particle irradiation. In our view it would be beneficial to develop general defect engineering strategies for 2D materials based on a thorough understanding of the defect creation mechanisms, which may significantly vary from the ones relevant for 3D materials. This paper reviews the state-of-the-art in defect engineering of 2D materials by electron and ion irradiation with a clear focus on defect creation on the atomic scale and by individual impacts. Whenever possible we compile reported experimental data alongside corresponding theoretical studies. We show that, on the one hand, defect engineering by particle irradiation covers a wide range of defect types that can be fabricated with great precision in the most commonly investigated 2D materials. On the other hand, gaining a complete understanding still remains a challenge, that can be met by combining advanced theoretical methods and improved experimental set-ups, both of which only now begin to emerge. In conjunction with novel 2D materials, this challenge promises attractive future opportunities for researchers in this field.

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Section: Defect Engineering By Particle Irradiation: State Of the mentioning

confidence: 99%

2D Material Science: Defect Engineering by Particle Irradiation

Schleberger

Kotakoski

2018

Materials

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“…The routes via graphene oxide result in defect‐rich materials, where the type and extent of defects strongly depend on the initial oxidation method employed . Alternative routes to covalently functionalized graphene employ various plasmas, atomic fluorine, or other radicals . As is the case for the oxidation strategy, efficient modification of the graphene is achieved, but the harsh conditions limit the scope of functional groups that can be introduced.…”

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confidence: 99%

White‐Light Photoassisted Covalent Functionalization of Graphene Using 2‐Propanol

Lundstedt

Papadakis

et al. 2017

Small Methods

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of molecular species causes more subtle changes. [6,7] The edges of a graphene sheet are more reactive than the basal plane positions; hence, most covalent functionalizations are edge-selective. [8] In order to covalently functionalize the basal plane, more vigorous reaction conditions are generally required. Many of the presently used methods are via oxidation of graphite into graphene oxide using metal oxides and strong oxidizing acids. [9,10] Post-oxidation secondary functionalization of the introduced oxygen-containing functional groups [4,11] or reduction results in different types of modified graphene. The routes via graphene oxide result in defect-rich materials, where the type and extent of defects strongly depend on the initial oxidation method employed. [12,13] Alternative routes to covalently functionalized graphene employ various plasmas, atomic fluorine, or other radicals. [14][15][16][17][18][19][20][21][22] As is the case for the oxidation strategy, efficient modification of the graphene is achieved, but the harsh conditions limit the scope of functional groups that can be introduced. Thus, there is an obvious need for efficient yet mild methods for modification of the basal plane of graphene.Recently, Papadakis et al. reported that graphene can be efficiently photo(hydro)silylated and photohydrogenated at ambient temperature using white-light irradiation, [23] with the transfer photohydrogenation of graphene with formic acid as hydrogen donor being of particular interest from a process perspective. Subsequently, Koutoulogenis et al. also reported on the hydrogen atom abstraction from aldehyde substrates by graphite achieved through irradiation of graphite flakes with visible light. [24] In the present study, we have explored aliphatic alcohols as reaction partners to chemical vapor deposition (CVD)-grown graphene on Si/SiO 2 , kish graphite as well as highly oriented pyrolytic graphite (HOPG) under white-light irradiation, and we report on a novel mode of covalent graphene functionalization by 2-propanol (isopropyl alcohol (IPA)) that results in significantly more polar material than what is obtained from photo(hydro)silylation or photohydrogenation.Similar to formic acid, IPA is a known transfer hydrogenation reagent in metal-catalyzed reactions, [25] but reactions employing IPA resulted in a substantial increase of the polarity of "on chip" graphene after white-light irradiation. This is very different from what was obtained using formic acid [23] and a strong indication that IPA, in contrast to formic acid, is not Herein, a photochemical method for functionalization of graphene using 2-propanol is reported. The functionalization method which is catalyst-free operates at ambient temperature in neat 2-propanol under an inert atmosphere of argon. The equipment requirement is a white-light source for the irradiation. The same methodology when applied to kish graphite results in a novel material, exhibiting significantly higher wettability than the starting material according to water contact angle ...

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“…Raman scattering and X-ray photoelectron spectroscopy. The comparison of the Raman spectra of pristine graphene 20,21 and GNS (shown in Fig. 2a) demonstrates that the GNS has clearly maintained the graphene signature with the sharp 2D band (at~2700 cm −1 with FWHM~30 cm −1 ) and the intensity ratio of more than three between the 2D band and G band (at~1580 cm −1 ).…”

Section: Gns Synthesis and Microscopic Analysismentioning

confidence: 98%

Superior adhesion of graphene nanoscrolls

Papadakis

Jafri

et al. 2018

Commun Phys

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An emerging material in the carbon family, a graphene nanoscroll (GNS) is composed of tubularly scrolled monolayer graphene and has shown superlubricity and large current sustainability, surpassing the properties of monolayer graphene itself. Here we report on the superior adhesion of GNS prepared with a high yield synthesis method that allows for mass production of high quality GNSs. Raman spectra indicate that the GNS still maintains the signature of monolayer graphene, implying the lacking of π-stacking between adjacent layers. Importantly, adhesion measurements using atomic force microscopy reveal these GNSs with height range of 120-130 nm show a 2.5-fold stronger adhesion force than pristine graphene. This result potentially indicates that the GNS has higher adhesion than monolayer graphene and even higher than the liquid-solid and hydrogen-bonding enhanced interfaces which are essential types of adhesions involved in the field of physical adhesions and thus, GNS could be a new candidate for super-strong and lightweight devices.

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Site-selective local fluorination of graphene induced by focused ion beam irradiation

Cited by 41 publications

References 39 publications

2D Material Science: Defect Engineering by Particle Irradiation

2D Material Science: Defect Engineering by Particle Irradiation

White‐Light Photoassisted Covalent Functionalization of Graphene Using 2‐Propanol

Superior adhesion of graphene nanoscrolls

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