JMST-2019-3706 Proof Hi PDF

Journal of Materials Science & Technology
Probing the compound effect of spatially varying intrinsic

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defects and doping on mechanical properties of hybrid

graphene monolayers
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Journal: Journal of Materials Science & Technology
Manuscript ID JMST-2019-3706
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Manuscript Type: Research Article

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Date Submitted by the

15-Dec-2019
Author:
Complete List of Authors: Gupta, Kritesh; National Institute of Technology Silchar

Mukhopadhyay, Tanmoy; Indian Institute of Technology Kanpur,
Roy, Aditya; National Institute of Technology Silchar
Dey, Sudip; National Institute of Technology Silchar
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defect in graphene, doped graphene, defected 2D material, temperature-

Keywords:
dependent mechanical properties, spatial sensitivity of defect and doping
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Elastic Properties, Failure, Mechanical Properties, Molecular Dynamics

Speciality:
Simulation
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Page 1 of 42 Journal of Materials Science & Technology
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3 Answers to Reviewers’ Comments:
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Title: “Probing the compound effect of spatially varying intrinsic defects and doping on
7 mechanical properties of hybrid graphene monolayers” submitted to Journal of Material
8 Science and Technology (Manuscript ID JMST-2019-2808).
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10 We are thankful to the reviewers for their constructive comments on our manuscript. As
11 suggested by the reviewers, the manuscript is revised with proper care wherever needed. The
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changes are incorporated in the revised manuscript using blue colour. The revised manuscript
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after incorporating the reviewers’ comments is significantly improved from the initial
15 version. Please find point-wise our reply against the reviewers’ comments, as given below:
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17 Reviewer 1:
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19 Comment: Authors studied the mechanical properties of defective and doped graphene
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sheets by performing classical molecule dynamics (MD) simulations based on the Tersoff
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22 potential. Authors show how the failure stress, failure strain and Young’s modulus of
23 graphene can be changed with defects and doping. Although the study is well conducted and
24 it investigate important issues, there are several concerns that are needed to be addressed
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25 appropriately, as follows:
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27 Our Reply: We are thankful to the reviewer for noting that the study is well conducted, and it
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investigates important issues. The paper has been carefully revised following the comments
30 of the reviewer, as discussed below.
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32 Comment 1: Please discuss if the defective graphene structures that are considered have
33 been already experimentally realized.
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35 Our Reply: The defects considered in the study such as nanopore and Stone-Wales are
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already well explained by previous research activities. However, systematic investigations
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38 focusing on the compound effect of such defects and doping considering different spatial
39 variations is scarce to find in the scientific literature. We have written the current paper to
40 address such critical issues. As per the reviewer’s suggestion, related experimental studies
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41 involving defects are included in the revised manuscript (see page 3 and 4 of the revised
42 manuscript).
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45 Comment 2: The predicted tensile strength of graphene is almost by 50% higher than
46 experimental report in Ref. 7. This issue can be resolved by modifying the cutoff of Tersoff
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potential. Authors can refer to the literature on the amorphized graphene mechanical
49 properties in which this issue was resolved and the experimental data was reproduced
50 accurately.
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52 Our Reply: We are thankful to the reviewer for the suggestion; the results of tensile strength
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54 comes much closer by implementing the optimized Tersoff potential. We have incorporated
55 the new results in Table 1. The suggested study by reviewer along with a few other relevant
56 literatures are included in the revised manuscript [40-42] along with a brief explanation in
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58 page 7.
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60 Comment 3: Authors studied the mechanical properties, however they did not discuss the
failure mechanism. Please investigate that how the crack initiates and grow in the studied
systems.
Journal of Materials Science & Technology Page 2 of 42
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3 Our Reply: Focus of the present investigation is the mechanical behaviour (mainly Young’
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5 modulus, failure stress, failure strain and stress-strain relation) of graphene subjected to
6 different defect concentration, dopant concentration and their compound effect. However, as
7 a part of the study we have presented few critical insights on failure mechanism which
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9 become apparent from the results. The evolution of crack in pristine graphene and the effect
10 of different forms of defects and doping in graphene are illustrated in Fig. 15. Typical results
11 for crack evolution under the compound influence of doping and defects are presented
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13 considering carbon isotope dopants (also refer to supplementary movies SM1 – SM2). The
14 study convincingly captures a general trend that the presence of defects in the nanostructure
15 accelerates the rate of crack evolution due to ease in propagation of the crack path under the
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17 influence of locally reduced stiffness distribution in the system and conjugation of the
18 adjacent defects. As per the aim of this paper, we have not investigated the detailed fracture
19 mechanism. However, we would definitely look into this aspect in our future works.
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22 Comment 4: When using the MD simulations to evaluate the mechanical properties, the
23 predicted stress-strain relations are dependent on the applied loading strain rate, this effect
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25 should be discussed in the revised manuscript.

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27 Our Reply: We completely agree with the reviewer that it has been widely reported by the
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researchers that the strain rate has a significant effect on the mechanical properties obtained
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from MD simulations. To investigate this effect on graphene, we have performed a separate
31 set of simulations with different strain rates (0.0001, 0.0005, 0.001, 0.0025, and 0.005/ps).
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32 The comparative results obtained from the strain rate-based simulations are depicted in Fig. 4
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(newly added in the revised manuscript), wherein it can be noticed that strain rate has
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35 significant effect on the failure stress, failure strain, Young’s modulus and the extent of
36 ductility.
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39 Comment 5: I recommend a general proofreading and cleanup of the language and
40 grammar. The paper is readable, but some sections could benefit in clarity from a tune-up of
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42 the wording used, often the language is confusing; detracting from the quality of the work.
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44 Our Reply: As per the reviewer’s suggestion, the revised manuscript has been thoroughly
45 proofread to rectify grammatical errors and typos.
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48 Comment 6: The complete details of some references are missing which should be
49 corrected, see for example Ref. 1 and Ref. 4
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51 Our Reply: We are thankful to the reviewer for pointing this out. The references have been
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53 corrected in the revised manuscript including Ref.1 and Ref. 4.
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55 Comment 7: The authors should also refer to and comment on the contribution in Journal of
56 Materials Chemistry A 6 (2019), 11022-11036.
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58 Our Reply: As per the reviewer’s suggestion it is incorporated in the revised manuscript
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60 including relevant comments (Ref. 8).
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3 Reviewer 2:
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6 Comment 1: Please explain why Si and 14C as doping atoms were used to study the effect
7 on mechanical properties of graphene. As we know, actually, N is the most common element
8 for the doping of graphene in many works. Please add the importance of Si and 14C doping
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10 in the introduction section.
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12 Our Reply: We agree that N is a common element for doping in graphene. However, one of
13 the popular methods to produce graphene is epitaxial growth of graphene over SiC substrate,
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which includes the thermal decomposition of graphene out of SiC substrate. The involvement
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16 of high temperature and chemical reactions during the production phase of monolayer
17 graphene, makes it prone to be subjected with dopants like Si and heavy carbon isotope in the
18 produced 2D material. Thus it becomes necessary to investigate the effect of Si and 14C
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20 doping in the mechanical properties of graphene. Besides that, Huelmo and Denis [31]
21 reported in their work that silicon dopants are readily preferable to replace carbon atoms and
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22 produce new two-dimensional material. Nguyen and Le [32] conducted the atomistic study
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24 on the SimCn sheets under uniaxial tension in its armchair direction and found that the
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25 mechanical properties (fracture strength, failure strain, and Young’s modulus) can be tuned
26 by the dispersion of silicon atom concentrations. For the above-mentioned reasons, here we
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28 aim to focus on Si and C14 doping in graphne.
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30 As per the reviewer’s suggestion, the manuscript has been revised to indicate the importance
31 of Si and 14C doping in the introduction section.
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33 Comment 2: Why the plastic deformation of graphene decrease when doping or defect was
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35 introduced?
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Our Reply: To address the reviewer’s comment, we have included the following sentences in
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38 the revised manuscript
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40 The disruption of bond structure and sp2 hybridization caused by introducing defects and
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substitutional dopant result in the creation of stress risers at location of defect and dopant
43 induction, which causes early failure of monolayer graphene and decrement in its apparent
44 strength (see Ref. 50). Due to early failure, the plastic deformation also reduces which occurs
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immediately before the failure.
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48 Comment 3: Why the two instances in figure 8b,c show the same mechanical properties?
49 However, the two instances in figure 8g,h show the different mechanical properties. Please
50 give an explanation. Because I think both of them are symmetrical relationship.
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Our Reply: Figure 8 depicts the variation in mechanical behaviour of graphene subjected to
54 different spatially distributed nanopore defects concentration. We agree with the reviewer,
55 and conducted new simulations to check the results further. We have corrected the figure 8
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accordingly in the revised manuscript, wherein it can be noticed that the mechanical
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58 properties (failure strength, failure strain, Young’s modulus and stress-strain curve) are
59 almost same for the defect location in left and right zones (figure 8g,h) and top and bottom
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zones (figure b, c).
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3 Comment 4: Whether the spatial location of defect in figure 12e,f is rational or not? Because
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5 I can’t agree that they can be considered as random distribution. Please supply more uniform
6 instances and the corresponding properties.
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8 Our Reply: As per the reviewer’s suggestion more uniform cases of random distribution of
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silicon atoms have been updated in the study by carrying out new simulations.
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12 Comment 5: Please check the main text carefully to avoid the spelling mistakes. For
13 example, the word “grapehne” should be “graphene”.
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15 Our Reply: As per the reviewer’s suggestion the revised manuscript has been proofread
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thoroughly to rectify grammatical and spelling mistakes including the typo mentioned by the
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18 reviewer.
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4 Probing the compound effect of spatially varying intrinsic defects and doping
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6 on mechanical properties of hybrid graphene monolayers
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8 K. K. Guptaa, T. Mukhopadhyayb,c*, A. Roya, S. Deya
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Department of Mechanical Engineering, National Institute of Technology Silchar, Silchar, India
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Department of Engineering Science, University of Oxford, Oxford, UK
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14 Department of Aerospace Engineering, Indian Institute of Technology Kanpur, Kanpur, India
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16 *Email address: tanmoy.mukhopadhyay@eng.ox.ac.uk (Tanmoy Mukhopadhyay)
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60 https://mc03.manuscriptcentral.com/jmst
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3 Research Article
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5 Probing the compound effect of spatially varying intrinsic defects
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and doping on mechanical properties of hybrid graphene
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10 monolayers
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12 Kritesh Kumar Gupta1, Tanmoy Mukhopadhyay2,3,*, Aditya Roy1, Sudip Dey1
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Department of Mechanical Engineering, National Institute of Technology Silchar, India
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16 Department of Engineering Science, University of Oxford, Oxford, UK
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18 Department of Aerospace Engineering, Indian Institute of Technology Kanpur, India
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E-mail address: tanmoy.mukhopadhyay@eng.ox.ac.uk (Tanmoy Mukhopadhyay).
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22 Abstract
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24 Doping in pristine 2D materials brings about the advantage of modulating wide range of
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26 mechanical properties simultaneously. However, intrinsic defects (such as Stone-Wales
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28 and nanopore) in such hybrid materials are inevitable due to complex manufacturing and
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synthesis processes. Besides that, defects and irregularities can be intentionally induced in
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31 a pristine nanostructure for multi-synchronous modulation of various multi-functional
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33 properties. Whatever the case may be, in order to realistically analyse a doped graphene
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35 sheet, it is of utmost importance to investigate the compound effect of doping and defects
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in such 2D monolayers. Here we present a molecular dynamics based investigation for
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38 probing mechanical properties (such as Young’s modulus, post-elastic behaviour, failure
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40 strength and strain) of doped graphene (C14 and Si) coupling the effect of inevitable
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42 defects. Spatial sensitivity of defect and doping are systematically analyzed considering
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44 different rational instances. The study reveals the effects of individual defects and doping
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along with their possible compounded influences on the failure stress, failure strain,
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47 Young’s modulus and constitutive relations beyond the elastic regime. Such detailed
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49 mechanical characterization under the practically relevant compound effects would allow
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51 us to access the viability of adopting doped graphene in various multifunctional
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53 nanoelectromechanical devices and systems in a realistic situation.
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55 Key words: defect in graphene; doped graphene; defected 2D material;
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57 temperature-dependent mechanical properties; spatial sensitivity of defect and doping
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2 1. Introduction
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4 The extraordinary characteristics of graphene have led to its wide utilization in the
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6 development of mass sensing nanoresonators[1], biosensors[2], nanocomposites[3-5] and various
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8 other nanoelectromechanical systems (NEMS). Following the successful extraction of
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monolayer graphene[6], this two-dimensional ‘wonder’ material has been one of the key
11 attractions of theoretical and experimental research to the scientific community. Since then a
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13 lot of research have been carried out in order to determine the exact mechanical properties and
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15 strength of monolayer graphene sheet. Graphene is found to be one of the lightest (0.7 7 mg/m2)
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17 and still stiffest material known. Its fracture strength and Young’s modulus are recorded as 1 30
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GPa and 1 TPa, respectively[7]. The 2D materials like graphene and their derivatives have
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20 demonstrated their usefulness in various domains such as biomedical, electronics, optics and
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22 nanomechanical; to this end Mortazavi et al. [8] conducted DFT and MD simulation of
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24 boron-graphdiyne and reported that the newly realized pi-conjugated 2D structure may
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withstand high temperatures like 2500K along with a capability of Na, Ca, Li-ion storage.
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27 Researchers have extensively investigated the mechanical properties of graphene, both

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29 experimentally and theoretically. For instance, Lee et al. [7] measured Young’s modulus and
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31 fracture strength of free-standing monolayer graphene experimentally by nanoindentation in an
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33 atomic force microscope. The findings of these experiments established the graphene as the
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strongest and stiffest material available. Papageorgiou et al. [9] characterized and studied the
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36 mechanical properties of graphite flakes and their nanocomposites using Raman spectroscopy.
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38 They also discussed the preparation strategies of bulk graphene nanocomposites. A few groups
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40 probed these findings using molecular dynamics (MD) simulations, Mortazavi and Cuniberti [10]
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42 performed molecular dynamics simulations to examine the mechanical properties of
43 ultrafine-grained graphene structure and also observed the mechanical response of graphene
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45 depending upon the different grain sizes. It was found in this study that ultrafine -grained
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47 graphene structure can present ultra-high tensile strength and elastic modulus. Tsai and Tu [11]
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49 characterized the mechanical properties of single graphene layer and graphite flakes using
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molecular dynamics simulation. It was found in the study that monolayer graphene possesses
52 better reinforcement properties than those of graphite flakes. In order to determine the elastic
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54 moduli and shear moduli of two-dimensional nanostructures, Mukhopadhyay et al. [12-13]
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56 developed an efficient closed-form expressions by implementing generalized analytical
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58 approach. Furthermore, Mahata and Mukhopadhyay [14], investigated the elastic moduli and
59 crack propagation behaviour of stanene with the help of MD simulations. They also pointed out
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the dependence of mechanical properties of single and bilayer stanene on the temperature and
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2 strain rate. Thomas and Ajith [15] carried out the MD simulation to study the structural,
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4 thermodynamic and mechanical properties of monolayer graphene. The findings of the
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6 aforesaid studies have established the mechanical properties of pristine graphene on a strong
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8 foundation.
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There are various methods to experimentally produce graphene keeping cost, quality and
11 volume of production in mind. In general, graphene can be manufactured through top -down
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13 synthesis using micromechanical cleavage, arc discharge, unrolling carbon nanotubes, chemical
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15 vapour deposition (CVD) and epitaxial growth of graphene on SiC. CVD methods may be
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17 utilized for commercialized large-scale production. Any of the above methods doesn’t ensure
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the pristine structure of produced graphene. The production methods (chemical and heat
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20 involvement) play a major role in the inculcation of defects and dopants while the production
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22 process. So far, a vast amount of research has been carried out to characterize the exact
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24 material properties of pristine graphene; however, the topological defects induced during the
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production phase (which is unavoidable) affect the mechanical properties of graphene. The
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27 application of graphene relies on overcoming the adverse effects of these structural

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29 irregularities of graphene. To assess the material properties over the nano-scale various
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31 experimental methods such as transmission electron microscope (TEM), scanning electron
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33 microscope and atomic force microscope (AFM) is commonly used [16]. To this end, various
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experimental techniques have been used to indicate that defects have a major role in deciding
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36 the electronic and chemical properties. In 2013, Robertson et al. [17] investigated the effect of
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38 the vacancy on the mechanical properties of graphene by utilizing atomic resolution imaging.
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40 Similarly, Zandiatashbar et al. [18] investigated the effect of vacancy defects on the mechanical
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42 properties of graphene. They reported in their experimental study that even a high density of
43 sp3 type defects does not significantly affect the elastic modulus of the graphene sheet,
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45 whereas the observed fracture strength showed a significant 14% reduction for defective
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47 graphene as compared to pristine graphene. On the other hand, a significant reduction in the
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49 mechanical properties was reported in the same paper with vacancy defects. Zandiatashbar et
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al.[18] also established the relationship between the mechanical properties of graphene and the
52 type and density of defects. Kotakoski et al.[19] observed the Stone-Wales type defect in
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54 high-resolution transmission electron microscopy images and reported that such defect may be
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56 formed by single electron impact. Similarly, Pourmand et al.[20] fabricated nanoporous
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58 graphene using CVD and demonstrated its application as nanosobent. The utilization of
59 experimental approaches to characterize nanoscale materials has its own challenges in terms of
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time, precision and cost. The extremely improved computational methods motivated
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2 researchers to carry out the simulations as an alternative to expensive experimentation.
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4 Ab-initio (first-principles approach) and semi-empirical (classical MD) are two commonly used
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6 methods of nanoscale modelling. The ab-initio methods are the most accurate techniques but
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8 have a disadvantage in terms of computational expense and the limitation of system size (a few
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hundred atoms). The semi-empirical methods are considered comparatively less
11 computationally expensive and can deal with the high number of atoms in comparison to
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13 ab-initio methods, which makes classical MD simulations perfect approach to perform a
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15 nanoscale simulation in many situations [16].
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17 Defects in graphene can be perceived in two different ways: first, intentionally induced in a
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pristine nanostructure for simultaneously modulating multi-functional properties (designed
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20 defects) and second, an inevitable consequence of complex manufacturing and synthesis of
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22 nanomaterials (intrinsic defects). Whatever the case may be, the change in mechanical
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24 properties due to the presence of defects and irregularities is of paramount interest to the
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scientific community. This has been stated by the researchers in the past that inducing defects
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27 or other irregularities along with various forms of uncertainties [21] in pristine two-dimensional
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29 materials may lead to altering its mechanical, electrical and electronic properties up to a
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31 significant level. Thus inducing the irregularities in graphene provides the scop e of altering its
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33 properties on the basis of its intended applications. Martinez and Caturla [22] presented a
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molecular dynamics simulations study for inducing defects by irradiating graphene with low
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36 energy carbon ions. The authors also simulated the selective creation of defect in graphene by
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38 tuning the parameters of carbon irradiation. Besides, intentional design of defects in graphene
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40 to modulate multi-functional properties, the defects and other irregularities in graphene are
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42 prone to get introduced in the form of intrinsic defects during processing and graphene growth,
43 as mentioned above. In order to give an understanding of various imperfections in graphene,
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45 Liu et al.[23] reviewed the generation and healing of defects in graphene and also pointed out
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47 the effects of defects on its properties. Ansari et al.[24] reported two types of defects viz. single
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49 vacancy and Stone-Wales defect and its effect on the fracture characteristics of graphene. The
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examination of loading in both of the directions, armchair and zigzag have been reported with
52 the conclusion that graphene is slightly stronger in armchair direction. Wang et al.[25]
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54 investigated the same defects present in monolayer graphene and analyzed the fracture strength
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56 at different temperatures. Zhao et al.[26] presented defective graphene as a Raman enhancement
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58 substrate with significant level of efficiency. They synthesized defective graphene films using
59 chemical vapour deposition (CVD) on Auand subsequently showed the advantages of the
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proposed method. Wang et al.[27] further reported the creation of 5-8-5 defects with different
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2 orientations in graphene to control the mechanical properties of graphene. Li et al.[28]
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4 investigated porous graphene paper for applications as supercapacitor. They developed a
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6 convenient method to prepare porous graphene papers of thickness 0.5mm by means of a
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8 thermal shock to graphene paper assembled on Cu foil with flowing nitrogen. Mortazavi et
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al.[29] investigated the mechanical response, thermal conductivity and electronic\optical
11 properties of single-layer nanoporous graphene (NPG) by density functional theory (DFT) and
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13 MD simulations. The results were compared in both the armchair and zigzag direction and it
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15 was found that in armchair direction NPG exhibits higher tensile strength and thermal
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17 conductivity by the factor of 1.6 and 2.3, when compared with its zigzag direction. It was also
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concluded on the basis of DFT results that NPG monolayer exhibits semiconducting electronic
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20 character with a direct bandgap of 0.68 eV.These studies reveal that there are several factors
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22 which affect the mechanical strength of graphene; in this context, Dewapriya and Rajapakse [30]
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24 investigated the strain rate and temperature-dependent variation in the mechanical strength of
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graphene. To further explore, they also induced vacancy concentration in the graphene sheet to
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29 Besides ‘defect engineering’ of graphene sheets, another prominent way of tuning the
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31 behaviour of graphene is by doping graphene with foreign atoms. As mentioned in the
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33 preceding section, one of the popular methods to produce graphene is epitaxial growth of
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graphene over SiC substrate, which includes the thermal decomposition of graphene out of
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36 SiC substrate. The involvement of high temperature and chemical reactions during the
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38 production phase of monolayer graphene makes it prone to be subjected to dopants like Si
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40 and heavy carbon isotope in the produced 2D material. Thus it becomes necessary to
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42 investigate the effect of Si and 14C doping in the mechanical properties of graphene.
43 Besides that, Huelmo and Denis[31] reported in their work that silicon dopants are readily
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45 preferable to replace carbon atoms and produce new two-dimensional material. Nguyen and
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47 Le[32] conducted the atomistic study on the Si mCn sheets under uniaxial tension in its
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49 armchair direction and found that the mechanical properties (fracture strength, failure strain,
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and Young’s modulus) can be tuned by the dispersion of silicon atom concentrations. For the
52 above-mentioned reasons, here we aim to focus on Si and C 14 doping in graphne. Lin et
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54 al.[33] investigated the performance enhancement of super capacitor electrode by using
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56 Nitrogen-doped graphene/carbon nano-composites. They noted that the significant
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58 performance enhancement in comprehensive electrochemical process can meet the future
59 need for efficient supercapacitor electrode material. In order to perform heteroatom doping
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with boron atom, Dieb et al. [34] followed machine learning approaches to find the stable
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2 structure of boron-doped graphene and they reported that the boron doping up to 3.1% can
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4 increase the work function of graphene by 0.7 eV. Another study by Han et al. [35] reported
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6 the mechanical properties of silicon, nitrogen, and boron-doped graphene, wherein it was
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8 observed that the silicon atom doping has a profound effect on the strength of graphene such
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as monotonic reduction in ultimate strength, ultimate strains, and energy absorption. Zhang
11 and Gu[36] reported the effect of number of layers, operating temperature and carbon isotope
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13 doping on the mechanical properties of graphene. They found that the layer number in
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15 multilayer graphene does not have much effect on the fracture strength and stiffness of
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17 graphene, while temperature increment leads to an adverse effect on the strength of graphene
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sheet. They further noticed that the isotope substitution in graphene does not play a
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20 significant role in modifying the properties of the graphene sheet.
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22 From the concise literature review presented above, it can be noticed that the mechanical
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24 behaviour of pristine graphene, as well as graphene sheets with defects and doping, have
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been studied extensively. However, the compound effect of defect and doping in graph ene
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29 inevitable in a doped graphene layer due to the presence of manufacturing defects. Besides
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31 that, it is also possible to intentionally introduce both doping and defects simultaneously to
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33 modulate multi-functional electronic, optical, thermal, chemical and mechanical properties
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leading to an effectively expanded design space. Either way, it is extremely important to
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36 characterize the mechanical properties of such hybrid nanostructures to ensure their viability
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38 of adoption in various nanoelectromechanical devices and systems. In the present stu dy, we
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40 aim to investigate the compound effect of defects (for example Stone-Wales defects and
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42 nanopores) and doping (such as Si atoms and a heavy isotope of carbon C 14 atoms) on the
43 mechanical properties of graphene monolayers (such as fracture strength, f ailure strain and
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45 stiffness, post-elastic constitutive behaviour) based on the molecular dynamics simulation
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47 approach.
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50 2. Modelling and Simulation
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52 In the current study, the atomistic simulations have been carried out to perform uniaxial
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tensile deformation and investigate the mechanical properties such as Young’s modulus,
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55 post-elastic behaviour, fracture strength and failure strain. The Tersoff potential h as been
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57 utilized as the force field between carbon atoms and dopant atoms (carbon isotope C 14 and
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59 Si) and an iso-strain approach has been used to calculate the mechanical properties based on
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molecular dynamics (MD) simulation. This section elaborates the adopted modelling and
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2 simulation methodology for pristine, defective and doped graphene sheets with the he lp of
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4 MD simulation.
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6 MD simulation helps in understanding the properties of atom assemblies and microscopic
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8 interactions between them. It comprises of the numerical step by step solving of the classical
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equations of motion, for a simple atomic system which may be written as
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15 Here fi represents the atomic force and U represents the potential energy. To solve in such a
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17 manner we need to find the atomic forces, which are usually derived from the potential
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19 energy between the atoms, as stated in the above equation. The potential energy between the
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atoms represents the inter-atomic interactions which are catered by using appropriate
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22 potential function [37]. In this study, the Tersoff inter-atomic potential is used, which mimics
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24 the interactions between the carbon atoms and also in between the carbon and dopant (C 14
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25
26 and Si) atoms. The Tersoff style in LAMMPS [38] is a pair potential which represents the
Re
27
28 potential energy between three individual atoms. The energy E between the atoms may be
29
represented as
vie
30
31 1
32 E=  Vij
2 i j i
(2)
33
w
34
35 where, Vij = fC (rij )[ f R (rij ) + bij f A (rij )] (3)
36
On
37 Here Vij represents the potential energy of the system. fR and fA refer to the repulsive and
38
39 attractive pair potentials, whereas fC stands for cut off function. The formula sums up the
40
potential energy of all the neighboring atoms (j and k) of atom i within the cut-off radius. rij
ly
41
42 represents the distance between the adjacent atoms i and j and bij is an empirical bond-order
43
44 coefficient, where fR and f A can be described as
45
46 f R = A e− 1 (4)
47
48
49 and f A = − B e− 2 (5)
50
51
52 A, B, λ1, and λ2 are the parameters used for two body interactions [39].
53 The accuracy of the results received through the MD simulations depends on the potential
54
55 field used. In the previous research papers, it can be found that Tersoff potential is extensively
56
57 used to simulate the graphene structures. It is also observed that the implementation of original
58 [40-42]
59 Tersoff potential generally overestimates the mechanical properties of graphene . To this
60
end, Lindsay and Broido [40] produced the optimized potential by implementing small changes
7
1
2 in two parameters (h and B) and produced the phonon dispersion data of graphite. Mortazavi et
3
4 al.[41] suggested a method to obtain the experimentally produced mechanical properties of
5
6 graphene by changing cut-off function of Tersoff potential from 0.18 nm to 0.2 nm. Similarly,
7
8 Rajsekaran et al.[42] clubbed the changes made by Lindsay and Broido [40] with implementing
9
10
the single cut-off value S, and reported the more accurate results. All these changes suggested
11 by the researchers are helpful in terms of producing accurate mechanical properties of perfect
12
13 and defective graphene. However, in the current study as we have also conducted the
14
15 simulations of the doped (Si and C 14) graphene that creates inhomogeneity to run the
16
17 simulations on two different set of potential parameters. Therefore, to make the study
18
homogeneous we adopted the original Tersoff potential.
19
20 As stated above, the inter-atomic potential leads to the determination of atomistic forces
21
Fo
22 and which in turn helps in finding the atomistic pressure or stress. In MD simulation
23
24 atomistic stresses are generally interpreted in two ways, namely Cauchy stress and virial
r
25
26
stress. The consideration of Cauchy stress has its own advantages in terms of computational
Re
27 efficiency. However, Cauchy stress induces inherent stresses in the atomic structure which
28
29 leads to higher stress values at zero strain. Due to this disadvantage, the present study adopts
vie
30
31 the virial stress determination. The virial stress is computed as symmetric pressure tensor,
32
33 stored as a 6-element vector which can be expressed as-
w
34
1 1 N   
 ij =    ( Ri − Ri ) Fj − m vi v j 
  
35 (6)
36 V   2  =1 
On
37
38 The first term of equation 6 uses the components of virial tensor and the second term use
39
40 the components of kinetic energy tensor. In this equation α and β refers to the number
ly
41
42 assigned to two adjacent atoms, while i and j indicate the directional indices, mα and viα are
43
44 the mass and velocity of the atom α, respectively. Ri β is the location of atom β in i direction;
45
46 Fjαβ is the force due to an atom β on atom α along the j direction; V refers to the total volume
47
48 of the material system. The virial stress represents a product of stress and volume i.e., the
49
50
stress value computed by LAMMPS would be in the units of pressure x volume; in order to
51 extract the stress from the computed value it is essential to divide the value calculated by the
52
53 LAMMPS with the total volume. Furthermore, in order to calculate the virial stress, the
54
55 instantaneous volume is used i.e. when the imposed strain is ‘ε’, the value of volume at the
56
57 given instant would be Vo (1+ ε), where V0 represents the initial volume of the system [30].
58
59
60
8
1
2 The stress tensors are further used to compute the elastic constants of the graphene by
3
4 implying the constant strain to the simulation box with a strain rate of 5 x 10-3/picoseconds
5
6 (ps). The relation between in-plane stress and strain can be expressed as
7
8   11   C11 C12 0   11 
    
  22  =  C21 C22 0    22 
9 (7)
10    0
11  12   0 C66    12 
12
13 Due to symmetry in the constitutive matrix, the values of elastic constants can be written as
14
15
C11 = C22 ,
16 C12 = C21 ,
17 (8)
18 C −C
C66 = 11 12
19 2
20
21 Finally, the Young’s modulus of graphene can be computed as [10]
Fo
22
C C − C12C21
23 E = 11 22 (9)
24 C22
r
25
26 In this study VMD (Visual Molecular Dynamics) [43], an open source molecular structure
Re
27
28 visualization program is used to model the square shape pristine system with the edge of 7.2
29
vie
30 nm. The pristine system contains 2040 carbon atoms. The data-files required in the MD
31
32 simulations were created by the topotool plugin of VMD. An open source atom manipulating
33 software, Avogadro[44] is also used to introduce the Stone-Wales and nanopore defects in the
w
34
35 pristine graphene; Fig.1 depicts the typical models of perfect and defective graphene as
36
On
37 considered in this study. The random substitution of silicon atom and carbon isotope C 14 is
38
39 also performed using Avogadro software. In order to run the MD simulations, an open
40
source code LAMMPS has been used. The periodic boundary conditions were applied in all
ly
41
42 the directions and an integration time step of 0.1fs (femtoseconds) is used for all the
43
44 simulations. The MD simulation starts with the relaxation of the structure by minimizing the
45
46 energy. The conjugate gradient method is used to equilibrate the structure with a runtime of
47
48 100 picoseconds. Once the atomic structure is relaxed, the velocity is imparted to t he atoms
49 at the concerning temperature and the structure is allowed to move with the given velocity.
50
51 At this point, a strain rate of 5 x 10-3/ps is applied to uniaxially deform the structure in the
52
53 x-direction. To maintain the uniaxial deformation, the deformations in lateral dimensions are
54
55 kept zero by controlling the pressure components in the said dimensions. The atomistic
56
57
stress in SLGS was captured by averaging the values after each 1000 time-steps of the
58 system of atoms in consideration. LAMMPS lacks the graphical user interface, which leads
59
60
9
1
2 us to the use of a visualization tool OVITO [45] (Open Visualization Tool) to capture the
3
4 snapshots of simulation after each time-step.
5
6
7
8
9 3. Results and discussion
10
11 We have first validated the molecular dynamics simulation results with the earlier reported
12
13
mechanical properties of perfect graphene in the armchair direction at 300K temperature. In
14 this regard we performed the MD simulation using both the optimized Tersoff potential [42] and
15
16 original Tersoff potential (refer to section 2). The Young’s modulus, fracture strength, and
17
18 failure strain are found to be in a good agreement with literature (refer to Table 1),
19
20 corroborating adequate confidence to the further analyses presented in this study. The
21 [7]
Fo
optimized Tersoff potential generates closer results to the experimental investigation for
22
23 tensile strength compared to original Tersoff potential. In the earlier investigations of graphene,
24
r
25 defects and doping have received immense attention from the scientific community from the
26
Re
27 viewpoint of modulating mechanical and other properties as well as to investigate the effect of
28 [23, 35, 51-54]
29
inevitable defects arising during synthesis . As discussed in section 1, the compound
vie
30 effect of multiple defects and most importantly, the compound effect of defect and doping have
31
32 received little attention. In the following subsections, we have systematically presented results
33
w
34 for temperature and chirality dependent mechanical properties of pristine single layer graphene
35
36 sheet (SLGS), graphene with multiple forms of defects, doped graphene and graphene with
On
37
both defects and doping.
38
39
40 3.1. Mechanical properties of pristine SLGS
ly
41
42 MD simulations were carried out for the perfect SLGS with the variation of temperature
43
44 (100K, 300K, 600K, 900K and 1200K) and the loading directions (leading to uniaxial
45
46 deformation in the armchair and zigzag directions). Fig.2 shows the temperature dependent
47
mechanical properties (such as fracture strength, failure stain, Young’s modulus and
48
49 stress-strain curve) of perfect graphene under uniaxial tensile deformation in the armchair
50
51 direction. It can be found from the figure that the fracture strength, failure stain and Young’s
52
53 modulus reduce with the increase in temperature. The failure stress of graphene is found to
54
55
reduce by 11% when the temperature increases from 100K to 1200K. The corresponding
56 reduction for failure strain and Young’s modulus are 40.69% and 5.63% respectively with
57
58 the increase in temperature from 100K to 1200K. The stress-strain plot reveals that the
59
60 graphene undergoes considerable yielding before the failure at the lower temperatures (100K
10
1
2 and 300K), while the yielding plateau reduces at high temperature with almost no su ch
3
4 yielding behaviour at 900K and 1200K (brittle failure).
5
6
7 The effect of chirality on the temperature-dependent mechanical properties of perfect
8
9
graphene is investigated in Fig. 3 considering the loading in zigzag direction. behavior of
10 perfect graphene at different temperatures, loaded in a zigzag direction. Even though a similar
11
12 trend as the armchair direction is found with the variation of temperature, it can be noticed that
13
14 the fracture strength, failure strain and Young’s modulus are higher in case o f zigzag direction.
15
With the increase in the temperature from 100K to 1200K the failure strength, failure strain and
16
17 Young’s modulus (zigzag direction) of graphene reduces by 35.08%, 33.75%, and 6.96%
18
19 respectively. It is observed that the graphene sheet fails at lower strains when subjected to
20
21 higher temperatures, irrespective of the loading direction [46]. This is due to the fact that the
Fo
22 increase in temperature further increases the kinetic energy of atoms, which leads to the
23
24 reduction in C-C bond strength in monolayer graphene.
r
25
26 Another interesting outcome of the investigation is that graphene shows a brittle failure
Re
27
28 for the zigzag direction (refer to Fig 3(c)) even in case of lower temperatures unlike the
29
armchair direction. In case of higher temperature, graphene shows the brittle behaviour for
vie
30
31
both the loading directions.
32
33 It has been widely reported by researchers that the strain rate has a significant effect on the
w
34
[30]
35 mechanical properties obtained from MD simulations . To investigate this effect on
36
On
37 graphene, we have performed a separate set of simulations with different strain rates (0.0001,
38
39
0.0005, 0.001, 0.0025, and 0.005/ps). The comparative results obtained from the strain
40 rate-based simulations are depicted in Fig. 4, wherein it can be noticed that strain rate has
ly
41
42 significant effect on the failure stress, failure strain, Young’s modulus and the extent of
43
44 ductility.
45
46
47
3.2. Mechanical properties of SLGS with defects
48
49 3.2.1. SLGS with Stone-Wales defect
50
51 In this subsection we have investigated the effect of Stone-Wales defect with different
52
53 concentration on the mechanical properties (such as failure stress, failure strain, Young’s
54
55
modulus and stress-strain behaviour) of graphene sheet. One of the principal attributes of
56 Stone-Wales defect is that it doesn’t lose any atom from the pristine graphene and is form ed
57
58 with the absence of dangling bonds [47]. Since the basic effect of loading direction would
59
60 have similar effects on the graphene sheets with defects and doping as described in the
11
1
2 preceding subsection, hereafter we have presented results considering the a rmchair
3
4 direction.
5
6 Fig. 5 illustrates the variation in failure strength, failure strain and Young’s modulus of
7
8 graphene with the varying concentrations of Stone-Wales defect from 0.1% to 0.5%. It’s is
9
10 observed that inducing up to 0.3% Stone-Wales defect concentration increases the fracture
11
12 strength about 2% by keeping Young’s modulus of graphene constant when compared with
13
14
perfect graphene, while the failure strain reduces by 23%. Further increasing the defect
15 concentration up to 0.5% reduces the fracture stress by 13% and Young’s modulus by 2%.
16
17 Fig. 5(c) shows the stress-strain behaviour of graphene sheets with Stone-Wales defect,
18
19 wherein it is interesting to find that the degree of brittleness increases with the increase in
20
21 defect concentration. It can be noted that such effect is analogous to increasing temperature
Fo
22
as shown in Fig. 2(c).
23
24
r
25
3.2.2. SLGS with nanopore defect
26
Re
27
28
In this subsection we have investigated the effect of nanopore defect with different
29 concentration on the mechanical properties (such as failure stress, failure strain, Young’s
vie
30
31 modulus and stress-strain behaviour) of graphene sheet. As depicted in Fig. 6, it can be found
32
33 that the induction of nanopores reduces the failure strength, failure strain and Young’s modulus
w
34
35 significantly. The variation of nanopore defect concentration from 0.1% to 0.5% reduces the
36 failure strength, failure strain and modulus of elasticity by 26%, 33%, and 9% respectively. The
On
37
38 nanopore sites in the graphene behave as stress concentration zone, which further nucleates the
39
40 crack and reduces the strength of graphene significantly. As the number of nanopore defects
ly
41
42 increase the crack nucleation sites also increases, resulting in an early failure of graphene. The
43
44
stress-strain behaviour of graphene sheets with nanopore defects (refer to Fig. 6(c)) reveals a
45 sudden transition of the ductile to brittle behaviour between pristine graphene and graphene
46
47 with nanopore defects, even at lower concentration. This behaviour is different from the effect
48
49 of Stone-Wales defect, where a gradual transition is noticed with increasing defect
50
51 concentration.
52
53 3.2.3. SLGS under the compound effect of Stone-Wales and nanopore defect
54
55 In order to investigate the compound effect of Stone-Wales defect and nanopore defect on
56
57 the mechanical properties of graphene, 0.5% concentration of each effect is induced in the
58
59 pristine graphene and the results are compared with perfect graphene along with 0.5%
60
individual defects concentration (refer to Fig. 7). It is can be noticed that same degree of
12
1
2 nanopore defect concentration shows more reduction in failure properties and Young’s
3
4 modulus compared to Stone-Wales defect, while the compound effect shows a somewhat
5
6 intermediate effect. A similar trend is also evident from the stress-strain relation (including the
7
8 post-elastic behaviour and extent of ductility) of the different cases depicted in Fig. 7(c).
9
10 3.2.4. Effect of the spatial distribution of nano-structural defects
11
12 The spatial distribution of defects may have significant influence on the mechanical
13
14 properties of graphene nanosheets even with same concentration of defect. To investigate
15
16 the effect of spatial location, we have considered eight different cases of nanopore defects as
17
18 shown in Fig. 8(a-h), wherein it can be noticed that the defects are systematically analysed
19
20
with locations near the four different edges, at the centre and randomly distributed in the
21
Fo
entire structure (two different random distributions are considered). However, the
22
23 concentration of defect is maintained constant at 1% for all the cas es. Here the results are
24
r
25 presented considering nanopore defect since the effect of this form of defect is found to be
26
Re
27 more predominant compared to stone-wales defect in the preceding results. The effect of
28
spatial distribution of stone-wales defects is expected to follow similar trend, albeit with a
29
vie
30 different degree of defect sensitivity.

31
32 From Fig. 8(i) it is evident that the same concentration of defect near the right and left
33
w
34 edges (i.e. the edges across the direction of application of strain) affect the failure stress and
35
36
strain most significantly, followed by the location of defect as random distribution throughout
On
37 the structure, centre, bottom and top edges, respectively. The Young’s modulus of a defected
38
39 graphene sheet shows similar sensitivity to the location of defect (refer to Fig. 8(j)). Fig. 8(k)
40
ly
41 shows that the ductile behaviour of a defected graphene sheet also reduces following the same
42
43 trend for different spatial locations of defect. It can be noticed that the mechanical properties
44
(failure strength, failure strain, Young’s modulus and stress-strain curve) are almost same for
45
46 the defect location in left and right zones and top and bottom zones, respectively. However,
47
48 strain rate could have significant effect on the location of defects, which needs further
49
50 investigation. In general, our analyses reveal that the spatial location of defect is a significant
51
52 parameter in addition to the concentration of defect for global mechanical properties of the
53 two-dimensional nanosheet.
54
55
56 3.3. Mechanical properties of doped SLGS
57
58 3.3.1. Effect of C 14 doping on the mechanical properties SLGS
59
60
13
1
2 The replacement of carbon atoms in the SLGS with the heavier isotope of carbon
3
4 (C14) in the concentrations of 1% to 5% is investigated in Fig. 9, wherein it is observed that
5
6 the isotope doping does not affect the Young’s modulus of graphene significantly and it has
7
8 little effect over the fracture strength and failure strain. The degree of ductility is found to
9
10
have negligible effect with the change in isotope doping concentration.
11
12 3.3.2. Effect of Si doping on the mechanical properties SLGS
13
14 Unlike the case of carbon isotope doping, the silicon atoms doping in the concentration of
15
1% to 5% shows reasonable effects on the mechanical properties of the graphene (refer to Fig.
16
17 10). The silicon doping can increase Young’s modulus of graphene by up to 1.5%, whereas the
18
19 failure strength and failure strain reduce by 21% and 35%, respectively. Inducing of silicon
20
21 dopant imparts residual stresses in the structure which causes the early failure of graphene.
Fo
22
23 With the increase in silicon doping concentration, the ductility is found to reduce as shown in
24 Fig. 10(c).
r
25
26
Re
27 3.3.3. Compound effect of C 14 and Si doping on the mechanical properties SLGS

28
29 The behaviour of graphene under compound dopant with 1% concentration of each
vie
30
31 carbon isotope and silicon atom doping is shown in Fig. 11. The results are compared with
32
33 the individual concentration of same concentration of doping. Similar to the observation of
w
34 the preceding section, the effect of carbon isotope doping is not found to be significant,
35
36 while the effect of silicon doping and the compound effect significantly affects the failure
On
37
38 properties and Young’s modulus. The compound doping reduces the failure strength and
39
40 failure strain of graphene by 2% and 23%, respectively; whereas it shows an increase of 1%
ly
41
42
in its Young’s modulus. From the stress-strain behaviour presented in Fig. 11(c), it can be
43 observed that the ductility slightly reduces in case of the carbon isotope doping, while in
44
45 case of the silicon isotope and compound doping a brittle behaviour emerges.
46
47
48 3.3.4. Effect of the spatial distribution of doping
49
50 The spatial distribution of doping may have significant influence on the mechanical
51
52
properties of hybrid graphene nanosheets even with same concentration of doping. To
53 investigate the effect of spatial location, we have considered eight different cases of Si
54
55 doping as shown in Fig. 12(a-h), wherein it can be noticed that the effect of doping is
56
57 systematically analysed with locations near the four different edges, at the centre and
58
59 randomly distributed in the entire structure (two different random distributions are
60 considered). However, the concentration of doping is maintained constant at 1% for all the
14
1
2 cases. Here the results are presented considering Si doping since the effect of this doping is
3
4 found to be more predominant compared to C14 doping in the preceding results. The effect of
5
6 spatial distribution of C 14 doping is expected to follow similar trend, albeit with a different
7
8 degree of doping sensitivity.
9
10
From Fig. 12(i) it is evident that the same concentration of doping near the right edge
11 (i.e. the edge across the direction of application of strain) affects the failure stress and strain
12
13 most significantly, followed by the location of defect near the left edge, centre, random
14
15 distribution throughout the structure, bottom and top edges, respectively. The Young’s
16
17 modulus of a doped graphene sheet shows more or less similar sensitivity to the location of
18
doping (refer to Fig. 12(j)). The slopes of stress-strain curves in the elastic region
19
20 corresponding to different cases in Fig 12(k) further confirm this observation. The
21
Fo
22 post-elastic mechanical properties in Fig. 12(k) show that the ductile behaviour of a doped
23
24 graphene sheet also reduces following the same trend as failure stress and strain for different
r
25
26
spatial locations of doping. Thus, our analyses reveal that the spatial location of doping is a
Re
27 significant parameter in addition to the concentration of doping for global mechanical

28
29 properties of the two-dimensional nanosheet.
vie
30
31
32 3.4. Compound effect of defects and doping on the mechanical properties of SLGS
33
w
34 3.4.1. Compound effect of defects (Stone-Wales and nanopore) and carbon isotope doping
35
36 It is established in the preceding sections that the effect of C 14 doping is not significant
On
37
38 on the mechanical properties of graphene, while nanopore defect affects the mechanical
39
40 properties more than Stone-Wales defect. A similar trend is observed in the comparative
ly
41
42
results presented in Fig. 13. The stress-strain curve shown in Fig. 13(c) reveals that only C 14
43 doping has negligible effect on the ductility, while the other cases affect the ductile
44
45 behaviour considerably.
46
47
48 3.4.2. Compound effect of defects (Stone-Wales and nanopore) and silicon doping
49
50 Fig. 14 illustrates the compound effect of silicon atom doping and defect concentrations
51
52
(Stone-Wales and nanopore) on the mechanical properties of graphene. It is evident from the
53 figure that 1% of silicon doping individually has comparatively lesser effect on the
54
55 mechanical properties. However, if the same concentration of silicon atom doping is
56
57 compounded with the defect concentration, it causes a significant reduction in fracture
58
59 strength and Young’s modulus. In the case of 1% Stone-Wales defect concentration along
60 with silicon doping, the fracture strength and failure strain reduce by 16% and 35%,
15
1
2 respectively. Although the Stone-Wales defect along with silicon doping has comparatively
3
4 lesser effect on Young’s modulus of graphene. On the contrary, the nanopore defect
5
6 concentration along with silicon doping concentrations reduces all the three properties
7
8 significantly (fracture strength, failure strain, and Young’s modulus by 30%, 33%, and 14%,
9
10
respectively). The reduction in ductile behaviour for different compound cases, as presented
11 in Fig. 14(c) is good agreement with their respective individual effect.
12
13 It is observed from the above study that the monolayer graphene loses the extent of
14
15 yielding capacity when induced with defects and dopants. The disruption in the C-C bond
16
17 structure and sp2 hybridization of carbon atoms caused by introducing defects and
18
substitutional dopant result in the creation of stress risers at location of defect and dopant
19
20 induction, which causes early failure of monolayer graphene and decrement in its apparent
21
Fo
22 strength[50]. Due to early failure, the plastic deformation also reduces which occurs
23
24 immediately before the failure. The failure strength and post-elastic constitutive relationship
r
25
26
between stress and strain essentially depend on the initiation of crack in a graphene sheet
Re
27 and its propagation. Multiple studies have been reported on the influencing factors related to
28
29 crack initiation and propagation in graphene including modulation of such mechanical
vie
30
31 behaviour[55, 56] . Here we concentrate on the influence of defects and doping (including their
32
33 compound effects) on the crack propagation behaviour of graphene. The evolution of crack
w
34
in pristine graphene and the effect of different forms of defects and doping in gra phene are
35
36 illustrated in Fig. 15. Typical results for crack evolution under the compound influence of
On
37
38 doping and defects are presented considering carbon isotope dopants (also refer to
39
40 supplementary movies SM1 – SM2). The study convincingly captures a general trend that
ly
41
42 the presence of defects in the nanostructure accelerates the rate of crack evolution due to
43 ease in propagation of the crack path under the influence of locally reduced stiffness
44
45 distribution in the system and conjugation of the adjacent defects. Subsequently, the elastic
46
47 modulus decreases with increasing degree of defect leading to lesser stiffness in the
48
49 nanostructure. As evident from the failure strain for different cases presented in Fig. 15, the
50
51
degree of ductility reduces with the increase in defects and presence of dopant.
52
53
4. Conclusion
54
55 We have investigated the compound effect of defect (such as nanopore and Stone-Wales)
56
57 and doping (such as C 14 and Si) on the mechanical properties of graphene in a systematic
58
59 way using molecular dynamics simulations. Spatial sensitivity of such defect and doping in a
60
graphene sheet is quantified by considering multiple rational instances. The effect of
16
1
2 temperature and chirality on the failure stress, failure strain, Young’s modulus and
3
4 stress-strain behaviour beyond the elastic regime are also investigated as a part of this study.
5
6 Defects in graphene can be perceived in two different ways: first, intentionally induced in a
7
8 pristine nanostructure for simultaneously modulating multi-functional properties (designed
9
10
defects) and second, inevitable consequence of complex manufacturing and synthesis of
11 nanomaterials (intrinsic defects). Either way the change in mechanical pr operties due to the
12
13 presence of defects and irregularities is of paramount interest to the scientific community.
14
15 Doping in a pristine graphene monolayer is normally adopted to modulate multifunctional
16
17 properties to achieve the multi-objective demands of modern devices and systems. The
18
compound effect of such defects and doping on the mechanical properties of the hybrid
19
20 nanostructure is of crucial importance to access the viability in adopting them as various
21
Fo
22 nanoelectromechanical systems and devices. This paper presents a comprehensive study on

23
24 the individual and compound effects of defect and doping considering multipl e critical
r
25
26
cases.
Re
27 The investigation reveals that failure stress, failure strain and Young’s modulus of a
28
29 graphene sheet reduce with the increase in temperature for both armchair and zigzag
vie
30
31 directions. The post-elastic region of stress-strain curve behaves differently for armchair and
32
33 zigzag directions; it is found that ductile behaviour reduces gradually with the increase of
w
34
temperature in case of the armchair direction, while negligible ductile behaviour is noticed
35
36 in case of the zigzag direction. With increasing concentration of defect, the nanopore defect
On
37
38 shows a more drastic reduction in Young’s modulus, failure stress and failure strain
39
40 compared to Stone-Wales defect. The effect of nanopore defect is also quite drastic on the
ly
41
42 reduction of ductile behaviour with increasing concentration of defect compared to the
43 Stone-Wales defect. However same concentration of the compound effect of these two types
44
45 of defects exhibits a somewhat intermediate effect. It is observed that same concentration of
46
47 silicon doping affects the mechanical properties much more than carbon isotope doping.
48
49 Interestingly, the compound effect triggered by the presence of both defect and doping with
50
51
different concentration may lead to a significant level of deviation in the mechanical
52 properties compared to the pristine graphene, primarily depending on the elementary
53
54 influences of the individual components. The spatial sensitivity analyses reveal that the
55
56 location of defect (and doping) is an influential parameter in addition to the concentration of
57
58 defect (and doping) for global mechanical properties of the two-dimensional nanosheet. An
59 in-depth study on the aspect of different individual and compound effects of defects and
60
doping in graphene, as presented in this paper, would serve as a critical reference for
17
1
2 modulating the multi-functional properties as well as accessing the effect of defects in such
3
4 hybrid nanostructures.
5
6
7 Acknowledgements
8
9 KKG would like to acknowledge the financial support received from Ministry of Human
10
11 Resource and Development (MHRD), Govt. of India during the period of this research
12
13
work.TM acknowledges the enhanced financial support from IIT Kanpur during this research.
14
15
16 References
17
18 [1] M.D. Dai, C.W. Kim, K. Eom, Nanoscale Research Letters. 7(2012) 499.
19 [2] T. Kuila, S. Bose, P. Khanra, A.K. Mishra, N.H. Kim, J.H. Lee, Biosensors and
20 Bioelectronics. 26(2011) 4637– 4648.
21
Fo
[3] S. Stankovich, D.A. Dikin, G.H.B. Dommett, K.M. Kohlhaas, E.J. Zimney, E.A. Stach,
22
23 R.D. Piner, S.T. Nguyen, R.S. Ruoff, Nature. 442(2006) 282-286.
24 [4] V.B. Mohan, K.T. Lau, D. Hui, D. Bhattacharya, Composites Part B: Engineering.
r
25 142(2018) 200-220.
26 [5] G. Wang, B.Wang, X. Wang, J. Park, S. Dou, H. Ahn and K. Kim, Journal of Materials
Re
27 Chemistry. 19(2009) 8378-8384.

28
29
[6] The history of graphene (Oct-26,2017) url-
vie
30 https://graphene-flagship.eu/material/Pages/The-history-of-graphene.aspx
31 [7] C. Lee, X. Wei, J.W. Kysar, J. Hone, Science. 321(2008) 385–388.
32 [8] B. Mortazavi, M. Shahrokhi, X. Zhuang, T. Rabczuk, Journal of Material Chemistry A.
33 6(2018) 11022-11036.
w
34
[9] D.G. Papageorgio, I.A. Kinloch, R.J. Young, Progress in Material Science. 90(2017)
35
36 75-127.
On
37 [10] B. Mortazavi, G. Cuniberti, Nanotechnology. 25(2014) 215704.

38 [11] J.L. Tsai, J.F. Tu, Materials and Design. 31(2010) 194-199.
39 [12] T. Mukhopadhyay, A. Mahata, S. Adhikari, M. Asle Zaeem, 2D Materials. 4(2016)
40
025006.
ly
41
42 [13] T. Mukhopadhyay, A. Mahata, S. Adhikari, M. Asle Zaeem, Nanoscale. 10(2018) 5280 –
43 5294.
44 [14] S. Thomas, K.M. Ajith, in: Proceedings to the International Conference on Advances
45 in Manufacturing and Materials Engineering, National Institute of Technology
46 Surathkal, Karnataka, India, March 27–29, 2014.
47
48
[15] A. Mahata, T. Mukhopadhyay. Physical Chemistry Chemical Physics 20(2018)
49 22768-22782.
50 [16] G. Rajasekaran, P. Narayanan, A. Parashar, Critical Reviews in Solid State and
51 Materials Sciences. 41(2015) 47-71.
52 [17] A.W. Robertson, J.H. Warner, Nanoscale. 5(2013) 4079-4093.
53
[18] A. Zandiatashbar, G. Lee, S.J. An, S. Lee, N. Mathew, M. Terrones, T. Hayashi, C.R.
54
55 Picu, J. Hone, N. Koratkar, Nature Communications. 5(2013) (3186)
56 [19] J. Kotakoski, J.C. Meyer, S. Kurasch, D. Santos-Cottin, U. Kaiser, A.V.
57 Krasheninnikov, Physical Review B. 83(2011) (24).
58 [20] S. Pourmand, M. Abdouss, A. Rashidi, Journal of Industrial and Engineering
59
Chemistry. 22(2014) 8-18.
60
[21] G. Dhaliwal, P. B. Nair, C. V. Singh, Carbon. 142(2019) 300-310.
18
1
2 [22] J. Martinez-Asencio, M.J. Caturla, Nuclear Instruments and methods in physics
3 research. 352(2014) 225-228.
4
[23] L. Liu, M. Qing, Y. Wang, S. Chen, A Review. J. of Materials Science & Technology.
5
6 31(2015) 599-606.
7 [24] R. Ansari, S. Ajori, B. Motevalli, Superlattices and Microstructures. 51(2012)
8 274-289.
9 [25] M.C. Wang, C. Yan, L. Ma, N. Hu, M.W. Chen, Computational Materials Science.
10
54(2012) 236-239.
11
12 [26] T. Zhao, Z. Liu, X. Xin, H. M. Cheng & W. Ren, Journal of Materials Science &
13 Technology. DOI: 10.1016/j.jmst.2019.05.012. (2019).
14 [27] S. Wang, B. Yang, J. Yuan, Y. Si, H. Chen, Scientific Reports. 5(2015) 14957.
15 [28] Q. Li, X. Guo, Y. Zhang, W. Zhang, C. Ge, L. Zhao, X. Wang, H. Zhang, J. Chen, Z.
16 Wang, L. Sun, J. Mater. Sci. Technol. 33(8) (2017) 793-799.
17
18
[29] B. Mortazavi, M.E. Madjet, M. Shahrokhi, S. Ahzi, X. Zhuang, T. Rabczuk, Carbon.
19 147(2019) 377-384.
20 [30] M.A.N. Dewapriya, R.K.N.D. Rajapakse, Journal of Applied Mechanics. 81(2014)
21 081010.
Fo
22 [31] C.P. Huelmo, P.A. Denis, The Journal of Physical Chemistry C. (2019) “DOI:
23
10.1021/acs.jpcc.9b07978”.
24
r
25 [32] D.T. Ngyuyen, M.Q. Le, Superlattices and Microstructures. 98(2016) 102-115.
26 [33] X.Q. Lin, W.D. Wang, Q.F. Lü, Y.Q. Jin, Q. Lin, R. Liu, J. Mater. Sci. Technol. 33(11)
Re
27 (2017) 1339-1345.
28 [34] T.M. Dieb, Z. Hou, K. Tsuda, J. Chem. Phys. 148(2018) 241716.
29
[35] T. Han, Y. Luo, C. Wang, Acta MechanicaSolidaSinica. 28(6) (2015).
vie
30
31 [36] Y.Y. Zhang, Y.T. Gu, Computational Materials Science. 71(2013) 197-200.
32 [37] M.P. Allen, Introduction to molecular dynamics simulation. Computational Soft
33 Matter: From Polymers to Proteins, Lecture notes, John von Neumann Institute for
w
34 Computing, Julich, 23(2004) 1-28.

35 [38] S. Plimpton, J. Comp. Phys. 117(1995) 1-19.
36
[39] J. Tersoff, Physical Review B. 37(1988) 6991-7000.
On
37
38 [40] L. Lindsay, D.A. Broido, Physical Review B. 81(2010) 205441.
39 [41] B. Mortazavi, Z. Fan, L.F.C. Pereira, A. Harju, T. Rabczuk, Carbon. 103(2016)
40 318-326.
ly
41 [42] G. Rajasekaran, R. Kumar, A. Parashar, Materials Research Express. 3(2016) 035011.

42
[43] W. Humphrey, A. Dalke, K. Schulten, J. Molec. Graphics. 14(1996) 33-38.
43
44 [44] M.D. Hanwell, D.E. Curtis, D.C. Lonie, T. Vandermeersch, E. Zurek, G.R. Hutchison,
45 Journal of Cheminformatics. 4:17(2012).
46 [45] A. Stukowski, Modelling Simul. Mater. Sci. Eng. 18(2010) 015012.
47 [46] M.A.N. Dewapriya, R.K.N.D. Rajapakse, A.S. Phani, Inter. J. Fracture. 187 199–212
48
(2014).
49
50 [47] G. Rajasekaran, A. Parashar, Proc. Materials Today. 5(2018) 6780-6788.
51 [48] H. Qin, Y. Sun, J. Zhe Liu, Y. Liu, Carbon. 108(2016) 204-214.
52 [49] Z. Ni, H. Bu, M. Zou, H. Yi, K. Bi, Y. Chen, Physica B. 405(2010) 1301-1306.
53 [50] R. lv, M. Tertones, Materials Letters. 78(2012) 209-218.
54 [51] R. Mukherjee, A.V. Thomas, D. Datta, E. Singh, J. Li, O. Eksik, V.B. Shenoy, N.
55
56
Koratkar, Nature Communications, 5(2014) 3710.
57 [52] D. Datta, J. Li, V. B. Shenoy, ACS Applied Materials & Interfaces. 6(2014)
58 1788-1795.
59 [53] A. Mahata, J. W. Jiang, D. R. Mahapatra, T. Rabczuk, Nano-Structures &
60 Nano-Objects. 18(2019) 100247.
[54] R. Majidi, T. Rabczuk, Journal of Physics and Chemistry of Solids. 135(2019) 109115.
19
1
2 [55] D. Datta, S. P. Nadimpalli, Y. Li, V. B. Shenoy, Extreme Mechanics Letters. 5(2015)
3 10-17.
4
[56] C. Cao, S. Mukherjee, J. Y. Howe, D. D. Perovic, Y. Sun, C. V. Singh, T. Filleter,
5
6 Science advances. 4(2018) eaao7202.
7
8
9 Figure and table captions
10
11
12 Table 1. Validation for the mechanical properties of pristine graphene
13
14
15
16
Fig. 1. Nanostructure of graphene with typical representation of defects and doping (a)
17 Schematic representation of graphene indicating the focus of this article (Defects in graphene
18
19 are required to be analysed either to characterize the effect of manufacturing anomalies or to
20
21 intentionally augment different multi-functional properties, i.e. defect engineering. Doping
Fo
22
(such as carbon isotope and silicon) is introduced for multi-functional property modulation.
23
24 Here we focus on the compound effect of defect and doping as depicted in the following
r
25
26 subfigures) (b) Typical representation of nanopore defect (c) Typical representation of
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27
28 Stone-Wales defect (d) Typical representation of compound defects (nanopore and Stone-Wales
29 defect) (e) Typical representation of doping (such as carbon isotope and silicon) (f) Typical
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31 representation of the compound effect of doping and nanopore defect (g) Typical representation
32
33 of the compound effect of doping and Stone-Wales defect
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34
35
36
Fig. 2. Temperature-dependent mechanical behaviour of pristine graphene (armchair
On
37
38 direction) (a) Fracture strength and failure strain (b) Young’s modulus (c) Stress-Strain
39
40 behavior
ly
41
42 Fig. 3. Temperature-dependent mechanical behaviour of pristine graphene (zigzag
44
45 behavior
46
47 Fig. 4. Strain rate-dependent mechanical behaviour of pristine graphene (armchair
48
50
51 behaviour
52
Fig. 5. Mechanical behaviour of graphene with different concentration of Stone -Wales
53
54 defect (armchair direction) (a) Fracture strength and failure strain (b) Young’s modulus (c)
55
56 Stress-Strain behavior
57
58 Fig. 6. Mechanical behaviour of graphene with different concentration of nanopore
59
60
defect (armchair direction) (a) Fracture strength and failure strain (b) Young’s modulus (c)
Stress-Strain behavior
20
1
2 Fig. 7. Mechanical behaviour of graphene under the compound effect of Stone-Wales (SW) and
3
4 nanopore (NP) defects (armchair direction)(a) Fracture strength and failure strain (b) Young’s
5
6 modulus (c) Stress-Strain behavior (the results are presented considering 0.5% Stone-Wales defect
7
8 concentration, 0.5% nanopore defect concentration and compound defect concentration of 0.5% each
9
separately)
10
11 Fig. 8. Effect of variation in spatial distribution of nanopore defects (armchair
12
13 direction) (a - h) Depiction of the spatial location of defect (i) Fracture strength and failure
14
15 strain (j) Young’s modulus (k) Stress-Strain behavior (here the strain is applied in the
16
17 horizontal direction along the right edge)
18
Fig. 9. Mechanical behaviour of graphene with different concentration of carbon
19
20 isotope C14 doping (armchair direction)(a) Fracture strength and failure strain (b) Young’s
21
Fo
22 modulus (c) Stress-Strain behavior

23
24 Fig. 10. Mechanical behaviour of graphene with different concentration of Si doping
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25
26
(armchair direction)(a) Fracture strength and failure strain (b) Young’s modulus (c)
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29 Fig. 11. Mechanical behaviour of graphene with compound effect of C 14 and Si doping
vie
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31 (armchair direction)(a) Fracture strength and failure strain (b) Young’s modulus (c) Stress-Strain
32
33 behavior
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Fig. 12. Effect of variation in spatial distribution of doping (Si) (a - h) Depiction of the
35
36 spatial location of defect (i) Fracture strength and failure strain (j) Young’s modulus (k)
On
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38 Stress-Strain behavior(here the strain is applied in the horizontal direction along the right
39
40 edge)
ly
41 Fig. 13. Mechanical behaviour of graphene with compound effect of C 14 doping and
42
43 defects (Stone-Wales and nanopore) in the armchair direction(a) Fracture strength and
44
45 failure strain (b) Young’s modulus (c) Stress-Strain behavior
46
Fig. 14. Mechanical behaviour of graphene with compound effect of silicon doping and
47
48 defects (Stone-Wales and nanopore) in the armchair direction. (a) Fracture strength and
49
50 failure strain (b) Young’s modulus (c) Stress-Strain behavior
51
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21
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2 Fig. 15. Effect of doping and defects on the failure behaviour of graphene (a - c) pristine
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4 graphene (d - f) graphene with Stone-Wales defect (g -i) graphene with nanopore defect (j - l)
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6 graphene with compound effect of carbon isotope doping and Stone-Wales defect (m - o)
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8 graphene with compound effect of carbon isotope doping and nanopore defect
9
10
11
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13
14
15 Table list:
16 Table 1. Validation for the mechanical properties of pristine graphene
17
18 Young’s Fracture
19
Failure strain
modulus (TPa) strength (GPa)
20
21 Lee et al. (AFM)[7] 1.02 130 0.25
Fo
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23 Ansari et al. (MD Tersoff-Brenner)[24] 0.790 123 0.233
24 Wang et al. (MD AIREBO) [25] - 90 0.25
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25 Zhang & Gu (MD AIREBO) [36] 1.09 115.9 0.138

26
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27 Qin et al. (MD L-J)[48] - 90.4 0.15

28 Ni et al. (Tersoff-Brenner)[49] 1.13 180 0.3248
29 Rajsekaran et al. (Optimized Tersoff) [42] - 150 0.225
vie
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31 Present Study (Optimized Tersoff) 1.217 110.2 0.1583
32 Present study (MD Tersoff) 0.952 195.9 0.36
33
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46 (e) (f) (g)
47 Fig. 1. Nanostructure of graphene with typical representation of defects and doping (a) Schematic
48 representation of graphene indicating the focus of this article (Defects in graphene are required to be
49 analysed either to characterize the effect of manufacturing anomalies or to intentionally augment
50 different multi-functional properties, i.e. defect engineering. Doping (such as carbon isotope and silicon)
51
is introduced for multi-functional property modulation. Here we focus on the compound effect of defect
52
and doping as depicted in the following subfigures) (b) Typical representation of nanopore defect (c)
53
Typical representation of Stone-Wales defect (d) Typical representation of compound defects (nanopore
54
55 and Stone-Wales defect) (e) Typical representation of doping (such as carbon isotope and silicon) (f)
56 Typical representation of the compound effect of doping and nanopore defect (g) Typical representation
57 of the compound effect of doping and Stone-Wales defect
58
59
60
23
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28 Fig. 2. Temperature-dependent mechanical behaviour of pristine graphene (armchair
29
direction) (a) Fracture strength and failure strain (b) Young’s modulus (c) Stress-Strain behavior
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Fig. 3. Temperature-dependent mechanical behaviour of pristine graphene (zigzag direction)
(a) Fracture strength and failure strain (b) Young’s modulus (c) Stress-Strain behavior
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Fig. 4. Strain rate (SR) dependent mechanical behaviour of pristine graphene (armchair
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28 direction) (a) Fracture strength and failure strain (b) Young’s modulus (c) Stress-Strain behaviour
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30 Fig. 5. Mechanical behaviour of graphene with different concentration of Stone-Wales defect

31 (armchair direction) (a) Fracture strength and failure strain (b) Young’s modulus (c) Stress-Strain
32 behavior
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Fig. 6. Mechanical behaviour of graphene with different concentration of nanopore defect
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32 behavior
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26 Fig. 7. Mechanical behaviour of graphene under the compound effect of Ston e-Wales (SW) and
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27 nanopore (NP) defects (armchair direction) (a) Fracture strength and failure strain (b) Young’s
28 modulus (c) Stress-Strain behavior (the results are presented considering 0.5% Stone-Wales defect
29 concentration, 0.5% nanopore defect concentration and compound defect concentration of 0.5% each
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separately)
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46 Fig. 8. Effect of variation in spatial distribution of nanopore defects (armchair direction) (a -
47 h) Depiction of the spatial location of defect (i) Fracture strength and failure strain (j) Yo ung’s
48 modulus (k) Stress-Strain behavior (here the strain is applied in the horizontal direction along the
49
50 right edge)
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30 Fig. 9. Mechanical behaviour of graphene with different concentration of carbon isotope C 14

31 doping (armchair direction)(a) Fracture strength and failure strain (b) Young’s modulus (c)
32
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28 Fig. 10. Mechanical behaviour of graphene with different concentration of Si doping (armchair
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28 Fig. 11. Mechanical behaviour of graphene with compound effect of C 14 and Si doping
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45 Fig. 12. Effect of variation in spatial distribution of doping (Si) (a - h) Depiction of the spatial
46
location of defect (i) Fracture strength and failure strain (j) Young’s modulus (k) Stress-Strain
47
48 behavior(here the strain is applied in the horizontal direction along the right edge)
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29 Fig. 13. Mechanical behaviour of graphene with compound effect of C14 doping and defects
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30 (Stone-Wales and nanopore) in the armchair direction (a) Fracture strength and failure strain (b)
31 Young’s modulus (c) Stress-Strain behavior
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28 Fig. 14. Mechanical behaviour of graphene with compound effect of silicon doping and defects
29 (Stone-Wales and nanopore) in the armchair direction. (a) Fracture strength and failure strain (b)
vie
30 Young’s modulus (c) Stress-Strain behavior

31
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w
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On
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ly
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54
55
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36
1
2
3
4
5
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11 (a) t = 66ps, ε = 33% (b) t = 66.2ps, ε = 33.1% (c) t = 66.5ps, ε = 33.25%
12
13
14
15
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17
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21 (d) t = 49.2ps, ε = 24.6% (e) t = 49.5ps, ε = 24.75% (f) t = 49.9ps, ε = 24.95%
Fo
22
23
24
r
25
26
Re
27
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29
vie
30
31 (g) t = 48.9ps, ε = 24.45% (h) t = 49.1ps, ε = 24.55% (i) t = 49.3ps, ε = 24.7%
32
33
w
34
35
36
On
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40
ly
41 (j) t = 51.4ps, ε = 25.7% (k) t = 51.7ps, ε = 25.85% (l) t = 52.1ps, ε = 26.5%

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51 (m) t = 50.8ps, ε = 25.4% (n) t = 51ps, ε = 25.5% (o) t = 51.5ps, ε = 25.75%
52
53 Fig. 15. Effect of doping and defects on the failure behaviour of graphene (a - c) pristine graphene (d
54 - f) graphene with Stone-Wales defect (g -i) graphene with nanopore defect (j - l) graphene with
55 compound effect of carbon isotope doping and Stone-Wales defect (m - o) graphene with compound
56 effect of carbon isotope doping and nanopore defect
57
58
59
60
37

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Journal of Materials Science & Technology

Probing the compound effect of spatially varying intrinsic

defects and doping on mechanical properties of hybrid

Journal: Journal of Materials Science & Technology

Manuscript Type: Research Article

Date Submitted by the

Complete List of Authors: Gupta, Kritesh; National Institute of Technology Silchar

defect in graphene, doped graphene, defected 2D material, temperature-

Elastic Properties, Failure, Mechanical Properties, Molecular Dynamics

25 should be discussed in the revised manuscript.

27 Researchers have extensively investigated the mechanical properties of graphene, both

27 application of graphene relies on overcoming the adverse effects of these structural

27 investigate the fracture characteristics.

30 different degree of defect sensitivity.

27 3.3.3. Compound effect of C 14 and Si doping on the mechanical properties SLGS

27 significant parameter in addition to the concentration of doping for global mechanical

22 nanoelectromechanical systems and devices. This paper presents a comprehensive study on

27 Chemistry. 19(2009) 8378-8384.

37 [10] B. Mortazavi, G. Cuniberti, Nanotechnology. 25(2014) 215704.

34 Computing, Julich, 23(2004) 1-28.

41 [42] G. Rajasekaran, R. Kumar, A. Parashar, Materials Research Express. 3(2016) 035011.

22 modulus (c) Stress-Strain behavior

25 Zhang & Gu (MD AIREBO) [36] 1.09 115.9 0.138

27 Qin et al. (MD L-J)[48] - 90.4 0.15

30 Fig. 5. Mechanical behaviour of graphene with different concentration of Stone-Wales defect

30 Fig. 9. Mechanical behaviour of graphene with different concentration of carbon isotope C 14

30 Young’s modulus (c) Stress-Strain behavior

41 (j) t = 51.4ps, ε = 25.7% (k) t = 51.7ps, ε = 25.85% (l) t = 52.1ps, ε = 26.5%

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