Graphene re-knits its holes

Recep Zan1,2, Quentin M. Ramasse3,*, Ursel Bangert2 and Konstantin S. No oselo

1 1

Sc!ool o" #!$sics and %stronom$, &!e Uni ersit$ o" Manc!ester, Manc!ester, M13 '#(, United Kingdom

Sc!ool o" Materials, &!e Uni ersit$ o" Manc!ester, Manc!ester, M13 '#(, United Kingdom
3

SuperS&)M (a*orator$, S&+, -ares*ur$ ,ampus, -ares*ur$ .%/ /%-, United Kingdom *&o 0!om correspondence s!ould *e addressed1 QMRamasse2superstem.org Abstract. Nano3!oles, etc!ed under an electron *eam at room temperature in single3

la$er grap!ene s!eets as a result o" t!eir interaction 0it! metal impurities, are s!o0n to !eal spontaneousl$ *$ "illing up 0it! eit!er non3!e4agon, grap!ene3li5e, or per"ect !e4agon 2- structures. Scanning transmission electron microscop$ 0as emplo$ed to capture t!e !ealing process and stud$ atom3*$3atom t!e re3gro0n structure. % com*ination o" t!ese nano3scale etc!ing and re35nitting processes could lead to ne0 grap!ene tailoring approac!es.

Keywords. 6rap!ene, Scanning &ransmission )lectron Microscop$, 2- materials etc!ing, sel"3!ealing.

TOC Graphic.

&!e de elopment o" grap!ene de ices !as entered a ne0 era1 grap!ene is rapidl$ mo ing "rom t!e la*orator$ to t!e "actor$ "loor 0it! an increasing e""ort directed to0ards ac!ie ing de ices t!at emplo$ suspended mem*ranes as 0ell as grap!ene o" de"ined geometries, e.g., nano3ri**ons and 7uantum dots, *ecause o" t!eir predicted no el, e4ceptional electronic properties.1,2 %s a result, t!e inter"aces *et0een grap!ene and ot!er components o" t!e de ices suc! as metal contacts are under intense scrutin$. .e !a e recentl$ s!o0n t!at in t!e presence o" metals grap!ene can *e etc!ed on t!e nano3scale3,/ under e4posure to an electron pro*e "ollo0ing a se7uence o" point de"ect reactions, a process di""erent "rom pre ious attempts at grap!ene etc!ing. 8n earlier studies, grap!ene and grap!ite 0ere etc!ed or tailored in a gas en ironment 9!$drogen or o4$gen: at !ig! temperatures.;3< 8n particular, t!e interaction o" metals 0it! t!e grap!ene sur"ace in suc! e4treme conditions 0as s!o0n *ot! e4perimentall$< and t!eoreticall$' to pro ide an e""icient means o" controlling t!e etc!ing process and e""ecti el$ sculpt grap!ene=grap!ite nanostructures. % recent re ie0 o" t!ese tec!ni7ues 0as "or instance compiled *$ Bir> and (am*in.< %dditionall$, a num*er o" papers !a e pre iousl$ discussed de"ects in grap!ene, eit!er "ollo0ing e4perimental transmission electron microscop$ 9&)M: studies,1?31@ 0!ere de"ects 0ere introduced *$ t!e electron *eam, or *$ simulations *ased on -ensit$ +unctional &!eor$ 9-+&: calculations.1A32/ -e"ects studies in all t!ose papers are *ased on reconstruction o" t!e grap!ene lattice as a result o" 5noc53on o" car*on atoms "rom t!e grap!ene lattice 9mono3 and multi3 acanc$: or=and as a result o" *ond rotations, e.g., t!e "ormation o" Stone3.ales 9;;3AA: and <3ring de"ects. -$namics, sta*ilit$ and "a oura*le arrangements o" t!e reconstructed lattice, 0it! t!e occurrence o" larger acanc$ aggregates and !oles, as 0ell as edge reconstructions t!ereo", are "urt!er aspects o" t!ose studies. +urt!ermore, ne0 structures 0it! long range order, suc! as !aec5elites1< consisting o" ;3, @3 and A3mem*er rings, or penta!eptides1A incorporating ;3 and A3mem*er rings, !a e *een proposed as result o" t!eoretical calculations. Bere 0e report t!e "irst o*ser ations o" reconstruction, i.e. t!e mending and "illing o" man$3 acanc$ !oles 9o er 1?? acancies: in grap!ene, in an electron microscope. .e s!o0 t!at pro ided a reser oir o" loose car*on atoms is readil$ a aila*le near*$, !oles in grap!ene can *e re3"illed 0it! eit!er non3!e4agonal near3amorp!ous or per"ectl$ !e4agonal 23dimensional structures.
2

&o stud$ atomic arrangements 0e emplo$ !ig! angle annular dar5 "ield 9B%%-+: imaging in a Nion UltraS&)M1??&M a*erration3corrected scanning transmission electron microscope 9S&)M:. &!e microscope 0as operated in C6entle S&)MC conditions2; at @? 5eD primar$ *eam energ$ to pre ent 5noc53on damage to t!e grap!ene s!eets, e en a"ter long inter als o" repeated scanning o" small areas o" a "e0 s7uare nanometers. &!e ultra3!ig!3 acuum 9UBD: design o" t!is instrument allo0s clean imaging conditions 0it! pressures *elo0 ;41?3' &orr near t!e sample. &!e *eam 0as set up to a con ergence semi3angle o" 3? mrad 0it! an estimated *eam current o" /; p%. 8n t!ese operating conditions t!e estimated pro*e siEe is 1.1 F, pro iding t!e per"ect tool "or atom3*$3atom c!emical anal$sis2@. &!ese e4perimental conditions 9scanning pro*e, lo0 primar$ *eam energ$, !ig! acuum conditions: are

signi"icantl$ di""erent "rom ot!er studies o" t!e d$namics o" de"ects and edges in grap!ene, 0!ic! emplo$ !ig!er *eam energies and are t$picall$ carried out in muc! poorer acuum conditions.12,2A,2< Samples 0ere o*tained *$ trans"er o" grap!ene mem*ranes gro0n *$ ,Don copper su*strates2' to &)M grids. &0o di""erent metals 0ere deposited *$ electron *eam 9#d: and t!ermal 9Ni: e aporation. %lt!oug! t!ere is no damage in"erred to pristine grap!ene 0it! a @? 5eD electron *eam, 0e !a e recentl$ demonstrated3,/ t!at in t!e presence o" transition3metal or silicon atoms, !ole "ormation does occurs under t!e e3*eam. 8t is *elie ed t!at t!e process occurs due to metal3catal$sed dissociation o" ,3, *onds, 0!ic! leads to point de"ect "ormation. &!e role o" t!e electron *eam in t!is is mainl$ to mo*ilise t!e metal atoms on grap!ene, and not to initiate t!e !ole "ormation in t!e "irst place, i.e., *$ car*on atom displacement. &!e *eam ma$ also act as a local !eat source and t!us !elp o ercome t!e de"ect "ormation energ$ *arrier./ &!is process is !o0e er di""erent "rom !ig!3 temperature &)M o*ser ations o" grap!ene using a dedicated !ot3stage !older, during 0!ic! amorp!ous contaminations la$ers 0ere s!o0n to eit!er *e remo ed totall$,3? t!us cleaning t!e grap!ene, or *e trans"ormed into cr$stalline patc!es.31 Bere, t!e resulting de"ects are enlarged in t!e presence o" "urt!er metal atoms, 0!ic! !a e migrated under t!e electron *eam to t!e edge o" t!e incurred !ole, upon 0!ic! t!e process repeats itsel". &!e nature o" t!e intentionall$3deposited metal impurities 0as con"irmed *$ single3atom sensiti e electron energ$ loss spectroscop$ 9))(S:./ .!en t!e reser oir o" metal atoms is e4!austed, t!e process stops and t!e !ole remains o" almost t!e same siEe,
3

alt!oug! t!e edges undergo repeated reconstruction in consecuti e scans. 8" metal impurities are not present and, at t!e same time, car*on atom suppl$ is 0arranted, e.g. t!roug! near3*$ !$drocar*on contamination attracted to0ards t!e !ole *$ t!e scanning pro*e, G"illingH occurs and t!e !ole mends itsel" *$ non3!e4agon arrangements. Bo0e er, i" no !$drocar*on contamination is present, !ealing can occur via reconstruction o" t!e per"ect grap!ene !e4agon structure. &!e "ollo0ing Z3contrast images depict t!e !ole e olution and t0o "illing scenarios, *$ non3!e4agon and *$ !e4agon structures, in "reel$ suspended grap!ene "ilms 0!ere !ea ier "oreign atoms are present eit!er as residual impurities or as a conse7uence o" metal e aporation. &!e deposition o" metal atoms on ,D-3gro0n grap!ene results in t!e "ormation o" nm3siEed metal clusters sitting pre"erentiall$ on patc!es o" ,3*ased sur"ace contamination, u*i7uitous in suspended grap!ene mem*ranes.32 #d atoms, dislodged "rom a near*$ #d cluster *$ t!e electron *eam and CdraggedC across t!e sample until t!e$ settle in a ne0 sta*le position as t!e *eam is *eing scanned, can *e seen in "ig. 1a to decorate a !ole in grap!ene. Ne0l$ arri ing #d atoms lead to !ole e4pansion 9"ig 1*:, 0!ereas in t!e a*sence o" metal atoms t!e !ole "ormation slo0s do0n and edge reconstruction ta5es place under t!e electron *eam 9"ig. 1c:. +urt!ermore, "igure 1 s!o0s t!at t!e !ole is *ordered *$ !$drocar*on contamination, 0!ic! constitutes t!e car*on reser oir "or t!e !ole !ealing descri*ed *elo0.

Figure 1. %tomic resolution B%%-+ images 9ra0 data: "rom consecuti e scans o" suspended grap!ene, s!o0ing a: an etc!ed !ole decorated 0it! #d atomsI *: t!e enlargement o" t!e !ole "ollo0ing "urt!er suppl$ o" #d atomsI c: t!e sta*iliEation o" t!e !ole siEe in t!e a*sence o" #d atoms at t!e edge.

+igure 2 s!o0s t!e same !ole as in "ig. 1. a"ter t!e metal reser oir !as *een mostl$ e4!austed. &!e !ole t!en starts to !eal 0it! car*on atoms *eing supplied *$ t!e contamination patc!es 9lig!t gre$ "eatures at t!e top and *ottom o" "ig. 1 and 2:. &!e image in "igure 2a 0as ta5en a"ter t!at in "ig. 1c and illustrates t!e start o" t!e !ealing process. &!e *lue dotted line in "ig. 2d s!o0s t!e *order o" t!e !ole at t!e pre3!ealing stage 9immediatel$ a"ter "ig. 1c 0as ac7uired:. %"ter a su*se7uent scan t!e !ole !as "illed completel$ 0it! 0!at can *e descri*ed as a 23dimensional amorp!ous car*on patc! 9"ig. 2*:, constituted almost randoml$ o" ;, @3, A3 and e en <3mem*er rings. Nota*l$ ;3A3= <3mem*er ring pairs can arise "rom dissociation o" lattice acancies and constitute dislocation dipoles.1' %dditional

impurit$ atoms are also captured 0it!in t!is ne0l$3"ormed CnetC1 *rig!t atoms are clearl$ seen on "ig. 2a and 2*. +igure 2c is o" a su*se7uent scan o" t!e same area as in "igs 2a and *. &!e deposition o" car*on ad3atoms, 0!ic! are dragged out o" t!e !$drocar*on contamination *$ t!e scanning *eam can *e seen "rom slig!tl$ lig!ter patc!es and strea5s on t!e car*on rings in "ig. 2c, ma5ing atomic position identi"ication slig!tl$ more di""icult. Ne ert!eless, a redistri*ution o" t!e de"ects is noticea*le, indicating *ond rotation during t!e scan1 nota*l$ in "ig. 2c t!e car*on atoms !a e re3organiEed t!emsel es solel$ into ;3A rings 0!ile t!e more unsta*le <3mem*er ring structure !as disappeared. &!e *ottom ro0 images are t!e same as in t!e top ro0 *ut in order to reduce t!e noise le els and to impro e t!e accurac$ o" t!e image anal$sis 9to s!o0 t!e car*on3atom Cnet0or5C more clearl$:, a pro*e decon olution algorit!m *ased on ma4imum entrop$ met!ods 0as applied to t!e ra0 Z3contrast images. &!is algorit!m also !as t!e ad antage o" remo ing t!e contri*ution o" t!e tails o" t!e "ocussed electron pro*e to t!e neig!*ouring atom intensities, 0!ic! is essential "or 7uantitati e contrast anal$sis.2@,33 &!is se7uence o" images s!o0s clearl$ t!at t!e "aults in t!e reconstructed grap!ene do not arise "rom damage *$ t!e e3*eam, *ut are gro0n3in "eatures as a result o" an Gepita4ialH3li5e gro0t!. &!e incorporation o" sets o" ;3, @3 and A3 mem*er rings structures, called Baec5elites, into !ig!l$ de"ected grap!ene 0as suggested *$ &errones et al.1< *ut !ad ne er *een o*ser ed e4perimentall$ !it!erto. +igure 2 s!o0s clearl$ t!at t!is 5ind o" structure can e4ist in suspended "orm alt!oug! t!e$ "orm !ere an amorp!ous patc! rat!er t!an organising t!emsel es into an ordered arra$ o" pol$gons.

Figure 2. %tomic resolution Z3contrast images illustrating t!e !ole "illing process in suspended grap!ene. a: a !ole created at t!e *order o" !$drocar*on contamination *: complete reconstruction 0it! incorporation o" ;3A rings and t0o ;3< rings, and c: redistri*ution o" de"ects in t!e GmendedH region, *$ ;3A rings. 8mages d3" are processed ersions o" a3c. % ma4imum entrop$ decon olution algorit!m 0as used and t!e contrast 0as optimised to isualise t!e car*on atoms. &!e car*on atom positions are !ig!lig!ted *$ lig!t green dots and pol$gons num*ered according to t!e num*er o" atoms in t!e rings. Suc! 23dimensional near3amorp!ous car*on la$ers can also gro0 Cepita4iall$H on grap!ene, as illustrated on "igure 3. %"ter long o*ser ations o" t!e same area o" single la$er grap!ene 9more t!an /? minutes o" o*ser ation in t!is case: some contamination can occasionall$ Ccreep inC and co er t!e grap!ene s!eet. &!e circled region on "igure 3a is a single additional car*on la$er 9as can *e clearl$ deduced "rom t!e contrast in t!e image:, 0!ic! !as "ormed on top o" t!e clean, underl$ing 9dar5: grap!ene patc! a"ter repeated scanning. &!e presence o" a MoirJ pattern indicates t!at t!is additional la$er !as a similar structure to t!e underl$ing grap!ene, *ut t!e patter is !ig!l$ irregular and interrupted 9as !ig!lig!ted *$ t!e arro0s:, unli5e t!e patterns o*ser ed in pure Bernal3stac5ed grap!ene.3/

Figure . %tomic resolution B%%-+ image 9ra0 data: o*tained a"ter repeated scanning o" t!e same areaI t!e circled area is an additional one3atom3t!ic5 car*on la$er t!at !as gro0n Gepita4iall$H as a result o" car*on atom suppl$ "rom t!e !$drocar*on contamination surrounding t!e pristine grap!ene patc!. &!e MoirJ pattern, !o0e er, is non3regular 9arro0:, indicating t!e e4istence o" random de"ected car*on ring net0or5s in t!e ne0l$3 gro0n la$er as 0ell as in t!e alread$ e4isting contamination. &!e ne0l$3gro0n la$er must t!ere"ore *e !ea il$ "aulted. 8t li5el$ contains a !ig! densit$ o" ;3 and A3mem*er rings, similar to t!e Gre35nittedH la$er in "ig 2*. &!is can again *e interpreted as an amorp!ous 23dimensional la$er 0it! some degree o" s!ort3range grap!ene3li5e order. &!e re3gro0n structures in "igs. 2 and 3 pro ide a remar5a*le glimpse into t!e atomic arrangements o" amorp!ous car*on structuresI t!e$ s!o0 t!e precise atomic arrangements o" a 23- amorp!ous car*on material.1/ B$ close inspection o" atomic resolution Z3contrast images o" grap!ene "ilms it can t!en *e concluded t!at a large "raction o" t!e u*i7uitous contamination 9suc! as t!e lig!ter patc!es in "ig. 3*: 0!ere material deposited on grap!ene sits pre"erentiall$, consists o" stac5s o" t!ese amorp!ous mono3la$er car*on "ilms. B$ contrast, 0!en a small !ole is created a0a$ "rom t!e !$drocar*on contamination, t!e sel"3!ealing mec!anism appears to lead to t!e "ormation o" per"ect !e4agons. &0o !oles are apparent in "ig. /a, *ot! created as a result o" Ni3atom mediated grap!ene etc!ing. &!e small !ole 0as created 0!en Ni atoms "rom t!e edge o" t!e larger !ole, 0!ic! !ad "ormed earlier, 0ere dislodged *$ t!e electron *eam and CdraggedC onto a clean patc! o" grap!ene
A

0!ere t!e etc!ing 0as initiated, t!roug! t!e e3*eam scanning motion. 8n su*se7uent scans, a"ter cessation o" t!e migration o" metal atoms to its edges, t!e small !ole is o*ser ed to "ill up 0it! per"ect car*on !e4agons 9"ig. /*:. &!is Cre35nittingC process !appened 0it!in a muc! s!orter time span 9less t!an 1? seconds1 t0o consecuti e scans: compared to t!e pre ious case 9"igs. 1K2:. 8mpurit$ atoms are again trapped 0it!in t!e ne0l$ "ormed lattice, suc! as t!e *rig!ter atom indicated in "ig. /* *$ an arro0. %"ter t!e contri*ution o" t!e electron pro*e CtailsC to t!e ra0 B%%-+ images !as *een remo ed 9using "or instance a ma4imum3 entrop$3*ased pro*e decon olution algorit!m33:, a care"ul comparison o" atomic intensities s. atomic num*er Z 0it! t!e model alue o" Z1.A "or B%%-+ imaging 9in our e4perimental conditions: can ena*le t!e c!emical identi"ication o" t!ese impurities.2@ +igure /c s!o0s a !istogram o" t!e "re7uenc$ o" occurrence o" atoms ersus t!eir B%%-+ intensit$ in t!e icinit$ o" t!e *rig!t atom in +ig. /*, o*tained "rom t!e decon oluted image in t!e inset in "ig. /c. &!e positions o" t!e intensit$ ma4ima are in t!e ratio o" 111.@@, 0!ic! is close to t!e Z1.A ratios "or Z L @ 9,: and Z L < 9M:, o" 111.@3. %lt!oug! t!ere is onl$ one suc! impurit$ in t!is image 9and t!e statistics are t!ere"ore lo0: t!is is a good indication t!at t!e *rig!ter atom is li5el$ o4$gen.

Figure !. %tomic resolution B%%-+ images 9ra0 data: "rom su*se7uent scans o" suspended grap!ene, s!o0ing a: t0o !oles as result o" Ni3mediated etc!ing, *: complete reconstruction o" small !ole 0it! per"ect !e4agon grap!ene structure. c: !istogram o" t!e atom intensities, in t!e icinit$ o" t!e *rig!ter atom1 t!e anal$sis 0as carried out a"ter processing image /* 0it! a pro*e decon olution algorit!m 9inset:. &!e siEe o" t!e !ole to "ill is an o* ious di""erence 0it! t!e pre ious case and ma$ e4plain t!e "ormation o" per"ect !e4agons1 argua*l$, de"ects are less li5el$ to "orm across suc! a s!ort gro0t! distance. Moreo er, t!e larger distance "rom t!e contamination reser oir and
<

t!e pro4imit$ to a muc! larger per"oration in t!e grap!ene s!eet ma$ also pla$ a role. )dges in grap!ene are 5no0n to *e more unsta*le e en at lo0 oltages12,1;1 atoms eNected "rom t!e edge o" t!is larger neig!*ouring !ole ma$ !a e *een captured during t!e re35nitting 0!ile t!e long edge ma$ !a e recon"igured to accommodate t!e ne0l$ "ormed material into t!e usual, energeticall$ "a oura*le !one$com* pattern. %dditionall$, using a lo0 primar$ *eam energ$ 9@? 5eD:, clean acuum conditions 9O;41?3' &orr: to reduce t!e ioniEation damage pro*a*ilit$, and a scanning pro*e, can !elp e4plaining our o*ser ations o" !ole3 "illing, 0!ic! contrast 0it! pre ious reports o" !ole3e4pansion at <? 5eD 0it! a stationar$ *eam.12,2< 8n conclusion, etc!ing o" grap!ene occurs in t!e presence o" metalsI 0!en t!e metal atom suppl$ ceases grap!ene reconstructs its !oles *$ "orming per"ect !e4agonal or pol$gonal, i.e. ;3, @3, A3 and <3mem*er ring structures, 0!ic! can e4ist eit!er in suspended "orm or gro0 Cepita4iall$C on top o" clean grap!ene. ,ar*on atoms 5noc5ed out "rom neig!*ouring edges, or supplied *$ near*$ !$drocar*on contamination patc!es, are incorporated into t!e !oles in a remar5a*le re35nitting process. &!is o*ser ation o" sel"3!ealing o" grap!ene mig!t open up possi*ilities "or t!e use o" e3*eam tec!ni7ues in tailoring grap!ene in a G*ottom3upH "as!ion via nano3scale3controlled etc!ing and epita4ial gro0t! "rom s!eet edges. "e#erences
1. 6eim, %. K.I No oselo , K. S. Nat Mater 2$$%& @, 93:, 1<331'1.

2. #onomaren5o, (. %.I 6eim, %. K.I Z!u5o , %. %.I Palil, R.I MoroEo , S. D.I No oselo , K. S.I 6rigorie a, 8. D.I Bill, ). B.I ,!eiano , D. D.I +al5o, D. 8.I .atana*e, K.I &aniguc!i, &.I 6or*ac!e , R. D. Nat Phys 2$11& A, 912:, ';<3'@1. 3. Zan, R.I Bangert, U.I Ramasse, Q.I No oselo , K. S. Journal of Physical Chemistry Letters 2$12& 3, ';33';<. /. Ramasse, Q. M.I Zan, R.I Bangert, U.I Bou5! alo , -. ..I Son, Q. ..I No oselo , K. S. ACS Nano 2$12, -M81 1?.1?21=nn3??/;2$. ;. Se erin, N.I Kirstein, S.I So5olo , 8. M.I Ra*e, P. #. Nano Letters 2$$'& ', 91:, /;A3/@1.

@. Boot!, &. P.I #iEEocc!ero, +.I %ndersen, B.I Bansen, &. ..I .agner, P. B.I Pinsc!e5, P. R.I -unin3 Bor5o0s5i, R. ).I Bansen, M.I Boggild, #. Nano Letters 2$11& 11, 9A:, 2@<'32@'2. A. -imie , %.I Kos$n5in, -. D.I Sinits5ii, %.I Slesare , %.I Sun, Z.I &our, P. M. Science 2$11& 331, 9@?21:, 11@<311A2. '

<. '. 1?.

Bir>, (. #.I (am*in, #. Carbon 2$1$& /<, 91?:, 2@AA32@<'. ,!an, K. &.I Neaton, P. B.I ,o!en, M. (. Physical Review B 2$$'& AA, 923:, 23;/3?. Bas!imoto, %.I Suenaga, K.I 6loter, %.I Urita, K.I 8iNima, S. Nature 2$$!& /3?, 9A??2:, <A?3<A3.

11. Me$er, P. ,.I Kisielo0s5i, ,.I )rni, R.I Rossell, M. -.I ,rommie, M. +.I Zettl, %. Nano Letters 2$$'& <, 911:, 3;<233;<@. 12. 6irit, ,. M.I Me$er, P. ,.I )rni, R.I Rossell, M. -.I Kisielo0s5i, ,.I Qang, (.I #ar5, ,.3B.I ,rommie, M. +.I ,o!en, M. (.I (ouie, S. 6.I Zettl, %. Science 2$$(& 323, 9;'22:, 1A?;31A?<. 13. Ban!art, +.I Kota5os5i, P.I Kras!eninni5o , %. D. ACS Nano 2$11& ;, 91:, 2@3/1.

1/. Kota5os5i, P.I Kras!eninni5o , %. D.I Kaiser, U.I Me$er, P. ,. Physical Review Letters 2$11& 1?@, 91?:, 1?;;?;. 1;. Kota5os5i, P.I Me$er, P. ,.I Kurasc!, S.I Santos3,ottin, -.I Kaiser, U.I Kras!eninni5o , %. D. Physical Review B 2$11& <3, 92/:, 2/;/2?. 1@. 6ass, M. B.I Bangert, U.I Bleloc!, %. (.I .ang, #.I Nair, R. R.I 6eim, %. K. Nat Nano 2$$'& 3, 911:, @A@3@<1. 1A. ,respi, D. B.I Benedict, (. R.I ,o!en, M. (.I (ouie, S. 6. Physical Review B 1(()& ;3, 92?:, R133?33R133?;. 1<. &errones, B.I &errones, M.I BernandeE, ).I 6ro*ert, N.I ,!arlier, P. ,.I %Na$an, #. M. Physical Review Letters 2$$$& </, 9<:, 1A1@31A1'. 1'. )0els, ,. #.I Beggie, M. 8.I Briddon, #. R. Chemical Physics Letters 2$$2& 3;1, 933/:, 1A<31<2.

2?. (ee, 6.3-.I .ang, ,. Z.I Qoon, ).I B0ang, N.3M.I Kim, -.3Q.I Bo, K. M. Physical Review Letters 2$$*& ';, 92?:, 2?;;?1. 21. 22. 23. 2/. Kras!eninni5o , %. D.I Ban!art, +. Nat Mater 2$$%& @, 91?:, A233A33. Peong, B. ..I 8!m, P.I (ee, 6.3-. Physical Review B 2$$'& A<, 91@:, 1@;/?3. (us5, M. &.I ,arr, (. -. Physical Review Letters 2$$'& 1??, 91A:, 1A;;?3. Kim, Q.I 8!m, P.I Qoon, ).I (ee, 6.3-. Physical Review B 2$11& </, 9A:, ?A;//;.

2;. Kri ane5, M. (.I -ell*$, N.I Mur"itt, M. +.I ,!is!olm, M. +.I #enn$coo5, &. P.I Suenaga, K.I Nicolosi, D. Ultramicrosco y 2$1$& 11?, 9<:, '3;3'/;. 2@. Kri ane5, M. (.I ,!is!olm, M. +.I Nicolosi, D.I #enn$coo5, &. P.I ,or*in, 6. P.I -ell*$, N.I Mur"itt, M. +.I M0n, ,. S.I SEilag$i, Z. S.I M4le$, M. #.I #antelides, S. &.I #enn$coo5, S. P. Nature 2$1$& /@/, 9A2<<:, ;A13;A/. 2A. .arner, P. B.I Rummeli, M. B.I 6e, (.I 6emming, &.I Montanari, B.I Barrison, N. M.I Buc!ner, B.I Briggs, 6. %. -. Nat Nano 2$$(& /, 9<:, ;??3;?/. 1?

2<. Russo, ,. P.I 6olo c!en5o, P. %. Procee!in"s of the National Aca!emy of Sciences 2$12, -M81 1?.1?A3=pnas.111'<2A1?'. 2'. (i, R.I ,ai, ..I %n, P.I Kim, S.I Na!, P.I Qang, -.I #iner, R.I Delama5anni, %.I Pung, 8.I &utuc, ).I BanerNee, S. K.I ,olom*o, (.I Ruo"", R. S. Science 2$$(& 32/, 9;'32:, 13123131/. 3?. an -orp, .. +.I Z!ang, R.I +eringa, B. (.I .agner, P. B.I Bansen, &. ..I -e Bosson, P. &!. M. Nanotechnolo"y 2$11& 22, ;?;3?3. 31. Barreiro, %.I Boerrnert, +.I % dos!en5o, S. M.I Relling!aus, B.I ,uni*erti, 6.I Ruemmeli, M. B.I Danders$pen, (. M. K. Unpu*lis!ed 2$12. 32. Zan, R.I Bangert, U.I Ramasse, Q.I No oselo , K. S. Nano Letters 2$11& 11, 93:, 1?<A31?'2.

33. 8s!iEu5a, K.I %*e, ). Proc. of the #$th %uro ean Microsco y Con"ress& 'nstrumentation an! Metho!olo"y 2$$!& 1, 11A. 3/. 1;<. Zan, R.I Bangert, U.I Ramasse, Q.I No oselo , K. S. Journal of Microsco y 2$11& 2//, 92:, 1;23

11