Su ace Chemis y
Deposi ing Molecula G aphene Nano ibbons on Ag(111) by
Elec osp ay Con olled Ion Beam Deposi ion: Sel -Assembly and
On-Su ace T ans o ma ions
Wei Ran, And eas Walz, Ka olina S oibe , Pe e Knech , Hongxiang Xu,
An houla C. Papageo giou,* Anne e Hue ig, Diego Co izo-Lacalle, Juan P. Mo a-Fuen es,
Au elio Ma eo-Alonso, Ha mu Schlich ing, Joachim Reiche ,* and Johannes V. Ba h*
Abs ac : The chemical p ocessing o low-dimensional
ca bon nanos uc u es is c ucial o hei in eg a ion in
u u e de ices. He e we apply a new me hodology in
a omically p ecise enginee ing by combining mul is ep
solu ion syn hesis o N-doped molecula g aphene nano-
ibbons (GNRs) wi h mass-selec ed ul a-high acuum
elec osp ay con olled ion beam deposi ion on su aces
and eal-space isualisa ion by scanning unnelling
mic oscopy. We demons a e how his me hod yields
solely a con ollable amoun o single, o he wise unsu-
blimable, GNRs o 2.9 nm leng h on a plana Ag(111)
su ace. This me hodology allows o u he p ocessing
by employing on-su ace syn hesis p o ocols and exploi -
ing he eac i i y o he subs a e. Following mul iple
chemical ans o ma ions, he GNRs p o ide eac i e
building blocks o o m ex ended, me al–o ganic coo di-
na ion polyme s.
In oduc ion
G aphene as well as o he 2D shee ma e ials a e ex emely
p omising o inno a i e o ganic nano-scale elec onics.
Howe e , geome ically and chemically ailo ed de i a i es
a e necessa y o ealize he en isioned ci cui s and ma e ials
o be employed in he mally and elec ically conduc ing
elemen s, senso s, anspa en elec odes o displays, sola
cells, ca alys s, elec odes o ba e ies and uel cells, and
o ganic ield-e ec ansis o s.[1] These include g aphene
nano ibbons (GNRs): a class o ma e ials whose elec onic,
op ical and mechanical p ope ies p esen signi ican appli-
ca ion po en ial in elec onics,[1c,2] pho onics,[3] and ene gy
s o age[4] and con e sion.[5] S uc u al modi ica ions o
con ol he semiconduc ing p ope ies a e achie ed by
limi ing he dimensions o na ow s ips, by designing edge
s uc u es, h ough doping he co e o edges wi h he e -
oa oms, o by in oducing he e ojunc ions.[5a,6]
The physical p ope ies o GNRs depend on he wid h,
leng h, edge s uc u e and doping loci, which makes syn-
hesis wi h a omic p ecision c ucial. Se e al op-down
s a egies including slicing o e ching o g aphene, cu ing,
oxida ion, in e cala ion, plasma e ching o nano ubes and
sonica ion o shee s equen ly ail in his espec : he
achie ed geome ies a e oo la ge, hei nanos uc u es
poo ly de ined, wi hou a omic p ecision. Thus, al e na i e
bo om-up solu ion[7] and on-su ace[8] syn hesis app oaches
we e in oked, since hey can p o ide con ol o e all he
s uc u al pa ame e s ha de e mine he GNR p ope ies.
On-su ace syn hesis ypically equi es a sublima ion p oce-
du e o con olled su ace deposi ion o he mally obus
p ecu so s unde ul a-high acuum (UHV) condi ions.
Non-UHV s a egies o deposi he eac an s on a gi en
subs a e, like spin coa ing, ink-je p in ing, d op-cas ing,
elec osp ay o chemical ba h deposi ion ypically do no
mee he necessa y pu i y equi emen s on an a omic scale
and hus well-de ined molecula laye s a e elusi e. By
deposi ing ailo ed molecules on well-de ined in e aces in
acuum, no el, in ica e s uc u es and de ice elemen s
come in each. Howe e , es ablished deposi ion me hod-
ologies wi h a omic inesse (e.g. o ganic molecula beam
epi axy) a e cu en ly limi ed o he mos able sublimable
molecules, whence a ple ho a o o ganic and almos all
biomolecules wi h hei ascina ing p ope ies a e excluded.
Such limi a ions can be o e come by deposi ion sys ems
using elec osp ay ionisa ion unde UHV.[9] This allows o
ul a-pu e laye s o so -landed and he e o e in eg i y-
p ese ed species, a p e equisi e o sophis ica ed high-le el
[*] D . W. Ran, D . A. Walz, D . K. S oibe , D . P. Knech , H. Xu,
D . A. C. Papageo giou, D . A. Hue ig, D . H. Schlich ing,
D . J. Reiche , P o . D . J. V. Ba h
Physics Depa men E20, Technical Uni e si y o Munich,
James F anck S aße 1, 85748 Ga ching (Ge many)
E-mail: [email p o ec ed]
[email p o ec ed]
[email p o ec ed]
D . D. Co izo-Lacalle, J. P. Mo a-Fuen es, P o . D . A. Ma eo-Alonso
POLYMAT, Uni e si y o he Basque Coun y UPV/EHU, A enida de
Tolosa 72, 20018 Donos ia-San Sebas ian (Spain)
P o . D . A. Ma eo-Alonso
Ike basque, Basque Founda ion o Science,
Bilbao (Spain)
© 2022 The Au ho s. Angewand e Chemie In e na ional Edi ion
published by Wiley-VCH GmbH. This is an open access a icle unde
he e ms o he C ea i e Commons A ibu ion License, which
pe mi s use, dis ibu ion and ep oduc ion in any medium, p o ided
he o iginal wo k is p ope ly ci ed.
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nano-scale ma e ial design and cha ac e iza ion.[10] Li e a-
u e p o ides many examples including biologically ele an
molecules ((poly)saccha ides,[9b,11] pep ides,[12] p o eins,[13]
DNA),[9c,14] o ganic molecules,[15] nano-clus e s,[9a,16] and cage
complexes.[17] Fo his pu pose and inspi ed by p e ious
achie emen s, we ha e de eloped a sys em wi h inno a i e
ea u es, designa ed elec osp ay con olled ion beam depo-
si ion (ES-CIBD), ha p ocesses eadily dissol able species
including he molabile and agile en i ies like mos o ganic
and biological molecules.[14] Ou ES-CIBD appa a us p o-
ides a p epa a i e ool using digi al ion-guiding and mass-
spec ome y elemen s o ans e sol a ed molecules unde
ambien condi ions on o well-de ined su aces unde UHV
condi ions wi h mass-selec i i y and uneable ene gy.
He ein, we demons a e he clean deposi ion o complex,
molecula GNRs, p esen ing a signi ican ad ancemen
beyond simple elec osp ay ionisa ion deposi ion o such
g aphene-based mac omolecules.[18] Once on he su ace, we
u he employ an on-su ace syn hesis me hodology,[19]
which may a o d polyme s ia su ace assis ed eac ions
igge ed by he mal annealing.[20] The GNR species em-
ployed exhibi s mul iple unc ional g oups, some o which
a e known o be qui e labile (e.g. ace als and silyl, Fig-
u e 1b). These unc ional g oups a e in oduced o ul il
se e al eac i i y and solubili y equi emen s o solu ion
syn hesis. Despi e hese moie ies’ labili y and he size o he
GNR backbone, he en i e species is deposi able, wi hou
any e idence o hype he mally induced
Figu e 1. Elec osp aying ollowed by con olled ion beam deposi ion o NR-10. a) Ions p oduced ia elec osp ay ionisa ion om a solu ion a e
ans e ed o ul a-high acuum by a ious ion guides in se e al p essu e s ages whe e neu al sol en molecules a e emo ed. Ionic impu i ies
a e elimina ed by a subsequen digi al quad upole mass spec ome e , which selec s he a ge ions acco ding o m/z. Fo so -landing, hese ions
a e deposi ed on a su ace wi h low kine ic ene gy ( ypically below 10 eV/z). The sample can be u he in es iga ed by a scanning unnelling
mic oscope. b) Chemical s uc u e o NR-10 (C148H190N8O8Si4). c) Mass spec um o NR-10 in THF solu ion. The main in ensi y a app oxima ely
1162 Th o igina es om he doubly cha ged monome . The ion beam was pu i ied wi h he dQMS acco ding o he deposi ion window ma ked by
he shaded ec angle o exclusi ely deposi he NR-10 a ibu ed ions.
Figu e 2. STM imaging o NR-10 on Ag(111). a) Su ace o e iew in long ange mic og aph (111 K, 1.76 V, 0.15 nA). b) Magni ied iew o sel -
assembled island (160 K, 2.1 V, 0.12 nA). c) C opped image o iden i ied single molecule, o e laid wi h NR-10 molecula model. C, N, O, Si and H
a e depic ed in black, blue, ed, pu ple and whi e, espec i ely.
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mechanochemis y,[21] gi ing ise o well-o de ed, sel -
assembled s uc u es on he Ag(111) su ace as shown by
scanning unnelling mic oscopy (STM) in es iga ions. Sim-
ila ly o he p o ec ion and dep o ec ion schemes used in
solu ion syn hesis, on he sil e su ace, he silyl solubilizing
g oups can be di ec ly clea ed and he ace als can be
ans o med in o he co esponding diones, enabling he
o ma ion o me al-o ganic coo dina ion polyme s. The
s epwise con e sion and polyme isa ion scheme o he small
GNR is cha ac e ised by analysis o high- esolu ion STM
images.
Resul s and Discussion
We employed a molecula N-doped conjuga ed polya o-
ma ic species, which is ob ained by mul is ep o ganic
syn hesis in solu ion.[7i] The molecule unde in es iga ion is a
linea nano ibbon wi h 10 conjuga ed linea ly used ings
(NR-10, Figu e 1b), a molecula mass o 2321.54 Da (calcu-
la ed om he iso opic composi ion and in ull ag eemen
wi h li e a u e)[7i] and a leng h o 2.9 nm.
The a omically clean deposi ion o non- ola ile mole-
cules in UHV is pe o med by ES-CIBD (schema ic shown
in Figu e 1a).[22] S a ing om a sample solu ion wi h
dissol ed analy e molecules, a beam o gas-phase ions is
gene a ed ia elec osp ay ionisa ion. T ans e ion guides
conduc he ion beam om he ambien condi ions o he
sp ay o UHV and a digi al quad upole mass spec ome e
(dQMS). He e, he beam ge s ei he analysed o i s
composi ion o il e ed acco ding o m/z o subsequen
deposi ion. The dQMS exclusi ely ansmi s a small window
o m/z alues wi h adjus able wid h and posi ion while all
o he ions a e emo ed om he beam. Finally, so -landing
o ions wi h low kine ic ene gies yields in ac molecules on
he sample su ace, whe e he co e age is con olled by he
inciden ion beam in ensi y. The combina ion wi h a a iable
empe a u e UHV-STM and an in si u ans e sys em
allows o in es iga ion and u he manipula ion o he
deposi ed laye s. The subsequen STM cha ac e isa ion
showed ha high-pu i y deposi ions we e achie ed.
Posi i e-mode elec osp ay o he NR-10 molecules
dissol ed in an acidi ied THF/wa e mix u e (c . Me hods)
esul ed in he mass spec um depic ed in Figu e 1c. The
doubly cha ged monome a a ound 1162 Th is he dominan
ion species and he e o e was selec ed o all deposi ions.
So -landing was pe o med wi h �2 eV/zkine ic ene gy pe
molecule (�4 eV a z=2) on he Ag(111) su ace held a
oom empe a u e.
The samples we e subsequen ly examined by STM.
Annealing o empe a u es up o 423 K a ec ed nei he he
single molecule appea ance no he long- ange o de .
Exempla y da a a e shown in Figu e 2. In gene al, on
a omically plana Ag(111) e aces we ound molecula
islands su ounded by di using molecules (see high con as
and s eaking obse ed ou side he molecula island) as
shown in Figu e 2a. Zooming in such an island allows o
iden i y he sel -assembly as a egula s uc u e which can be
desc ibed by he epi axial ma ix 10 15
43
!(Figu e 2b).
This a angemen is p esumably media ed by an-de -Waals
Figu e 3. On-su ace double dep o ec ion o NR-10. a) O e iew STM
image (130 K, 1.25 V, 0.09 nA) o NR-10 on Ag(111) a e annealing a
503 K. b) Magni ica ion o he a ea indica ed in (a) o e laid wi h
p oposed molecula model o NR-10’. C, N, O and H a e depic ed in
black, blue, ed and whi e, espec i ely. c) Scheme o p oposed on-
su ace NR-10 o NR-10’ ans o ma ion.
Figu e 4. On-su ace polyme isa ion o NR-10’. a) Dis ibu ions o
polyme ized GNR leng h as a unc ion o empe a u e. b) O e iew
STM image (159 K, 1.7 V, 0.11 nA) a e annealing o 583 K.
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in e ac ions be ween he i-isobu ylsilyl (TIBS) subs i u-
en s. Di e en packing geome ies we e ound (see Suppo -
ing In o ma ion Figu e S1), a u he es amen o he lack
o a s ong molecula egis y o he Ag(111) as well as
di ec o ial in e molecula in e ac ions. Wi hin he sel -
assembled s uc u es, we can iden i y he single molecules
(Figu e 2c). Thei con as is domina ed by he opog aphi-
cally p o uding moie ies. B igh e , asymme ic p o usions
signi y he bulky TIBS g oups. Two smalle , ound p o u-
sions ma k he posi ions o he e minal ace als.
We p oceeded o in es iga e sys ema ically he on-
su ace he mal chemis y and polyme isa ion o hese well-
de ined nano ibbons by annealing in s eps o 20 K ollowed
by STM examina ion (see Suppo ing In o ma ion Figu e S2
o a compila ion o STM images o all he annealing s eps).
A e annealing a 483 K, we obse ed ha some NR-10
molecules loose he b igh e p o usions co esponding o
he TIBS g oups and almos all o hem we e emo ed by
annealing a 503 K (Figu e 3a,b). The nano ibbon is now
cha ac e ised by h ee pai s o less b igh p o usions
co esponding o he e ia y bu yl ( Bu) subs i uen s and a
ain appea ence o he GNR backbone.[23] This is a ibu ed
o on-su ace dep o ec ion o he TIBS- e mina ed alkyne
moie ies, analogous o he dep o ec ion o ime hylsilyl
e mina ed alkynes on he same su ace.[24] The clea ed
TIBS g oups we e no iden i ied in ou STM images. The
TIBS dep o ec ion can lead o diace ylene linked monome s
o o su ace-s abilised adicals.[24,25] As he TIBS dep o-
ec ed NR-10 molecules showed no e idence o a eac i e
alkynyl g oup, and gi en he small esidual p essu e o H2
gas (�1×1010 mba ) in he UHV en i onmen , we p opose
a H passi a ion o he alkynyl g oup.[26] The TIBS dep o-
ec ed NR-10 seem o be in e ac ing by an de Waals o ces
o in e digi a ed Bu g oups. Ou side he sel -assembled
island, one can iden i y s eaking, p esumably caused by
mobile adso ba es. These may be a ibu ed o pa ially
TIBS dep o ec ed NR-10 o which he in e digi a ion o Bu
g oups, and hence hei immobiliza ion in he wo-dimen-
sional s uc u e, canno be accommoda ed.
We u he no ice he lack o opog aphic ea u es in he
posi ions o he e minal g oups, which, based on he STM
con as ,[23] indica es hei dep o ec ion.[7i] The e o e we
p opose he chemical ans o ma ion o NR-10 o he doubly
dep o ec ed NR-10’(Figu e 3c).
In he subsequen annealing s ep a 523 K, we obse e
he onse o an on-su ace ex ension o NR-10’by linking a
he e minal posi ions o he nano ibbon. The polyme -
isa ion is p omo ed by inc easing annealing empe a u es
(Figu e 4a), whe eby e en ually he su ace is co e ed by
molecula chains (Figu e 4b). Along wi h he polyme isa-
ion, we also obse e he onse o decomposi ion a he Bu
g oups, as judged by occasionally diminished con as a he
ela ed posi ions. As a uni o m con as o he Bu g oups is
ound in he STM images a e annealing a 503 K (see
Figu e 3) and Bu g oup de ec s occu mo e equen ly a e
annealing a 573 K (see Figu e 5b), his decomposi ion can
be a ibu ed o he highe empe a u e annealing, in good
acco d wi h ou ea lie epo o a sho e e ake one
monome .[27]
To iden i y he linking mode wi hin he chains, we
p epa ed a su ace o lowe molecula co e age (Figu e 5a).
He e we could clea ly ind chains cons uc ed o single
molecules, occasionally in e linking wi h segmen s ha pi o
a pa icula nodes. Thus, we can deduce he ollowing:
1) he polyme links a e no uni o m ac oss he NR-10’
polyme and 2) he chain is obus ly linked. The links ha e
been analysed as de ailed in he Suppo ing In o ma ion
Figu es S3, S4. Among he links we can iden i y p e iously
epo ed nodes o Ag-O4, o ming wi h he na i e Ag
ada oms (indica ed by blue ames).[27] The di e en appa-
en heigh o he me al node migh o igina e om a
a ia ion in he adso p ion si e, accommoda ion o mo e
han a single ada om o liga ion o small adduc s (due o
esidual gases in he acuum o molecula agmen s ela ed
o he monome ’s chemical modi ica ion). Thei o ma ion is
linked o he hyb idisa ion o he e minal ke one g oups
wi h he sil e and hei con e sion o ca echola es. In
addi ion, we can ecognise nodes wi h pai ed b igh
p o usions (g een and o ange ames). Thei imaging being
Figu e 5. Polyme node iden i ica ion. a) STM image showing obus chain binding wi h di e en node lexibili y (167 K, 1.8 V, 0.15 nA). b) High-
esolu ion STM image displaying ou di e en ypes o dime nodes (123 K, 1.5 V, 0.07 nA). c) Magni ica ion o he nodes iden i ied in he STM
image in (b) di ec ly compa ed wi h p oposed molecula model. Ag, C, N, O and H a e depic ed in yellow, black, blue, ed and whi e, espec i ely.
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in good acco d wi h epo s o Ag a oms in plana o gano-
me allic complexes,[28] we en a i ely a ibu e hese o Ag
ada oms. Using he de e mined posi ions o he Bu sub-
s i uen s o e alua e he dis ance be ween he monome s
(Figu e S3), we ind ha he assigned Ag ada oms a e
loca ed a posi ions ha canno accommoda e he e minal
O a oms in a plana geome y (as illus a ed in Figu e S3 ).
We he e o e p opose ha hese species a e di ec ly linked
o he e minal C a oms o he nano ibbon monome s.
Hence we de i e a model ha ea u es he consecu i e
exp ession o links wi h double b idges o ei he
CAgOC ( amed in g een in Figu e 5b,c) o di ec
CAgC ( amed in o ange in Figu e 5b,c). In e media e
s eps in he linking may esul in a il ed geome y be ween
he monome s (example indica ed by a ow in Figu e 5b).
He e, wi hou he clea signa u e o he posi ion o an Ag
ada om, i is no possible o p opose an exac bonding
mo i e (see Suppo ing In o ma ion Figu e S4).
Conclusion
We ha e demons a ed ha ES-CIBD is a p omising
me hod o con olling he deposi ion and p ocessing o
he molabile nanog aphenes. The exquisi e con ol o e he
p ocess allows o high-quali y deposi ions wi h small
amoun s o analy e o a bulky N-doped GNR. The well-
de ined na u e o he deposi ed species is cha ac e ized by
STM, e ealing a long- ange in e acial o de ing on he
Ag(111) su ace. Acco dingly, such p epa a ions a e sui able
o ab ica ing samples o be u he sc u inized by space-
a e aging analysis echniques owa ds ob aining comple e
in o ma ion abou he physicochemical p ope ies o he
su ace-con ined GNRs. Mo eo e , empe a u e-induced
ans o ma ions o N-doped GNR a o ded me al–o ganic
polyme s o up o 50 nm leng h. These a e assigned o a
a ia ion o me al–o ganic and o ganome allic nodes inco -
po a ing na i e Ag ada oms, based on high- esolu ion STM
insigh s. Thus, ES-CIBD is an icipa ed o acili a e u he
no el schemes o on-su ace syn hesis and in eg a ion o
nanog aphenes o nano-objec s in unc ional a chi ec u es a
in e aces.
Acknowledgemen s
This p ojec has ecei ed unding om he Eu opean
Union’s Ho izon 2020 esea ch and inno a ion p og amme
unde g an ag eemen s No. 946223 and No. 899895.
Financial suppo was p o ided by he Ge man Resea ch
Founda ion (DFG) h ough he TUM In e na ional G adu-
a e School o Science and Enginee ing (IGSSE), Excellence
Clus e e-con e sion, and he p io i y p og amme 1928
COORNETs, he China Schola ship Council (CSC) and he
Eu opean Resea ch Council (ERC) (no. 722951). This
p ojec has ecei ed unding om he Eu opean Resea ch
Council (ERC) unde he Eu opean Union’s Ho izon 2020
esea ch and inno a ion p og amme (G an Ag eemen No.
722951). This wo k was ca ied ou wi h suppo om he
Basque Founda ion o Science (Ike basque), POLYMAT,
he Uni e si y o he Basque Coun y, Gobie no Vasco
(BERC p og amme). Technical and human suppo p o-
ided by SGIke o UPV/EHU and Eu opean unding
(ERDF and ESF) is acknowledged. Open Access unding
enabled and o ganized by P ojek DEAL.
Con lic o In e es
The au ho s decla e no con lic o in e es s.
Keywo ds: Elec osp ay Deposi ion ·G aphene Nano ibbons ·
Scanning Tunnelling Mic oscopy ·Ul a-High Vacuum ·
On-Su ace Syn hesis
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