De elopmen s in di ec nanopa e ning o g aphene; Towa ds di-
ec w i e.
Szymon Ab ahamczyk* Ondřej Sak eida Alicja Bachma iuk G ažyna Simha Ma ynko á Ma k H.
Rümmeli*
D . Szymon Ab ahamczyk
EBEAM Cen e, CNT, CEET, VŠB TUO, Os a a, 708 00, Czechia
Email Add ess: [email p o ec ed]
P o . D . Ma k H. Rümmeli
EBEAM Cen e, CNT, CEET, VŠB TUO, Os a a, 708 00, Czechia
The Leibniz Ins i u e o Solid S a e and Ma e ials Resea ch D esden (IFW D esden), Helmhol zs . 20,
D esden, D-01069, Ge many
Soochow Ins i u e o Ene gy and Ma e ials Inno a ionS (SIEMIS), Op oelec onics and Ene gy & Col-
labo a i e Inno a ion Cen e o Suzhou Nano Science and Technology, and Key Labo a o y o Ad anced
Ca bon Ma e ials and Wea able Ene gy Technologies o Jiangsu P o ince, School o Ene gy, Soochow
Uni e si y, Suzhou, 215006, China. Email Add ess: [email p o ec ed]
Ing. Ondřej Sak eida
EBEAM Cen e, CNT, CEET, VŠB TUO, Os a a, 708 00, Czechia
P o . D . Alicja Bachma iuk
EBEAM Cen e, CNT, CEET, VŠB TUO, Os a a, 708 00, Czechia
Facul y o Chemis y, W oclaw Uni e si y o Science and Technology, Wyb zeze Wyspia skiego 27, W o-
claw 50-370, Poland
P o . G ažyna Simha Ma ynko á
Nano echnology Cen e, CEET, VŠB-TUO, 708 33, Czechia
Keywo ds: G aphene Nanopa e ning, Focused Elec on Beam-Induced Deposi ion (FEBID), Lase -Induced
G aphi isa ion, Di ec W i e, Focused Ion Beam Milling (FIBM), Polyme - o-G aphene Con e sion (P2G),
Gas Injec ion Sys em (GIS)
Abs ac
G aphene, wi h i s excep ional elec onic, mechanical, and he mal p ope ies, emains a co ne s one ma-
e ial o nex -gene a ion nanoelec onics. Howe e , con en ional li hog aphic app oaches o g aphene
pa e ning a e augh wi h challenges, including con amina ion, alignmen complexi y, and scalabili y
cons ain s. This e iew c i ically examines he e ol ing landscape o di ec -w i e g aphene echnologies,
ocusing on o e on s a egies such as ocused elec on beam-induced deposi ion (FEBID), polyme - o-
g aphene (P2G) con e sion, ocused ion beam (FIB) modi ica ion, and lase -assis ed g aphi isa ion. These
echniques ep esen a depa u e om adi ional op-down o ans e -based me hods by enabling bo om-
up, spa ially esol ed pa e ning wi hou in e media y masking s eps. Pa icula a en ion is de o ed o he
physicochemical mechanisms ha unde lie elec on- and pho on-media ed g aphi isa ion, he ole o p ecu -
so chemis y and subs a e in e ac ions, as well as he in luence o beam pa ame e s on sp2-ca bon con en
and s uc u al o de ing. The e iew u he delinea es he limi a ions in insic o cu en me hodologies,
including pa ial g aphi isa ion, esolu ion ideli y, and ha dwa e cons ain s, and p oposes a oadmap o
achie e uly ’di ec ’ g aphene w i ing. This includes in si u p ocessing unde con olled en i onmen s,
ad anced beam con ol sys ems, and he adop ion o ca aly ic and g aphi isable p ecu so s. Collec i ely,
his wo k p o ides a comp ehensi e ounda ion o he a ional design o nex -gene a ion nano ab ica ion
p o ocols and unde sco es he ans o ma i e po en ial o di ec -w i e echniques in enabling scalable,
high- ideli y g aphene-based de ices.
1
1 In oduc ion
1.1 Wha is g aphene?
G aphene was i s con i med and isola ed as a s able ee-s anding s uc u e by No oselo e al. in 2004
using he amous Sco ch ape me hod.[1–3] This ma ked he beginning o he ’gold ush’ in g aphene
esea ch has exploded in physics, ma e ials science and enginee ing, leading o ex ensi e s udies on i s
applica ions in elec onics, nano echnology, and ene gy s o age.[4, 5] The non-exhaus i e lis o no able
de elopmen s would include ad anced syn hesis echniques such as chemical apou deposi ion (CVD),
epi axial g ow h on SiC, py olysis, liquid phase ex olia ion (LPE), polyme - o-g aphene con e sion (P2G),
educ ion o g aphene oxide e c. [6], elucida ion o he elec onic and quan um p ope ies o g aphene
(g aphene ansis o s, quan um e ec s, high- equency elec onics)[7], in oduc ion in o ma e ials science
and enginee ing (composi es, ene gy s o age, he mal managemen )[8] and biomedical and en i onmen al
applica ions (biosenso s, d ug deli e y, wa e il a ion and desalina ion)[9].
G aphene’s unique s uc u e con e s ema kable p ope ies, including high elec ical conduc i i y, me-
chanical s eng h, and he mal s abili y, making i ideal o nano echnology applica ions.[2] A single p is-
ine laye o g aphene (SLG) is a ze o-bandgap ma e ial allowing a conduc ion o massless Di ac e mions
making i an excellen conduc o wi h elec ical conduc i i y o a ound 105S m−1, compa able o ha o
me allic sil e in bulk app ox. 6.2 ×107S m−1.[2, 10] The de e io a ion o he conduc i i y o me als
in nanoscale due o quan um size e ec s and su ace sca e ing o he elec ons (down o < 104S m−1)
p o ides single laye p is ine g aphene a signi ican bene i o applica ion in nanome ic-scale elec onics
as a conduc o .[11, 12] Howe e , his ad an age is highly dependen on he quali y and ab ica ion me hod
o he g aphene used.
The quali y o g aphene o en e e s o he numbe o laye s, he p esence o de ec s, he chemical
uni o mi y, and he size o he g aphene domain.[13, 14] Fo example, a double laye g aphene has an o de
o magni ude lowe elec ical conduc i i y (104S m−1) han ha o SLG.[15] While in SLG he conduc ion
(CB) and alence bands (VB) a e ouching a a single Di ac poin , he g aphene bilaye exhibi s in e laye
in e ac ions ( an de Waals and π−πspin-o bi coupling) in e ec c ea ing a ini e bandgap (< 0.2 eV),
making he elec ons beha e much mo e as pa icles wi h an e ec i e mass.[16] Fu he s acking and de ec s
will also a ec he conduc i i y o he syn hesised g aphene, making his ma e ial di icul o p ocess.[17–
19]G aphene de ec s a e ypically classi ied in o se e al ypes: poin de ec s such as acancies[21, 24],
in e s i ial de ec s, subs i u ions[25–27], o ada oms[28]; line de ec s such as g ain bounda ies[29] and
disloca ions[22, 29]; plane de ec s such as mul ilaye egions, olds, and w inkles[30]; s uc u al dis o ions,
including S one-Wales de ec s[31], ipples, and co uga ions; and chemical and unc ional de ec s such
as oxidised and hyd ogena ed a eas, as well as edge de ec s[20]. These dopan s and de ec s a es will
signi ican ly a ec he elec onic s uc u e o g aphene and in oduce a band gap.[13, 32] Figu e 1 illus a es
how his doping migh appea in a g aphene shee . These, depending on he si ua ion, can be conside ed
as unwan ed de ec s ha de e io a e he quali y o g aphene, o dopan s ha make g aphene a ma e ial
wi h a highly uneable bandgap.[13, 33]
Chemical doping can be in oduced in o g aphene by inco po a ing he e oa oms (B[34], N[34–36], P[37,
38], O[39], S[40], F[41], Cl[42, 43], Al[27], Co[44], H[45, 46], Si) in o he g aphene la ice ha dona e
o accep elec ons, unc ionalisa ion o g aphene (oxida ion o GO) ha dis up s he g aphene’s sp2
hyb idisa ion, o e en adso p ion o me al a oms, pa icles, o e en moleculae ha would ans e hei
cha ge o he g aphene su ace. The chemical doping gi es a lo o con ol o e he ype and deg ee o
doping, allowing bandgap uning om 0 - 2.9 eV.
Howe e , s uc u al changes such as single o mul iple acancies ha allow o chemical homogenei y
a e no cu en ly di icul o in oduce wi h con olled p ocesses. These can al e he elec onic p ope ies
o g aphene by he in oduc ion o s ains, o a ions, and la ice misma ches. [47]
The las bu no leas ype o g aphene quali y pa ame e is i s g aphene domain size. Small g aphene
domains ha e signi ican ly o de s o magni ude lowe ca ie mobili ies as a esul o phonons and im-
pu i y sca e ing con ibu ing o esis i i y, whe eas in la ge g aphene domains he anspo is mo e
2
1.2 Timeline o g aphene ab ica ion me hods
Figu e 1: A) Simpli ied chemical s uc u e o a g aphene shee , and examples o possible doping/de ec s a es. All he image
ha e a whi e scale ba ep esen ing 2 nm. The edge e ec , poin acancy, and mul iple acancy TEM images a e ep oduced
om Wa ne e al.[20], Robe son e al.[21], and Leh inen e al.[22], espec i ely. B) Recognised p ocesses used o g aphene
ab ica ion. In e p e a ion o simila igu es om ci a ions [23] and [17].
ballis ic.[1] The small domains domains below 10 nm can e en expe ience quan um con inemen e ec s
shi ing he Di ac cone o opening a bandgap.[48] Fu he mo e, he alignmen and o ien a ion o g aphene
domains, especially in polyc ys alline ilms, can lead o he o ma ion o g ain bounda ies and wis ing
be ween domains, signi ican ly impac ing bo h cha ge mobili y and s uc u al s eng h. Depending on
he wis angle, hese wis ed domains can display moi é supe la ice pa e ns, gi ing ise o no el elec-
onic e ec s, including la bands and co ela ed insula ing phases, as seen in wis ed bilaye g aphene.
Consequen ly, p oducing la ge-a ea, single-c ys al g aphene is c ucial o high-pe o mance elec onic and
op oelec onic applica ions. These monoc ys alline g aphene shee s educe g ain bounda y sca e ing and
main ain g aphene’s inhe en p ope ies, such as i s ex emely high ca ie mobili y and linea band s uc-
u e. Signi ican e o has been in es ed in e ining CVD me hods o manage nuclea ion densi y and
g ow h kine ics, enabling cen ime e-scale single-c ys al domains.
The quali y o g aphene can be quan i ied using mul i echnique app oach combining s uc u al cha ac-
e isa ion (Raman spec oscopy, TEM and AFM), elec ical p ope ies (4-poin p obe, Kel in p obe and
cAFM), chemical pu i y and dopan quan i ica ion (XPS, FTIR and TGA). Figu e 2 shows he di e en
s ages o g aphi isa ion o o ganic, ca bon- ich ma e ials. These changes can be moni o ed as a change in
he line shape o a Raman spec um, as can be seen u he in Figu e 3. In amo phous ca bon, he bands
a e e y b oad, he 2D peak is usually no onse , and he posi ions o he peaks also di e . In g aphi ic ma-
e ial, he ull wid h a hal -maxima (FWHM) o he G and 2D bands becomes much sha pe . Fo ew-laye
g aphene, in e p e ing he decon olu ion o he G, D, and 2D bands allows o quali y assessmen .
1.2 Timeline o g aphene ab ica ion me hods
Al hough he e m ‘g aphene’ gained p ominence in he ea ly 2000s, heo e ical in e es in i s p ope ies
da es back o mid-20 h cen u y. Fo ins ance, Wallace p edic ed in 1947 i s unique band s uc u e, and
Semeno in 1984 desc ibed he massless Di ac e mion beha iou o elec ons in g aphene.[50, 51] Since
i s i s isola ion by Geim and No oselo in 2004, g aphene has d i en ad ances in a wide ange o ields,
3
1.2 Timeline o g aphene ab ica ion me hods
Figu e 2: A schema ic ep esen a ion o deg ee o g aphi isa ion. Rec ea ed om he g aphic abs ac by Schuep e e al.[49]
om elec onics o nano echnology.[1, 3, 5]
The pas wo decades ha e allowed o he de elopmen o ad anced syn hesis echniques. Cu en
g aphene ab ica ion p ocedu es can be di ided in o a ious g oups, including ex olia ion (physical, chemi-
cal, o mechanical e c.), decomposi ion o o ganic ma e ials (ca aly ic o non-ca aly ic), chemical educ ion
o g aphene oxide (GO) in o educed GO ( GO) o epi axial g ow h (CVD).[17] G aphene ab ica ion me h-
ods a e usually seg ega ed in o bo om-up and op-down app oaches, as was done by Yan e al. and Wu
e al.[17, 23] Fo he pu pose o his e iew, he g aphene ab ica ion echniques we e seg ega ed in o
bulk g aphene ab ica ion (ex olia ion), ilm g ow h (CVD, PVD) and di ec g aphene w i ing (wi h lase ,
elec ons e c.) as lus a ed in he Figu e 1.
1.2.1 G aphene ab ica ion om bulk ma e ials
Fab ica ion o g aphene o en en ails he b eakdown o bulk g aphi e in o indi idual g aphene laye s o
small s acks, which dis inguishes i ma kedly om bo om-up app oaches ha syn hesise g aphene om
molecula p ecu so s o ca bon- ich ma e ials.
Among bulk g aphene ab ica ion s a egies, ex olia ion is p edominan and encompasses mechanical,
chemical, and liquid-phase me hods. Table 1 con ains summa y o he key ex olia ion echniques used o
ab ica e bulk g aphene. The mos iconic example is mechanical ex olia ion ia he "Sco ch ape me hod",
i s used by No oselo e al. o isola e p is ine monolaye g aphene, an achie emen ha la e ea ned he
Nobel P ize in Physics (2010).[1, 2] Al hough his me hod emains he benchma k o p oducing de ec - ee
monolaye s, i s lack o scalabili y limi s i s indus ial applicabili y.[52]
In con as , chemical ex olia ion in oduces in e cala ing agen s, such as acids o alkali me als, o
expand he in e laye spacing wi hin g aphi e, ollowed by sonica ion o yield g aphene shee s.[53–55]
This app oach, o en used in he educ ion o g aphene oxide (GO), is scalable bu ypically in oduces a
high densi y o s uc u al de ec s, necessi a ing u he pos - ea men .
Liquid phase ex olia ion (LPE), ano he scalable ou e, dispe ses g aphi e in sol en s unde sonica ion
o o e come an de Waals in e ac ions.[56–58] The su ace ene gy o he sol en mus be ca e ully ma ched
wi h ha o g aphene o main ain s able dispe sions and p e en eagg ega ion.[59, 60]
While hese ex olia ion echniques ha e acili a ed he in eg a ion o g aphene in o comme cial p oduc s,
hey s ill su e om c i ical limi a ions, including poo con ol o e domain size, numbe o laye s, and
de ec densi y. Mo eo e , pa e ning o g aphene ab ica ed using hese me hods is nea ly exclusi ely
possible by li hog aphy, li -o o p ecise ans e .
4
1.3 G aphene p ocessing and pa e ning limi a ions
Table 1: Summa y o ex olia ion echniques used o ab ica e bulk g aphene.
Ex olia ion Quali y Applica ions P os Cons Re e ences
Sco ch ape
me hod
P is ine monolaye s,
la ge domains, mini-
mal de ec s
Fundamen al esea ch,
ansis o s, quan um
de ices
Highes quali y
g aphene, ideal o
esea ch
Low yield, no scalable,
manual p ocess
[1, 2]
LPE Small lakes, a iable
de ec s, ew-laye
g aphene
Coa ings, composi es,
inks, ene gy s o age
Scalable, cos -e ec i e,
solu ion-p ocessable
High de ec densi y, sol-
en con amina ion
[56–60]
Chemical
g aphene oxide
educ ion
High de ec densi y,
oxidized, educed
conduc i i y
Bulk g aphene oxide,
ene gy applica ions,
memb anes
La ge-scale p oduc ion,
inexpensi e
Reduces elec ical
p ope ies, equi es
pos - ea men
[61–63]
Elec ochemical Mode a e de ec
densi y, ew-laye
g aphene
Flexible elec onics, su-
pe capaci o s
En i onmen ally
iendly, scalable
Di icul hickness con-
ol, lowe quali y han
mechanical
[64–66]
In e cala ion-
assis ed
Laye -by-laye ex oli-
a ion, lowe de ec s
Ba e y elec odes,
p in ed elec onics
Selec i e ex olia ion,
con olled quali y
Requi es specialized
chemicals, limi ed scala-
bili y
[67, 68]
1.2.2 Film g ow h
G aphene may also be syn hesised di ec ly on a subs a e, a p ocess commonly known as bo om-up
g ow h. G aphene syn hesis ia bo om-up me hodologies p ima ily in ol es he inco po a ion o ca bon
a oms in o he g aphene la ice h ough su ace-ca alysed chemical p ocesses.
A widely adop ed me hod is chemical apou deposi ion (CVD), in which gaseous ca bon sou ces like
me hane o ace ylene disin eg a e on ca aly ic me allic su aces such as coppe o nickel, acili a ing he
p oduc ion o high-quali y monolaye g aphene. This echnique o e s subs an ial con ol o e he laye
coun , c ys allini y, and domain size o he g aphene ilms p oduced.[17]
Some new app oaches in CVD also implemen polyme - o-g aphene con e sion, in which a hin ilm
o a polyme (mos o en PMMA) is deposi ed on o a subs a e om solu ion.[69, 70] The ilm is hen
con e ed in o g aphene wi h he help o ele a ed empe a u e (> 800 ◦C), applica ion o educing agen
(H2and A gas mix ) and ca alys s (Cu, Ni, C [71]).
Fac o s such as he empe a u e o he subs a e, he deposi ion a e, and he ype o me al ca alys
employed play oles in de e mining he quali y and numbe o g aphene laye s o med. Fo example, Wu e
al. indica e ha Cu subs a es a e conduci e o he g ow h o single-laye g aphene due o hei low ca bon
solubili y, while nickel ends o p oduce mul iple laye s h ough ca bon dissolu ion and p ecipi a ion upon
cooling.
Epi axial g ow h on SiC subs a es yields high-quali y, wa e -scale g aphene wi h excellen c ys allini y
and minimal de ec s, bu i is hinde ed by i s high cos and limi ed scalabili y due o subs a e cons ain s
and he need o ul a-high empe a u es (>1200 ◦C).[72] Py olysis o ca bon- ich ma e ials, pa icula ly
polyme p ecu so s, p o ides a acile, ans e - ee ou e owa ds di ec g aphene o ma ion on a ious
subs a es, and i can be spa ially con ined o pa e ning, bu i su e s om limi ed s uc u al con ol and
a highe deg ee o diso de , making i less sui able o elec onic-g ade applica ions. [73, 74] Collec i ely,
while epi axy ensu es quali y, CVD balances quali y and scalabili y, and py olysis o e s simplici y and
in eg a ion e sa ili y a he expense o s uc u al p ecision.
1.3 G aphene p ocessing and pa e ning limi a ions
The comme cialisa ion o g aphene-based elec onic de ices has been hinde ed by a se ies o ab ica ion and
scalabili y challenges. Chie among hese is he eliance on con en ional li hog aphic p ocesses, which o en
in ol e mul iple s eps, such as masking, e ching, and ans e , which in oduce de ec s, con amina ion, o
alignmen issues, pa icula ly when aiming o nanoscale p ecision o he e ogeneous in eg a ion[77]. Mo e-
o e , high-pe o mance de ice ab ica ion commonly equi es he syn hesis o uni o m la ge-a ea monolaye
g aphene ia CVD, a p ocess cons ained by high empe a u es, speci ic subs a e compa ibili y, and limi ed
pa e ning capabili ies[69, 78]. These limi a ions collec i ely educe h oughpu and inc ease p oduc ion
cos s.
5
Figu e 3: A) SEM image and a Raman spec um o g aphene g own using epi axial g ow h on SiC.[75] B) HRTEM image
and Raman spec um o a g aphene ob ained as a esul o py olysis o g een ea ex ac a 1100 ◦C.[74] C) SEM image and
a Raman spec um oF a monolaye g aphene shee g own using CVD and ans e ed on o Si.[76] All Raman spec a we e
ep oduced and digi ised om plo s in he ci a ions [74–76]
Nume ous a emp s ha e been made o imp o e he p ocessabili y o g aphene, one o which in ol es
poly(ac yloni ile) (PAN) as a ans e medium.[79] The s udy in es iga es he use o PAN as a ans e
medium o wa e -scale g aphene. The au ho s ound ha PAN can e ec i ely se e as a ans e medium,
simul aneously acili a ing he encapsula ion and ans e o la ge-a ea g aphene ilms. This app oach
add esses common issues in g aphene ans e p ocesses, such as con amina ion and mechanical damage,
he eby imp o ing he quali y and scalabili y o g aphene-based applica ions.[79] T ans e ed g aphene
would s ill need o be pa e ned in con en ional ways.
An inno a i e echnique called The mal, Elec ical, and Wa e Assis ed Reac ion (TEAWAR) acili a es
he ans o ma ion o polyme hyl me hac yla e (PMMA) and simila o ganic esidues in o g aphene.[80]
The TEAWAR p ocess le e ages he syne gis ic e ec s o he mal ene gy, elec ical s imula ion, and wa-
e media ion o achie e his con e sion. This app oach o e s a no el pa hway o g aphene syn hesis,
po en ially enhancing he e iciency and sus ainabili y o g aphene p oduc ion om polyme ic ma e ials.
A emp s o c ea e g aphene- ich inks o 3D p in ing we e e iewed by Jiang e al. The e iew ou lines
ecen de elopmen s in 3D p in ing o g aphene-based ma e ials and hei applica ions in ene gy s o age
and con e sion de ices and discusses he ex usion-based di ec ink w i ing echnique, emphasising he
heological beha iou o g aphene oxide (GO) dispe sions and s a egies o p epa ing p in able GO inks.
The e iew highligh s how 3D p in ing enables he design o ad anced elec ode a chi ec u es, po en ially
imp o ing he pe o mance o ene gy s o age de ices.[8] This me hodology, howe e does no align wi h
he scope o his e iew and g aphene-ink based addi i e manu ac u ing me hods will no be conside ed
u he .
6
Figu e 4: Venn diag am showing a ious ad an ages sh ed be ween EBL, CVD, Addi i e manu ac u ing (AM) wi h elec on
beam induced deposi ion sha ing all hese. The p ocesses a e also summa ised as diag ams whe e CVD was ec ea ed om
Esmaeilpou e al.[81] and AM omManok uang[82].
2 Focused elec on beam induced deposi ion (FEBID)
2.1 Fundamen als o elec on-ma e ial in e ac ions
Focused elec on beam-induced deposi ion (FEBID) elies on in ica e in e ac ions be ween he elec on
beam and, o example, eac i e gas, hin ilms, and e en subs a es, o ans o m ma e ials and deposi
i di ec ly and in con olled mannne on a nanoscale. These p ocesses esemble he ones occu ing du ing
elec on beam li hog aphy (EBL) which has simila modus ope andi, hus bo h o hese esea ch a eas use
simila app oaches and e minology. Bo h p ima y elec ons (PE) and seconda y elec ons (SE), as well as
subs a e-media ed e ec s, play c i ical oles in hese ma e ial ans o ma ions. PEs, ypically gene a ed
a ol ages be ween 0.1–30 kV, pene a e he subs a e and lose ene gy ia inelas ic collisions, gene a ing
cascades o seconda y elec ons (SEs) wi h ene gies usually below 50 eV. These SEs a e la gely esponsible
o he su ace-localised dissocia ion o p ecu so molecules in FEBID due o hei highly localised ene gy
deposi ion. Highe ene gy PEs esul in b oade in e ac ion olumes, whe eas lowe accele a ion ol ages
con ine he e ec nea he su ace. Backsca e ed elec ons (BSEs), mo e p ominen on high-a omic-
numbe subs a es such as Cu o Ni, con ibu e o a la e al b oadening o he deposi ion a ea.[83] In
pa allel, elec on-induced ionisa ion leads o adiolysis, whe e p ecu so bonds can be clea ed o o m
adicals and ola ile species such as CO, CO2, and H2O. The amoun o elec on adia ion equi ed o
achie e he ma e ial ans o ma ion, called dose (D) is de ined as:
D=1
AZ
0
i( )d
whe e A is a ea, is ime, and i is cu en . Typically in EBL, his dose is a ep esen a ion o he
minimal alue a which he esis (usually polyme ) ans o ms by bond clea age, o c oss-linking. A high
7
2.2 Sepa a ion in o g aphi isable and non-g aphi isable ma e ials
doses, his esidual ca bon can ansi ion in o amo phous o sp2- ich ca bon domains, se ing he s age
o g aphene-like s uc u es. Fo con e sion o polyme o g aphene (P2G) hese alues a e expec ed o
be much highe han o EBL as he eac ion end is expec ed no as ini ial ans o ma ion bu a he as
comple e g aphi isa ion. IIn FEBID, his alue indica es he amoun o adia ion needed o con e he
gaseous p ecu so and deposi he solid on o a subs a e e.g. by he emo al o ligands om he p ecu so
which makes i ola ile o bond clea age and o ma ion o adicals ha eassemble and deposi as solid.[84,
85] Al hough knock-on displacemen ypically equi es elec on ene gies abo e 80–100 keV—beyond he
ange o s anda d SEM-based EBID—ligh e a oms like hyd ogen and oxygen may s ill be displaced,
con ibu ing o he pu i ica ion o he deposi . Subs a e p ope ies also signi ican ly in luence he p ocess:
conduc i e subs a es (e.g., Cu, Ni, doped Si) dissipa e cha ge and o en ca alyse g aphi isa ion, whe eas
insula ing subs a es (e.g., SiO2, glass) can accumula e cha ge, leading o beam dis o ion. Va iable
p essu e condi ions wi h ine gases may help mi iga e cha ging wi hou in e e ing chemically. Subs a e
a omic numbe a ec s BSE yield and, consequen ly, he spa ial ex en o deposi ion. Impo an ly, ca aly ic
subs a es such as Cu can aid ca bon a om di usion and eo ganisa ion, acili a ing highe -quali y g aphene
g ow h. Collec i ely, he combina ion o SE-d i en dissocia ion, adioly ic decomposi ion, selec i e knock-
on displacemen , and ca aly ic subs a e in e ac ion would d i e he success o EBID in o ming g aphene
nanos uc u es.
2.2 Sepa a ion in o g aphi isable and non-g aphi isable ma e ials
The sepa a ion o g aphi isable and non-g aphi isable ma e ials is a undamen al concep in ca bon ma e-
ial science, pa icula ly ele an o he ab ica ion o g aphene and o he g aphi ic s uc u es.[86] Upon
he mal ea men , ca bon- ich p ecu so s exhibi di e gen s uc u al ans o ma ions depending on hei
molecula s uc u e and bonding cha ac e is ics.
G aphi isable ma e ials, such as ce ain pi ches and polycyclic a oma ic hyd oca bons and ce ain poly-
me s, unde go s uc u al eo de ing upon hea ing, e en ually o ming c ys alline g aphene laye s wi h high
s acking o de and ex ended la e al dimensions. This ansi ion is acili a ed by he absence o c oss-linking
side g oups and a high deg ee o a oma ici y, allowing ca bon a oms o ea ange in o he he modynami-
cally a ou able g aphi ic la ice. In con as , non-g aphi isable ma e ials, PMMA, possess a c oss-linked,
amo phous s uc u e due o he p esence o he e oa oms and unc ional g oups such as hyd oxyls. These
g oups hinde he alignmen and g ow h o o de ed g aphene laye s, esul ing in ma e ials ha emain
la gely diso de ed e en a ele a ed empe a u es. The dis inc ion be ween hese wo classes o ma e ials
could be pa icula ly signi ican in he con ex o elec on beam p ocessing, whe e he s uc u al p edis-
posi ion o he p ecu so de e mines he easibili y and quali y o g aphi isa ion, wi h di ec implica ions
o he elec onic, op ical and mechanical p ope ies o he esul ing ca bon ilms.[86, 87]
I seems ha he as majo i y o esea ch on polyme - o-g aphene con e sion is in luenced by he
esea ch on elec on beam li hog aphy on PMMA as a esis ma e ial.[88]
2.3 Polyme - o-g aphene (P2G) con e sion using elec on beam
EBID enables he di ec ans o ma ion o polyme ic p ecu so s in o g aphenic ma e ials h ough a com-
bina ion o adioly ic and he mal e ec s.[89] Upon e-beam i adia ion, he polyme ma ix unde goes
ioniza ion and bond scission, p oducing ee adicals ha ecombine o o m a c oss-linked, ca bon- ich
ne wo k. Simul aneously, dehyd ogena ion and deoxygena ion expel he e oa oms such as hyd ogen, oxygen,
and ni ogen, en iching he sp²-ca bon con en . Polyme s like PMMA, polys y ene, PAN, polyimides, and
phenolic esis s (e.g., SU-8 o AZ5214) display dis inc esponses unde EBID, in luenced by hei molec-
ula s uc u e. Fo ins ance, PMMA ca bonizes in o amo phous ea u es, while PAN unde goes elec on-
induced cycliza ion, mimicking he mal s abilisa ion and yielding ni ogen-doped g aphenic ca bon.[88,
90, 91] Polyimides, ich in he e oa oms, can o m po ous, conduc i e g aphi e oams unde high-dose i -
adia ion.[92] Beyond chemical changes, he e-beam also induces localised hea ing ia inelas ic sca e ing,
acili a ing py olysis and bond econ igu a ion. Subs a e e ec s u he in luence his p ocess; conduc i e
me als like Cu o Ni no only dissipa e hea bu also ca alyse dehyd ogena ion and induce plana isa ion.
8
2.4 Elec on beam induced modi ica ions in SAMs
Figu e 5: A) The p ocess low diag am o he e-beam li hog aphic p ocess o he ab ica ion o g aphene nanos uc u es on
coppe subs a e. Low-quali y g aphene was o med a s ep 3, and he high-quali y g aphene a s ep 6. B) Raman spec a
o he sample a he di e en p epa a ion s ages Rec ea ed om Bi e al.[88]
Pos -i adia ion annealing— ypically a 300–800 ◦C in ine o educing a mosphe es—signi ican ly en-
hances s uc u al o de ing and conduc i i y, d i ing he eo ganisa ion o diso de ed ca bon in o g aphi ic
domains. While EBID alone o en yields amo phous o u bos a ic ca bon, sus ained i adia ion o he -
mal ea men p omo es g aphi isa ion, especially in he p esence o ca aly ic subs a es. The inal ma e ial
ypically comp ises nanoc ys alline g aphi e o a mosaic o small g aphene domains, wi h esis i i ies ang-
ing om 10−4 o 10−3Ωcm, which a e su icien o use in mic oelec odes, senso s, and o he unc ional
ca bon nanos uc u es. Thus, EBID o e s a con ollable, li hog aphy-compa ible me hod o bo om-up
ab ica ion o g aphenic nanoma e ials, wi h unable p ope ies go e ned by p ecu so chemis y, elec on
dose, and he mal condi ions.
2.4 Elec on beam induced modi ica ions in SAMs
Elec on beam-induced modi ica ions in sel -assembled monolaye s (SAMs) o e a powe ul and e sa ile
app oach o ailo ing su ace chemis y and nanoscale pa e ning wi h high spa ial esolu ion. Upon expo-
su e o low-ene gy elec on i adia ion, ypically below 100 eV, SAMs unde go a a ie y o physico-chemical
ans o ma ions, including bond clea age, deso p ion, c oss-linking, and eo ien a ion o molecula back-
bones. In pa icula , SAMs ea u ing ca boxylic acid (CA) ancho ing g oups on coinage me al subs a es
such as sil e ha e demons a ed p onounced suscep ibili y o elec on-induced eac ions. These modi-
ica ions a e d i en by elec on-s imula ed clea age o he ca boxyla e–me al bond, leading o pa ial o
comple e deso p ion o molecules, ollowed by he o ma ion o a ca bonaceous esidue ia c oss-linking
o he emaining o ganic agmen s. The p esence o a oma ic backbones in CA-based SAMs enhances
he p opensi y o c oss-linking due o delocalised π-elec ons, enabling he con e sion o he monolaye
in o a obus , insoluble ca bon nanomemb ane. Fu he mo e, elec on i adia ion can induce signi ican
con o ma ional and o ien a ional changes in he SAMs, such as eo ien a ion o diso de ing o he molec-
ula packing. These e ec s a e highly dependen on he molecula s uc u e, packing densi y, and ene gy
and dose o he elec on beam. Such con olled modi ica ions a e inc easingly exploi ed in applica ions
anging om li hog aphy and su ace pa e ning o he ab ica ion o chemically and mechanically s able
nanos uc u es[94–96]
9
and edge sha pness. The en i onmen al chambe , hough indispensable o in si u gas-phase eac ions o
p essu e- egula ed p ocesses, in oduces complica ions in elec on sca e ing and beam s abili y, he eby
equi ing p ecise egula ion o chambe p essu e and gas composi ion o mi iga e image deg ada ion and
ensu e beam ideli y.
The GIS, a c i ical enable o in oducing ca bonaceous p ecu so s o o ming gas, can pose con ami-
na ion isks i no inely calib a ed, po en ially leading o undesi able ca bon deposi ion on non- a ge ed
a eas o e en op ical componen s such as elec on lenses e c.. Addi ionally, he inco po a ion o a hea ing
s age, essen ial o pos -i adia ion con e sion o ca aly ic enhancemen , demands he mal isola ion and
obus ma e ial compa ibili y o p e en o -gassing o s uc u al wa ping unde p olonged hea ing cycles.
Impo an ly, he BSD de ec o , o en si ua ed close o he sample chambe , is ulne able o con amina-
ion om ola ilised p ecu so s o beam-induced spu e ing in gas- ich en i onmen s. P olonged exposu e
o eac i e gases, especially unde ele a ed empe a u es and elec on bomba dmen , can deg ade de ec-
o sensi i i y o induce ouling on sensi i e componen s, including scin illa o s o pho omul iplie ubes.
P ope shielding, con olled gas low pa hs, and egula main enance schedules become impe a i e o p o-
ec de ec o in eg i y and o e all ins umen longe i y. These mul i ace ed cons ain s unde sco e he
necessi y o ca e ully o ches a ed ha dwa e con igu a ions and ope a ional p o ocols o enable eliable,
ep oducible, and uly "di ec " g aphene w i ing in SEM pla o ms.
6 Fu u e Wo k
Eme ging di ec ions in FEBID and LIG o g aphene pa e ning e lec a con luence o echnological inno-
a ion and sus ainabili y conside a ions. Low-dose p ecu so - o-g aphene s a egies a e being explo ed o
pa e ning on lexible subs a es, such as hose used in pape -based elec onics, enabling ligh weigh and
disposable g aphene-based de ices. Hyb id wo k lows ha in eg a e elec on beam li hog aphy wi h chemi-
cal apou deposi ion (CVD) o e p omising a enues o spa ially selec i e doping, enhancing unc ionali y
a he nanoscale. The implemen a ion o machine-lea ning algo i hms o op imise beam pa e ning pa am-
e e s is poised o signi ican ly imp o e p ecision, h oughpu , and ep oducibili y simul aneously being able
o a oid p oximi y e ec s, d i s e c. Concu en ly, he de elopmen and deploymen o en i onmen ally
benign p ecu so s a e gaining ac ion, d i en by he impe a i e o sus ainable and less haza dous e-beam
p ocessing p o ocols. Fu he mo e, he ield is wi nessing a g owing in e es in he iden i ica ion and classi-
ica ion o g aphi isable ma e ials sui able o elec on beam-induced deposi ion (EBID) o g aphene. This
necessi a es a e ised amewo k o guide he a ional selec ion o p ecu so s based on hei s uc u al
e olu ion unde elec on i adia ion.
Acknowledgemen s
All au ho s hank he Eu opean Union’s Ho izon Eu ope esea ch and inno a ion p og amme unde he
g an ag eemen No. 101087143 (Elec on Beam Eme gen Addi i e Manu ac u ing (EBEAM)) M.H.R.
hanks o unding om he Na ional Na u al Science Founda ion o China (G an No. 52071225)
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