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Siliciul ajunge din urm grafenul

Pentru prima dat cercettorii au obinut un strat monoatomic de siliciu,


anun revista Physical Review Letters. Se presupune c noul material ar trebui
s semene foarte mult cu grafenul dup proprieti: acelai strat monoatomic
de carbon, prin urmare materialul a fost numit dup analogie cu grafen siliciu.
Mai mult dect att, siliciu ar trebui s se ncorporeze mai uor dect grafenul n
dispozitivele electronice convenionale bazate pe cipuri de siliciu. i asta
nseamn

noi

oportuniti

pentru

dezvoltarea

sistemelor

electronice

miniaturizate.
Siliciu este un analog al grafen-ului.
n timp ce lumea tiinific i pseudo-tiinific, discut cu nesa proprietile uimitoare
ale grafenului - un strat de carbon de o grosime doar de un atom, pn cnd toi i-au
aplaudat pe Andre Geim i Constantin Novoselov, ali cercettori au ncercat s
construiasc structuri similare monoatomice din alte materiale chimice. i mai nti de
toate, privirea lor a fost ndreptat spre ntr-un alt element rspndit n natur - siliciu.
Acum, n jurul acestei probleme se desfoar o adevrat dram i curse pentru primul
loc ntre oamenii de tiin din mai multe centre de cercetare.

Siliciul este materialul de baz pentru crearea dispozitivelor electronice. n tabelul


periodic a lui Mendeleev acest element este adiacent cu carbonul i are caracteristici
aproape similare. Filmul silicic monoatomic ar fi fcut un progres mare n industria
electronic. Cu toate acestea, crearea unui astfel de film de siliciu nu a fost posibil, chiar
i ipotetic, legturile atomice ale elementului dat, nu admit acest lucru. Cu toate acestea,
dup cum s-a dovedit, straturile monoatomice de siliciu totui exist. Dei nu ntr-o form
complet plat, bidimensional, ci tridimensional.

Foi ondulate de siliciu


n anul 2000, n revista Physical Review a fost publicat un articol intitulat "Calculele
preliminare ale proprietilor unui material ipotetic - nanotuburi de siliciu" Autorii acestui
articol, fizicienii brazilieni au examinat proprietile fizice ale nanotuburilor de siliciu cu un
singur perete i au constatat c n funcie de chiralitate ( direcia de rsucire a
nanotuburilor) ele pot avea proprieti metalice sau semiconductoare, deci ar trebui s se
comporte ca i nanotuburile de carbon. Se poate spune c activitatea oamenilor de tiin
din Brazilia, a fost primul pas pe calea obinerii siliciului.
Ce au comun nanotuburile i siliciul plat? Teoria, care este folosit pentru a descrie
proprietile nanotuburilor, indiferent de carbon sau de siliciu , poate fi folosit cu
uurin pentru cazul n care tuburile sunt prezentate n form plat, devenind respectiv,
grafen sau siliciu. Apropo, nanotuburi de siliciu au fost deja, recent obinute - n anul
2005.
n curnd au fost elaborate ipotezele teoretice privind existena unor frunze structurale
specifice din siliciu, groase doar de un atom, dar nu plate, ci ondulate. Acest lucru l-au
reuit s-l fac fizicienii de la Universitatea din Wright (SUA): n 2007 ei au justificat
posibilitatea existenei unei panglici monoatomice de siliciu. Ei au inventat, de asemenea,
numele acestui film - siliciu.
La reuniunea Societii Americane de Fizica din Dallas, pe 24 martie 2011, Flerens
Antoine, fizicianul care lucreaz la Institutul de tiin si Tehnologie din Ishikawa
(Japonia), a prezentat un nou material i a descris detaliat tehnologia procesului de
producere. Flerens Antoine i colegii lui japonezi, au crescut foi de siliciu pe suprafaa
substratului ceramic din zirconium diboride. Radiografia fcut ulterior a artat c noul
material are aceeai structur hexagonal de fagure ca i grafenul. Dar, de dragul
adevrului s spunem c primul film de siliciu a reuit s obin alt savant. n 2010, Guy
Le L, fizician de la Universitatea din Provence, Marseille, Frana, a reuit s creasc pe
suprafaa cristalului de argint benzi de siliciu de o lime de 1.6 nm. Aceste panglici pot
avea n lungime sute de nanometri.

Datele publicate de grupul japonez i grupul Le L, indic faptul c, n afara structurii


similare, grafenul i siliciul au un numr de alte proprieti similare, inclusiv cele electrice.
Cu toate acestea, studiile efectuate de oameni de tiin francezi din grupul Le L, nu au
determinat proprietile electrice ale noului material, deoarece filmul a fost cultivat pe
suprafaa de argint care este un conductor electric. Iar, japonezii au crescut frunze de
siliciu pe un substrat izolator, i acest lucru le-a dat o oportunitate de a studia
proprietile electrice ale materialului nou i a determina faptul c efectele cuantice, care
ofer grafenului proprieti remarcabile, lucreaz precum i cu siliciu.
Cu toate acestea, ntre aceste dou materiale au fost gsite diferene importante. Una
dintre ele este o stabilitate chimic mai mare a benzilor de siliciu comparativ cu grafenul.
Este vorba de o activitate chimic puternica a atomilor de carbon, situate la marginile
benzilor de grafen, n timp ce marginile de siliciu sunt mai puin expuse fenomenul dat.
Cu alte cuvinte, a pstra siliciu n mini i a nu-l distruge este mult mai uor dect a pstra
grafenul.

Siliciu i apr drepturile


Totui, n ciuda unor progrese realizate de diferite grupuri de cercetare, dovada de
obinere a siliciului a fost doar indirect i se baza foarte mult pe presupuneri teoretice. n
acest sens, studiul recent realizat de un german, Patrick Vogt, de la Universitatea Tehnic
din Berlin i Paola De Padova, de la Institutul de Structur a Materialelor (Italia), a
determinat proprietile reale ale probelor concrete de siliciu.
Problema publicaiilor anterioare privind siliciu, potrivit lui Vogt, const n faptul c
singura dovad de obinere a siliciului de ctre aceti savani au fost doar rezultatele de
scanare a probelor de microscopia tunelului. Acest lucru nu este suficient, a spus Vogt,
pentru a face concluzii cu privire la stratul monoatomic de siliciu. Vogt i colega lui De
Padova, au ncercat s reproduc rezultatele descrise n articolul "pionierilor" de siliciu
precedeni, dar nu au reuit.
n lucrarea lor original, cercettorii au ncercat s obin siliciu printr-o depunere simpl
din faza de vapori pe suprafaa unui cristal de argint. Vogt, a remarcat c ntreaga sum
de informaii privind structura materialului, distanele interatomice i proprietile
electronice ale modelului experimental, Structuri i parametrii structurale ale (a)
structurat diamant siliciu, (b) grafen, (c) i disilene (d) ipotetic, silicene de sine statatoare.
( tiin i Tehnologie materialelor avansate)
Oamenii de tiin din Japonia au comparat proprietile unui sine stttor strat-un atomgros ipotetic de siliciu ntr-o foaie similar dezvoltat pe un substrat de metal. Dei
promitoare, aceast a doua form "epitaxial" prezint diferene importante. Pornirea

materialul ipotetic ntr-o realitate rmne o provocare major, de 20 de ani dupa ce a fost
raportat primul.
n 1994, oamenii de stiinta a publicat primul lor raport teoretic pe cel mai subtire form
posibil de siliciu. Printre multe alte utilizri, de siliciu este ncorporat ca un
semiconductor n circuite integrate, n funcie de cele mai multe calculatoare.
Dar a fost doar zece ani mai trziu, n 2004, atunci cnd un alt material, graphene, a fost
raportat, c oamenii de tiin au nceput s apar un real interes, i, eventual, numele
materialului, "silicene".
Grafen este un strat-un atom-gros de carbon care a fost demonstrat pentru a gzdui cele
mai rapide transportatorii de energie electric nc gsite. Comparativ cu silicon, cu toate
acestea, graphene nu este un semi-conductor, deoarece nu se poate comuta ntre
desfurarea i nu efectuarea de state. Acest lucru face foarte dificil s-l aplice ntr-un
dispozitiv de comutare, cum ar fi un tranzistor.
Acesta este motivul pentru silicene este att de interesant. n forma sa de sine
statatoare, acest strat-un atom-gros de atomi de siliciu are operatori de telefonie mobil,
cum ar fi grafen, precum i este metalic. Pe de alt parte, de exemplu prin aplicarea
tulpina sau un cmp electric, acesta ar putea, de asemenea, fi transformat s se
comporte ca un semiconductor. Aceasta se datoreaz faptului c structura ar putea fi
uor modificate sau comutate pe scara atomica. n plus, aceasta ar fi compatibil cu
circuite pe baz de siliciu deja existente. Acest lucru este prevzut s conduc la
dezvoltarea de electronice, chiar mai mici dect cele n prezent pe pia.
Datorit potenialului su interesant, demonstrarea experimental a existenei silicene
fost extrem de anticipat. n 2012, mai multe grupuri au raportat in curs de dezvoltare cu
succes silicene "epitaxiale": foi de silicene formate pe substraturi metalice. O echipa de
oameni de stiinta japonezi au comparat proprietile caracteristice ale teoretic silicene de
sine statatoare a epitaxial silicene au produs pe un substrat de zirconiu diborur. Ei au
descoperit c structura cristalin a silicene epitaxial fost puternic influenat de
substratul su metalic, rezultnd astfel proprieti electronice diferite de cele prezise
pentru forma de sine stttoare ipotetic.
Sinteza sine statatoare silicene rmne o provocare major i multe dintre proprietile
forma sa epitaxial nu sunt nc pe deplin nelese. Cu toate acestea, echipa de oameni de
stiinta japonezi au alturat de alte cteva grupuri la nivel mondial va lucra n continuare
pe nelegerea mecanismului de formare a silicene epitaxiale i interaciunea acestuia cu
substratul. Pe baza nelegerii profunde a acestei chestiuni, este anticipat de munc
prezente i viitoare de a duce la evoluiile necesare, cum ar fi formarea de silicene pe o

platform de izolare i ncapsularea cu succes. Acest lucru ar duce apoi la aplicatii


practice ale materialului.
Sursa: Institutul Naional de Stiinta Materialelorse acord perfect cu pronosticurile
teoretice.
Urmtoarea sarcin este de a crete siliciu pe materiale izolante, n scopul de a determina
proprietile electrice i a nelege mai bine modul n care acest material poate fi folosit la
fabricarea dispozitivelor electronice. Totodat ,Vogt a spus c cercettorii s-au gndit deja,
la sinteza i studierea materialului similar, bazat pe germaniu - germanicene. Avnd n
vedere faptul c de acum nainte n tiina materialelor a fost descoperit o ntreag clas
de structuri similare stratificate, groase de un atom, lucrul cu ele va fi mult mai uor i
mai promitor.

Sursa: facepla.net

Cercetatorii japonezi de la Institutul de Stiinta si Tehnologie Avansata au creat silicenul,


un material minune care ar putea revolutiona electronicele. Silicenul este obtinut dintrun singur strat de atomi de silicon si poate miniaturiza gadgeturile in mod semnificativ.
Dupa descoperirea grafenulului, un singur strat de atomi de carbon, silicenul ar putea fi cel mai
important pas pentru miniaturizarea fizica a gadgeturilor, scrie ZDNet.

Spre deosebire de grafen, silicenul este mai compatibil cu electronicele si ar putea fi folosit mai
rapid in productia de gadgeturi mai mici.
Densitatea atomica a grafenului si silicenului le face materiale perfecte pentru tehnologiile cele mai
noi, insa cercetatorii din Japonia spun ca cercetarile nu sunt finalizate si va mai trece timp pana
cand vor tine in mana electronice produse cu silicen.

Cercetatorii de la Institutul de Stiinta si Tehnologie Avansata al Japoniei au creat silicenul. Silicenul


este echivalentul siliconic al grafenului, explica Yukiko Yamada-Takamura, profesor la acest institut,
lider mondial in cercetarea acestui material. La fel cum grafenul este alcutuit dintr-un singur strat de
atomi de carbon, silicenul este alcatuit dintr-un singur strat de atomi de siliciu.

Foita de silicen. Foto: dradiowissen.de


Grafenul si silicenul sunt asemanatoare in multe privinte, insa, fata de omolugul sau carbonic, silicenul
are un avantaj crucial: este compatibil cu circuitele electrice bazate pe siliciu existente deja. Asta
inseamna reducerea masiva a timpului si bugetului alocat pentru cercetarea si scoaterea pe piata a
unor produse bazate pe silicen. Grafenul mai este depasit dintr-o alta perspectiva, cea a flexibilitatii
structurale. El nu poate lua decat o singura forma, perfect orizontala, silicenul este flexibil si la scara
atomica, adica unii atomi pot sa iasa din plan, explica Yamada-Takamura. Acest lucru se traduce prin
faptul ca proprietatile sale electrice pot fi variate, ceea ce implicit creste numarul de aplicatii.
Desi silicenul pare superior grafenului, inca este departe de gloria si popularitatea de care se bucura
acesta, precum si de numarul urias de cereri de brevet iscate de grafen. Dar, dupa parerea multora,
silicenul este cel care, in viitor, va avea impactul mai mare asupra vietilor noastre.

Graphenes cousin silicene makes transistor


debut
Creation of electronic device using atom-thin silicon sheets could boost work on other flat
materials.

Seven years ago, silicene was little more than a theorists dream. Buoyed by a frenzy of interest
in graphene the famous material composed of a honeycomb of carbon just one atom thick
researchers speculated that silicon atoms might form similar sheets. And if they could be used to
build electronic devices, these slivers of silicene could enable the semiconductor industry to
achieve the ultimate in miniaturization.

This week, researchers took a significant step towards realizing that dream, by unveiling details of
the first silicene transistor1.
Although the devices performance is modest, and its lifetime measured in mere minutes, this
proof of concept has already been causing a stir at conferences, says Deji Akinwande, a nanomaterials researcher at the University of Texas at Austin who helped to make the transistor. Guy
Le Lay, a materials scientist at Aix-Marseille University in France, agrees.
Nobody could have expected that in such a short time, something that didnt exist could make a
transistor, he says.
Le Lay was one of the first scientists to create silicene in the lab 2, in 2012 (see The rise of
silicene). The debut coincided with a growing sense that graphene was unsuitable for making
transistors. Graphene may be the worlds most conductive substance, but it is missing a crucial
characteristic. Unlike the semiconductors used in computer chips, it lacks a band gap the
energy hurdle that electrons must vault before they can carry a current. Band gaps enable
semiconductor devices to switch on and off and to perform logic operations on bits.
The rise of silicene
Its carbon-based cousin graphene gets more attention, but silicene is catching up.

Ref. 1

1994 First calculation of the structure of two-dimensional crystals of silicon (pictured) and of
germanium.
2004 Andre Geim and Konstantin Novoselov report isolation of graphene.
2007 The name silicene is coined.
2009 Fabrication of silicene nanoribbons; flurry of theoretical papers on silicene and germanene
begins.
2010 Geim and Novoselov bag Nobel Prize in Physics for their experiments on graphene.
2012 Six independent reports of silicene sheets (formed on silver).
2015 First demonstration of silicene transistor.
For logic applications, graphene is hopeless, says Le Lay. By contrast, silicene can boast a
band gap, because some of its atoms buckle upwards to form corrugated ridges, which puts
some of its electrons in slightly different energy states. What is more, makers of electronic chips
have been wary of ditching decades of silicon-manufacturing experience in favour of carbon, says
Lok Lew Yan Voon, a theoretical physicist at the Citadel, the Military College of South Carolina in
Charleston, who first named silicene and modelled its properties back in 2007 (ref. 3).
But handling silicene in the lab has been a huge challenge. The material cannot be peeled from a
solid block using sticky tape, as graphene can from bulk graphite. Instead, researchers produce it
by letting a hot vapour of silicon atoms condense onto a crystalline block of silver in a vacuum
chamber, a much trickier process. And unlike robust graphene, naked silicene is extremely
unstable in air, making it difficult to transfer the gossamer sheet to more useful substrates such

as the guts of a transistor. As recently as last year, some researchers were still questioning
whether silicene even existed.
So Akinwande joined forces with Alessandro Molle at the Institute for Microelectronics and
Microsystems in Agrate Brianza, Italy, to offer silicene some protection. They formed a silicene
sheet on a thin layer of silver, and added a 5-nanometre-thick layer of alumina on top. Then they
peeled this silicene sandwich off its mica base, flipped it silver-side-up, and laid it on an oxidizedsilicon substrate. Finally, they gently etched away some of the silver to leave two islands of metal
as electrodes, with a strip of exposed silicene between them.
Its a very clever trick, says Le Lay, who is planning to try the process with germanene, a
capricious, similarly structured two-dimensional material made from germanium that his team
created last year4.
Clever it may be, but the transistor will not be making an appearance in mobile phones any time
soon: the exposed silicene degrades in about two minutes. Still, that is long enough to measure
its properties. Although its electrons are sluggish in comparison to graphenes, the device does
indeed have a small band gap.
Laying an extra coating on top of the silicene transistor could also extend its life. Akinwande has
used Teflon to help flakes of phosphorene another air-sensitive, two-dimensional material,
made of phosphorus to survive for months 5. Other researchers have shown that using multiple
layers of silicene could allow the sacrificial top layers to protect those beneath for 24 hours 6.
Crucially, the technique used to make the silicene transistor could now help to test all of these
ideas, and more, with various air-sensitive materials. Its definitely a game-changer, says Lew
Yan Voon. This is the paper weve been waiting for in the field.
Not everyone is so enthusiastic about silicenes prospects. Theres a lot of talk about silicene,
germanene and phosphorene, says Jari Kinaret of Chalmers University of Technology in
Gothenburg, Sweden, who is the director of the European Unions Graphene Flagship, a 1billion (US$1.1-billion) research project to study two-dimensional materials and develop
applications for them, but the difficulties with them are still quite substantial.
Le Lay, however, is convinced that researchers will flock to silicene. Now that a device has been
made, he says, other scientists will see it is not a dream material, it is a practical thing.
Nature

518,

1718

(05 February 2015)

doi:10.1038/518017a

Researchers have produced the first transistors made of silicene, a material that is
just one atom thick and known to be the "thinnest silicon" in the world.
The latest development offers great promise in enhancing the speeds of computers
and electronics.
Scientists at the University of Texas at Austin's Cockrell School of Engineering, who
created the transistors made of silicene, believe the new material has exceptional

electrical properties. Until now, it has been very difficult to work with and produce
silicene.
Deji Akinwande, assistant professor in the Cockrell School's Department of Electrical
and Computer Engineering, along with his team, claims to have solved a key
challenge that surrounds silicene. The researchers showed that the material can be
created into transistors. A transistor is a semi-conductor device, which is used to
switch and amplify electrical power and electronic signals.
Akinwande posits that the new material can revolutionize the semiconductor industry
and help in the development of superfast and energy-efficient chips.
Several years back silicene made by humans was just a theoretical material.
Researchers looked at carbon-based graphene, which is also an atom-thick material
with potential for chip development, and wondered if silicon atoms could also be
structured in a similar way.
"Apart from introducing a new player in the playground of 2-D materials, silicene, with
its close chemical affinity to silicon, suggests an opportunity in the road map of the
semiconductor industry," said Akinwande.
Akinwande also believes that it is the first time a silicene device has been made and
fabricated at low temperature.
Silicene, according to the researchers, is very difficult to work with when it is exposed
to air due to its instability and complexity. To overcome this challenge, the
researchers developed a novel method of fabricating silicene, which reduces air
exposure.
How exactly did they produce the material?
The scientists allowed silicon atoms in the form of vapor to condense onto a
crystalline block of silver, which was in a vacuum chamber. A silicene sheet was then
formed on a thin layer of silver. A nanometer-thick layer of alumina on top was added
to the sheet.
"Because of these protective layers, the team could safely peel it off its base and
transfer it silver-side-up to an oxidized-silicon substrate. They were then able to
gently scrape some of the silver to leave behind two islands of metal as electrodes,
with a strip of silicene between them," the researchers noted.
The transistor has just been tested in vacuum conditions and is yet to be tested in
open air. Even though it is not possible to have vacuum conditions in the real world,

researchers suggest it is still an important step toward the development of silicenebased transistors.
The study was published in the journal Nature Nanotechnology.
Note: The spelling of silicene was corrected in several instances on Feb. 5.

Silicene
From Wikipedia, the free encyclopedia

STM image of the first (44) and second layers (33-) of silicene grown on a thin silver film. Image size 1616
nm.[1]

Silicene is a two-dimensional allotrope of silicon, with a hexagonal honeycomb structure similar


to that of graphene.

History[edit]
Although theorists had speculated about the existence and possible properties of silicene, [2][3]
[4]

researchers first observed silicon structures that were suggestive of silicene in 2010. [5][6] Using

a scanning tunneling microscope they studied self-assembled silicene nanoribbons and silicene
sheets deposited onto a silver crystal, Ag(110) and Ag(111), with atomic resolution. The images
revealed hexagons in a honeycomb structure similar to that of graphene. Density functional
theory (DFT) calculations showed that silicon atoms tend to form such honeycomb structures on
silver, and adopt a slight curvature that makes the graphene-like configuration more likely.
However, such a model has been invalidated for Si/Ag(110): the Ag surface displays a missingrow reconstruction upon Si adsorption
[8]

[7]

and the honeycomb structures observed are tip artefacts.

In 2015, a silicene field-effect transistor made its debut [9] that opens up new opportunities for

two-dimensional silicon for various fundamental science studies and electronic applications, [10][11][12]

Similarities and differences with graphene[edit]


Silicon and carbon are similar atoms. They lie next to each other in the same group on
the periodic table and have an s2 p2 electronic structure. The 2D structures of silicene and
graphene also are quite similar but have important differences. [13] While both form hexagonal
structures, graphene is completely flat, while silicene forms a buckled hexagonal shape. Its
buckled structure gives silicene a tuneable band gap by applying an external electric field.
Silicene's hydrogenation reaction is more exothermic than graphene's. Another difference is that
since silicon's covalent bonds do not have pi-stacking, silicene does not cluster into a graphitelike form.[14]
Silicene and graphene have similar electronic structures. Both have a Dirac cone and linear
electronic dispersion around the k point. Both also have a quantum spin Hall effect. Both are

expected to have the characteristics of massless Dirac fermions that carry charge, but this is only
predicted for silicene and has not been observed, likely because it is expected to only occur with
free-standing silicene which has not been synthesized. It is believed that the substrate silicene is
made on has a substantial effect on its electronic properties. [14]
Unlike carbon atoms in graphene, silicon atoms tend to adopt sp3 hybridization over sp2 in
silicene, which makes it highly chemically active on the surface and allows its electronic states to
be easily tuned by chemical functionalization. [15]

Band gap[edit]
Early studies of silicene showed that different dopants within the silicene structure provide the
ability to tune its band gap.[16] Very recently, the band gap in epitaxial silicene has been tuned by
oxygen adatoms from zero-gap-type to semiconductor-type. [15] With a tunable band gap, specific
electronic components could be made-to-order for applications that require specific band gaps.
The band gap can be brought down to 0.1 eV, which is considerably smaller than the band gap
(0.4 eV) found in traditional field effect transistors(FETs).[16]
Inducing n-type doping within silicene requires an alkali metal dopant. Varying the amount adjusts
the band gap. Maximum doping increases the band gap 0.5eV. Due to heavy doping, the supply
voltage must also be ~30V. Alkali metal-doped silicene can only produce n-type semiconductors;
modern day electronics require a complementary n-type andp-type junction. Neutral doping (itype) is required to produce devices such as light emitting diodes (LEDs). LEDs use a p-i-n
junction to produce light. A separate dopant must be introduced to generate p-type doped
silicene. Iridium (Ir) doped silicene allows p-type silicene to be created. Through platinum (Pt)
doping, i-type silicene is possible. [16] With the combination of n-type, p-type and i-type doped
structures, silicene has opportunities for use in electronics.
Power dissipation within traditional metal oxide semiconductor field effect transistors (MOSFETs)
generates a bottleneck when dealing with nano-electronics. Tunnel field-effect transistors (TFETs)
may become an alternative to traditional MOSFETs because they can have a
smaller subthreshold slope and supply voltage, which reduce power dissipation. Computational
studies showed that silicene based TFETs outperform traditional silicon based MOSFETs.
Silicene TFETs have an on-state current over 1mA/m, a sub-threshold slope of 77 mV/decade
and a supply voltage of 1.7 V. With this much increased on-state current and reduced supply
voltage, power dissipation within these devices is far below that of traditional MOSFETs and its
peer TFETs.[16]

Close up of one hexagonal ring in silicene with displayed buckled structure.

Properties[edit]
2D silicene is not fully planar, apparently featuring chair-like puckering distortions in the rings.
This leads to ordered surface ripples. Hydrogenation of silicenes to silicanes is exothermic. This
led to the prediction that the process of conversion of silicene to silicane (hydrogenated silicene)
is a candidate for hydrogen storage. Unlike graphite, which consists of weakly held stacks of
graphene layers through dispersion forces, interlayer coupling in silicenes is very strong.
The buckling of the hexagonal structure of silicene is caused by pseudo-Jahn-Teller
distortion (PJT). This is caused by strong vibronic coupling ofunoccupied molecular
orbitals (UMO) and occupied molecular orbitals (OMO). These orbitals are close enough in
energy to cause the distortion to high symmetry configurations of silicene. The buckled structure
can be flattened by suppressing the PJT distortion by increasing the energy gap between the
UMO and OMO. This can be done by adding a lithium ion.[14]
In addition to its potential compatibility with existing semiconductor techniques, silicene has the
advantage that its edges do not exhibit oxygen reactivity.[17]
In 2012 several groups independently reported ordered phases on the Ag(111) surface. [18][19]
[20]

Results from angle-resolved photoemission spectroscopy (ARPES) appeared to show that

silicene would have similar electronic properties as graphene, namely an electronic dispersion
resembling that of relativistic Dirac fermions at the K points of the Brillouin zone,[18] but the
interpretation was later disputed and shown to arise due to a substrate band. [21][22][23][24][25][26] The
existence of Dirac fermions for silicene on Ag(111) was later reported from scanning tunneling
spectroscopy measurements.[27]
Besides silver, silicene has been reported to grow on ZrB
2,[28] and iridium.[29] Theoretical studies predicted that silicene is stable on the Al(111) surface as a

honeycomb-structured monolayer (with a binding energy similar to that observed on the 4x4
Ag(111) surface) as well as a new form dubbed "polygonal silicene", its structure consisting of 3-,
4-, 5- and 6-sided polygons. [30]
The p-d hybridisation mechanism between Ag and Si is important to stabilise the nearly flat silicon
clusters and the effectiveness of Ag substrate for silicene growth explained by DFT calculations
and molecular dynamics simulations.[26][31] The unique hybridized electronic structures of epitaxial 4
4 silicene on Ag(111) determines highly chemical reactivity of silicene surface, which are
revealed by scanning tunneling microscopy and angle-resolved photoemission spectroscopy. The
hybridization between Si and Ag results in a metallic surface state, which can gradually decay
due to oxygen adsorption. X-ray photoemission spectroscopy confirms the decoupling of Si-Ag
bonds after oxygen treatment as well as the relatively oxygen resistance of Ag(111) surface, in
contrast to 4 4 silicene [with respect to Ag(111)].[26]

Functionalized silicene[edit]
Beyond the pure silicene structure, research into functionalized silicene has yielded successful
growth of organomodified silicene oxygen-free silicene sheets functionalized withphenyl rings.
[32]

Such functionalization allows uniform dispersion of the structure in organic solvents and

indicates the potential for a range of new functionalized silicon systems and organosilicon
nanosheets.

The mechanical stabilities of planar (g) and low-buckled (b) honeycomb monolayer structures of silicon under
various large strains are investigated using density functional theory (DFT). The mechanical properties, including
the ultimate stresses, ultimate strains, and high order elastic constants of silicene are predicted, as well as the
structure evolutions. Both g-Si and b-Si can sustain large strains ( 0.15) for armchair, zigzag, and biaxial
deformation. The third, fourth, and fifth order elastic constants are indispensable for accurate modeling of the
mechanical properties under strains larger than 0.03, 0.06, and 0.08 respectively. The second order elastic
constants, including in-plane stiffness, are predicted to monotonically increase with pressure while the Poisson
ratio monotonically decreases with increasing pressure. Our results on the positive ultimate strengths and strains,
second order elastic constants, and the in-plane Young's modulus indicate that both g-Si and b-Si are
mechanically stable.

Nanotechnology
Silicene: atom-thick silicon with tunable properties
Rainer Friedlein, Antoine Fleurence, Yukiko Yamada-Takamura and Taisuke Ozaki
Silicon atoms crystallize in bonding configurations that are similar to those in graphene, opening up the
potential for exceptional electronic properties with possible applications in nanoscale electronics.
7 June 2013, SPIE Newsroom. DOI: 10.1117/2.1201305.004854

Silicon, the most commonly used semiconducting material, is intrinsically 3D.


Although the element silicon lies directly beneath carbon in the periodic table, it
does not easily form the crystalline bonding present in graphite because the
arrangement is energetically unfavorable.1 However, if this bonding were to be
realized in crystals made of silicon atoms, the resulting material could prove to be
as exciting as the ultimately thinNobel Prize-winning2D form of graphite:
graphene. It has been predicted2 that with only three strong directional bonds for
each atom, instead of the four formed in the diamond structure of silicon, silicene (the silicon analogue
of graphene) could possess highly mobile charge carriers with exotic properties.
Despite being predicted to be unstable in ambient conditions, 1 we have succeeded in creating silicene
on the surface of zirconium diboride (ZrB 2), a metallic ceramic material.3 Silicene has also been
created by a number of researchers on silver surfaces.46 To prove the presence of silicene, a
comprehensive characterization of the structural, electronic, and chemical properties is essential.

However, the properties of these samples differ from those of the (currently hypothetical) free-standing
silicene because the silicene is in close contact with the substrate surface.
The silicene that we produced rests on thin, single-crystalline ZrB 2 films with silicon wafers as
substrates (see Figure 1). Silicene is formed by surface segregation at elevated temperatures, under
ultra-high vacuum (UHV) conditions.3 In this process, silicon atoms diffuse from the silicon wafer to the
diboride surface and segregate to spontaneously form silicene. Although the silicene is oxidized on
exposure to air, it can be formed again at the same time as the oxide is removed by an annealing
procedure in UHV. In this way, we were able to study silicene in different complementary experimental
set-ups, using scanning tunnelling microscopy, angle-resolved photoelectron spectroscopy, and a
number of other surface science techniques.

Figure 1. Illustration of a silicene sheet (gray) on a zirconium diboride (ZrB 2) substrate. Red: Zirconium
atoms. Blue: Boron atoms.
Our data provides clear evidence for the presence of a silicene sheet that exhibits lattice-matching with
respect to the substrate: see Figure 2(a). As can be seen in Figure 2(b), the honeycomb lattice of
silicene is bumpy, or buckled. Buckling describes the displacement of the neighboring silicon atoms
from the plane. Although graphene is perfectly planar, free-standing silicene has been predicted to be
most stable in its regularly buckled form because of the interplay of electrostatic interactions related to
both electrons and atomic nuclei, which varies between the elements. 2 When this silicene is placed on
a substrate, individual silicon atoms adopt a different height with respect to the outermost layer of
zirconium atoms. This adaptation also enables the in-plane lattice parameters to match those of the
substrate surface.

Figure 2. (a) High-resolution scanning tunneling microscope image of silicene on ZrB 2thin films
prepared on silicon (Si) wafers. The unit cell and honeycomb mesh of silicene are emphasized by
green and blue lines, respectively. (b) Calculated height profile of silicene on the Zr-terminated
ZrB2surface. (c) Angle-resolved photoelectron spectrum plotted as a function of the electron
momentum (k||), showing an upward curved, low-energy electronic band (X2). : 1010m. eV:
Electronvolt. (Adapted with permission.3)
Although the electronic states of silicene are generally expected to mix with those of metallic
substrates, our recent experimental results indicate that the interactions of silicene with the
ZrB2 surface are rather weak. However, using quantum-chemical calculations, we have found that the
internal buckling is responsible for modifying the properties of low-energy electrons in silicene. 3 In
particular, occupied, low-energy electronic bandssee Figure 2(c)do not include electrons with zero
binding energy in silicene as they do in graphene. Accordingly, although graphene is a semi-metal,
silicene on ZrB2 is a semiconductor with a direct band gap,3 which means that the material can emit
light much more efficiently than 3D silicon. This important property might enable the use of silicene in
electronic devices that emit light or perform logical operations.
The chemistry of silicene provides further points of interest. Our recent, yet unpublished, results
indicate that silicene behaves quite differently compared with the reactive surfaces of both 3D silicon
and graphite. For instance, although they are unstable at atmospheric conditions, both silicene

nanoribbons7 and silicene on ZrB2 films resist oxidation at relatively high oxygen levels. In other
experiments, we found that organic molecules physically adsorb on the surface of silicene. Compared
with those at the surface of graphite, the inhomogeneous charge density distribution associated with
the buckling of silicene causes slightly stronger interactions with the adsorbates.
In summary, with bonding configurations and electronic and chemical properties close to those of
graphene, the evidence for silicene on metallic substrates is mounting. The growth with good lattice
matching on large-scale silicon wafers via diboride buffer layers provides a way to integrate silicene
into existing silicon-based technologies, which currently face intrinsic limitations with top-down
approaches. Our next step is to investigate the way in which silicene is formed, and how the
interactions with the substrate and non-metallic capping layers will influence its electronic properties.
Once created on an insulating platform, silicenewith its specific structural and electronic properties
might challenge the dominance of graphene in nanoscale physics and technological applications.

Rainer Friedlein, Antoine Fleurence, Yukiko Yamada-Takamura


School of Materials Science
Japan Advanced Institute of Science and Technology
Nomi, Japan
Rainer Friedlein is an associate professor. He works with photoelectron spectroscopic techniques on
the electronic structure of organic materials and organic/inorganic interfaces. His recent work focuses
on novel low-dimensional -electronic materials self-assembled at surfaces.
Taisuke Ozaki
Research Center for Simulation Science & School of Materials Science
Japan Advanced Institute of Science and Technology
Nomi, Japan

References:
1. M. T. Yin, M. L. Cohen, Structural theory of graphite and graphitic silicon, Phys. Rev. B29(12), p. 6996-6998,
1984. doi:10.1103/PhysRevB.29.6996
2. K. Takeda, K. Shiraishi, Theoretical possibility of stage corrugation in Si and Ge analogs of graphite, Phys. Rev. B 50(20), p. 1491614922, 1994. doi:10.1103/PhysRevB.50.14916
3. A. Fleurence, R. Friedlein, T. Ozaki, H. Kawai, Y. Wang, Y. Yamada-Takamura, Experimental evidence for epitaxial silicene on diboride
thin films, Phys. Rev. Lett. 108(24), p. 245501, 2012. doi:10.1103/PhysRevLett.108.245501
4. C.-L. Lin, R. Arafune, K. Kawahara, N. Tsukahara, E. Minamitami, Y. Kim, N. Takagi, M. Kawai, Structure of silicene grown on
Ag(111), Appl. Phys. Express 5, p. 045802, 2012.doi:10.1143/APEX.5.045802
5. H. Jamgotchian, Y. Colignon, N. Hamzaoui, B. Ealet, J. Y. Hoarau, B. Aufray, J. P. Bibrian, Growth of silicene layers on Ag(111):
unexpected effect of the substrate temperature, Phys. Condens. Matter 24(17), p. 172001, 2012. doi:10.1088/0953-8984/24/17/172001
6. P. Vogt, P. De Padova, C. Quaresima, J. Avila, E. Frantzeskakis, M. C. Asensio, A. Resta, B. Ealet, G. Le Lay, Silicene: compelling
experimental evidence for graphene-like two-dimensional silicon, Phys. Rev. Lett. 108(15), p. 155501,
2012.doi:10.1103/PhysRevLett.108.155501
7. P. De Padova, C. Quaresima, B. Olivieri, P. Perfetti, G. Le Lay, Strong resistance of silicene nanoribbons towards oxidation

Silicene may join graphene as wonder material


By Jude Dineley
Cosmos Online

Japanese researchers have produced silicene, a one-atom-thick layer of silicon similar to


graphene, that could work in microprocessor chips and could result in the ultimate
miniaturisation of devices.

Silicene is a one atom thick layer of silicon that could result in the ultimate miniaturisation of electronic devices.
The latest study synthesised the material (blue) silicon wafer coated with a Zirconium diboride film (green).
Credit: Antoine Fleurence & Taisuke Ozaki

SYDNEY: Japanese researchers have produced silicene, a one-atom-thick layer of


silicon similar to graphene, that could work in microprocessor chips and could result in
the ultimate miniaturisation of devices.

Graphene, a one-atom-thick mesh as well, but made of carbon, is the most conductive
known material, and has been touted as the future of computing. It could be a critical
component of better batteries, as well as lightweight, flexible devices.
Silicene, which was first reported in April by European researchers, is predicted to
share some of the impressive properties of its carbon cousin, graphene. Importantly,
however, silicene could be integrated with current silicon-based electronic devices,
whereas graphene is incompatible.
Yukiko Yamada-Takamura, senior author of the study published in Physical Review
Letters and materials scientist at the Japan Advanced Institute of Science and
Technology, in Nomi, describes the material as a sensation.
Ultimate miniaturisation possible
Silicene is the thinnest possible form of silicon, which is the unbeatable, dominant
electronic material used in many devices around us. Ultimate miniaturisation of such
devices should be achieved if silicene is made available for applications, said YamadaTakamura.
But she is also quick to point out that a lot of research questions remain outstanding.
This research is really in its infancy, she said.
The latest study synthesised silicene with a buckled, bumpy appearance, with silicon
atoms at three different heights. With this buckled structure, researchers observed a
bandgap a no-go zone for electrons.
Opens the way to nanoscale semiconductors
The band gap means that nanoscale semiconductors which are at the heart of almost
every electronic device could be developed, with myriad applications including light
emitting diodes and microprocessor chips. To date, researchers been unable to achieve
such a bandgap with graphene.
The structure was a consequence of the structure of the substrate on which the
researchers synthesised the silicene, the ceramic Zirconium diboride. YamadaTakamura predicts a large family of silicene may be waiting to be discovered, each
material having tunable electronic properties according to the substrate used.
The European researchers who produced silicene in April, however, point out that a key
feature is missing. In both graphene and the European silicene, there was something
called a Dirac cone, which allows electrons to behave like massless particles, enabling
them to zip through materials at speeds close to the speed of light.
Controversy over claims of silicene
The Dirac cone occurs when the valence band of an atom overlaps with the conduction
band of an atom.
The presence or lack of a Dirac cone is the source of some disagreement among
researchers as to whether the Japanese study actually synthesised silicene in the first
place.
I think that this study is really nice, because this is the demonstration of the growth of
honeycomb silicon on another substrate. However, since no Dirac cone was found one
can doubt that this is really silicene, said Paola De Padova, a physicist from the Italian
National Research Council in Rome, who was involved in the original European study.
Yamada-Takamura argues that the definition of silicene should not be narrowed down
at this early stage in the research of the material.

The definition of silicene is not decided, yet. Our finding is particularly interesting in the
sense that we demonstrated that the structure of silicene can be modified easily, and
we can have an atom thick layer of silicon with different properties, said YamadaTakamura.
Hurdles to jump before industrial application
Shu-jen Han, a researcher at the IBM T.J. Watson Research Centre in New York State
specialises in nanoelectronics. Hes pragmatic regarding the industrial application of
silicene.
Successful formation of silicene is a major step forward. However, before silicene can
be grown or transferred on insulating substrates for electrical measurements, [and] thus
be compared to graphene for their transport properties, we will hold our excitement,
said Han.
De Padova concurs there is still much to do, but also thinks theres plenty to look
forward to.
The determination of the electronic and structural properties of silicene, the capability
to growth this new allotrope silicon on several substrates and finally the hard task to
isolate the silicene, will open the way forwards a research rich of new discovery, said
De Padova.
More information:
Europan study, reported in Physical Review Letters
Yamada-Takamuras research group homepage
Study by Japanese group, in Physical Review Letters

The deposition of one silicon monolayer on Ag(111) gives rise to a set of


superstructures depending on growth conditions. These superstructures are
correlated to the epitaxy between the honeycomb structure of silicon (so
called silicene) and the silver substrate. In this paper, from a detailed reanalysis of experimental results, obtained by scanning tunneling
microscopy and by low energy electron diffraction on the (2323)R30
structure, we propose a new atomic model of the silicene layer based on
periodic arrangements of perfect areas of (2323)R30 surrounded by
defect areas. A generalization of this model explains the main experimental
observations: deviation of the average direction, Moir patterns and
apparent global disorder. In the frame of the proposed model, the apparent
disorders observed on the STM images, would be topological effects, i.e. the
silicene would keep a quasi-perfect honeycomb structure.

Sticky problem snares wonder material


Graphene-like form of silicon proves hard to handle.

In 2011, physicist Guy Le Lay stood before a half-filled room on the last day of the American
Physical Societys March meeting in Dallas, Texas, and presented data on a new form of
silicon. In his laboratory at Aix-Marseille University in France, Le Lay had grown sheets of
honeycombed silicon with layers just one atom thick. He had only preliminary evidence that
was unpublished at the time. It was a risk, you know? he says now of his decision to present
the data.
At this years meeting, on 1822 March in Baltimore, Maryland, scientists will deliver about
two dozen talks on silicene (see Speaking of silicene), the material that Le Lay tentatively
described two years ago.
The name recalls graphene, the current darling of the materials-science world and the
flurry of interest suggests that silicene could be the next one. But for that to happen, Le Lay
and others will have to overcome silicenes unfortunate tendency to stick to practically
everything it touches.
Structurally, silicene looks a lot like graphene, which is also a honeycombed sheet, but of
carbon atoms rather than silicon. Silicenes two-dimensional structure should lead to strange
quantum effects and allow electrons to streak across it at incredible speed properties that,
in graphene, have entranced physicists and builders of electronic devices since it was first
characterized in 2004. In 2010, work on graphene won a Nobel prize, and earlier this year,
graphene research was selected by the European Commission as one of its billion-euro
flagship projects (see Nature 493, 585586; 2013).

Expand

Silicene could even have some extra attractions. It is predicted to have characteristics similar
to topological insulators materials that conduct electrons only on their outer surfaces
another trendy area of research.
Above all, silicene is made of silicon, the same material that drives the modern electronics
industry. Bringing it all together could lead to a new era in silicon electronics, says Kehui
Wu, a physicist at the Chinese Academy of Sciences Institute of Physics in Beijing.
Theres just one problem: silicene is super sticky. Graphene is a very stable material, says
Franois Peeters, a condensed-matter theorist at the University of Antwerp in Belgium. But
silicene reacts easily with the environment oxidizing in the air and bonding chemically
with other materials. And unlike graphene, which lies flat, silicene crinkles into bumps and
ridges as a result of the way neighbouring silicon atoms bond with each other. That makes it
more likely to stick to surfaces.
Silicenes reactivity makes it much harder to produce than graphene. The Nobel prizewinning
work on graphene began by peeling sheets from a block of graphite with a piece of sticky
tape. Silicene, by contrast, can only be grown in an ultra-high vacuum on top of a material
that matches its natural structure (see Making silicene).

Expand

Crystalline silver has proved to be the best fit because its atomic structure allows it to lock
together with silicenes wavy ridges, and the silvers non-reactive surface means that it
doesnt pull the silicene apart, Le Lay says. Reversing a technique he honed for depositing
silver onto silicon, Le Lay grew the first samples of silicene on silver1.

Only two other materials have been found to support silicene up to now. One, zirconium
diboride, has the advantage of naturally sucking silicene onto its surface from a block of
silicon positioned below2. The other, crystalline iridium, was reported as a possibility only in
January this year3.
Unfortunately, all three of these materials conduct electricity, says Yukiko Yamada-Takamura,
a materials scientist at the Japan Advanced Institute of Science and Technology in Nomi. The
bulky conductors mask silicenes delicate electrical properties, making it impossible to check
whether the theoretical predictions of strange quantum effects are correct.
To see if silicene performs as expected, experimentalists will have to find a semiconducting or
insulating surface on which to grow it. Better still would be to develop a technique to create
free-standing sheets of silicene, Yamada-Takamura says. Its not entirely clear how that would
be done, but given the increasingly competitive nature of the field, she says, I will not tell
you even if I had an idea.
As Peeters isnt racing to grow silicene himself, hes more willing to speculate. He thinks that
sandwiching silicene between two sheets of another material, such as graphene, could
stabilize it and prevent it from reacting with the outside world.
I think if it will be used, it will be used in sandwich form, because thats the way in which
you can stabilize it, he says. The outer sheets can be any material; it really depends on what
you want to do with it.
Despite its troubles, silicenes future looks bright. It has been included as part of Europes
massive graphene programme, and is catching on in the United States, Le Lay says.
The talks on it at the March meeting are likely to be more popular than they were two years
ago, but Le Lay wont be there to find out. Hes too busy giving seminars at departments
everywhere from Hawaii to Austria to Japan. Its crazy, he says. But its good!
Nature
495,
152153
(14 March 2013)
doi:10.1038/495152a

Initial geometries, interaction mechanism and


high stability of silicene on Ag(111) surface

Using ab initio methods, we have investigated the structures and


stabilities of SiN clusters (N 24) on Ag(111) surface as the initial
stage of silicene growth. Unlike the dome-shaped graphene
clusters, Si clusters prefer nearly flat structures with low buckling,
more stable than directly deposition of the 3D freestanding Si
clusters on Ag surface. The p-d hybridization between Ag and Si is
revealed as well as sp 2 characteristics in Si N@Ag(111). Three types
of silicene superstructures on Ag(111) surface have been
considered and the simulated STM images are compared with
experimental observations. Molecular dynamic simulations show
high thermal stability of silicene on Ag(111) surfaces, contrast to
that on Rh(111). The present theoretical results constitute a
comprehensive picture about the interaction mechanism of silicene
on Ag(111) surface and explain the superiority of Ag substrate for
silicene growth, which would be helpful for improving the
experimentally epitaxial growth of silicene.

Silicene grown for (probably) the first time


18 April 2012

A one atom-thick layer of silicon - a material dubbed silicene - has been created for perhaps the first time. If fully
tamed, this material might match graphene's useful electrical properties. It could also be much easier to integrate
with normal silicon-based circuits, meaning the development of super-miniaturised electronic devices could be
accelerated.

Over the last decade, research groups from around the world have produced a spate of papers, each claiming to
have prepared silicene. But according to Patrick Vogt of Berlin's Technical University, Germany, and Paola De
Padova from the Istituto di Struttura della Materia in Italy who led the latest effort to synthesise the material, these
groups provided scant evidence that the material existed at all.
Vogt says that the problem with the previous reports of silicene was that they only provide scanning tunnelling
microscopy (STM) images as evidence of the material's existence. 'It's difficult to conclude anything from STM
images alone,' he says. De Padova says the previous claims are 'highly dubious'. Vogt and De Padova tried and failed - to replicate work described in one of the rival papers.1 That paper reported silicon-silicon atomic
distances that are 'almost impossibly short', Vogt says.
The new work used simple vapour deposition techniques to grow a one atom-thick silicon layer on a silver crystal
surface.2 'We've looked at the chemical structure, the electronics and dimensions of the material we produced,
and if you combine all these observations you can really be sure you're looking at silicene,' Vogt says. The
structural parameters observed, like bond angles and lengths, matched density functional theory calculations
excellently.
Vogt says it is difficult to predict how 'good' silicene might be in electronics compared with graphene. 'We're very
much at the beginning of looking at this material,' he says, 'and there are other options too. It might be worth
looking at germanium, which would give germanicene.'

Andrei Khlobystov, an associate professor of inorganic chemistry at the University of Nottingham,UK, says 'people
are struggling to integrate graphene into electronic devices' and agreed there was 'promise' that silicene might
circumvent that problem. 'If you look at the detail of the experimental and theoretical calculations, [silicene] is not
flat - it's corrugated,' he adds. 'For that reason, you'd expect quite different electronic and structural properties
from graphene. But surprisingly, to me, this paper reckons that the properties would be very similar, in terms of
the conductivity, the absence of a band gap and the mobility of the charge carriers.' Khlobystov says the next
important step would be to measure the properties of the material without the metal support.
Josh Howgego

Progress review in the materials


science of silicene
(Nanowerk News) Silicene is the thinnest form of silicon. It is metallic, has
graphene-like mobile carriers and can behave like a semiconductor. The
wonder material could lead to even smaller electronics but challenges remain
in this review published in the Science and Technology of Advanced
Materials ("Progress in the materials science of silicene").

Structures and structural parameters of (a) diamond-structured silicon, (b)


graphene, (c) disilene and (d) hypothetical, freestanding silicene. ( Science
and Technology of Advanced Materials)
Scientists in Japan compared the properties of a hypothetical freestanding
one-atom-thick layer of silicon to a similar sheet developed on a metal
substrate. Although promising, this second epitaxial form shows important
differences. Turning the hypothetical material into a reality still remains a
major challenge, 20 years after it was first reported.
In 1994, scientists published their first theoretical report on the thinnest
possible form of silicon. Among many other uses, silicon is incorporated as a
semiconductor in integrated circuits, the basis of most computers.
But it was only ten years later in 2004, when another material, graphene,
was reported, that scientists started showing a real interest, and eventually
named the material, silicene.
Graphene is a one-atom-thick layer of carbon that has been shown to host
the fastest carriers of electricity yet found. Compared with silicon, however,
graphene is not a semi-conductor because it cant switch between
conducting and not conducting states. This makes it very difficult to apply it
in a switching device such as a transistor.
This is why silicene is so exciting. In its freestanding form, this one-atomthick layer of silicon atoms has graphene-like mobile carriers as well and is
metallic. On the other hand, for instance by applying strain or an electric
field, it could also be turned to behave like a semiconductor. This is because
the structure could be easily modified or switched on the atomic scale. In
addition, it would be compatible with already existing silicon-based circuitry.
This is envisaged to lead to the development of even smaller electronics than
those currently on the market.
Because of its exciting potential, the experimental demonstration of the
existence of silicene was highly anticipated. In 2012, several groups reported
successfully developing epitaxial silicene: silicene sheets formed on
metallic substrates. A team of Japanese scientists compared the
characteristic properties of theoretical freestanding silicene to epitaxial

silicene they had produced on a zirconium diboride substrate. They found


that the crystal structure of epitaxial silicene was strongly influenced by its
metal substrate, thus resulting in electronic properties different from those
predicted for the hypothetical freestanding form.
The synthesis of freestanding silicene remains a major challenge and many
of the properties of its epitaxial form are not yet fully understood. However,
the team of Japanese scientists joined by a few other groups worldwide will
further work on the understanding of the formation mechanism of epitaxial
silicene and its interaction with the substrate. Based on the deep
understanding of this matter, present and future work is anticipated to result
in the required developments such as the formation of silicene on an
insulating platform and its successful encapsulation. This would then lead to
practical applications of the material.
Source: National Institute for Materials
Science

Read more: Progress review in the materials science of silicene

Progress in the materials science of


silicene
In its freestanding, yet hypothetical form, the Si counterpart of graphene
called silicene is predicted to possess massless Dirac fermions and to
exhibit an experimentally accessible quantum spin Hall effect. Such
interesting electronic properties are not realized in two-dimensional (2D) Si

honeycomb lattices prepared recently on metallic substrates where the


crystal and hybrid electronic structures of these 'epitaxial silicene' phases
are strongly influenced by the substrate, and thus different from those
predicted for isolated 2D structures. While the realization of such lowdimensional Si materials has hardly been imagined previously, it is
evident that the materials science behind silicene remains challenging. In
this contribution, we will review our recent results that lead to an
enhanced understanding of epitaxial silicene formed on diboride thin films,
and discuss the remaining challenges that must be addressed in order to
turn Si 2D nanostructures into technologically interesting nanoelectronic
materials.

Introduction
Silicon is the most commonly used material in the semiconductor industry
and is made of sp3-hybridized silicon (Si) atoms adopting the threedimensional diamond structure (figure 1(a)). As a consequence, valence
electrons localized in bonds are less mobile than those in graphite in
which the sp2 hybridization of carbon (C) atoms (figure 1(b)) leads to the
formation of extended electronic states at low binding energies.
Although the element Si is right below C in the periodic table,
the sp2 hybridization is energetically unfavorable [1] but occurs for
instance in disilene molecules [2] (figure 1(c)) and at reconstructed Si(111)
surface [3]. If this type of bonding were to be realized in two-dimensional
(2D) crystals made of Si atoms, the resulting material could be as exciting
as the ultimately thin form of graphite: graphene. In analogy to this
exciting material, an atom-thick, 2D honeycomb layer made of Si atoms
possessing electronic states [4] has been coined 'silicene' [5]. However,
while the first report on a theoretical study of silicene has been published
20 years ago [6], it was only after the enormous success of graphene
[7, 8] that the study of silicene-related materials has received an explosion
of interest.

Zoom In Zoom Out Reset image size

Figure 1. Structures and structural parameters of (a) diamond-structured


silicon, (b) graphene, (c) disilene [2], and (d) hypothetical, freestanding
silicene [6]. In the insets, thesp2 and sp3 types of hybridization are
sketched.
Already in the early study carried out by Takeda and Shiraishi [6], the
crystal and electronic structures of a single, isolated or 'freestanding'
silicene sheet (figure 1(d)) had clearly been pointed out. While silicene is
the bigger cousin of graphene, there are notable and important differences
and similarities between the two materials. The crystal structure of the yet
hypothetical, freestanding silicene is similar to graphene: both are formed
by honeycomb networks that differ, however, in the in-plane lattice
constants and in the degree of flatness. In particular, while graphene is
perfectly planar, silicene is predicted to be more stable when 'corrugated'
[6], or in another word 'buckled' [9], in a way in which the two sublattices
are displaced from each other in the out-of-plane direction. Note that
originally, only the perfectly planar graphene analog has been called
'silicene' while the buckled form has been called a 'Si(111) sheet' [5].
Nowadays, the term 'silicene' is used to describe any 2D honeycomb
structure made of Si atoms, even those in which the buckling could exhibit
larger-scale periodicities [10]. Note that in its hypothetical, freestanding
form, an infinite honeycomb Si sheet prefers to be buckled with two
sublattices displaced from each other in the out-of-plane direction thus
indeed resembling the Si(111) bilayer. While the nomination 'Si(111) sheet'
[5] might structurally be appropriate, it does not suggest the hybridization

to be different from diamond-structured silicon thus capturing the


essential differences in electronic properties that make silicene special [4].
Bond lengths are indeed predicted to be shorter (2.24 ) [6] than single
bonds in the bulk of diamond-structured silicon (2.35 ) and longer than
typical but rarely occurring double bonds between Si atoms in disilenes
(2.142.16 ) [2]. This is indicative of a mixture of the sp2 and sp3types of
hybridizations [6]. As a result, freestanding silicene is predicted to be
flatter while having a lattice constant of 3.855 similar to that of the
Si(111) bilayer (3.84 ) [6]. In spite of this mixture, freestanding silicene is
predicted to possess bands with Dirac cones at the K points [6]. The
overall band width is reduced as compared to graphene largely because
of the smaller overlap integrals between nearest neighbors which itself
is related to the larger atomic radius of Si atoms [6].
More recently, as a hypothetical concept, silicene has been a productive
playground with exotic electronic effects. In particular, it started to attract
interest as a 2D topological insulator [1113] and since it exhibits an
experimentally observable quantum spin Hall effect (QSHE) that derives
from a large effective spinorbit coupling (SOC). The large SOC originates
from the buckled nature that relates to the sp2/sp3 mixed hybridization
[11]. In addition, it is large as compared to graphene, which exhibits a
QSHE only at extremely low temperature [14], since the SOC scales with
the fourth power of the atomic number. The SOC-induced transition to the
quantum spin Hall insulator state should therefore occur at a much higher
temperature as compared to graphene [11, 13]. While planar silicene is
predicted to have only a vanishing gap (0.07 meV) opened by the SOC at
the Dirac points, the gap opens to 1.55 meV in buckled silicene which can
be further increased to 2.90 meV by applying in-plane stress [11].
Additionally, under an external, out-of-plane electric field, the two
sublattices are no longer equivalent, such that the size of the band gap
might be tuned [12, 13]. Eventually, by increasing the strength of the
electric field, a transition from the topological insulator state to a band
insulator is predicted to occur [12, 13].
Due to the predictions of graphene-like properties and those of a
topological insulator emerging in a single material, the experimental
demonstration of the existence of silicene has been highly anticipated. The
report of the successful experimental realization of 'epitaxial', or lattice
matching, 2D silicene sheets on metallic substrates by several groups
beginning in 2012 therefore caused a stir [4, 1518] but provoked a
heated discussion on the experimental evidence related to the
characteristic properties of silicene [1922]. To sum up the present state of
characterization of these epitaxial silicene phases, silicene with Dirac
fermions or topological insulator-like properties has not been
experimentally demonstrated with conviction. This is not surprising since
quite obviously, for such epitaxial sheets on metal surfaces, it is the
electronic coupling to the substrates that determines both the crystal and
electronic structures of the hybrid systems. In order to reveal differences
and similarities to the yet hypothetical freestanding silicene, a
comprehensive characterization by a number of experimental techniques
is essential and must be performed in situ.

Beside the basic surface science characterization, in order to explore the


electronic transport properties of silicene and its potential applications in
electronic or spintronic devices, the growth on insulating or
semiconducting substrates, instead of the metallic substrates reported so
far, is highly desired. In addition, as silicene is not chemically inert
[23, 24], a capping layer is needed for ex situ characterizations, i.e.,
outside ultra-high vacuum (UHV) environments.
In this review, we summarize our recent experimental and theoretical
efforts to synthesize, characterize, understand, and engineer the crystal
and electronic structures of epitaxial silicene on zirconium diboride (ZrB 2)
thin films in relation to those of hypothetical, freestanding silicene, and
discuss challenges in the materials science on the way towards a future
silicene nanoelectronics.

2. The theoretical concept and the experimental realization of epitaxial silicene


2.1. Theoretical predictions for freestanding silicene

While at a first glance, the crystal structure of silicene is similar to


graphene, it is not as simple as it seems. In the case of graphene, the
honeycomb lattice is planar and the lattice constant remains hardly
modified. On the other hand, over a large range of in-plane lattice
constants, freestanding silicene is predicted to be stable in the so-called
'low-buckled' or 'regularly buckled' structure [9, 10], shown in figure 2(a),
in which two sublattices of the bipartite lattice are at different heights
[6, 9]. Even if regularly buckled, the atomic orbital mixing is close to that
of the sp2 hybridization such that freestanding silicene is expected to
display electronic properties similar to those of graphene [6, 9, 10]. As it
can be recognized in the band structure shown in figure 3(a), in particular,
most prominent is the absence of the opening of a recognizable gap
in bands at the Dirac point located at KSi(1 1). This indicates that the
buckling is not associated with a gain in band energy [10] and the stability
of the buckled silicene over the planar one may instead relate to an
instability in the phonon part that involves the lattice repulsive potential
and the response of electrons to the lattice vibration [6, 9, 10]. Of course,
due to the smaller size of interatomic overlap integrals, the overall band
width is reduced by a factor of about 3 [5, 6, 9,10].

Figure 2. Structural configurations of freestanding, 2D Si nanostructures


in side and top views: (a) regularly buckled and (b) (3 3)reconstructed, planar-like silicene phases. The bond lengths and the
degree of buckling of the two phases are indicated for the calculated
lattice constant of 6.35 that corresponds to that of the (2 2) unit cell of
ZrB2(0001) surface. (c) MoS2-type single layer of Si atoms. Panels (a) and
(b) are reproduced from C-C Lee et al 2013 Phys. Rev. B 88 165404. Panel
(c) is reproduced from F Gimbert et al 2014 Phys. Rev. B 90 165423. Both
articles published under a Creative Commons Attribution 3.0 Unported (CC
BY 3.0) License.

Figure 3. The electronic band structures of the freestanding (a) regularly


buckled and (b) planar-like phases as unfolded from the (3 3) unit cell
(using the calculated in-plane lattice constants of the (2 2) unit cell of
ZrB2(0001) surface of 6.35 ) into the first Brillouin zone of (1 1) silicene.
The s and pz characters of bands are colored in magenta and black,
respectively, and that of px and py orbitals in green. Adapted and
reproduced from C-C Lee et al 2013 Phys. Rev. B 88 165404. Article
published under a Creative Commons Attribution 3.0 Unported (CC BY 3.0)
License.
Under out-of-equilibrium conditions, the degree of buckling of the
honeycomb structure of freestanding silicene does vary widely as a
function of the in-plane lattice constants [9, 10]. Additionally, the buckling
could vary locally on the atomic length scale. This can be described as a
reconstruction of the 'original' honeycomb, or (1 1) lattice. In particular,
for a certain range of lattice constants, a (3 3)-reconstructed phase,
called the 'planar-like' phase [10], turns out to be quite stable. Its crystal
and band structures (unfolded [25] into the (1 1) unit cell) are shown in
figures 2(b) and 3(b), respectively.
Note that the importance of this phase lies in its relevance for epitaxial
silicene: while for freestanding layers, the planar-like phase is less stable
than the regularly buckled form of silicene [10], in its form with stripes
[26], it becomes the ground state on the ZrB2 surface [10,27]. Note that it
has also been calculated to form on the Ag(111) surface [28].
In this planar-like phase, all but one of the Si atoms per hexagon reside in
a single plane. In this way, it is able to sustain a longer in-plane bond
length as compared to the planar phase such that the bond length
becomes closer to that of the regularly buckled phase [10]. Due to the
(3 3) reconstruction, the symmetry is broken which causes back-

folding of electronic states into the reduced Brillouin zone and the lifting of
the degeneracy of bands. As can be recognized in figure 3(b), some
resemblance to the band structure of regularly buckled silicene can be
found. For instance, cone-like band dispersions are still noticeable even
under the (3 3) reconstruction, which, however, leads to the opening
of a small gap and an up-shift of the corresponding features [10]. This can
be visualized at the KSi(1 1) point via unfolding, as shown in figure 3(b).
Previously, the search for the lowest-energy structures of freestanding 2D
Si allotropes has been focused on honeycomb lattices that relate to either
regularly-buckled, unreconstructed [5, 6, 9,10] or (3 3)-reconstructed
[10] silicene phases. However, very recently, it has been shown that the
addition of Si adatoms to silicene results in the formation of a dumbbell
structure with a lower energy per atom [29, 30]. Towards the complete
coverage, the periodic dumbbells can be recognized to form the structure
of a well-known single layer of MoS2 that possesses a lower total energy
per atom than regularly buckled silicene [31]. Although hypervalent Si
atoms in heteroatomic molecules have been known since the 19th century
[32, 33], this came as a surprise to us since by considering the 4-fold
coordination realized in the sp3 bonding of Si atoms, it is difficult to
understand why bonding with 6-fold coordination could be formed by Si
atoms in the MoS2 structure. Here, the new form of bonding expressed
by three cigar-shaped orbitals coexist with an extended electronic
structure. The direction of these orbitals has changed from the typical inplane direction of the orbitals in the sp2 hybridization (see figure1(b)) to
the out-of-plane direction to form cigar-shaped, so-called 'nematic' orbitals
[31]. Quite clearly, such a previously unimagined bonding configuration
and structure must be considered as a candidate for epitaxial 2D Si layers,
as just predicted for the (3 3) phase on Ag(111) [34].
2.2. The experimental realization of silicon honeycomb structures on surfaces

Honeycomb Si structures occur in disilicides [3537], in Si sheets


chemically exfoliated from calcium disilicides [38], and can even exist as a
single sheet on an erbium-covered Si(111) single-crystal surface [39].
Such Si sheets in disilicides are characterized by charge transfer from the
metals and a substantial amount of hybridization between the electronic
states derived from the two subsystems.
More recently, Si nanoribbons with an internal honeycomb structure have
been obtained by the deposition of Si atoms on the Ag(110) surface [40
44]. The epitaxial Si nanoribbons observed by scanning tunneling
microscopy (STM) are uniformly 1.6 nm in width and 0.2 nm in height [40].
Density functional theory (DFT) calculation of a structure model with Si
honeycombs based on STM observations resulted in an average SiSi
distance of 2.24 [42], a value which is close to that of freestanding
silicene [6]. Along the long direction of the ribbons, dispersive states
reminiscent of electronic states of graphene have been observed [43].
These states are cone-like and split with a gap of 0.5 eV, centered at 0.6
eV below the Fermi level (EF) at the high symmetry point corresponding to
the silicene KSi(1 1) point. In the short direction, states are localized
revealing the one-dimensional (1D) character of this nanostructure [43].

The Ag(110) surface has a rectangular lattice which is ideal for the
template of parallel 1D nanoribbons. On the other hand, in order to form
2D sheets with honeycomb structures, hexagonal lattices are the natural
choice. Following the preparation and study of silicene nanoribbons, in
2010, the highly contested possible formation of a silicene sheet on
Ag(111) surface has been reported [45]. In 2012, several groups described
the formation of better-characterized Si honeycomb structures on Ag(111)
[1518] and ZrB2(0001) thin film [4] surfaces, of which both have
hexagonal symmetry.
The deposition of Si atoms on Ag(111) single crystal surfaces under UHV
conditions and in the typical substrate temperature range between 250 C
and 300 C leads to a number of surface reconstructions depending on the
amount of Si atoms and the temperature during deposition. Since
independently well-calibrated Si sources are needed to precisely establish
the amount of Si atoms deposited onto the surface, the interpretation of
the obtained surface reconstructions differs among these reports. As such,
(23 23) [45] and (4 4) [1517] reconstructions of the Ag(111)
surface, and a reconstruction corresponding to a (3 3)-reconstructed
silicene lattice [18] have been reported as silicene sheets on the Ag(111)
surface. These reconstructions may represent various phases of epitaxial
silicene or alternatively, as has been discussed, of Si networks that consist
of incomplete honeycombs [18] or possibly bilayer [46] structures.
It is obvious that control of the source conditions and of the temperature is
key to the formation of silicene phases by a deposition process. The
advantage of this process is that different substrate materials can be
easily tested. This lead to the reports on Ir(111) [47] and ZrC(111) [48] as
possible substrates.
On the other hand, epitaxial silicene on ZrB2(0001) thin films forms by a
completely different process: surface segregation at elevated
temperatures. We found that on the surface of oxide-free, singlecrystalline ZrB2 thin films grown epitaxially on Si(111) wafers, epitaxial
silicene forms spontaneously [4]. The thin films of metallic ceramic
zirconium diboride, with the thickness of about 1530 nm, have been
grown by UHV-chemical vapor epitaxy and exhibit the epitaxial
relationship described by ZrB2(0001)//Si(111) and ZrB2[10 0]//Si[11 ] [49].
In the case of surface segregation, the source of Si atoms is the silicon
substrate of the diboride film. The process is governed by thermodynamic
equilibrium conditions and thus self-terminating. Following the transfer
under ambient conditions, native oxides including those containing Si
atoms formed upon exposure to air are easily removed by heating to 800
C under UHV conditions such that the diboride surface is again
spontaneously and uniformly covered with epitaxial silicene. Importantly,
under optimal conditions, this procedure highly reproducibly leads to
samples with more than 99.5% of the surface covered with ZrB2(0001)
terraces, and thus with single-crystalline-like silicene [49, 50]. Different
from the deposition technique, surface segregation processes are
materials specific and are thus not applicable to any kind of substrate. But
for example, it is known that on AlN(0001) epilayers grown with Si-doping
or on Si-containing substrates, Si-induced surface reconstructions are

observed [51]. Here, surface-segregated Si atoms work as a surfactant


[51] just like in the case of ZrB2 thin films grown on Si wafers. If a
comprehensive characterization would be applied to this surface, one may
possibly find epitaxial silicene on an insulating substrate.
2.3. The decisive role of a comprehensive characterization of epitaxial silicene phases

As many controversial discussions of early results have shown, evidence


for epitaxial silicene should come from a combination of comprehensive
experimental characterization techniques and first-principles calculations
covering both structural and electronic properties. STM performed in UHV
is the most frequently used characterization method for epitaxial silicene
[4,1518, 45, 47], and in the most cases [15, 16, 18, 45, 47], combined
with an electron diffraction technique, the only characterization method.
But clearly, STM images alone are not enough to claim the formation of
silicene since it provides limited information about the electronic structure
of the surface layer.
For instance, in our original [4] and subsequent studies [27, 5254],
structural evidence for epitaxial silicene on diboride thin films grown on Si
wafers has been obtained from atomic-resolution surface imaging using
STM, chemical information such as on the elemental composition and the
chemical environment of Si atoms from high-resolution, core-level
photoelectron spectra measured at a synchrotron radiation facility, and
band structure-related information from the combination of angle-resolved
photoelectron (ARPES) spectra and DFT calculations. Complementary and
additional structural information might be obtained for instance by
reflection high-energy electron diffraction (RHEED) [49], low-energy
electron diffraction (LEED) [52] and from the analysis of incident electron
beam energy dependent intensities (IV) of LEED spots [55].
Why so many characterization techniques are needed is because (i) there
is no single, reliable identification method for epitaxial silicene, and (ii)
epitaxial silicene phases are always in a kind of hybrid state with the
surface of the respective substrates and thus not well-defined in terms of
isolated, freestanding or 'ideal' silicene. Since epitaxial silicene is not
stable under ambient conditions, the characterization must be
performed in situ inside the UHV set-up accompanying the preparation of
silicene. In order to then obtain the required variety of meaningful data,
the samples should reproducibly be synthesized in different experimental
set-ups. This makes experimental research very challenging and that is
why the number of groups working on the synthesis and characterization
of epitaxial silicene is small compared to those who are carrying out
theoretical studies.

3. Evidence for epitaxial silicene on zirconium diboride thin films


3.1. Surface reconstruction and large-scale stripe formation

Figure 4(a) shows the typical large-scale STM image of epitaxial silicene
observed as a (2 2) surface reconstruction of ZrB2(0001) thin films
grown on Si(111) wafers [4]. For the first time, this reconstruction has
been observed by us nearly 10 years ago [56], but it was not until recently

and only in combination with the use of additional characterization


methods and calculations that we were able to relate this surface structure
to an atom-thick, buckled honeycomb structure made of Si atoms sitting
on top of the diboride surface.

Figure 4. STM images of the (2 2)-reconstructed ZrB2(0001) surface


with different length scales: (a) 20 nm 9.5 nm, (b) 4.2 nm 2 nm. The
white lines emphasize the direction of offsets between successive
domains. The (2 2) unit cell and the honeycomb mesh are emphasized
by green and blue solid lines, respectively. Reproduced from A
Fleurence et al 2012 Phys. Rev. Lett. 108 245501. Article published under
a Creative Commons Attribution 3.0 Unported (CC BY 3.0) License.
Under good experimental conditions, fine details can be recognized in
constant-current STM images as shown in figure 4(b) [4]. The fine details
are related to both the structure of the layer [4] and electronic properties
[53]. It is understood that the layer corresponds to a honeycomb mesh
with the lattice constant of about 3.65 . The layer is compressed by 5%
with respect to a bulk Si(111) bilayer, and is thus similarly compressed
with respect to hypothetical, freestanding silicene. It is (3 3)reconstructed such that its unit cell is adjusted to that of the ZrB2(0001)(2 2) unit cell [4].
Apart from the surface reconstruction, stripe domains that are offset with
respect to each other are recognized [4]. The repetition of the spacing
between boundaries and the alternation of the direction of the offsets are
signature of the spontaneous formation of stress domains as a result of
large-scale interactions within a 2D layer of these adatoms.

Very recently, the origin of the large-scale stripe pattern has been
suggested by first-principles calculations [26]. In short, without stripes, the
(3 3)-reconstructed, one-atom-thick Si layer has been found to exhibit
a 'zero-frequency' phonon instability at the M point. In order to avoid a
divergent response, the relevant phonon mode triggers the spontaneous
formation of a new phase with the observed particular stripe pattern
offering a way to lower both the atomic surface density and the total
energy of silicene on the particular substrate.
3.2. The chemical states of Si atoms

While STM images of the (2 2)-reconstructed ZrB2(0001) surface provide


evidence for the presence of surface ad-atoms, proof for their elemental
and chemical nature has been derived from Si 2p core-level photoelectron
spectra obtained at various photon energies, h, at beamlines 18 and 13
at the KEK-PF (photon factory) synchrotron radiation facility, located in
Tsukuba, Japan. The surface-sensitive spectrum obtained with h = 130 eV
and in the normal emission geometry, shown in figure 5(a) shows the Si
2p doublet in which the spinorbit splitting amounts to 600 5 meV and in
which each of the main lines consists of two peaks with binding energies
that relate to distinct chemical environment of the Si atoms [4, 54].

Zoom In Zoom Out Reset image size

Figure 5. Chemical states and structural details of epitaxial silicene on


ZrB2(0001) thin films. (a) Surface-sensitive Si 2p photoelectron spectrum
recorded at normal emission. Chemical states identified by a peak fitting
procedure are labeled , and . (b) STM image of the (2 2)reconstructed ZrB2(0001) thin film surface, with the (2 2)-reconstructed
unit cell of ZrB2(0001) shown in green and the model honeycomb lattice
shown in blue. (c) Model of the Si honeycomb structure on the topmost Zr
layer of ZrB2(0001). Chemically different types of Si atoms 'A', 'B' and 'C'
are indicated. (d) and (e) Calculated structure of (3 3)-reconstructed,
planar-like silicene on the Zr-terminated ZrB2(0001) surface, as seen in the
top and side views, respectively. Panels (a), (b) and (c) are adapted and
reproduced from A Fleurence et al 2012 Phys. Rev. Lett. 108245501.
Article published under a Creative Commons Attribution 3.0 Unported (CC
BY 3.0) License. Panels (d) and (e) are adapted and reproduced from C-C
Lee et al 2014 Phys. Rev. B 90 075422. Copyright 2014 by the American
Physical Society.
The bulk 2p3/2 component of the clean Si(111)-(7 7) surface as assigned
in [57, 58] appears at a binding energy of about 99.43 eV. The peaks
associated with the 2p3/2 line of silicene are shifted by about 450710 meV
towards lower binding energy [4, 54].
The observed binding energy difference is reminiscent of the one observed
between the C 1selectrons of diamond and graphene. Note that the C
1s binding energy of sp3-hybridized carbon atoms in the bulk of diamond
(~285.0 eV [59]) is about 0.8 eV higher than that of sp2-hybridized atoms
in graphene (~284.2 eV [60]). This suggests that the low Si 2p binding
energy is related to a certain degree of sp2 hybridization for all of the Si
atoms within the buckled honeycomb lattice of epitaxial silicene.
In initial attempts to identify components related to chemically distinct Si
atoms in a spectrum related to chemical environments obtained with a
lower experimental resolution, three components labeled , and have
been identified by a peak fitting procedure and assigned to three chemical
environments of the Si adatoms [4], denoted A, B and C in figure 5(c).
3.3. Structure model of epitaxial silicene

While in a wide range of in-plane lattice constants, freestanding silicene is


predicted to be stable only with a single type of buckling, until now,
experimentally found epitaxial silicene phases are all 'reconstructed' in
terms of the (1 1) lattice. This means that the buckling varies locally on
the atomic length scale in order to find 'epitaxial' conditions with the
respective substrates. As such, the phases formed on ZrB2(0001) and
Ag(111) surfaces differ from each other in lattice constants and
reconstructions.
For silicene on ZrB2(0001), the existence of the three chemical
environments , and as derived from the surface-sensitive Si
2p spectrum is consistent with an in-plane structure model that has been
concluded from STM images (figures 4(b) and 5(b)) for the center of the
stripe domains [4] accommodating the (3 3)-reconstructed Si

honeycomb lattice that matches the (2 2) unit cell of the ZrB2(0001) thin
film surface. For this model (figure 5(c)), the Si atomic ratio is 2 : 3 : 1,
among the A, B and C atomic sites. Two SiA atoms per unit cell are sitting
on hollow sites of the Zr lattice, three SiB atoms are located at the
intermediate position between top and bridge sites, or so called 'nearbridge' sites, and one SiC atom is on top of a Zr atom.
Note that from our later work using spectra obtained with a higher
experimental resolution, it has clearly been suggested that additional
chemical states must be present that cannot be properly resolved by the
fitting procedure [54]. The corresponding atoms may be located in
extended boundary regions separating stripe domains. In particular, since
on-top positions are the energetically least favorable ones [10], at the
boundaries, SiC atoms might be shifted away from on-top sites towards
near-bridge sites [54].
While the in-plane structure model for the center of the stripe domains
could be derived at an early stage of the study, the out-of-plane atomic
positions related to the buckling have been proven difficult to determine
experimentally e.g. from photoelectron diffraction effects observed as
strong angle- [4] and photon-energy-dependent [54] intensity variations of
the Si 2p core-level components.
While initially [4, 53], our interpretation related to the buckling of epitaxial
silicene on the ZrB2(0001) thin film surface leaned towards a metastable,
so-called 'regularly-buckled-like' phase, the controversial issue in favor of
the theoretically preferred 'planar-like' structural modification [10], shown
in figures 5(d) and (e), in the top and side views, respectively, has been
only resolved in very recent work [27] by finding substantial agreement
between the results of DFT calculations and ARPES data obtained in a wide
energy range. That is, it turns out that the substratesilicene hybrid
electronic band structure can be the most useful fingerprint of the
structural configuration of adsorbed Si layers, a fact that is due to the high
sensitivity of electronic to structural properties. As our work shows, the
agreement between calculations and the ARPES spectra has in part been
achieved by slightly increasing the in-plane lattice constant. It has been
pointed out that this has been necessary in order likely to account for a
misestimate of the exchange-correlation energy in the generalized
gradient approximation and to simulate the effect caused by the larger
lattice constant of ZrB2 thin films and the expected lower surface density
of the Si atoms induced to avoid epitaxial strain [27].
The results of the calculations and the agreement with the experimental
ARPES data provide the strongest evidence so far for the presence of the
so-called (3 3)-reconstructed, 'planar-like' silicene phase on the
ZrB2(0001) thin film surface.
3.4. The valence electronic structure

Since the electronic structure of epitaxial silicene is expected to be


modified from that of the predicted one of freestanding silicene in terms of
a modified crystal structure (that is by a different degree of buckling, by
the reconstruction and different lattice constants) and by hybridization
with the electronic states of the substrate surface, and also because bulk

electronic states of substrate are measured as well, the interpretation of


ARPES data is not so straightforward. First-principles calculations are
necessary to understand the band dispersions; and to be able to calculate,
one needs a structure model as a starting point.
Figures 6(a) and (b) show the measured ARPES spectra along the
KSi direction of epitaxial silicene on ZrB2 thin film as a function of the inplane wave number k|| [27]. Note that due to the (3 3) reconstruction
of the Si honeycomb layer, the KSi and MSi points of unreconstructed,
hypothetical, freestanding silicene (with a unit cell containing two Si
atoms) coincide with the and points of the repeated Brillouin zone of
the reconstructed surface, respectively.

Figure 6. (a) ARPES spectra along the KSi direction of epitaxial silicene
on the ZrB2(0001) surface as a function of the in-plane wave number k||.
(b) ARPES spectra with guiding curves. (c) Corresponding DFT band
structure of the planar-like phase. Reproduced from C-C Lee et
al 2014 Phys. Rev. B 90 075422. Copyright 2014 by the American Physical
Society.

Features denoted 'S1' and 'S2' have been assigned [49] to surface states
characteristic for the unreconstructed Zr-terminated ZrB2(0001) surface
[61]. Since the Zr-derived surface states are robust, the outermost Zr layer
must be considered structurally intact [4]. Other features, among those
denoted 'X1', 'X2', 'X2' and 'X3', do not have a counterpart in the calculations
for the unreconstructed Zr-terminated ZrB2(0001) surface [61] and are
therefore related to the presence of silicene [4]. In particular, the intense
features X2 and X3 approach EF by up to about 250 meV at the KSi point and,

owing to back-folding, are mirrored as 'X2' with weak intensity in the first
Brillouin zone [4, 27]. The upward curvature of X2 bears some resemblance
to the predicted Dirac cone of bands of freestanding, nonreconstructed
silicene at KSi [4]. The intensity changes have been discussed to be related
to the sensitivity of the ARPES cross section to the selected Brillouin zone.
These changes as well as the energy and dispersion of the spectral
features could be represented well by DFT calculations [27].
Even if the actual stripe pattern is not accounted for, the comparison
between the ARPES data and the results of the calculations shown in
figure 6(c) provide a conclusive interpretation of the nature and orbital
character of the states at the silicene/ZrB2(0001) interface [27]. It has
been confirmed that all silicene-derived bands are hybridized to some
extent with Zr d electronic states, which is consistent with non-negligible
interactions at the interface. While the upward curved bands in the vicinity
of EF at KSi, denoted p2 and p3 (that correspond to features X2 and X3), are of
partial character indeed, they are actually formed by a hybridization of
Si s, px, pyand pz and Zr d orbitals. This hybridization reflects the
intermediate sp2/sp3 hybridization of epitaxial silicene and its interactions
with the metallic substrate [27].
Because of the presence of Zr-derived surface states and because of the
hybridization of Si-derived orbitals with Zr d states, the surface involving
silicene is metallic. However, band edges of the occupied, upward curved
p2 and p3 bands, on one side, and of the downward curved band p5, on the
other, provide a high density of states that has strong contributions within
the silicene layer. Since using the ARPES technique, only the filled
electronic states can be probed, the energetic separation between the
band edges and thus the size of the silicene-related gap should be
measured with other techniques. Scanning tunneling spectroscopy
performed at temperatures as low as 5.5 K revealed a 350 meV gap, with
its center shifted 60 meV below the Fermi level [53]. Although the
tunneling conductance was not zero inside this gap, the observed position
of band edges is consistent with the silicene-related character of the p 2,
p3 and p5 states and the close proximity of X5 and the Fermi level that has
been observed by ARPES in doping experiments [52].

4. The engineering of epitaxial silicene in the light of a future silicene-based


nanoelectronics
4.1. Doping by foreign atom adsorption

Like for graphene [62, 63], in a rigid band picture, the reaction of
freestanding silicene with strong donors like alkali and alkaline earth metal
atoms is expected to shift EF with respect to the bands such rendering
semi-metallic silicene metallic [64, 65]. According to the predictions,
potassium (K) atoms adsorb preferentially on hollow sites [64, 65]. As we
have already discussed for the case of silicene on ZrB2(0001) thin films,
the low-energy band structure of epitaxial silicene phases is different from
that predicted for freestanding silicene but it is still expected that upon
alkali metal adsorption, charge is donated to originally unoccupied
electronic states with silicene or contributions.

Recently, we have performed an experiment where small amounts of K


atoms (with up to about 0.18 K atoms per Si atoms) have been deposited
on epitaxial silicene formed on a ZrB2 thin film [52]. As the LEED pattern
and even the LEED IV have barely changed upon adsorption, it has been
concluded that the type of reconstruction as well as the degree of buckling
of the Si honeycomb layer remains close to that of the original one [52].
This is consistent with the prediction made for freestanding silicene in
which it has been found that K adsorption does not lead to major structural
changes [64].
Potassium adsorption leads to charge donation to the silicene lattice, thus
n-type doping, and to the partial filling [52] of a previously almost
unoccupied band, denoted 'X5', with contributions from Si pz and
Zr d orbitals [27]. Due to the charge donation, occupied states with a
partial character in the vicinity of the KSi(1 1) point corresponding to
the unreconstructed silicene lattice shift by about 100 meV towards higher
binding energy. According to a rigid band picture and n-type doping, this
confirms their character as silicene-derived states.
On the other hand, while not additionally filled, a diboride surface state is
affected as well which indicates an enhancement of interactions at the
silicenediboride interface upon K adsorption [52].
Since n-type doping can approximately be described by a rigid band
picture, it can be expected that electron withdrawal by acceptors, e.g.
iodine molecules, will lead to an upward shift of bands with
(partial) character.
4.2. Tuning of the interactions with substrates

Since epitaxial silicene phases are stabilized and since their electronic
properties are determined by interactions with their respective substrates,
the key for any advance towards a future silicene nanoelectronics is in the
understanding of these essential interactions. So far, there are still very
few cases in which epitaxial Si honeycomb lattices could be created and
characterized. Most of them had been found by trial-and-error approaches
or during work on unrelated topics. A more systematic approach would rely
on the knowledge of the fundamental principles behind the formation
mechanisms of silicene.
As already mentioned in the previous section, Si honeycomb structures
have been known to exist in disilicides [3537]. It should therefore be a
matter of the strength of interactions between these honeycomb
structures and the metal layers in contact if these 2D layers exhibit
freestanding silicene-like properties or not. While the role of metal atoms
(and in particular of delectronic states) for the stabilization of Si
honeycomb lattices is still not fully understood, it might be expected that
the change from a 'disilicide' picture to an 'epitaxial silicene' picture is
gradual.
One way the interaction strength is expressed is in the hybridization
between silicene and substrate electronic states. Another expression lies
in differences in the thermal stability. Silicene on ZrB2 thin films is
destabilized at temperatures above 650 C which is observed as the

ZrB2(0001)-(2 2) to (1 1) phase transition [66] in which fractional


streaks or spots corresponding to the silicene-(3 3) pattern disappear
upon heating. This transition is reversible, and upon cooling, silicene
'crystallizes' again. A similar phase transition is observed for silicene on
ZrC(111) at about 730 C [48]. On the other hand, a silicene phase on
Ag(111) observed as a Ag(111)-(23 23) reconstruction is known to be
irreversibly destroyed upon heating beyond 330 C [18] and also by the
deposition of additional Si atoms causing a phase transition to a structure
involving sp3-hybridized Si atoms and the simultaneous exposure of the
Ag(111) substrate surface [67]. Obviously, interactions of silicene with the
Ag(111) surface are weaker as compared to those with the outermost Zr
layers of ZrB2(0001) or ZrC(111). This may actually be expected with
regard to the tendency of zirconium forming a number of crystalline SiZr
phases [68] while silver forms only metastable ones [69].
In the previous section, we introduced the results of K adsorption in which
charge donation from K atoms to silicene has been observed. This charge
donation increased the hybridization between the silicene-related and
diboride-related states resulting in stronger interactions at the interface
[52]. If charge donation results in stronger interaction, charge withdrawal
may result in the weakening of the interactions. Further experimental
efforts to engineer the interface property of epitaxial silicene by foreign
atom adsorption and/or intercalation may be the key to realize silicene
with properties close to those of the hypothetical, freestanding one.
4.3. Stability against oxidation and perspectives for capping layers

Like for silicene nanoribbons [70] and silicene sheets [23], both prepared
on Ag surfaces, silicene on zirconium diboride substrates resists oxidation
to some extent as well. As such, while due to the presence of dangling
bonds, Si(111) and Si(001) are easily oxidized, the Si 2p spectra of silicene
on ZrB2(0001) thin films are hardly affected upon exposure to 4500
Langmuir (L) of molecular oxygen (O2) [24]. These spectra, shown in
figure 7(a), have been measured at beamline D1011 of the MAX-Lab
synchrotron radiation facility located in Lund, Sweden.

Figure 7. Si 2p spectra before and after exposure to particular O2 doses:


100 L and 4500 L, of (a) pristine silicene on ZrB2(0001) thin films and of (b)
silicene covered with Al atoms at the Al/Si ratio of about 0.38. All spectra
have been offset for clarity. Adapted and reproduced with permission from
R Friedlein et al 2014 J. Chem. Phys. 140 204705. Copyright 2014, AIP
Publishing LLC.

Still, epitaxial silicene is immediately oxidized once removed from the UHV
environment. In order to be able to handle it in air, a capping layer is a
must. Such layers should ideally be insulating and non-interacting, if the
silicene sheet should be employed in electronics applications.
Alternatively, temporary metallic capping layer could serve as protection
during the transport from one UHV system to another, as long the layer
can be removed at moderate temperatures.
Recently, it has been suggested that aluminum oxide (Al2O3) could be a
suitable, non-destructive encapsulation material for silicene on Ag(111)
[23]. However, as our study of silicene on the ZrB2(0001) thin film surface
covered with a submonolayer of Al atoms shows, upon exposure to 4500 L,

a large fraction of the Si atoms becomes oxidized (figure 7(b)) [24]. This is
attributed to dissociative chemisorption of O2 molecules by Al atoms at the
surface, producing reactive atomic oxygen species that cause the
oxidation. It is concluded that aluminum oxide overlayers prepared in this
fashion on silicene on ZrB2(0001) thin films are not suitable for
encapsulation since they do not prevent but actually enhance the
degradation of silicene [24].
In one of our yet unpublished studies [71], it has been found that nondestructive encapsulation of silicene on the ZrB2(0001) thin films by
aluminum nitride deposited at elevated temperatures using
trimethylaluminum and ammonia precursors is not achieved either.
4.4. Integration with organic electronic devices

At present, silicon-based semiconductor and organic electronics are largely


separated fields. In order to achieve an integration of the two
technological areas, hybrid organic/semiconductor junctions shall be
created in which interfaces must be well defined and in which each of the
thin films shall be crystalline. Since Si atoms favor sp3 hybridization and
the formation of the diamond crystal structure, at the related
semiconductor surfaces, the presence of reactive, dangling bonds leads to
chemisorption of organic molecules bound with strong covalent bonds
[72]. This often prevents the formation of ordered adlayers.
In our recent, yet unpublished work, the electronic and crystal structures
of thin anthracene (Ac) films grown on epitaxial silicene formed on singlecrystalline ZrB2 thin films have been studied using RHEED and ultraviolet
photoelectron spectroscopy [73]. At 140 K, Ac multilayer films grow with
the orientation of the long molecular axis aligned parallel to the surface.
The films consist of layers in which the herringbone-stacked molecules
have alternating tilt angles. The stacking distance is close to that
between bc-planes in the Ac bulk crystal under ambient conditions [74].
The lattices of the organic film and the substrate have a commensurate
relationship indicating the presence of an epitaxial relationship. This result
shows that ordered multilayer films of an oligoacene molecule can be
grown epitaxially on silicene.
With a low, possibly monolayer coverage, the Ac molecules also adsorb on
silicene even at room temperature. This fact indicates that the interactions
between Ac molecules and silicene are stronger than those on the graphite
(0001) [75, 76] surface and enhanced by the atomic-site specific charge
distribution associated with the buckling of silicene.
On the other hand, the chemical properties of epitaxial silicene are also
quite different from those on reactive [72] Si surfaces. This enables the
formation of a sharp, well-defined interface between organic molecules
and silicene without the formation of covalent bonds.
In summary, the atomic-scale buckling of silicene does not prevent the
growth of highly ordered organic multilayer films provided that epitaxial
conditions are met. If in this way epitaxial conditions are obtained
throughout device structures, highly ordered organic films can be prepared
on both ultimately thin honeycomb Si layers and on widely used silicon
wafers via buffer layers. The growth of ordered organic thin films on

silicene may then represent a promising bottom-up approach for the


integration of silicon-based and organic electronics under highly controlled
conditions at various length scales.

5. Perspectives
With bonding configurations and properties close to but distinctively
different from those of graphene, expectations for silicene are rising.
Silicene is predicted to possess extremely light charge carriers with a high
mobility like those of graphene in an ultimately thin sheet made of an
element that dominates the semiconductor industry. The large SOC may
allow the creation of perfect spin filters essential for spintronic applications
[77]. Furthermore, as discussed theoretically, owing to its large surface
area, silicene could serve for hydrogen storage and as a high-capacity host
of lithium in Li-ion secondary batteries [78]. Silicene layers are calculated
not to suffer from irreversible structural changes as sp3-type silicon anodes
do, which has so far limited the commercialization of Si-based anode
materials.
Although the synthesis of freestanding silicene with its exciting predicted
properties remains a major challenge, and while more than two years after
its experimental verification in the epitaxial form, results are limited and
many properties are not fully understood, epitaxial silicene provides
opportunities for the further engineering of its properties aiming practical
applications. In particular, as our initial investigations show, the structural
flexibility of silicene gives rise to altered electronic properties that may be
tuned by applying an external stress [4]. This can be realized, for instance,
through epitaxial growth on an appropriate substrate with selected lattice
parameters. The introduction of a band gap through the modification of
the buckling might enable the use of silicene in electronic devices that
emit light or perform logical operations, something that is difficult to
achieve in graphene. The gap may possibly even be tuned by an external,
out-of-plane electric field [12, 13].
Given that existing Si-based technologies currently face intrinsic limits
with top-down approaches, the growth of silicene with good lattice
matching on large silicon wafers via buffer layers provides a way to
integrate silicene nanoscale devices on silicon platforms [4]. In this
context, it is essential to find ways (i) to prepare silicene on insulating
substrates and (ii) for a non-reactive encapsulation in order to be able to
use it outside of UHV environment. Additionally, the use of silicene in
combination with ceramic buffer layers on widely used Si wafers
represents even a promising bottom-up approach for the integration of
silicon-based and organic electronics under highly controlled, epitaxial
conditions.
While the progress in the materials science of epitaxial silicene is rapid, it
remains challenging. With the promise of exceptional properties, it is clear,
however, that the drive towards exciting nanoscale physics and
technological applications is unstoppable.

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