PartII LowdimensionalcarbonmaterialsCarbon nanotubes (CNTs)andGraphene

Outline
Carbonnanomaterials
Types yp ofcarbonnanomaterials

Graphene andCNT
Introduction I d i Synthesis Specifictopics Application

CarbonNanomaterials
3D
Graphite Diamond

2D
Graphene

1D
Carbonnanotube

0D
Fullerene
3

Cabon-related nanomaterials
3D Diamond and Graphite

(2010 Nobel prize in physics

2D Graphene discoveredbyProf.Ijima,1991
(1996 Nobel priz in Chemistry

1D Carbon C b nanotube b
en.wikipedia.org craigbanksresearch.com grapheneindustries.com

0D Bulkyball(C B lk b ll(C60)

21.IntroductionofCNT

CNTHistory
1952: 19 2 1991: named 1992: 1997:
6

Radushkevich d hk i h and dLukyanovich k i h found f d nanosizedcarbonfibers(Russian) CNTswerediscoveredbyProf.Ijima and Theoreticalpredictionsofthe electronicpropertiesofSWCNT FirstCNTtransistor

StructureofCNT
SingleWalledCNT (SWCNT) MultiWalledCNT (MWCNT)

(10,0)

(6,0)+(15,0)+(24,0)
Theinterlayerdistanceinmultiwalled nanotubesisclosetothedistancebetween graphene layersingraphite,approximately3.4.

StructureofCNT
SimilartoGNRs,weshouldtakethechirality ofCNTsintoaccount

(10,0)ZCNT

(6,6)ACNT
8

PhysicalPropertiesofCNT
S Semiconductor i d ormetal. l (depending (d di onthe h chiral hi l angle) Excellentmechanicalproperties Excellentelectricaltransport(ballistictransport) Excellentthermalconductivity y Difficulty Difficulty Controlthechiralty

1Dnanomaterials (Carbonnanotube)

DiscoveredbyIijima(1991)

BandStructuresofCNT
(10,10) (9,0) (10,0)

Bandstructuresof(a)(10,10) (10 10)(b)(9,0) (9 0)(c)(10,0) (10 0)CNTs

A.Baskinetal.,ScientificReports1,36(2011) 11

ElectronicProperties p ofCNT

Energy gap changes E h with chirality and diameter

Tightbinding calculations

Experiments

Nature 391,62, 1998

StructuralMaterials
Duetotheoutstandingmechanicalproperties and dlight li h weighted, i h d CNTi isapotential i lmaterial i l forsomespecialusages
Spaceelevator Bulletproofcloth,shield,glass Bicyclecomponents

13

MechanicalProperties
CNTisoneofthestrongestmaterialsinnature
Very ystrong gintheaxialdirection
Youngsmodulus (GPa) SWCNT Steel Diamond >1000 186214 1220 Tensilestrength(GPa) 1353 0.381.55 2.8 Elongationat break(%) 16 1550

Veryhard; evenharderthanthediamond
Bulkmodulus (GPa) SWCNT Steel Diamond 462546 160 442
Belluci,S.etal.,Phys.StatusSolidiC 2 (1),34(2005) Sinnott,S.B.etal.,Crit.Rev.SolidState 26 (3),145(2001) 14

ElectronicProperties

Tang,Z.K.etal.,Science292(5526),2462(2001) 15

Interconnects
SimilartoGNRs,CNTsarepotentialmaterials p metal( (suchthatCu,Au) )asnon toreplace metalhighconductivityinterconnectsinthe integratedcircuits

Y.Zhaoetal.,ScientificReports1,83(2011)

16

TransportofCNT
Nanotubeeldeecttransistor

Ambipolar ElectricalTransportin SemiconductingSingleWallCarbonNanotubes

A.Jorio,et.al.TopicsAppl.Physics111,455493

17

CNTTransistor
VarioustypeofCNTtransistorshadbeendeveloped
Backgated Wraparoundgate

SanderJ.Tans,et.al.,Nature 1998,393,4952

Topgated
Chen,Z.,et.al.,IEEEELECTRONDEVICE LETTERS,VOL.29,NO.2,0741.

Suspended

Wind,S.J.et.al.,2002AppliedPhysicsLetters 80 (20):3817

Cao.J.,et.al.NatureMaterials 4,745 749(2005)

18

DesignsofCNTTransistors
B kgated Back d T gated Top d

FirstCNTFETbeinvented.Theprocessis y,buttherearemany ydrawbacks easy, 1. Contactresistanceexistsbetween metalandCNT 2. Hardtoswitchoffusinglowvoltage 3. PoorcontactbetweenSiO2 andCNT

AdvanceddesignsfrombackgateFET. gatedielectriclowerthe Thethinnerg switchoffvoltage,whichisthemain advantageofthetopgateFET.

19

DesignsofCNTTransistors
Wraparoundgate Suspended

Developedin2008.Thisdesign 1. Improvetheon/offratioandthe performance 2. Reducetheleakagecurrent

Z.Chenetal.,EDL 29 (2),183(2008) J.Caoetal.,NatureMaterials 4,745(2005)

Developedin2005.Thisdesignreduces thescatteringattheinterfaceoftheCNT substrate. However,materialsofdevicesarelimited. Itisonly yforstudying y gtheproperties p p of cleanCNTandcannotbecommercialized.

20

OpticalPropertiesofCNT

(M11)

(S11)

(S22)

VanHovesingularity: g y Thediscontinuity yofDOSof1Dmaterials

21

OpticalProperties
Becauseofthesharptransitions,wecanselectively excite(n,m)CNT;namely,wecandetectoptical signalsinordertoidentify(n,m)CNT
Kataura plot

R.B.WeismanandS.M.Bachilo,NanoLett. 3 (9),1235(2003)

22

PhotoluminescenceofCNT
ProcessofPL
1. ExciteS22 ( (C2V2)andcreatetheexciton p pair 2. RelaxtoC1 andV1 respectively 3 RecombineandemitlightwithS11 (C1V1)energy 3.

Animportanttoolsforcharacterizing semiconductingCNT

R.B.WeismanandS.M.Bachilo,NanoLett. 3,1235(2003) 23

PLMappingofCNT

S22 of[9,8]CNT

S11 of[9,8]CNT

24

Applications:OpticalandElectricalProperties ofSWNTElectrode
100

Trans smittance (% %)

90 80 70 60 50 40 30 20 400 500 600

FiltrationVolume 0.5ml 0 75ml 0.75 1ml 2ml 3ml ITO

700

800

Wavelength (nm)
95

(a)
Transm mittance (%)
90

85

80

SWNT untreated SWNT HNO3 treated

2 3 4 5

SWNTelectrodehashighflexibilityand excellentmechanicalstrength g SheetresistanceofSWNTelectrodecanbe furtherreducedbyHNO3 treatment Sh tresistance Sheet it ~100 /sq / with ith 75%transparency@550nm

75

10

Sheet Resistance (/sq)

10

10

10

25

25

EnergyandEnvironmentalScience,4.3521,(2011)

Nanocarbon basedpolymersolarcellsbysolutionprocesses
Cocktailnanocarbonpolymersolarcell !
6
2

Cur rrent Density y (mA/cm

4 2 0 -2 -4 -6 -8 -10 -0.1 0.0

SWNT without GO Layer SWNT with GO Layer

PCBM(0D)

0.1

0.2 0.3 0.4 Voltage (V)

0.5

0.6

0.7

SWNT WithoutGO WithGO

Voc(V)

Jsc(mA)

FillFactor

PCE(%)

0.48 0.57 0.57

8.33 10.3 11.0

0.42 0.53 0.57

1.67% 3.1% 3.57%

26

GO(2D)

CNT(1D)

ITO/PEDOT:PSS

EnergyandEnvironmentalScience,4,3521,(2011)

CarbonNanotube on photovoltaicandLED applications

SiliconCNT heterojunction solarcell

Hightransparencyonvisibleand NIRrange Good dconductivity d Flexible

TopEmissionOLED

Jia,Y.et.al.,NanoLett,2011,11,1901.

Chien,Y.M.et.al,Nanotechnology,2010,21, 134020

27

OtherApplications
Fuelcells
StoreH2 inCNT

Gasdetector

Wang,S.Et.al.,J.Am.Chem.Soc., 2011, 133 (14),5182

MoleculesadsorbonthechannelofCNTFET, modifyingtheelectricalpropertiesofCNT

G Lu, G. L L.E. L E Ocola O l J. J Chen, Ch Adv. Ad Mater, M t 2009, 2009 21, 21 2487 28

ApplicationsofCarbonNanotube Field Emitter Hydrogen Storage

Li-ion battery anode

Logic gate by IBM

ApplicationsofCNTsinelectronicdevices
CNT field emission display p y
E field

CNT Field effect transistor

Small dimension High local field

From IEEE spectrum 2003

Electronic structure changes

From IBM

11.IntroductionofGraphene

31

Graphene History
Early: l Theoretical h ld description 1962:NamedbyHannsPeterBoehm(Graphite+ene) 2004:Singleatomthick, thick freestandinggraphene isextracted(by AndreGeimandKonstantinNovoselov,ManchesterUniversity,U.K.)

2005: AnomalousquantumHalleffectwasobserved 2010: NobelprizeinPhysicsforAndreGeimandKonstantin N Novoselov l Now:Stimulatewideresearchesandbeappliedtovarious fields

32

Fromg graphite p tog graphene p

Graphene Monoatomiclayer~1nm (109m) )

Graphite Multilayercarbonatom

Graphene
Whatisgraphene?
Asingle g layer y ofgraphite g p 2Dmaterial
Graphene Graphite

Structure St t
Oneatomthickplanarsheet sp2bondedcarbonatoms Honeycomblattice

34

2010TheNobelPrizeinPhysics
Prof.AndreGeim andKonstantin Novoselov attheU.Manchesterfor groundbreakingexperimentsregarding the2Dmaterialgraphene
Graphite Graphene

Howtofindtheatomiclayergraphenefrom repeatedly dl split li graphite hi crystals l by b adhesive dh i tape

Thepropertiesofgraphene
Theatomicstructure, twodimensionalcrystals ThethinnestMaterials

Kraner et al. Chem. Rev. 2010,110,132

Rao et al, Angew. Chem., 2009,48,7752

Graphene
Dirac point p

Electronics

Zeroeffective Z ff ti massnearthe th Dirac Di point i t Highcarriermobility>15,000cm2/V1s1 LowResistivityabout106 cm,(<siliver) etc

Optics

1 Oneatomiclayerabsorption =c = = 2.3% 1. 2. Hightransparency

Nair et al., al Science, Science (2008)

e2

2010NobelprizeawardinPhysics

38

ElectronicStructureofGraphene
AllCatomsaresp2bondedto adjoiningCatoms
sp2 electronsform bonds
FormthehoneycombnetofCatoms

Delocalizedpelectronsform bonds
Catom

2s

2px

2py

2pz

sp2

sp2

sp2

Graphene

sp2

sp2

sp2

sp2

sp2

sp2

sp2

Delocalizedp bonded
39

bonded

ElectronicStructureofGraphene
(a) (b)

(a)STMimageofgraphene

(b)TEMimageofgraphene clusterswithingraphene oxide

40

Graphene transistordevicewithhighmobility
(a) ( )
5 4

B=9T T=2K -10 10 -6 6 -2 2 2 6 10

Rxx (k)

3 2 1 0 -60

-40

-20

20

40

60

VG (Volt)

(b)
12 10

-10 -6

-2

10

G (e /h) )

8 6 4 2 0 -60 -40 -20 0 20 40 60

B=9T T=2K

VG (Volt)

NanoLetters,12,964969,(2012)

12.SynthesisofGraphene

42

SynthesisofGraphene
Mechanicalexfoliation Epitaxial p growth g onsiliconcarbide Epitaxialgrowthonmetalsubstrates Reductionofgraphene oxide
=>solutionprocessible,massproducible, simpleandcheap
Graphene/SiC Graphene/Cu
Novoselov et al., Science (2004)

Solution process

de Heer et al, , Science ( (2006) )

ff et al., Science, vol. 324, Ruoff pp1312-1314, 2009

Sasha Stankovich, Stankovich et al., al Nature 442, 442 282-286, 2006 43

13.PropertiesofGraphene

44

BandStructureofGraphene
Diracpoint

ThevalencebandandtheconductionbandmeetatDiracpoint
Metallicbehavior Semimetalorzerobandgap semiconductor

LinearEkdispersionnearDiracpoint
Masslesselectronsandholes
45

BandStructureofGraphene
Howaboutmultilayeredgraphene?

[8]MarcusFreitag,NaturePhysics 7,596(2011)

46

ElectronicProperties
Semimetal
Zerobandgap

Highelectronmobilityatroomtemperature
Excessof15,000cm2V1s1

Canbedoped
Inordertoincreasethecarrierconcentration
Graphenetransistor

NanoLett., 2010, 10 (12),pp 49754980 47

DopedGraphenebyheteroatoms
Dopingbyheteroatoms
ptype yp doping p g
GroupIIIA,suchasB
holes electrons

Pristine

ptype

ntype

ntypedoping
GroupVA,suchasNandP
ptype:
sp2 sp2 sp2 sp2 sp2 sp2 sp2 sp2 sp2 Delocalizedp sp2 sp2 sp2 sp2 sp2 sp2 sp2 sp2 sp2 Delocalizedp
48

Createholes

ntype: yp

Createelectrons

DopedGraphenebychemicalmodification
Dopingbychemicalmodification
Charge g transfer Moleculesadsorbongraphene,actingasdonors oracceptors Epitaxialgraphenecanbedopedbythesubstrate
Ptype Ntype

49

SubstrateDopingofGraphene

(a) Graphene isntypedopedbyTirichTiO2 surface (b) Graphene isptypedopedbyOrichTiO2 surface

PH Ho,CWChenetal.,ACSNano 6(7),6215(2012)

50

DopedGraphenebyelectricfield
Dopingbyelectricfield
UseelectricfieldtoshifttheFermilevelof graphene

B.Guoetal.,InsciencesJ. 1(2),80(2011)

51

AnomalousQuantumHallEffect

pseudospin

Novoselov,K.Setal.,Nature 438,197(2005) 52

RamanSpectraofgraphene
2Dband

Identify ythelayers y ofg graphene p

A.C.Ferrarietal.,PRL 97,187401(2006) 53

14.ApplicationsofGraphene

54

Graphene Transistor

[20]S.Herteletal.,Nat.Commun.3,957(2012) 55

Graphene Transistor

MaxC.Lemmeetal.,EDL 28 (4),282(2007) 56

Graphene Transistor

[22]NanoLett. 12 (2),964(2012) 57

Next generation production ?

SAMSUNG

NOKIA

High conductivity High transparency Good mechanical property p p y Flexible Good thermal conductivity etc.

Household appliances

HP

Communication production

E-paper

OptoelectronicsapplicationofGraphene
Transparent T conducting d i electrode l d
TouchPanel SolarCell LightEmittingDiode

Bae,S.etal. NatureNanotech.4,574578(2010).

DeArco,L.G.etal ACSNano4,28652873(2010) ( )

UltrafastPhotodetector

Matyba, y ,P.etal. ACSNano4,637642(2010).

59

Xia,F. etal.NatureNanotech.4,839843(2009).

LargeareaCVDgrowngraphenefor optoelectonic applications

Rollerprinting

Scaleup

Touchpanel
Baeetal.NatureNanotechnology5,574578(2010) 60

FabricationofCVDGraphene Electrodeon PET

GrapheneonCufoilbyCVD

HeatingRoller

Cufoilonthermalrelease tape

Cuetching

byFe(NO3)3

transfergrapheneto substrate

1,000 800 600 400 200 0 1

Tran nsmittance@ @550nm (%) )

Sheetresistance
pristine graphene HNO3 graphene

Transmittance
100

Grapheneelectrode

Sheet Resista ance (/)

95

90

1
pristine graphene HNO3 graphene
2 3

85

80

Number of layers

Sheet Resistance (/sq)

10

10

61

(~55/sq)atatransparency.(~90%)

PolymersolarcellsbasedonUltrathinGraphene/GO anodeby yRolltorolltechnology gyonPET

graphene grapheneoxide
Height ( (nm)

Ultrathinanode

2 1 0 -1 -2

GO(1~2nm) Graphene(3~5nm)

0.0

Height

1.7m

Graphene(3nm)/GO(2nm) ITO(100nm)/PEDOT:PSS(30nm) ( )/ ( )

Polymersolarcellbasedongrapheneplatform!
4 Current Densit ty (mA/cm2) 2 0 -2 -4 -6 -8 -10 0.0

Deviceperformance

Graphene/GO/P3HT:PCBM/Al

Graphene/GO/P3HT:PCBM/Al

0.1

0.2

0.3 0.4 0.5 Voltage (V)

0.6

0.7

0.8

62

Toplaminatedgrapheneelectrodeinasemitransparent polymersolarcell

Topelectrode Bo omelectrode

80 70

Transmission(%) )

60 50 40 30 20 10 0 400 500

Semitransparent
600 700 800

Wavelength (nm)

ACSNano,Vol.5,6564,(2011)

Deviceperformanceofabifacialpolymersolarcell usinggraphenetopelectrode
Bifacialsolarcell

ACSN Nano,5,6564, 5 6564 (2011) Voc(V) Grapheneside ITOside Agelectrode 0.54 0.54 0.52 Jsc(mA/cm2) 7.7 10.1 11.5 FF 0.49 0.44 0.55 PCE(%) 2.04 2.50 3.30
64

~75%ofastandard opaquedevice

GraphenebasedmaterialsforPolymerandQDLED

PFO

MEHPPV

PolymerLED

QDLED

JournalofPhysicalChemistryC,116,10181,(2012)

65

OtheroptoelectronicsapplicationofGraphene
Transparent T conducting d i electrode l d
TOUCHPANEL SOLARCELL Lightemittingdiode

Bae,S.etal. NatureNanotech.4,574578(2010).

DeArco,L.G.etal ACSNano4,28652873(2010) ( )

UltrafastPhotodetector

Matyba, y ,P.etal. ACSNano4,637642(2010).

66

Xia,F. etal.NatureNanotech.4,839843(2009).

TunablePLofGraphene /GO

CTChien,CWChenetal.,Angew.Chem.Int.Ed. 51 (27),6662(2012) 67

Advanced Materials,22,505, (2010) Angewandte Chemie, (2012)

EndofPartII