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NanoB PART II 20121101
NanoB PART II 20121101
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
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)
ElectronicProperties p ofCNT
Tightbinding calculations
Experiments
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
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
18
DesignsofCNTTransistors
B kgated Back d T gated Top d
19
DesignsofCNTTransistors
Wraparoundgate Suspended
OpticalPropertiesofCNT
(M11)
(S11)
(S22)
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 (% %)
700
800
Wavelength (nm)
95
(a)
Transm mittance (%)
90
85
80
SWNTelectrodehashighflexibilityand excellentmechanicalstrength g SheetresistanceofSWNTelectrodecanbe furtherreducedbyHNO3 treatment Sh tresistance Sheet it ~100 /sq / with ith 75%transparency@550nm
75
10
10
10
10
25
25
EnergyandEnvironmentalScience,4.3521,(2011)
Nanocarbon basedpolymersolarcellsbysolutionprocesses
Cocktailnanocarbonpolymersolarcell !
6
2
PCBM(0D)
0.1
0.5
0.6
0.7
Voc(V)
Jsc(mA)
FillFactor
PCE(%)
GO(2D)
CNT(1D)
ITO/PEDOT:PSS
EnergyandEnvironmentalScience,4,3521,(2011)
TopEmissionOLED
Jia,Y.et.al.,NanoLett,2011,11,1901.
Chien,Y.M.et.al,Nanotechnology,2010,21, 134020
27
OtherApplications
Fuelcells
StoreH2 inCNT
Gasdetector
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
ApplicationsofCNTsinelectronicdevices
CNT field emission display p y
E field
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.)
32
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
Thepropertiesofgraphene
Theatomicstructure, twodimensionalcrystals ThethinnestMaterials
Graphene
Dirac point p
Electronics
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
Graphene transistordevicewithhighmobility
(a) ( )
5 4
Rxx (k)
3 2 1 0 -60
-40
-20
20
40
60
VG (Volt)
(b)
12 10
-10 -6
-2
10
G (e /h) )
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
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
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
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
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
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
59
Xia,F. etal.NatureNanotech.4,839843(2009).
Rollerprinting
Scaleup
Touchpanel
Baeetal.NatureNanotechnology5,574578(2010) 60
HeatingRoller
Cufoilonthermalrelease tape
Cuetching
byFe(NO3)3
transfergrapheneto substrate
Sheetresistance
pristine graphene HNO3 graphene
Transmittance
100
Grapheneelectrode
95
90
1
pristine graphene HNO3 graphene
2 3
85
80
Number of layers
10
10
61
(~55/sq)atatransparency.(~90%)
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
0.6
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
66
Xia,F. etal.NatureNanotech.4,839843(2009).
TunablePLofGraphene /GO
CTChien,CWChenetal.,Angew.Chem.Int.Ed. 51 (27),6662(2012) 67
EndofPartII