Graphene

Castro-Neto, et al.
Rev. Mod. Phys. 81
(2009) 109

Single atomic layer of graphite

I. Graphene Electronic Properties

(isolated graphene sheets)
II.Graphene FormationGrowth on SiC
III.Graphene Growth on BN, Co3O4, etc.

Castro-Neto, et al.
Rev. Mod. Phys. 81
(2009) 109

Graphenes band structure

yields unusual properties

Castro
Neto

EF

Effective mass (m*) ~ [dE2/dk2]-1

Most semiconductors, 0.1 m0 < m* < 1 me
Graphene, m* < 0.01 m0 (depending on number
of carriers)
Therefore, expect VERY high mobility in graphene

The velocity of an
electron at the Fermi
level (vF)
Is inversely related to
meff

Effective mass for graphene does

get very small as n~ 1012

Castro-Neto, et al. Rev. Mod.

Phys. 81 (2009) 109

The Big Problem with graphene: an

imagined conversation:
A. OK: Graphene is great, lots of interesting
properties for devices!
B. How do you make a device?
A. You need a sheet of graphene!
B. OK, how do you get a sheet of graphene?
A. HOPG, scotch tape, and tweezers!
B.

!@#$%%

How do you grow graphene?

You can evaporate Si from SiC(0001) (either face)
Popularized by the de Heer group at Georgia Tech.

Can grow multilayer films of graphene on SiC

(azimuthally rotated from each other
electronically decoupled!)
Anneal at 1350 C
Interfacial layer
(anneal at 1150 C)
SiC

Auger, graphene growth on SiC, deHeer et

al.
9

Inverse photoemission and LEED (Forbeaux, et al, PRB, 58 (1998) 16396)

Growth of graphite on SiC(0001)

*
feature

10

Angle resolved UPS (Emtsev, et al, PRB

77(2008) 155303) shows transition to
graphene band structure

11

Adjacent layers on graphene /SiC are decoupled from

each other,
Due to azimuthal rotation

12

Graphene on SiC(0001) Not uniform on an atomic level,

different regions due to different #s of layers,Morientations

13

Graphene/SiC photoemission: varying hv can vary

the sampling depth (Emtsev, et al, PRB 77 (2008)
155303

14

The covalently bound stretched graphene (CSG

model)
Emtsev, et al., PRB 77 (2008) 155303

15

Pertinent Questions: How do Adjacent Graphene Sheets couple

electronically?
When/how this transition
Single layer Graphene (good) occurs is very pertinent to
devices
Many layerGraphite (meh!?)
Answer: On SiC, Adjacent Sheets apparently not coupled due
to azimuthal rotation

16

Core (left) and valence band

(right) PES graphene growth
on SiC (Emtsev, et al)
Explain the implications of this for graphene coupling
between layers

17

Motivation: Direct Growth on Dielectric Substrates:

Toward Industrially Practical, Scalable GrapheneBased
Devices
Graphene Growth: Conventional
transfer
Approaches
CVD graphene monolayer
Metal or HOPG

SiC(0001)

Our Focus:
Direct CVD,
PVD or MBE
On
Dielectrics

SiO
2

Si
Si evaporation
> 1500 K
SiC(0001)

Charge-based devices

Result: graphene
monolayer, interfacial inhomogene
Result: graphene
monolayer or multilayer
onSiC
(0001)

FET: Band gap

n

Spintronics

Coherent-Spin
FET:

Top
Gate
graphene

MgO(111)
Si(100)
graphen
e
) or
Co(111
Si(100)
gate

Co3O4(1
11)
Multi-functional,
non-volatile
devices
18

Direct Growth of Graphene on Dielectric Substrates: Summary

19

Gate
valves BCl

NH3

MB
E

Butterfly
valve
Turbo

Intro/
transfer deposition

Auger

Graphene/Co3O4
Sample heating
to 1000 K @ 1
Torr

STM

Graphene/MgO(111
LEED I(V)

UHV chamber, 1011

Torr

Free
radical
source

ALD or
PVD

Hemispheri
cal analyzer
(XPS)

LEED

Graphene growth
&
characterization

Sampl
e Intro
chamb
er P = Sample processing P = 10-9
-10-3 Torr
103
UHV Analysis
Torr
Chamber
20
10-6
P ~ 5 x 10-10 Torr

Graphene/BN/Ru(0001): Bjelkevig, et al
LEED shows BN and Graphene NOT azimuthally rotated!

Orbital
hybridizat
ion with
Ru 3d!

21

Gr/BN/Ru(0001): Inverse photoemission. * not observed!

BN layer does NOT screen graphene from orbital

hybridization and charge transfer from Ru!

22

Graphene on Co3O4(111): Molecular Beam

Epitaxy
Substrate Preparation
Evaporato
r

P~ 10-8 Torr

750 K
Sapphire(0001
)

~3 ML
Co3O4(111)

Co(111)+ dissolved
O
Sapphire(0001
)
1000 K/UHV

Co(111)

O segregation

Sapphire(0001
)

23

Graphene growth on
Co3O4(111)/Co(0001)
MBE (graphite source)@1000 K:
Layer-by-layer growth
1st
ML

3 ML

2nd ML
0.4
ML

M. Zhou, et al., J. Phys.: Cond. Matt. 24 (2012) 072201

24

Graphene
Domain Sized
(from FWHM)
~1800
Oxide spots
(comp. to
attenuated
HOPG)
with
increasing
Carbon
coverage

G1

40000

graphene

G2

35000

0.4
ML

Intensity

30000

O1 Co3O4(111)

25000

O2

20000
15000
10000
5000

40000

3 ML

400

300

200

100

Pixel Position

65 eV beam energy
G1

35000

Intensity

LEED:
Oxide/Carbon
Interface is
incommensur
ate:
Different than
graphene on
SiC or BN!

G2

30000

2.5
2.8

25000

O1

20000

O2

15000
10000
5000

400

300

200

100

Pixel Position
M. Zhou, et al., J. Phys.: Cond. Matt. 24
(2012) 072201

2.8 O-O surface repeat

distance on Co3O4(111)
W. Meyer, et al. JPCM 20 (2008) 265011

25

XPS: C(1s) Shows system:

Binding Energy indicates
graphene oxide charge
transfer

XPS (separate chamber):

Al K
source

284.9(0.1) eV
binding
energy:
Interfacial
polarization/ch
arge transfer
to oxide
No C-O bond
formation

26
M. Zhou, et al., J. Phys.:
Cond. Matt. 24 (2012)

Directly grown
graphene/metals and
dielectrics:
Inverse photoemission and
charge transfer

Ef

n-type

charge
transfer p-type

Position of * (relative to EF)

indicates direction of interfacial
charge transfer
(Kong, et al., J.Phys. Chem. C.
114 (2010) 21618

Forbea
ux, et
al.

Multilayers

27

Generalization, Directly Grown Graphene and

Charge Transfer: Oxides (p-type) vs. Metals (ntype)
graphene
e-

Transition
metals
(Ru, Ni, Cu, Ir)

graphene
eOxides, SiC

EF
n-type; metal to
graphene charge
transfer

p-type;
graphene to
substrate
charge transfer
EF
28

Suspended
graphene

Graphene (few layer) on

Co3O4:
Much more conductive than
suspeneded graphene
Why??
Significant doping?????
High mobility (How
high)?????

29

Conclusion:
Graphene:
Large area growth on
practical substrates
critical for device
development.
Interactions with
substrates and (maybe)
other graphene layers are
critical to device
properties

30