Mapping of nanomechanical and electronic properties of

quasi-free standing graphene

C. Melios1,2, V. Panchal1, C. Giusca1, N. Kay3, O. Kolosov3, W. Strupinski4 and O. Kazakova1
1National

Physical Laboratory, Hampton Road, Teddington, TW11 0LW, UK

2Advanced Technology Institute, University of Surrey, Guildford, Surrey, GU2 7XH, UK
3 Department of Physics, Lancaster University, Lancaster, LA1 4YB, UK
4 3Institute of Electronic Materials Technology, Warsaw, Poland
*E-mail: christos.melios@npl.co.uk

Methods

Introduction

sample = Tip - eUCPD

Interfacial

layer (IFL) is a (6 3 6 3 )30 reconstructed layer, topographically similar to

graphene.
Significant amount of carbon atoms still covalently bonded to the SiC(0001) surface.
Charge transfer from the IFL results in intrinsic electron doping of graphene grown on SiC(0001) [1].
Alters the electronic properties and reduces the carrier mobility of the first graphene layer.

Hydrogen intercalation decouples IFL from the substrate and converts it to a monolayer graphene
(1LG).
Hydrogen intercalation breaks the Si-C bonds and creates Si-H bonds, lifting the IFL and converting
it to a quasi free-standing one layer graphene (QFS1LG) [2, 3].

Graphene layers were grown on semi-insulating on-axis oriented 4H-SiC (0001) substrates.
Intercalation of hydrogen was achieved by annealing the sample in hydrogen [2].
Quasi-free standing 1LG

As-grown graphene on SiC

Quasi-free standing 2LG

Ultrasonic Force Microscopy (UFM):

Sample is oscillated by a piezo transducer at high frequency (MHz range)
but low amplitude.
High frequency vibrations increase of the cantilevers rigidity detect
the non-linear interaction forces of cantilever.

Frequency modulated-Kelvin probe force microscopy (FM-KPFM):

Cantilever at its mechanical resonant frequency (f0) plus AC voltage
(fmod f0).
f0fmod side lobes monitored by a PID feedback loop, compensation DC
voltage minimizes them[4, 5].

Detects force gradient using the frequency shift.

Spatial resolution of <20 nm, allowing for measuring

As-grown graphene on SiC

Tip indents the surface when set force (F0) is applied. When an ultrasonic
vibration (ac-hard, ac-soft) is applied to the sample, the averaged
instantaneous force (F) is different form the initial set force slopedependent static deflection of the cantilever.
Static deflection of the cantilever is measured to calculate the elastic
moduli, and therefore the stiffness of the material [3].

potential (UCPD) for different graphene layers[4, 5].

The work function (WF) of the tip (TIP) was calibrated against a gold
(measured using ultra-violet photoelectron spectroscopy) in vacuum
using TipAu+eUCPD [4].

Quasi-free standing 2LG

Quasi-free standing 1LG

Ultrasonic force microscopy

3 k/m

4 k/m

12 k/m

0.002

0.0006

0.0005

2LG

0.0004

Counts

Counts

Counts

the surface

0.001

0.0003
0.0002

3LG

2LG

0
2.0

2LG
2.2

2.4

2.6

2.8

3.0

3.2

0.0000

0.000
0.5

3.4

1.0

2.0

2.5

1 = 4.33

2 = 4.36

= 4.40
1 = 4.66

2 = 4.75

2LG

= 4.88

2LG

1LG

3LG

Calibrated WF measurements in
vacuum:
WF increases with increasing graphene
layers.

1LG

1LG

= 5.6 1012 2
= 860 2 1 1

2LG

4LG

3LG

2LG

Calibrated WF measurements in
vacuum:
WF increases with increasing graphene
layers.

= 1.2 1013 2
= 3200 2 1 1

= 1.3 1013 2
= 3900 2 1 1

= 5.24

Calibrated WF measurements in
vacuum:
WF increases with increasing graphene
layers.

1LG

3 = 5.21 4

3LG

3LG

2LG

2 = 5.09

4LG

3LG

2LG

12

No apparent changes in stiffness

between QFS2LG (terraces) and QFS3LG
(edges).
2 > 1
Defective (lower stiffness) wrinkles at
the edges.

Raman spectroscopy/mapping
2D-Peak Shift
3LG

2704 cm-1
1LG
2LG

Terraces: covered with

1LG (single
symmetrical 2D peak)
and 2LG islands
(asymmetrical 2D
peak).
Edges: covered with
2LG (asymmetrical 2D
peak).

0.4
0.3
0.2
0.1
0.0
-0.1
-0.2
1500

2000

2500
-1

Raman shift (cm )

2600

1.2

2730 cm-1

2700

2800
-1

Raman shift (cm )

2LG

2700 cm-1

0.3
0.6

= 532

2740

2D-Peak Shift

2LG

1LG

2LG

0.3
0.5

0.5

G-Peak Intensity

cm-1

3LG
1LG

0.6

2750

2D-Peak Shift

= 532

0.5

1.0

1LG
2LG

Intercalation of the IFL

QFS1LG covering
the terraces (single
symmetrical 2D peak).
QFS2LG covering
the edges
(asymmetrical 2D
peak).

0.4
0.3
0.2
0.1
0.0
-0.1
-0.2
1500

2000

2500

2600

2700

0.4
0.2
0.0
1500

2000

Raman shift (cm )

5.5

14000

van der Pauw Hall effect measurements:

n-doped p-doped after intercalation.
Significant increase in mobility for higher carrier concentration after intercalation.
Raman spectroscopy/mapping:
As-grown layers (n) have been transformed into (n+1)LG after intercalation.

4.0

Stiffness
As-grown WF
QFS1LG WF
QFS2LG WF

8000
6000

3.5

4000
2000
0

0.0
As-grown

QFS1LG

Sample

QFS2LG

Work Function (eV)

4.5

Stifness (Nm-1)

Kelvin probe force microscopy:

As-grown sample: Terraces covered by 1LG film and 2LG islands edges covered 2-3LG
QFS 1LG: SiC terraces covered with free standing 1LG and 2-3LG at the edges
QFS 2LG: SiC terraces covered with free standing 2LG and 3-4LG at the edges
Increase in WF of the intercalated graphene compared to the as grown, Fermi energy crosses the Dirac point.
WF is increasing for increasing number of graphene layer in vacuum

12000
10000

2600

2700

2800

Raman shift (cm-1)

Acknowledgments
5.0

Ultrasonic force microscopy:

No apparent changes in stiffness between thicker graphene at the edges
QFS2LG exhibits much higher stiffness than QFS1LG

2500
-1

Layers
1
2
3

Intercalation of the 1LG

QFS2LG covering the
terraces (asymmetrical
2D peak).
thicker graphene
covering the edges
(broader 2D peak).

0.6

2800

Conclusions
We have successfully showed that with the H2-intercalation of graphene, IFL is transformed into a QFS1LG and
1LG into QFS2LG

0.8

Raman shift (cm )

Raman shift (cm )

2LG
3LG

= 532

-1

-1

2700 cm-1

0.7
Normalized intensity ( a. u)

1.0

G-Peak Intensity

cm-1

Normailzed Intensity (a. u.)

G-Peak Intensity

Normailzed Intensity (a. u.)

10

Frequency-modulated Kelvin probe force microscopy

3LG

8
Stiffness (N m )

No apparent changes in stiffness

between QFS1LG (terraces) and
QFS2LG (edges).
Defective (lower stiffness) wrinkles at
the edges.

1LG

-1

Stiffness (N m )

No apparent changes in stiffness

between 1LG (terraces) and 2LG
(edges).
Defective (lower stiffness) wrinkles
at the edges.

1.5
-1

Stiffness (kN m-1)

1LG

0.0001

We acknowledge support of EC grants Graphene Flagship

and the IRD Graphene Project. The work was carried out as
part of an Engineering Doctorate Programme in Micro- and
NanoMaterials and Technologies, financially supported by
the EPSRC, the University of Surrey and the National
Physical Laboratory. The authors are grateful to Steve
Spencer for UPS measurements on gold.
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