Effect of humidity on electronic properties of CVD graphene

C. Melios1,2, V. Panchal1, C.E. Giusca1, A. Centeno3, A. Zurutuza3, S.R.P. Silva2 and O. Kazakova1
1National

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

2Advanced Technology Institute, University of Surrey, Guildford, Surrey, GU2 7XH, UK
3Graphenea SA, 20018 Donostia-San Sebastin, Spain
Email: christos.melios@npl.co.uk

Introduction

Methods

The two-dimensional nature of graphene makes it sensitive to environmental doping.

With water vapour being a significant component of the ambient air, graphene-based devices designed to operate in
ambient air (e.g. sensors) will be significantly affected, as their electronic properties can change with humidity.
For the successful commercialisation of graphene-based devices, the complete understanding of the water-graphene
interactions is necessary.
We employ simultaneously local Kelvin probe force microscopy (KPFM) and global transport measurements in the van
der Pauw geometry to observe the effects of water on the work function (WF) and carrier concentration of chemical
vapour deposition (CVD) grown graphene of different thicknesses transferred on SiO2.
We probe the local electronic properties of mono- and bi-layer graphene in a series of measurements in controlled
environments, starting from ambient (~30 % R.H.), to vacuum, pure nitrogen and 20-60% relative humidity (RH).
Raman spectroscopy and mapping is used to assess the graphene thickness and structure.

Tip calibration: TipHOPG+eUCPD (HOPG =4.48 eV)

Scanning probe microscopy transport in variable environments

Frequency-modulated Kelvin probe force microscopy
Work function maps of the mono-layer graphene transferred to SiO2 (with 2LG islands) in controlled environmental conditions.
eV

Ambient

Vacuum

N2

20% R.H.

40% R.H.

60% R.H.

eV

60% R.H.

eV

2LG
island

Mono-layer

Work function maps of the bi-layer graphene transferred to SiO2 in controlled environmental conditions.

Ambient

Vacuum

eV

N2

20% R.H.

40% R.H.

Substrate
Bi-layer

Mono-layer WF
2LG islands WF
Bi-layer WF
Mono-layer hole concentration
Bi-layer hole concentration

5.2
5.1

Work function (eV)

20

5.0

18
16
14

4.9
12
4.8
10
4.7
8

4.6

4.5

bi
en
t

Significant decrease of WF and hole concentration in vacuum desorption of water and other p-dopants present on
the graphene surface.
Gradual increase of WF and hole concentration water is a strong p dopant.
Saturation of WF and hole concentration water saturates the graphene surface and is not the only dopant in
ambient air.
Bi-layer graphene behaves as two decoupled layers, with only the top layer affected by humidity (response similar to
mono-layer).
Weak interaction between mono-layer and twisted 2LG results in different response compared to de-coupled bilayers.

Am

.
60
%

.H

.
.H
R
40
%

.H
R
20
%

itr
o
N

Va

Am

ge
n

4.3

cu
um

bi
en
t

4.4

Hole concentration (1012 cm-2)

5.3

Environmental condition

Conclusions

KPFM showed significant decrease of WF in vacuum which is associated with

desorption of water and other p-dopants present in ambient air. This was also
observed as a decrease in hole concentration (transport measurements).
In vacuum, both the hole concentration and WF are higher for the mono-layer
compared to bi-layer graphene on SiO2 screening of substrate charges.
Introduction of nitrogen and water vapour mixture with a gradual change of
humidity from 20 to 60% RH results in an increase in the hole concentration
and WF, however the value does not reach ambient levels water vapour is
not the only p-dopant in the ambient air that affects graphene.

Ambient

Vacuum

Nitrogen

20 % R.H.

40 % R.H.

60 % R.H.

Raman characterisation
3000

G-Peak intensity

1450

2D-Peak intensity

1610 cm-1

Ambient

G D

G-Peak shift

2LG
islands

2D
Mono-layer
2LG island 1
2LG island 2
2LG island 3
= 532

Mono-layer
680

680

1570 cm-1

Mono-layer graphene: Narrow and symmetrical 2D peak substrate is

covered with mono-layer graphene.
1200
2LG islands: Narrow and symmetrical, but shifted 2D peak twisted (not
AB stacked) 2LG graphene.

Graphene surface saturates with water at humidity levels higher than ~40% R. H. This can be seen from the
saturation in hole concentration and WF.
Upon exposure to ambient air, the carrier concentration is not fully restored long restoring time is needed.
Raman spectroscopy/mapping indicated that the mono-layer sample is covered with 1LG film, decorated with
twisted 2LG nucleation islands. The bi-layer samples are covered with decoupled (not AB stacked) 2LG films.

1400

1600

2600

2700

Raman shift (cm-1)

Acknowledgments
We acknowledge the support of EC grants Graphene Flagship
and the IRD Graphene Project. The work was carried out as
part of an Engineering Doctorate Program in Micro- and
NanoMaterials and Technologies, financially supported by the
EPSRC, the University of Surrey and the National Physical
Laboratory.

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