Annealing Free, High Quality CVD

Graphene Growth and Transfer

R. Brajpuriya, T. Dikonimos, F. Buonocore and N. Lisi

Abstract Among the different graphene synthesis methods, chemical vapor

deposition of graphene on low cost copper foil shows great promise for large scale
applications. Here we report on the growth and transfer of uniform and continuous
large-sized thin-films composed of single- and few-layered graphene. The foils
were grown by chemical vapor deposition (CVD) on polycrystalline copper
(Cu) foils at low pressure using ethanol and were transferred onto the destination
substrates using a cyclododecane supporting layer. Structural and optical charac-
terizations indicate that the graphene films are composed of single or few layers
depending on the growth conditions and exhibit low defect density. The graphene
films can be transferred to arbitrary substrates with the help of a green transfer
method based on an organic molecule, cyclododecane.

1 Introduction

Today graphene, with other 2D materials, is considered as an encouraging material

that could be the foundation for future generations of low-power, faster, smaller and
economic electronic devices [1, 2]. The route toward the commercial exploitation of
graphene’s unique properties hinges entirely on the development of adequate gra-
phene growth and integration technologies, which is still a great challenge. The key
to solving this challenge requires us to develop synthesis and transfer methods to
employ in the fabrication and transfer of single layer graphene films with an optimal
degree of control. In this paper, therefore, our aim is to obtain improved and

R. Brajpuriya (&)
Amity Institute of Nanotechnology, Amity University Haryana, Manesar,
Gurgaon 122413, Haryana, India
e-mail: ranjeetbjp@yahoo.co.in
T. Dikonimos
F. Buonocore
N. Lisi
Surface Technology Laboratory Materials Technology Unit,
Casaccia Research Centre, ENEA, Rome 00123, Italy

© Springer International Publishing Switzerland 2017 325

V.K. Jain et al. (eds.), Recent Trends in Materials and Devices,
Springer Proceedings in Physics 178, DOI 10.1007/978-3-319-29096-6_44
326 R. Brajpuriya et al.

sustainable growth method of high-quality graphene and a green method which

permits the transfer of continuous and crackles films onto arbitrary substrates.

2 Experimental Details

Sample Growth: Continuous graphene films were grown on 25 μm thick Cu foils

using low-pressure CVD technique and ethanol diluted in Argon as carbon precursor
[3]. Before synthesis, the as-received Cu foils of a few cm2 were pre-cleaned by
ultra-sonication in acetone and ethanol. The boat supporting the Cu foils was inserted
into a hot zone, and the samples were annealed in Ar/H2:20/20 sccm for 20 min at
1000 °C. Afterwards, the gaseous carbon source, ethanol (C2H5OH) diluted in Ar
(0.5 % in 20 sccm of Ar) was introduced in the tube with 100 sccm of H2 for 30 min
to perform the graphene growth. Finally, the samples were rapidly cooled under Ar
down to ambient temperature before being removed from the chamber.
Sample Transfer: After the growth the graphene film must be removed from the
metal substrate and transferred onto the appropriate substrate for characterizations
and use. Conventional wet etching chemical transfer methods involve the use of
protective supporting layers for graphene, such as PMMA, during the metal etch-
ing. Such layers need further processing steps for their complete removal, typically
solvents and heat treatments, which are not always compatible with many desirable
polymeric substrates [4]. Thus, for the necessary development and possible com-
mercialization of high-performance electronic devices based upon graphene
improved graphene transfer processes free from contaminations are desirable. Such
methods should at the same time inhibit the formation of cracks and holes during
transfer but it is desirable that it could also be non-toxic, fast and green.
At the ENEA laboratories, a new procedure has been developed [5] based on
cyclododecane (CDD) as support material and a protective layer. In this work, the
films were transferred onto a Si/SiO2 (300 nm) substrate by using CDD. Due to
ability to sublimate completely at ambient conditions, Graphene transfer using CDD
is a fast and green method and does not result in the presence of contamination from
resist residues. The graphene transfer process is shown schematically in Fig. 1.
The first step consists of the removal of graphene from the back surface of the Cu
foil, by oxygen plasma treatment (30–90 s, 100 W RF power). Then a thin layer of
cyclododecane (20 wt% up to saturation) diluted in ethyl ether or cyclohexane, was
spin-coated onto graphene over the front side of the Cu foil at (1500 rpm for 60 s).
The Cu substrate was then etched in a 50 g/l aqueous solution of Ammonium
Per-sulphate (PSA). The graphene/CDD film floating on the solution was then
thoroughly rinsed with DI water to remove any process residues. It has been reported
[6] that when graphene film is transferred from water to the target substrate, the stack
might not make a full contact with the surface and that the unattached region tends to
break and form the cracks. Therefore, it is expected that the hydrophilicity of the
surface of the substrate onto which the CDD/graphene stack will be transferred will
have a crucial impact on the formation of the folds. A hydrophilic surface will spread
Annealing Free, High Quality CVD Graphene Growth and Transfer 327

Fig. 1 Improved wet chemical process

Fig. 2 Photographs of as-received Cu foil (left), and graphene film grown on Cu substrate
(Centre). On the right the Graphene films transferred onto a SiO2/Si substrate

the water more evenly during transfer and improve the smoothness of the
CDD/graphene stack contact with the target.
In the present approach, we have transferred floating stack onto oxygen plasma
treated hydrophilic SiO2 (300 nm)/Si target substrate. In the last step, cyclodode-
cane/graphene/SiO2 (300 nm) is heated in air at 70 °C for the final removal of
cyclododecane and interfacial water trapped underneath graphene. Since CDD
melts at 62.5 °C, during this final step it should release the surface tensions
improving the transfer. Figure 2 shows the appearance of graphene film after
growth and transfer process.
Characterization methods: The morphology and microstructure of both as
grown and transferred graphene films are investigated using a field emission
scanning electron microscope (SEM) and X-ray photoelectron spectroscopy
(XPS) measurements.
328 R. Brajpuriya et al.

3 Results and Discussion

The cleanliness of the as-grown graphene film deposited on Cu foil was checked by
XPS, as displayed in Fig. 3. It is very clear from the figure that only peaks cor-
responding to Carbon and Cu were present and all other peaks were absent, indi-
cating that the deposited film does not contain any impurity or contaminants. The
graphene film after its transfer onto the Si/SiO2 (300 nm) substrate was examined
using SEM, as displayed in the Fig. 4. The film is continuous and shows wrinkles
and folds on its surface, which appear during cooling after the chemical vapor
deposition (CVD) synthesis due to the difference in the thermal expansion coeffi-
cient of Cu and graphene [3]. It is also possible to observe the presence of regions
with different numbers of layers since; different areas of the image appear with a
different brightness.

Fig. 3 Survey scans of graphene film grown on Cu foil

Fig. 4 SEM image of

transferred graphene film
Annealing Free, High Quality CVD Graphene Growth and Transfer 329

Fig. 5 Optical micrograph of

transferred few layer graphene

The optical micrograph of the sample after transfer (Fig. 5) also show a film
which is continuous and uniform; there are no holes or cracks, also it is evident the
presence of secondary nucleation stripes, due to the copper lamination. These
results imply that with this approach clean, crackless transfer of graphene is pos-
sible in a process requiring a very small amount of solvents, namely the few drops
utilised during spin coating.
Further measurements are under way to demonstrate that no other impurities
were added to graphene during the whole process and confirming effectiveness and
cleanness of the transfer protocols.

4 Conclusions

In summary, authors have developed a method for the growth of large-area, con-
tinuous and uniform graphene films with ethanol as carbon precursor, and a green
transfer method based on an organic molecule, cyclododecane, which grants high
fidelity transfer onto arbitrary surfaces, including substrates which are sensitive to
heat and to solvents. By combining an effective metal cleaning process, we have
developed and demonstrated a transfer process that can improve both device yield
and performance uniformity.

Acknowledgments The author (R. B) would like to acknowledge ENEA for providing the
International Research Fellowship.
330 R. Brajpuriya et al.

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