Toward fabrication of graphene based devices:

graphene transfer, processing, and characterization

Anca-Ionela Istrate*, Monica Veca, Florin Nastase, Angela Baracu,

Raluca Gavrila, Florin Comanescu

CENASIC - Research Centre for integrated systems nanotechnologies and carbon based nanomaterials
National Institute for Research and Development in Microtechnologies - IMT Bucharest, Romania
*E-mail: anca.istrate@imt.ro

Abstract—The current work presents our group's
progress toward a graphene transfer and graphene-Si
junctions. We perform graphene transfer from copper to
SiO2/Si and Si substrate using electrochemical
delamination. We processed and characterized graphene
on SiO2/Si and Si. Finally we manufactured several
junctions with graphene-Si. The I-V curve is symmetric
with respect to the bias voltage, therefore one can infer
that there is no Schottky contact at the interface. For
larger bias voltages, the I-V characteristics are non-linear
of second order.
Keywords—graphene, transfer, electrochemical
delamination, recyclability, graphene-Si junction.
1. Introduction
Graphene (GR) offers the possibility of
integration with the existing semiconductor
technology for next-generation electronic and
sensing devices [1] due to its two dimensional
nature, with mobility above 15,000 cm2Ví1sí1 in
ambient conditions [2], attractive for high
frequency electronics [3] and ease of
manipulation. One of the most advanced
methods in GR synthesis is chemical vapor
deposition (CVD) on copper, but for devices
fabrication [4,5], GR must be transferred from
the growth metallic substrate to a device-
compatible one. There are many different ways
to transfer GR, but for practical applications, a
reproducible and low-cost method of GR transfer
is significant. Consequently, in our previously
paper [6] we have tested three wet chemical
methods for GR transfer. The highest quality and
yield of GR flakes were obtained by
electrochemical delamination. The advantage of
this technique is the lack of corrosion of the
metallic foil, process repeatability, as well as the
reusability of the metal foil in multiple growth
and delamination cycles [7]. The novelty of the
present study, employing electrochemical
delamination, for transferring GR from metal to
SiO2/Si and Si, consist in a reduced time of GR
transfer from 60 to 10 minutes. Further, we have
fabricated and analyzed GR-Si junctions with
square geometry and side lengths of: 6 μm, 20
μm, 40 μm and 70 μm placed on the same chip.
Raman fingerprint of GR have allowed us to
identify the defect density in the transferred GR
sheet with respect to the as grown specimen,
while optical and atomic force microscopy
revealed the transfer efficiency of GR flakes. The
electrical characteristics of GR-Si junctions were
also evaluated to identify possible applications.
2. Experimental Details
A. Transfer process of graphene
The single layer GR on copper foil was
provided by Graphene Supermarket. The GR on
metal were transferred to SiO2/Si and Si by
Electrochemical Delamination. The system of
contacting electrodes used in this process of
transfer is home-made and is shown in Fig. 1.
Fig. 1. Electrochemical delamination system of GR from Cu
foil. In inset, image showing the peeling of the “whole film”
PMMA-covered GR from the Cu foil.
Electrochemical cell includes two electrodes:
PMMA/GR/Cu used as the cathode, and the
anode is graphite. The two electrodes are
connected to an electrical source. The electrolyte
used was a dilute solution of K2S2O8. The
principle is based on the electrochemical
delamination and consists of releasing the
hydrogen at the cathode, which leads to

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 detachment of PMMA/GR from the metal. The
process of electrochemical delamination include:
(a) Deposition of polymethylmethacrylate,
PMMA over GR/Cu by spin-coating; (b)
Electrochemical delamination (25-30 V); (c) The
SiO2/Si and Si substrates are then used to fish the
GR directly from the liquid; (d) PMMA is
removed in acetone.
B. Fabrication of GR/Si junctions
Technological flow diagram of the GR/Si
junction fabrication is presented in Fig. 2.
(a) (b)
(d) (c)
study the surface topography of transferred GR
flakes. The electrical characteristics of GR-Si
junctions were measured by means of 4200-
SCS/C/Keithley system.
3. Results and Discussion
3.1 Optical microscopy
In figure 4 are presented optical micrographs
of GR transferred from Cu to SiO2/Si (Fig. 4a)
and Si (Fig. 4b). A good optical contrast shows
GR coverage of oxidized silicon areas as results
from Fig. 4a. In Fig. 4b is presented an optical
micrograph of a square GR/Si junction having a
side legth of 70 μm. Due to the poor optical
contrast single layer GR is not visible on silicon
areas (the inner rectangle – Fig 4b).
(a)

Fig. 2. Schematic diagram of the GR/Si junction fabrication

process: (a) Thermal oxidation of the Si substrate; (b) Cr/Au
deposition; (c) Litho-patterning of metal (Cr-Au); (d) SiO2
wet etching.

The n-type <100> Si wafers have been used as

substrates in order to manufacture the GR/Si
junction. After a standard cleaning process, a (b)
thin film of 300 nm SiO2 has been grown. The
metal film consisting of Cr/Au, with a thickness
of 10/100 nm has been deposited. After SiO2
back side etching, the metallic film has been
patterned by using the first photolithographic
mask (M1). The second mask (M2) has been
used to etch the SiO2 on the front side of the
wafer, in order to contact the Si substrate. In Fig. Fig. 4. Optical micrograph of GR transferred from Cu on
3 we present the masks used: M1 and M2. SiO2/Si (a) and on Si (b). Scale bar, 20 μm.

3.2 Raman Spectroscopy

Raman Spectra performed on GR sheet after
being transferred on to SiO2/Si and Si substrate
are comparatively shown in Fig. 5.

2D
Fig. 3. The designed square geometry of GR-Si junction
G
Transferred GR was investigated by means of
micro-Raman Spectroscopy, Horiba Labram Hr D
800 equipment having a 633 nm He-Ne laser.
The same equipment was also used for obtaining
optical pictures. Atomic Force Microscope
(NTEGRA Aura – NT-MDT model) was used to Fig. 5a. Raman Spectra of GR transferred on SiO2/Si.

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 (polymer residues) left by the incomplete
2D removal of the support polymer (PMMA
employed for the transfer process).

G
3.3 Electrical analysis
D
Electrical measurements of GR/Si junction
are performed and the electrical characteristics
obtained were presented in Fig. 7-10.

Fig. 5b. Raman Spectra of GR transferred on Si.

The main Raman bands of GR (D ~ 1335 cm-1, G

~ 1580 cm-1 and 2D ~ 2670 cm-1) are evidenced
by both spectra thus confirming that GR was
transferred on both oxidized silicon and silicon
areas. Characteristic parameters of the Raman
spectra are given in Table 1.
Table 1. Parameters extracted from GR Raman spectra
presented in Fig. 5.
Type of ID/IG I2D/IG FWHM–2D
substrate (cm-1) Fig. 7. I-V characteristic on GR/Si junction.
SiO2/Si 0.2 2.2 27.89
Si 0.69 4.25 26.96 The I-V characteristics is symmetric with respect
to bias voltage hence, one can infer that there is
The Raman bands and the extracted no Schottky contact at the interface (Fig. 7).
parameters (I2D/IG and FWHM-2D) are The non-linear I-V characteristics suggest
confirming the existence of single layer GR both that junctions are more than an ohmic contact
on silicon and oxidized silicon areas. The GR formed at the GR/Si interfaces.
quality indicator (I2D/IG) corresponding values We tried to verify if there is any tunneling
and FWHM of 2D band which is lower than 30 mechanism represented by Fowler-Nordheim
cm-1 are confirming the presence of single layer formula [9]. We represented I/V2 versus 1/V
GR on both oxidized silicon and silicon areas on (Fig. 8) and we found a linear dependence for
the sample [8]. large 1/V, i.e. for small bias voltage V. In other
words, at small bias voltages the I-V is linear,
3.2 Atomic force microscopy which is consistent with Simon’s model for
Surface topography images of GR film rectangular barrier mechanism [10].
transferred to SiO2/Si and Si wafer, (Fig. 6) by
electrochemical delamination are confirming the
successful GR transfer.

(a) (b)

Fig. 6. AFM images of the surface of GR sheet on SiO2/Si

(a) and Si (b) after transfer from Cu foil.
Fig. 8. I/V2 vs. 1/V characteristic, calculated on
The morphology of GR transferred is fairly GR/Si junction.
smooth, making it possible to identify the GR
Results I-V, (Fig. 9) are indicating that the
islands, mostly monolayer. As evident from Fig.
highest current is obtained on the structure of 70
6, submicrometer features can be observed on the
μm side length; while the lowest current was
GR, mainly represented by contaminations
obtained for the one of 6 μm side length. For the

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 high bias voltage, the tunneling barrier may start The non-linear I-V characteristics suggest that
thinning and may become triangular where the junctions are more than an ohmic contact formed
tunneling follows the Fowler-Nordheim [10-11]. at the GR/Si interfaces.

Acknowledgments. This research was

supported by Project CORE No. PN 16320203 /
2016: “Experimental studies on transfer methods
of graphene on various substrates”.

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