Colloids and Surfaces A: Physicochem. Eng.

Aspects 452 (2014) 65–72

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Effect of substrate and subphase conditions on the surface

morphology of graphene oxide sheets prepared by Langmuir–Blodgett
technique
V. Divakar Botcha a , Pavan K. Narayanam a , Gulbagh Singh a , S.S. Talwar a , R.S. Srinivasa b ,
S.S. Major a,∗
a
Department of Physics, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India
b
Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• Langmuir monolayer characteristics

of GO sheets are highly sensitive to
subphase pH.
• Compressible Langmuir monolayers
prone to morphological deformation
during transfer.
• RCA-1 treatment of Si and SiO2 essen-
tial for transfer of flat and adherent
GO sheets.
• Microscopic inhomogeneities on Si
critically influence the morphology of
GO sheets.
• Morphology of GO sheets on SiO2 is
insensitive to subphase and transfer
conditions.

a r t i c l e i n f o a b s t r a c t

Article history: Graphene oxide (GO) sheets were transferred by Langmuir–Blodgett technique on Si and SiO2 /Si sub-
Received 22 January 2014 strates. The surface pressure – area isotherms of ‘amphiphilic’ GO sheets at the air–water interface are
Received in revised form 21 March 2014 found to be highly sensitive to subphase pH, which significantly affects their hydrophilicity and the inter-
Accepted 22 March 2014
action between the sheets. The surface morphology of GO sheets transferred under different subphase
Available online 2 April 2014
and transfer conditions has been studied. RCA-1 (NH4 OH:H2 O2 :H2 O – 1:1:2) treatment of Si is found to
be necessary for the transfer of GO sheets. The deposition on RCA-1 treated Si, is also highly sensitive to
Keywords:
the compressibility of the Langmuir monolayer. Thus, transfer of well defined, uniformly distributed and
GO sheets
Langmuir–Blodgett
flat GO sheets on Si is possible only in a narrow window of process parameters, namely, subphase pH,
Langmuir monolayer target pressure and lifting speed. In contrast, the transfer behavior and morphology of GO sheets on RCA-
RCA-1 treatment 1 treated SiO2 /Si is practically insensitive to changes in subphase pH, target pressure and lifting speed.
Hydrophilicity This behavior is attributed to the uniformly strong hydrophilic character of SiO2 /Si surface, compared to
Surface morphology that of Si. The different behavior of Si surface, even after RCA-1 treatment, is attributed to its microscopic
chemical and topographical inhomogeneities.
© 2014 Elsevier B.V. All rights reserved.

∗ Corresponding author. Tel.: +91 22 25767567; fax: +91 22 25767552.

E-mail addresses: divakarbotcha@gmail.com (V.D. Botcha), phypavan@gmail.com (P.K. Narayanam), gulbaghsinghspn@gmail.com (G. Singh),
satya.talwar@gmail.com (S.S. Talwar), raman.srinivasa@gmail.com (R.S. Srinivasa), syed@iitb.ac.in (S.S. Major).

http://dx.doi.org/10.1016/j.colsurfa.2014.03.077
0927-7757/© 2014 Elsevier B.V. All rights reserved.
66 V.D. Botcha et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 452 (2014) 65–72
1. Introduction
Graphene oxide (GO) has recently been attracting attention
as a novel material. This is because, its electrical properties can
be modified by a variety of de-oxygenation processes to form
reduced graphene oxide (RGO), which is considered to be an
alternative to graphene for applications in nanoelectronics, pho-
tovoltaics and sensors [1–3]. GO sheets consist of a mixture of sp2
and sp3 hybridized carbon atoms, bonded with hydroxyl and epox-
ide groups on the basal plane, and ionizable carboxylic acid and
phenolic groups at the edges [4–6]. The poly-aromatic islands of
un-oxidized benzene rings on the basal plane impart hydrophobic
character to GO sheets [4]. Owing to the presence of hydrophilic
and ionizable carboxylic groups at the edges, GO sheets behave
as amphiphilic ‘molecules’ and can be spread as a Langmuir
monolayer at the air–water interface [7]. In a pioneering work
[8], the amphiphilic nature of GO has been exploited to trans-
fer GO sheets from air–water interface on to solid substrates by
Langmuir–Blodgett (LB) technique. Thick films of GO sheets have
also been obtained by several approaches, such as, drop casting
[9], spin casting [10], dip coating [11], spray coating [12] and elec-
trophoretic deposition [13]. Most of these approaches often yield
agglomerates of GO and overlapping sheets with folds and wrinkles,
formed during solvent evaporation [3,11,13]. In contrast, LB tech-
nique can be used to transfer GO sheets of controlled morphology
on solid substrates [8,14–16]. LB technique has also been extended
to deposit GO multilayers by sequential transfer of GO sheets [8].
LB transferred GO sheets, after subsequent reduction to RGO and
O2 plasma etching, have been used to obtain a graphene nanomesh,
which has been utilized as a channel in field effect transistors [17].
There are limited studies on the surface pressure – area
isotherms of GO sheets at the air–water interface and their trans-
fer behavior under different subphase and LB transfer conditions.
Imperiali et al. [18] have studied the stability and structure of GO
sheets at the air–water interface after different number of cycles
of compression and expansion. They have shown that GO sheets
rearrange upon repeated compression, without any loss of mate-
rial at the air–water interface, and display reversibility of wrinkle
formation, like elastic membranes. Cote et al. [19] have shown that
subphase pH has a significant influence on the hydrophilicity of GO
sheets and hence, on their packing at the air–water interface and
transfer to hydrophilic substrates. Wang et al. [20] have shown that
the size of the transferred GO sheets is influenced by the pH of the
spreading solution. Zheng et al. [16] have used different levels of
centrifugation to control the size of GO monolayers dispersed in
water–methanol mixture. They have shown that the density of GO
sheets and wrinkle formation depend on transfer conditions, such
as, target surface pressure and dipper speed. In a different approach,
Szabo et al. [21] have used GO sheets dispersed in water as subphase
and a spreading solution of octadecyl ester of rhodamine B (RhB18)
in chloroform, to form a hybrid monolayer. They have observed that
the architecture of the hybrid monolayer is controlled by subphase
pH and concentration of GO in the subphase.
It is expected and known to certain extent that the subphase
pH dependent hydrophilicity of GO [19] and the wettability of the
substrate play significant roles in the transfer of GO sheets from the
air–water interface to solid substrates. However, despite several
reports, a complete understanding of the role of subphase pH and
LB transfer conditions in determining the surface morphology of GO
sheets transferred on technologically important substrates, such
as Si and SiO2 , is lacking. It may be pertinent to note that different
forms of GO, namely, sheets of different sizes, multilayers, graphitic
particles and aggregates, having different levels of hydrophilicity
are present in the GO dispersion. This work attempts to system-
atically analyze the effect of subphase pH, together with other LB
transfer parameters, such as, target pressure and lifting speed, on
10 6.5 5.5 3.5
Surface pressure (mN/m)
8
6
4
2
0
0 100 200 300 400 500 600 700 800
Area (cm2)
Fig. 1. Surface pressure – area isotherms of GO sheets at different subphase pH, as
indicated in the figure.
the surface morphology of GO transferred on to Si and SiO2 sur-
faces, with wettabilities modified by RCA-1 (NH4 OH:H2 O2 :H2 O –
1:1:2) treatment [22]. Further, it explores the relative importance
of substrate wettability vis-à-vis, the subphase and LB transfer con-
ditions and attempts to identify the processing conditions, under
which, uniformly distributed, morphologically flat, wrinkle-free
and adherent GO sheets can be transferred on Si as well as SiO2
substrates. Our results show that GO sheets with morphological
features as above, can be transferred on RCA-1 treated SiO2 sub-
strates having low contact angles (∼5◦ ) under a wide range of
subphase pH and LB transfer conditions. In contrast, Si substrates
having nearly the same contact angle require a stringent control
of the process parameters, which is attributed to the presence of
microscopic inhomogeneities on the surface of Si, even after RCA-1
treatment.
2. Experimental details
GO was synthesized by a modified Hummers–Offeman’s method
[23], as described earlier [14]. The GO collected after exfoliation and
centrifugation was dispersed in water–methanol mixture (1:5) to
form a colloidal dispersion, which was used as spreading solution.
Ultra-filtered and de-ionized water (Millipore, 18.2 M cm) was
used as subphase. The subphase pH was varied between 2 and 7
by adding dilute HCl/NaHCO3 solution, as required. Concentration
of GO in the spreading solution was maintained by monitoring the
absorbance of the GO dispersion. For all LB deposition experiments,
20 ml of GO dispersion was spread on the subphase, and allowed
to stabilize for 60 min before compression. The Langmuir mono-
layer thus formed, was compressed at a constant barrier speed of
5 mm/min. Silicon wafers, with and without thermally grown SiO2
layer (∼100 nm) were used as substrates. Si and SiO2 /Si substrates
were initially cleaned with organic solvents and rinsed ultrason-
ically with de-ionized water. LB deposition was carried out on Si
and SiO2 /Si substrates, with and without the RCA-1 treatment.
GO sheets were transferred at target pressures, in the range of
1–30 mN/m. Owing to the hydrophilic nature of the substrates and
the GO sheets, LB transfer took place only during the lifting of the
substrate from the subphase. The lifting speed was varied in the
range of 0.5–10 mm/min.
The surface morphology of GO sheets transferred on Si and
SiO2 /Si substrates was studied with a Digital Instrument Veeco-
Nanoscope IV Multimode scanning probe microscope in tapping
mode. Micro-Raman spectroscopy was carried out with a Horiba
Jobin Yvon HR800 confocal Raman microprobe, equipped with a
514 nm Ar+ laser. The hydrophilicity of Si and SiO2 /Si substrates,
 V.D. Botcha et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 452 (2014) 65–72 67

Fig. 2. AFM images of (a) untreated Si and (b) untreated SiO2 /Si, subsequent to the LB transfer process at subphase pH of 5.5. The corresponding contact angles and surface
profiles are shown as insets.

Fig. 3. AFM images of GO sheets transferred on RCA-1 treated Si (a–c) and RCA-1 treated SiO2 /Si (d–f) at different subphase pH, as indicated in the figures. The insets in (a)
and (d) show the contact angles for the two surfaces after RCA-1 treatment. The height profiles of the sheets are also shown as insets.
68 V.D. Botcha et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 452 (2014) 65–72
with and without RCA-1 treatment, was evaluated with a GBX
Digidrop contact angle meter. Static contact angle measurements
were performed by employing /2 method and using photographic
images of ∼1 ␮l water droplets.
3. Results and discussion
Surface pressure – area isotherms of GO sheets at the air–water
interface have been studied in the subphase pH range of 2–7. Fig. 1
shows the isotherms at subphase pH of 3.5, 5.5 and 6.5, which rep-
resent the typical behavior in the subphase pH ranges of 2–4, 5–6
and 6–7, respectively. In all the cases, the GO sheets at the air–water
interface exhibit gas phase behavior at large areas. On compression,
an increase in surface pressure is observed below a certain area,
which progressively shifts to smaller values, with increase in sub-
phase pH. The isotherm recorded at subphase pH of 3.5 exhibits a
continuous increase of slope, displaying high compressibility of the
Langmuir monolayer, which decreases with decrease of area. Such
features are usually associated with the liquid-expanded behav-
ior of Langmuir monolayers of amphiphilic molecules [24]. With
increase in subphase pH, the liquid expanded behavior becomes
less pronounced and the isotherms exhibit progressive decrease
of compressibility, as shown typically, for a subphase pH of 5.5. In
contrast, the isotherm recorded at subphase pH of 6.5 exhibits a
sharp increase in surface pressure and displays a solid region with
nearly constant slope, and hence, a much smaller and nearly con-
stant compressibility. These features are similar to those observed
for Langmuir monolayers of ionized fatty acids [25,26].
The variations observed in the isotherms, over a small range of
subphase pH in the acidic region, can be understood by recogniz-
ing that the GO dispersion contains an assortment of GO sheets of
varying sizes in the range of 5–50 ␮m [14,20]. Owing to the large
variations in the C/O content of these sheets, their pH dependant
amphiphilicity and dispersibility may be significantly different, as
has been shown earlier [7]. It may be noted that the acidic functional
groups on the GO sheets, such as carboxylic, phenolic and hydroxyl
are known to exhibit a distribution of pKa values due to their surface
heterogeneity [27]. It has recently been shown [28] that with pKa
values in the range 2–12, GO ionizes to varying degrees, depending
on subphase pH and hence its dispersibility is strongly pH depend-
ent. The carboxylic groups exhibit two maxima at pKa values of
4.3 and 6.6 [28], which indicates their dominant role within the
investigated range (2–7) of subphase pH. Accordingly, the limiting
ionization of GO sheets of different sizes is expected to be strongly
pH dependent.
The liquid-expanded-like isotherm of GO sheets at subphase pH
of 3.5 may be attributed to a large surface density of unionized GO
sheets of relatively low hydrophilicity at the subphase surface, and
hydrogen bond interaction between carboxylic acid groups present
at the edges, as suggested earlier [19]. The increase of subphase pH
and the consequent limited ionization results in the increase in
hydrophilicity and dispersibility of the partially ionized GO sheets,
especially those, of smaller size, having low C/O ratios. This in turn,
has significant influence on the surface density of GO sheets at the
air–water interface and the interaction between them. At higher
subphase pH, substantially smaller areas are required to increase
surface pressure, which is primarily attributed to the enhanced dis-
persibility of GO sheets into the subphase [28], and a consequent
decrease in surface density of GO sheets at the air–water inter-
face. Another factor that may contribute to this behavior is the
possible overlapping of negatively charged GO sheets, facilitated
by water-molecule lubrication, as suggested by Cote et al. [8]. The
solid region seen at subphase pH of 6.5, displaying low compress-
ibility, is attributed to enhanced ionization of GO sheets and hence,
a stronger repulsive interaction between them.
(a) D G
pH-3.5
pH-5.5
pH-6.5
Intensity (a.u.)
(b)
pH-3.5
pH-5.5
pH-6.5
1200 1400 1600 1800
Wavenumber (cm-1)
Fig. 4. Typical Raman spectra of GO sheets transferred at different subphase pH (as
indicated in the figures) on (a) RCA-1 treated Si and (b) RCA-1 treated SiO2 /Si.
The transfer behavior of GO sheets on Si and SiO2 /Si substrates
was studied. Initial studies were carried out on both substrates
without RCA-1 treatment (to be referred as ‘untreated’) at sub-
phase pH of 5.5, target pressure of 10 mN/m and lifting speed of
3 mm/min. These results are shown in Fig. 2. The AFM image in
Fig. 2(a) shows that no GO sheets are transferred on untreated Si.
In contrast, Fig. 2(b) shows that uniformly distributed and closely
spaced GO sheets are transferred on SiO2 /Si. It is, however, noticed
that the GO sheets on SiO2 /Si have curled up edges all around
the sheets, implying poor adhesion and exhibiting the tendency
to peel off. These features are clearly seen from a typical height
profile across a sheet, shown as inset in Fig. 2(b). In order to under-
stand the difference in the transfer behavior of GO sheets on Si
and SiO2 /Si substrates, the hydrophilicity of the two substrate sur-
faces has been evaluated by contact angle measurements, and the
results are shown as insets in Fig. 2(a and b). The contact angles
of water on untreated Si and SiO2 /Si substrates are found to be
43◦ and 28◦ , respectively. The lack of transfer of GO sheets on
untreated Si is attributed to its relatively high hydrophobicity, as
indicated by the large contact angle. The carboxylic groups at the
edges and OH groups on the basal plane, which are responsible
for the hydrophilicity of the amphiphilic GO ‘molecule’, appear to
prevent its transfer from the air–water interface to a hydropho-
bic surface. In contrast, the untreated SiO2 /Si surface has a lower
hydrophobicity, which allows the transfer of GO sheets, although
with poor adhesion.
A substantially different transfer behavior of GO sheets is
observed after RCA-1 treatment of the two substrates. The AFM
images of GO sheets transferred at subphase pH of 5.5 on RCA-1
treated Si and SiO2 /Si substrates are shown in Fig. 3(a and d) respec-
tively, along with the corresponding contact angle measurements,
 V.D. Botcha et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 452 (2014) 65–72
Fig. 5. AFM images of GO sheets transferred on RCA-1 treated Si (a, b) and RCA-1 treated SiO2 /Si (c, d) at different target pressures, as indicated in the figures. The height
profiles of the sheets are shown as insets.
as insets. Uniformly distributed and closely spaced GO sheets are
transferred on both substrates, without any curled-up edges. This
is clearly seen from the corresponding height profiles at the edges,
which show that the thickness of the sheets is ∼1 nm, in agreement
with earlier studies [14,29] and hence, confirms the monolayer
character of GO transferred on solid substrates in this work. This
behavior is attributed to the high hydrophilicity of RCA-1 treated Si
and SiO2 /Si substrates, both of which, exhibit contact angles in the
range of 5–6◦ . It may be mentioned that it was not practically pos-
sible to distinguish between the contact angles for RCA-1 treated Si
and SiO2 /Si substrates. The substantial increase in hydrophilicity of
Si and SiO2 /Si after RCA-1 treatment is attributed to the formation
of silanol (Si-OH) groups on both surfaces. The drastic influence
of the silanol groups on the transfer behavior of GO sheets on Si
substrate indicates that the presence of a native oxide layer over
untreated Si is not sufficient to impart the hydrophilicity required
for the transfer of GO sheets.
The effect of subphase pH on the transfer behavior of GO sheets
on RCA-1 treated Si and SiO2 /Si substrates has been studied. Typical
Raman spectra of GO sheets transferred at different subphase pH
on both substrates are shown in Fig. 4. All these spectra show two
prominent peaks at 1340 ± 2 cm−1 and 1600 ± 2 cm−1 , associated
with the well known D- and G-modes of GO [30,31], confirming
the transfer of GO sheets at all subphase pH, studied in this work.
The spectra also show similar features, including the positions of
the two peaks, suggesting that there are no distinguishable dif-
ferences in terms of bonding defects/disorder. In contrast, the GO
sheets transferred on the two substrates, show significantly differ-
ent morphological features, which are discussed below.
The AFM images of GO sheets transferred on RCA-1 treated Si
and SiO2 /Si substrates at subphase pH of 3.5 and 6.5 are included in
Fig. 3, along with the images of the sheets transferred at subphase
69
pH of 5.5 (which were discussed above). GO sheets transferred on
Si at subphase pH of 3.5 are found to be rough and crumpled, while
those transferred at subphase pH of 5.5 and 6.5 are well defined
and morphologically flat. In contrast, well defined and morpholog-
ically flat GO sheets are transferred on SiO2 /Si at all subphase pH.
The rough and crumpled morphology of GO transferred on Si at sub-
phase pH of 3.5 is attributed primarily to the higher compressibility
of the Langmuir monolayer. It appears that the variations in surface
pressure during the transfer process make the GO sheets prone to
morphological deformations. Interestingly, the same, highly com-
pressible Langmuir monolayer (at subphase pH of 3.5) does not
result in a crumpled morphology of GO sheets, when transferred
on SiO2 /Si substrate. This behavior shows that the nature of inter-
actions of the amphiphilic GO ‘molecule’ with RCA-1 treated Si and
SiO2 /Si surfaces are significantly different, despite the two sub-
strates exhibiting nearly equal contact angles. The origin of this
difference may lie in the differences between the native oxide and
the thermally grown oxide on Si. The native oxide is known to be
thin (∼1.5 nm) and irregular, having high roughness of the order
of its thickness [32,33]. The native oxide is also reported [32] to
have a slightly different molecular structure from that of the ther-
mally grown oxide. Due to the above factors, the Si surface with a
native oxide is known to be chemically more reactive, compared
to the surface of thermally grown oxide [34]. RCA-1 treatment not
only leads to the formation of Si-OH groups on Si surface, but is also
reported to increase its surface roughness and the irregularity of the
native oxide layer over it [35], due to the formation of nascent oxy-
gen. In comparison, the interaction of nascent oxygen with a thick,
thermally grown SiO2 results in a marginal increase in its porosity
and disorder [36], concurrent with the formation of uniformly dis-
tributed Si-OH groups on the surface. The strong polar interaction
of the amphiphilic GO ‘molecule’ with uniformly distributed Si-OH
70 V.D. Botcha et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 452 (2014) 65–72
Fig. 6. AFM images of GO sheets transferred on RCA-1 treated Si (a and b) and RCA-1 treated SiO2 /Si (c and d) at different lifting speeds, as indicated in the figures. The height
profiles of the sheets are shown as insets.
groups on SiO2 /Si, resists the tendency of morphological defor-
mation of GO sheets during the transfer process. As a result, well
defined, flat and adherent GO sheets are transferred under all sub-
phase pH conditions. In contrast, RCA-1 treated Si surface behaves
differently, essentially due to its microscopic chemical and topo-
graphical inhomogeneities. The microscopic inhomogeneities on
RCA-1 treated Si appear to significantly affect the morphology of
GO sheets, when transferred from a highly compressible Langmuir
monolayer (at low subphase pH). However, these inhomogeneities
do not significantly influence the transfer behavior of GO sheets
from a Langmuir monolayer of low compressibility (at high sub-
phase pH) and high hydrophilicity. These observations also show
that the membrane-like, 1 nm thick GO sheets are vulnerable to
morphological deformations during the transfer process and are
thus highly sensitive to the nature of substrate surface. This is in
contrast with the behavior of long chain amphiphilic molecules
during LB transfer process, which can adopt slightly different ori-
entations under such influences.
GO sheets transferred at higher subphase pH on RCA-1 treated
Si and SiO2 /Si, exhibit dense packing and substantial overlap, as
shown typically for subphase pH of 6.5, in Fig. 3(c and f), respec-
tively. The substantial overlap of GO sheets transferred at higher
subphase pH is consistent with the steep solid region of the cor-
responding isotherm (Fig. 1). This is an additional evidence for the
increase in hydrophilicity of the GO sheets at higher subphase pH
and the role of a water lubricating layer [8], which may facilitate
the overlapping of sheets during the compression and transfer pro-
cesses.
In order to study the effect of target pressure, GO sheets have
been transferred on RCA-1 treated Si and SiO2 /Si substrates at sub-
phase pH of 5.5 and lifting speed of 3 mm/min. It was shown in
Figs. 3(a and d) that uniformly distributed GO sheets are transferred
on RCA-1 treated Si and SiO2 /Si, at a target pressure of 10 mN/m.
Typical AFM images of GO sheets transferred on RCA-1 treated Si
at target pressures of 5 mN/m and 30 mN/m are shown in Fig. 5(a
and b), respectively, and the images of those transferred on RCA-
1 treated SiO2 /Si at target pressures of 1 mN/m and 20 mN/m are
shown in Fig. 5(c and d), respectively. At a relatively low target
pressure of 5 mN/m, GO sheets transferred on Si exhibit crum-
pled morphology, with large surface roughness, as observed for
the transfer at low subphase pH. In contrast, on SiO2 /Si, decrease
of target pressure to values as low as 1 mN/m does not result in
GO sheets with crumpled morphology. The crumpling of GO sheets
transferred at low target pressure on Si is attributed to variations
in surface pressure during the transfer process. It can be seen from
Fig. 1 that the compressibility of Langmuir monolayer at subphase
pH of 5.5 increases with decrease of surface pressure, resulting in
the morphological deformation of GO sheets. The absence of crum-
pling in GO sheets transferred at the same or even lower target
pressures on RCA-1 treated SiO2 /Si, in contrast to RCA-1 treated Si,
strongly supports that substrates play a significant role in resisting
morphological deformation of GO sheets. As was shown in Fig. 3(a
and d), GO sheets transferred at target pressures in the range of
10–15 mN/m, on both Si and SiO2 /Si substrates do not exhibit crum-
pled morphology. This is attributed to the relative incompressibility
of the Langmuir monolayer under these conditions and marginal-
ization of the role of the substrate in the transfer process. With
increase in target pressure to 20 mN/m or higher, the sheets begin
to exhibit substantial overlap. This is shown typically for GO sheets
transferred on Si at 30 mN/m (Fig. 5(b)) and on SiO2 /Si at 20 mN/m
(Fig. 5(d)).
The effect of lifting speed on the transfer of GO sheets on RCA-1
treated Si and SiO2 /Si has been studied at subphase pH of 5.5 and
target pressure of 10 mN/m. It was shown above in Fig. 3(a and d)
 V.D. Botcha et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 452 (2014) 65–72
that well defined, morphologically flat and uniformly distributed
GO sheets are transferred on RCA-1 treated Si and SiO2 /Si at a lift-
ing speed of 3 mm/min. Fig. 6 shows the AFM images of GO sheets
transferred at lifting speeds of 0.5 mm/min and 10 mm/min on both
substrates. Fig. 6(a and b) shows that the GO sheets transferred on
Si at a low lifting speed of 0.5 mm/min as well as at a high lifting
speed of 10 mm/min, are of extremely poor quality, compared to
those shown in Fig. 3(a and d). Interestingly, under the same condi-
tions, the morphology of GO sheets transferred on SiO2 /Si remains
unaffected by the change of lifting speed, as shown in Fig. 6(c and
d). It may be mentioned that the GO sheets transferred on both sub-
strates at all lifting speeds, exhibit nearly identical Raman spectra
(not shown), similar to those in Fig. 4. The AFM image and height
profiles of GO transferred on Si at a lifting speed of 0.5 mm/min
show an extremely rough morphology, which is attributed to the
presence of monolayers, multilayers and graphitic particles. Sim-
ilarly, the AFM image of GO transferred on Si at a lifting speed
of 10 mm/min, shows the presence of GO sheets with crumpled
morphology, as well as some multilayers. These observations are
also attributed to the presence of a variety of GO structures at the
air–water interface, as mentioned above. At low lifting speeds, all
these structures, including the particles are transferred, while at
high lifting speeds, only the GO sheets and some multilayers are
transferred on Si. It is inferred that an optimized and moderate lift-
ing speed in the range of 3–5 mm/min is essential for the selective
transfer of amphiphilic GO sheets on Si, without any morphologi-
cal deformation. The observation that GO particles/structures other
than highly amphiphilic GO sheets are not transferred on SiO2 /Si,
irrespective of the lifting speed, is attributed to the uniformly strong
hydrophilic character of SiO2 surface and its interaction with the
GO sheets. In contrast, the microscopic chemical and topographical
inhomogeneities of RCA-1 treated Si surface allow the transfer of
different kinds of GO structures present at the air–water interface,
under non-optimized lifting speeds.
4. Conclusions
The surface pressure – area isotherms of GO sheets at the
air–water interface are highly sensitive to subphase pH, which
strongly influences the extent of ionization and hence, their
hydrophilicity and dispersibility as well as the nature of interaction
between GO sheets. In addition to the subphase and LB transfer con-
ditions, the hydrophilicity of the substrate has a strong influence on
the morphology of the transferred GO sheets. Consequently, RCA-1
treatment is essential for the transfer of GO sheets on Si, while it
is important for obtaining flat and adherent GO sheets on SiO2 /Si.
RCA-1 treated Si displays a much higher sensitivity to subphase and
LB transfer conditions, compared to RCA-1 treated SiO2 /Si. In the
highly acidic region (subphase pH of 3.5), GO sheets with crum-
pled and rough surface morphology are transferred, owing to the
high compressibility of the Langmuir monolayer. In comparison,
well defined, uniformly distributed, flat and adherent GO sheets
are transferred in the moderately acidic region (subphase pH range
of 5.0–6.5). Further, at a subphase pH of ∼5.5, crumpled GO sheets
are transferred at low target pressures (∼5 mN/m) and a mixture of
crumpled GO sheets, multilayers and graphitic particles are trans-
ferred at low (0.5 mm/min) and high (10 mm/min) lifting speeds.
Thus, an optimized window of operation defined by subphase pH
of 5.0–6.5, target pressure of 10–15 mN/m and lifting speed of
3–5 mm/min is required to transfer well defined, morphologically
flat and uniformly distributed GO sheets on RCA-1 treated Si. In con-
trast, the transfer behavior and morphology of GO sheets on RCA-1
treated SiO2 /Si is practically insensitive to changes in subphase pH,
target pressure and lifting speed, which is particularly noteworthy.
It shows that although both Si and SiO2 /Si substrates, after RCA-1
71
treatment, exhibit nearly equal contact angles with water, SiO2 /Si
behaves as a ‘superior’ hydrophilic surface, particularly for the LB
transfer of GO sheets. Its uniformly strong polar interaction with
the hydrophilic groups of the amphiphilic GO ‘molecule’ appears
to play a crucial role in preventing any morphological deformation
of GO sheets during the transfer process, even under conditions,
wherein, the Langmuir monolayer has high compressibility. The
RCA-1 treated SiO2 /Si substrate, thus facilitates the transfer of
well defined, morphologically flat and adherent GO sheets under
a wide range of subphase and transfer conditions. The stringent
requirement of optimized process conditions for the transfer of
GO sheets on RCA-1 treated Si is attributed to microscopic, chem-
ical and topographical inhomogeneities on the substrate surface.
These inhomogeneities appear to cause morphological changes in
GO sheets transferred from Langmuir monolayers of relatively high
compressibility.
Acknowledgments
The authors would like to thank FIST (Physics)-IRCC Central SPM
facility, IIT Bombay for AFM measurements, Centre for Research
in Nanotechnology and Science (CRNTS), IIT Bombay for Raman
spectroscopy measurements and Centre for Excellence in Nano-
electronics (CEN), IIT Bombay for contact angle measurements.
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