Carbon 95 (2015) 843e851

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Graphite mediated reduction of graphene oxide monolayer sheets

Gulbagh Singh a, V. Divakar Botcha a, D.S. Sutar b, S.S. Talwar a, R.S. Srinivasa c,
S.S. Major a, *
a
Department of Physics, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India
b
Central Surface Analytical Facility, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India
c
Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India

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

Article history: Large area graphene oxide (GO) monolayer sheets were transferred on Si and SiO2/Si substrates by
Received 29 May 2015 LangmuireBlodgett technique and reduced by heat treatment in the presence of graphite powder, inside
Received in revised form an evacuated and sealed enclosure. Reduction at 1000
C results in a decrease of sheet thickness to
12 August 2015
~0.5 nm without any morphological changes, and de-oxygenation (O/C ratio 5%) accompanied by
Accepted 21 August 2015
Available online 3 September 2015
enhancement in sp2-C to 84%. Red-shift of G-peak to ~1585 cm1, decrease in I(D)/I(G) ratio and
appearance of an intense G0 -peak as a single Lorentzian, are indicative of substantial reduction in defects
and restoration of graphitic network. Ultraviolet photoelectron spectroscopy (UPS) studies show large
increase in density of states (DOS) in the immediate vicinity of Fermi level and decrease in work function
after reduction. Bottom gated field effect transistors fabricated with isolated RGO sheets display ambi-
polar behavior, with charge neutrality point at a positive gate voltage, indicating p-type nature,
consistent with UPS results. RGO sheets exhibit conductivity of (2e3)  103 S/cm and field effect mobility
of (20e45) cm2/Vs, which are substantially higher than the values usually reported for RGO sheets,
particularly those obtained by chemical reduction followed by heat treatment.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction (2e20)  103kU/sq (conductivity, (0.5e5) S/cm) [7,8]. GO sheets

Reduction of chemically exfoliated GO to form reduced gra-
phene oxide (RGO) has currently been attracting enormous atten-
tion. RGO is considered to be a versatile, low cost and scalable
alternative to graphene for various potential applications in nano-
electronics, optoelectronics, sensors and photovoltaic devices
[1e3]. Chemically exfoliated GO consists of a mixture of sp2 and sp3
hybridized carbon atoms bonded with various oxygen functional
groups on the basal plane and periphery, which makes GO sheets
insulating. Various reduction approaches have been developed for
the removal of the oxygen functional groups and restoration of sp2
network, leading to the formation of RGO sheets on solid sub-
strates, with improved electrical conductivity. Hydrazine and its
derivatives are most commonly used for the reduction of GO sheets
in solution as well as in solid state [4e6]. Typically, RGO monolayer
sheets obtained by hydrazine treatment followed by heat treat-
ment ~400
C in Ar atmosphere display sheet resistance of
* Corresponding author.
E-mail address: syed@iitb.ac.in (S.S. Major).
that have been reduced at temperatures in the range of
800e1100
C result in sheet resistance values of (150e500) kU/sq
(conductivity, (20e67) S/cm) [5,9,10]. Several chemical reduction
approaches have been used to obtain RGO sheets [11,12], yielding
conductivity values in the range of (0.5e350) S/cm. GO sheets have
also been reduced by some unusual approaches, such as, reduction
by alcohol vapors at 1000
C in H2 atmosphere [13], by a copper cap
layer at 900
C in H2 atmosphere [14], by methane plasma at 575
C
[15] and by hydrogen plasma at RT [16,17], yielding RGO sheets with
conductivity in the range of (30e1590) S/cm. Metal nanoparticles
catalyzed reduction [18,19] and reduction by UV irradiation have
also been employed to obtain RGO sheets [20,21]. It has been re-
ported that the graphitic network of free standing hydrazine
reduced GO film can be fully restored at temperatures in the range
of 1500e2700
C [22]. Recently, it has also been shown that the
graphitic structure of substrate supported, highly reduced GO
sheets can be fully restored by heat treatment at a temperature of
1800
C [23]. It is seen from above that the conductivity of RGO
remains nearly two orders of magnitude lower than that of gra-
phene. Hence, there is considerable scope for developing newer
approaches to improve the conductivity of RGO monolayer sheets,

http://dx.doi.org/10.1016/j.carbon.2015.08.067
0008-6223/© 2015 Elsevier Ltd. All rights reserved.
844 G. Singh et al. / Carbon 95 (2015) 843e851
particularly on insulating substrates, so as to be amenable to the
development of various device structures.
The amphiphilic character of GO sheets makes them amenable
to form monolayer sheets at the airewater interface, which can be
transferred by LangmuireBlodgett (LB) technique to obtain GO
sheets of controlled morphology and surface density onto a variety
of substrates [7,24]. In the present work, we report a novel and
effective, single step reduction method for obtaining highly
reduced, large area, LB monolayer sheets of GO on Si and SiO2/Si
substrates, by heat treatment in the presence of graphite powder,
inside an evacuated and sealed enclosure. The morphological sta-
bility, chemical and electronic structure of RGO monolayer sheets
obtained by heat treatment at different temperatures have been
systematically investigated by X-ray and UV photoelectron spec-
troscopy (XPS, UPS), Raman spectroscopy, followed by their elec-
trical characterization in bottom-gated field effect geometry. These
studies have shown that the proposed reduction method, carried
out under optimized conditions, results in a substantial de-
oxygenation (O/C ratio ~5%) and effective restoration of the
graphitic network (sp2-C ~84%), to an extent, that has not been
reported earlier for RGO monolayers. The RGO monolayer sheets,
thus obtained, exhibit ambipolar field effect characteristics, dis-
playing unusually high electrical conductivity in the range of
(2e3)  103 S/cm and carrier mobility of (20e45) cm2/Vs. The
proposed single step reduction method thus provides a new and
simple route to obtain large area, highly reduced GO monolayer
sheets on solid substrates.
2. Experimental details
GO sheets were chemically exfoliated from graphite (Bay car-
bon, SP-1) by HummerseOffeman's method [25]. LB technique was
used to transfer GO monolayers onto Si and SiO2/Si substrates un-
der the optimized conditions, as described earlier [24]. The samples
prepared on SiO2/Si substrates were used for the electrical mea-
surements in field effect transistor (FET) geometry, while all other
characterizations were carried out on the samples prepared on Si
substrates. As-transferred GO monolayer samples were placed in
close proximity to graphite powder inside a quartz tube, which was
evacuated (~103 Pa) and sealed. A schematic diagram of the
reduction set-up is shown in the Supplementary Information as
Fig. S1. The sealed quartz tubes were heated in a muffle furnace at
different temperatures ranging from 600 to 1100
C for 6 h, to
reduce the GO monolayers. For the purpose of comparison, GO
monolayer samples were also subjected to a similar heat treatment
without graphite powder inside the sealed tube. Scanning electron
microscopy (SEM) and atomic force microscopy (AFM) were
respectively carried out by using a Raith 150-Two instrument (at
10 kV) and a Digital Instrument's Veeco-Nanoscope IV Multimode
scanning probe microscope in tapping mode. Micro-Raman spec-
troscopy was performed by using a Horiba Jobin Yvon HR800
confocal Raman microprobe equipped with a 5 mW Arþ laser
(514 nm). A PHI500 Versa Probe II instrument equipped with a
concentric hemispherical analyzer was used for XPS measure-
ments. The XPS measurements were performed in ultrahigh vac-
uum at a base pressure ~107 Pa, using a monochromatic 100 W Al
Ka (1486.6 eV) X-ray source. XPS peak fit 4.1 software was used for
data analysis. For XPS data analysis, the background was considered
to be of Shirley type and each component peak was considered to
be a mixture of Lorentzian and Gaussian (L/G ~30%). A Thermo-VG
Scientific photoelectron spectrometer (Multilab) equipped with a
concentric hemispherical analyzer was used for UPS measurements
with a He discharge lamp operated to emit He-I (21.2 eV) and HeeII
(40.8 eV). For UPS data analysis, Avantage V3.9 software was used
with Shirley type background fitting and by considering each
component peak as Gaussian. The overall energy resolution was
0.5 eV for XPS and 0.1 eV for UPS measurements. Work function
measurements were performed by recording He-I spectra with
applied sample bias of 3 V to accelerate the low energy secondary
electrons. Electrical measurements were carried out using a
Keithley 4200-SCS semiconductor characterization system. The
electrical conductivity of GO and RGO sheets was measured using a
two-probe arrangement and the field effect mobility was measured
in bottom-gated FET geometry. The device structures were fabri-
cated by transferring isolated GO monolayer sheets under low
surface pressure conditions on 110 nm thick SiO2 layer over Si
substrate, as mentioned above. For patterning of source and drain
electrodes, ~100 nm thick Au electrodes were thermally evaporated
on GO/RGO sheets through a Cu grid (G200F2, 200 mesh, spacing
12e25 mm) as a shadow mask. Aluminum back gate (~100 nm)
contact on Si was deposited by thermal evaporation. The channel
length and width were in the range of 12e25 mm and 10e30 mm,
respectively.
3. Results and discussion
LB sheets of GO transferred on Si and SiO2/Si substrates were
reduced by heat treatment at different temperatures in the range of
600e1100
C, in the presence of graphite powder, inside an evac-
uated and sealed quartz tube. The RGO samples thus obtained will
henceforth be denoted by sample codes, Gr-T, where T (in
C)
represents the heat treatment temperature. For comparison, GO
sheets were also reduced at 1000
C without graphite powder in-
side the quartz tube, and will be referred as GO-1000. A typical SEM
image of as-transferred GO sheets in Fig. 1(a) shows the presence of
uniformly distributed, closely packed and practically non-
overlapping sheets of size 10e50 mm on the substrate. Fig. 1(b)
shows a typical SEM image of Gr-1000, which shows no signifi-
cant change in the overall morphology and density of the sheets.
A detailed investigation of the morphology of GO sheets after
reduction at various temperatures has been carried out by AFM.
Fig. 2 shows the AFM images of the as-transferred GO sheets and
RGO sheets obtained by heat treatment at different temperatures,
in the presence of graphite powder. The thickness of the GO sheets
was found to be in the range of 1e1.3 nm, which agrees well with
the monolayer character of GO sheets [24,26]. The larger thickness
of GO sheets as compared to that of graphene is attributed to the
presence of oxygen functional groups on GO sheets. No significant
changes in the overall surface morphology of the sheets are seen
after heat treatment at temperatures up to 1000
C. However,
morphological damage of the sheets appears in the form of holes,
after heat treatment at 1100
C. A high resolution AFM image of the
damaged sheets is shown in Fig. S2 of Supplementary Information.
The thickness of the sheets remains practically unchanged for
reduction temperatures up to 700
C, but a progressive decrease of
thickness is observed with further increase in reduction tempera-
ture. The average sheet thickness decreases to 0.8e0.9 nm for Gr-
800 and Gr-900, and to 0.5e0.6 nm for Gr-1000 and Gr-1100, as
shown in Fig. S3 of Supplementary Information. The large decrease
in thickness of GO sheets, particularly after reduction at 1000
C, is
attributed to substantial removal of oxygen functional groups, thus
resulting in the formation of RGO sheets, with thickness close to
that reported for graphene [27].
The presence of various oxygen functional groups in GO sheets
and the extent of de-oxygenation in RGO sheets have been assessed
by C-1s core level measurements by XPS. Fig. 3(a) shows the C-1s
core level spectra of GO and RGO sheets. GO sheets exhibit a broad
C-1s spectrum ranging from 280 to 290 eV. The de-convoluted C-1s
spectrum shows the presence of sp2-C at 284.4 eV, sp3-C/damaged
alternant hydrocarbon structure at 285.4 eV, CeO at 286.4 eV, C]O
 G. Singh et al. / Carbon 95 (2015) 843e851 845

Fig. 1. SEM images of (a) as-transferred GO sheets and (b) RGO sheets obtained by heat treatment in the presence of graphite powder at 1000
C.

Fig. 2. AFM images of as-transferred GO sheets and RGO sheets obtained by heat treatment at different temperatures, as indicated by the sample codes. The corresponding height
profiles are shown as insets. For Gr-1100, the encircled regions in the image indicate morphological damage of the sheets. (A colour version of this figure can be viewed online.)
846 G. Singh et al. / Carbon 95 (2015) 843e851

Fig. 3. (a) C-1s core level spectra of as-transferred GO sheets and RGO sheets obtained by heat treatment at different temperatures, as indicated by the sample codes. The atomic
percentages of various oxygen functional groups (CeO, C]O and COOH), (sp2-C content and O/C ratio) and FWHM of C-1s peak are plotted against the reduction temperature in (b),
(c), and (d), respectively, for RGO sheets along with the data for GO sheets (as indicated). (A colour version of this figure can be viewed online.)

at 287.2 eV, COOH at 288.6 eV and pep* shake up satellite of the
284.4 eV peak at 289.6 eV [28,29]. The peak positions along with
the relative integrated intensities of various de-convoluted com-
ponents are shown in Table S1 of Supplementary Information. For
GO sheets, the O/C ratio estimated from C-1s core level is found to
be 50.4%. The contributions from sp3-C/damaged alternant hydro-
carbon structure and other oxygen functionalities to the C-1s peak
are referred to as ‘non-graphitic’ carbon. The integrated intensity
ratio of non-graphitic carbon to that of graphitic carbon (sp2-C) is
denoted as ‘X’ in Table S1 of Supplementary Information and is 1.46
for GO sheets.
The C-1s core level spectra have also been recorded for RGO
sheets and Fig. 3(a) shows the de-convoluted C-1s spectra for
typical cases of Gr-600, Gr-800, Gr-1000 and Gr-1100. All these
spectra show the dominance of sp2-C along with contributions from
sp3-C and the oxygen functional groups. With increase in reduction
temperature, the intensities of the peaks corresponding to sp3-C/
damaged alternant hydrocarbon structure, CeO, C]O and COOH
are found to decrease monotonously up to 1000
C. This behavior is
shown in Fig. 3(b) for all the oxygen functional groups. Table S1 of
Supplementary Information shows that the decrease in oxygen
functional groups and sp3-C results in a decrease of X, which ex-
hibits the smallest value of 0.19 for Gr-1000. A corresponding
decrease of O/C ratio and increase in sp2-C with increase in
reduction temperature is also shown in Fig. 3(c). It is noticed from
Fig. 3(b) that after reduction at 600e700
C, the C]O and COOH
contents decrease to 2e3%, while the CeO content remains ~10%.
On further increase of reduction temperature, the CeO content is
also found to decrease substantially, resulting in the lowest value of
O/C ratio (5%) and the highest value of sp2-C (84%), as shown in
Fig. 3(c) for Gr-1000. Fig. 3(d) shows the plot of full width at half
maximum (FWHM) of C-1s peak (~284.5 eV) versus the reduction
temperature. GO sheets show a broad C-1s peak with FWHM of
1.6 eV. With increase in reduction temperature, the FWHM of C-1s
peak decreases and reaches its minimum value of 1.0 eV for Gr-
1000. The decrease in FWHM of C-1s peak to a value of ~1 eV is
attributed to the substantial recovery of sp2-C network as well as
the removal of oxygen functional groups and sp3-C/damaged
alternant hydrocarbon structure. It may be noted that the FWHM of
crystalline graphite (without any heat treatment) was found to be
 G. Singh et al. / Carbon 95 (2015) 843e851 847

~0.8 eV, as indicated by a band in Fig. 3(d). Interestingly, it is
observed from Fig. 3(aed) and Table S1 of Supplementary
Information that reduction at 1100
C results in marginally larger
oxygen functional groups and sp3-C, and consequently, slightly
smaller sp2-C content. It may be mentioned that though marginal,
but this behavior is consistently and reproducibly observed for Gr-
1100, in which, morphological damage in the form of holes was also
found to appear. It is thus inferred that the optimum reduction of
GO sheets in a sealed enclosure in the presence of graphite powder
takes place at ~1000
C. Fig. 3(a) also includes the C-1s core level
spectrum of GO-1000, which was obtained by heat treatment at
1000
C in the absence of graphite powder within the sealed
enclosure. It is clearly seen that this sample exhibits a much
broader C-1s peak (FWHM ~1.34), arising from larger sp3-C and
oxygen functional groups and smaller sp2-C content (sp2-C ~68%,
sp3-C ~17.8%, O/C ratio ~15.4% and X ~0.49, as given in Table S1 of
Supplementary Information) compared to Gr-1000. The shoulder
(non-fitted) seen on the lower binding energy (<284 eV) of C-1s
peak for GO-1000 samples, may be attributed to carbon atoms near
saturated vacancies [30,31]. These observations confirm that the
presence of graphite powder in the sealed enclosure significantly
enhances the effectiveness of the reduction process of GO sheets.
Raman spectroscopy has been performed on GO and RGO sheets
and the results are shown in Fig. 4(a). Table S2 of Supplementary
information provides all the Raman peak positions and important
peak intensity ratios for GO and RGO sheets. The Raman spectrum
of GO shows two prominent peaks associated with D and G modes
at (1339 ± 1) cm1 and (1602 ± 2) cm1, respectively, and two weak
bands associated with G0 and S3 modes at (2687 ± 6) cm1 and
(2926 ± 3) cm1, respectively. The D-mode is a disorder induced
Raman feature and is not observed in highly crystalline graphitic
forms but has been reported to appear at ~1350 cm1 for graphene/
graphite with defects [32e34]. The G-mode corresponds to the
first-order Raman scattering due to E2g vibrations and is known to
appear in the range of 1584e1588 cm1 for graphene [3,35,36]. The
G0 -mode is a second order double resonant Raman scattering mode
from zone boundary phonons and appears as a single and sharp
peak for single sheet of graphene [32e34]. The S3 peak is a defect
induced second order D þ G combination mode [34].
Fig. 4(a) shows that after reduction of GO sheets in a sealed
enclosure in the presence of graphite powder, the G-peak red-shifts
monotonously with increase in reduction temperature up to
1000
C. The lowest value of G-peak position is observed at
1585 cm1 for Gr-1000, which is close to the corresponding peak

Fig. 4. (a) Raman spectra of as-transferred GO sheets and RGO sheets obtained by heat treatment at different temperatures, as indicated by the sample codes. The de-convoluted G-
mode peaks for typical cases and Lorentzian fitting of G0 -peak for Gr-1000 are shown in (b) and (c), respectively. (A colour version of this figure can be viewed online.)
848 G. Singh et al. / Carbon 95 (2015) 843e851

position usually reported for pristine graphene [35,36], and is seen oxygen in the ampules (at ~105 mbar), although the contribution
to result from the substantial reduction of GO in this case. The I(D)/ to the formation of CO during the thermal decomposition of GO
I(G) ratio, which is used to characterize the disordered carbon monolayer sheets [42e44] cannot be completely ruled out. It has
content, bonding defects and sp3/sp2 fraction in carbon based ma- been reported that heat treatment of GO in CO ambient results in
terials [34,37] is found to be 1.6 for GO sheets and remains nearly the removal of oxygen with simultaneous healing of the defects in
unchanged for reduction at temperatures up to 600
C. However, graphitic network [45]. In the present case, the reaction of CO with
reduction above 600
C results in a significant decrease in I(D)/I(G) GO produces CO2, which may diffuse towards graphite and produce
ratio, which exhibits the lowest value of 1.2 for Gr-1000. It is CO by Boudouard reaction [46] at 1000
C, thus establishing a self-
observed that further increase in reduction temperature to 1100
C, sustained cyclic process, which may be responsible for the pro-
results in a relatively smaller red-shift of G-peak to 1587 cm1 and a longed and effective reduction of GO and restoration of the
significantly larger I(D)/I(G) ratio of 2.0. It is also seen from Fig. 4(a) graphitic network. It may also be mentioned that during the cooling
that the GO sheets heat treated at 1000
C in the absence of of the furnace, the local equilibrium of Boudouard reaction is likely
graphite powder (GO-1000) exhibit a much smaller red-shift of G- to shift towards the formation of CO2 and C, the latter being active
peak to ~1595 cm1 and significantly large I(D)/I(G) ratio of 1.9. carbon may further function as a reducing cum healing agent. The
These features corroborate well with the XPS results and support inferior quality of Gr-1100 sample, as reflected by their XPS and
the assertion that the optimum reduction of GO sheets takes place Raman features described above, is attributed to significant modi-
at 1000
C in a sealed enclosure, only in the presence of graphite fication in the chemical structure and associated morphological
powder. damage appearing in the form of holes. It has been recently shown
It is noticed from Fig. 4(a) that the G-peak for RGO exhibits a that GO sheets tend to disintegrate at higher temperatures
shoulder in all the cases, which becomes most prominent for Gr- (~1500
C), owing to the removal of carbon atoms as CO and CO2,
1100. In order to understand this feature, the G-peaks have been particularly from the highly oxidized regions [23]. It has also been
de-convoluted for GO, Gr-1000 and Gr-1100 and shown in Fig. 4(b). reported [43] that there is a strong desorption of CO from GO sheets
The de-convoluted G-peak of GO reveals the presence of G-mode at at ~1000
C. It thus appears that the enhanced evolution of CO and
~1598 cm1 along with two additional components at ~1555 cm1 CO2 from GO sheets results in a substantial loss of carbon at higher
and ~1618 cm1, which are attributed to the defect activated, D00 - temperatures, which dominates over the restoration of graphitic
mode [38,39] and D0 -modes respectively [32,34]. The reduction of network by the replenishment of C from graphite powder, as dis-
GO at 1000
C (Gr-1000) results in substantial decrease in the in- cussed above.
tensities of D0 and D00 modes, concurrent with the large red shift of The changes in the valence band (VB) electronic structure and
G-peak to 1585 cm1. These features are indicative of decrease in DOS at the Fermi level of highly reduced GO sheets (Gr-1000) have
defects and disorder, consistent with the increase in sp2-C content
and decrease of O/C ratio, as inferred from XPS studies. Interest-
ingly, Gr-1100 shows a substantially stronger D0 mode, indicating a
larger extent of defects, consistent with XPS and AFM observations.
Fig. 4(a) also shows the presence of broad G0 and S3 peaks for GO
sheets. The intensity ratios I(G0 )/I(G) and I(G0 )/I(S3) were found to
be 0.08 and 0.66 for GO sheets. The ratios increase monotonously
with increase in reduction temperature, and exhibit their respec-
tive highest values of 0.35 and 2.95 for the reduction temperature
of 1000
C. The increase in I(G0 )/I(G) and I(G0 )/I(S3) ratios is indic-
ative of the recovery of the sp2-C network in graphitic materials
[40,41]. Further increase in the reduction temperature to 1100
C
results in a marginal decrease in I(G0 )/I(G) ratio to 0.26 and I(G0 )/
I(S3) ratio to 1.37. Fig. 4(a) also shows that with increase in reduc-
tion temperature, the FWHM of G0 -peak (292 cm1 for GO) de-
creases to its lowest value of ~80 cm1 for Gr-1000. It is also found
that the G0 -peak for Gr-1000 can be fitted with single Lorentzian
peak, as shown in Fig. 4(c). It may be noted that a single Lorentzian
fitting of, G0 -peak (with FWHM of 25e30 cm1) is usually consid-
ered to be an evidence for the monolayer character of graphene
[35]. Such a behavior in the present case is another indication of the
effective reduction of GO sheets. The increase in reduction tem-
perature to 1100
C, however results in a marginally higher FWHM
(103 cm1) of G0 -peak. It may also be mentioned that heat treat-
ment at 1000
C in the absence of graphite powder (GO-1000) re-
sults in much smaller values of I(G0 )/I(G) and I(G0 )/I(S3) ratios (0.11
and 1.11, respectively) and substantially larger FWHM of G0 -peak
(200 cm1).
The above results have shown that graphite mediated reduction
of GO sheets inside an evacuated and sealed enclosure at 1000
C,
results in RGO sheets with an exceptionally low O/C ratio of 5% and
high sp2-C content of 84%. It has also been conclusively evidenced
that the reduction process is highly effective and results in a sub-
Fig. 5. De-convoluted HeeII valence band spectra of as-transferred GO sheets and RGO
stantial restoration of graphitic network, only if carried out in the sheets obtained by heat treatment in the presence of graphite powder at 1000
C (Gr-
presence of graphite powder. The efficient reduction is primarily 1000). The inset shows the secondary electron threshold region of He-I UPS spectra. (A
attributed to CO formed by the reaction of graphite with residual colour version of this figure can be viewed online.)
 G. Singh et al. / Carbon 95 (2015) 843e851 849

Table 1
De-convoluted peak positions of HeeII UPS valence band spectra of as-transferred
GO sheets and RGO sheets obtained by heat treatment in the presence of graphite
powder at 1000
C (Gr-1000). The values are in eV.
Sample code C 2p-p C 2p-(pes) overlap C 2p-s C 2se2p mix
GO 3.8 e 6.4 9.6
Gr-1000 3.6 6.3 8.8 10.7
been studied by UPS measurements. Fig. 5 shows the HeeII UPS VB
spectra of GO and Gr-1000 sheets after the subtraction of Shirley
type background and de-convolution into Gaussian component
peaks. The zero binding energy position refers to the Fermi level
position. The HeeII UPS VB spectrum of crystalline graphite (not
shown) is used as a reference. The VB spectrum of crystalline
graphite exhibits five component peaks corresponding to C 2p-p
(~3.5 eV), C 2p-(pes) overlap (~5.5 eV), C 2p-s (6.0e8.0 eV), C
2se2p mixed state (8.8e10.5 eV) and C 2s state (~13.5 eV), as re-
ported earlier [8,47]. De-convoluted peak positions of HeeII UPS VB
spectra of GO and Gr-1000 sheets are listed in Table 1. The VB
spectrum of GO exhibits only four component peak associated with
C 2p-p (3.8 eV), C 2p-s (6.4 eV), C 2se2p mixed state (9.6 eV) and C
2s state (13.6 eV). The absence of C2p-(pes) overlap (5.5 eV) peak is
consistent with the weak C 2p-p peak, which is associated with the
small sp2-C content of GO, as seen from XPS studies. In Gr-1000, the
C 2p-p peak at ~3.8 eV shows a large increase in intensity and is
accompanied by the appearance of C 2p-(pes) overlap peak at
C 2s 6.3 eV. The C 2p-s, C 2se2p mixed state and C 2s state are also found
13.6 to shift to higher BE values in Gr-1000. In the near Fermi level re-
13.9 gion, the valence band edge (VBE) has been determined by locating
the onset of rapid rise of DOS and is shown by arrows in both the
cases. The GO sheets show negligible DOS near the Fermi level, with
the VBE located at ~1.5 eV below the Fermi level. In contrast, for Gr-
1000, the DOS increases steeply near the Fermi level, indicating
that the VBE is close to it. This behavior is attributed to the increase
in intensity of C 2p-p states and is indicative of the p-type nature of
Gr-1000. The increase in C 2p-p peak intensity, appearance of C 2p-
(pes) overlap peak and the blue-shift of C 2p-s state are associated
with the increase in graphitic carbon content of Gr-1000. The inset
of Fig. 5 also shows the low kinetic energy regime of He-I UPS
spectra for GO and Gr-1000. The work function was determined
from secondary electron threshold region and is found to be ~4.4 eV
for GO and ~3.6 eV for Gr-1000. The decrease of work function after
reduction is attributed to the removal of oxygen functional groups
and increase in graphitic carbon content within RGO sheets [8,48].
The electrical characteristics of GO and RGO sheets have been

Fig. 6. (a) Schematic of a bottom-gated FET and (b) optical image of a typical RGO sheet (Gr-1000) in two probe contact geometry. IeV plots of the as-transferred GO sheets and RGO
sheets obtained by heat treatment at different temperatures (as indicated by the sample codes) are shown in (c) and the transfer characteristic of RGO sheets obtained by heat
treatment in presence of graphite powder at 1000
C is shown in (d), along with the output characteristics as inset. The conductivity and field effect mobility of RGO sheets are
plotted against the heat treatment temperature in (e) and (f), respectively, along with the data for GO (as indicated). (A colour version of this figure can be viewed online.)
850 G. Singh et al. / Carbon 95 (2015) 843e851
studied in bottom gated field effect transistor (FET) geometry. The
schematic of the FET and the optical image of an RGO monolayer
sheet in two probe contact geometry are shown in Fig. 6(a) and (b),
respectively. Fig. 6(c) shows the IDSeVDS curves for GO and RGO
sheets obtained by heat treatment in the presence of graphite
powder at different temperatures and the corresponding conduc-
tivity values are plotted in Fig. 6(e). It is seen that GO sheets exhibit
insulating behavior with conductivity in the range of
(106e105) S/cm. The conductivity of RGO sheets increases with
increasing reduction temperature and reaches its highest value in
the range of (2e3)  103 S/cm for Gr-1000, which is substantially
higher than most of the previously reported values for RGO sheets
[4e17,44,49e53]. The corresponding sheet resistance of RGO sheets
is in the range of (7e10) kU/sq. The transfer and output charac-
teristics were measured for all the RGO samples and the latter are
shown for a typical case of Gr-1000 sheet in the inset of Fig. 6(d). A
typical transfer characteristic (at VDS ¼ 1 V) for a FET fabricated
with a Gr-1000 sheet as channel is shown in Fig. 6(e). The device
exhibits ambipolar behavior with the charge neutrality point at ~7
V, which is indicative of the p-type nature of the RGO sheets,
consistent with UPS results, described above. Fig. 6(f) shows the
plot of field-effect mobility versus the reduction temperature for all
the RGO samples. The field effect mobility was calculated by using
the expression, m ¼ (L/W CGVDS) (ΔIDS/ΔVG), where L and W are the
channel length and width, respectively, CG is the gate capacitance
and (ΔIDS/ΔVG) has been extracted from the slope in the linear re-
gion of the IDSeVG curve. The field effect mobility of holes has been
estimated for several devices on each RGO sample and the average
mobility values along with the standard deviation are shown in Fig.
6(f). The field effect mobility was found to be <1 cm2. Vs for RGO
sheets obtained by reduction at 700
C and shows a significant
enhancement after reduction at higher temperatures. The RGO
sheets obtained by heat treatment at 1000
C exhibit substantially
large field effect mobility values in the range of (20e45) cm2 V1
s1. The values of field effect mobility observed in the present work
are much larger than those reported for RGO monolayer sheets
obtained by heat treatment at temperatures ~1000
C directly or
after hydrazine treatment [40,53,54]. The significant enhancement
in conductivity and mobility of RGO sheets obtained by heat
treatment in a sealed enclosure at 1000
C, in the presence of
graphite powder is attributed to the effective de-oxygenation of GO
sheets and substantial reduction in defects, under these conditions,
as described above.
4. Conclusions
Large area GO sheets transferred on Si and SiO2/Si substrates by
LB technique were reduced by heat treatment inside an evacuated
and sealed enclosure in the presence of graphite powder. Reduction
at 1000
C by the above method, results in a large decrease in sheet
thickness to ~0.5 nm (close to that of the pristine graphene),
without adversely affecting the morphological stability of the
sheets. The large sp2-C content of 84%, low O/C ratio of 5%, low non-
graphitic carbon to graphitic carbon ratio of 0.19 and narrow C-1s
peak indicate unusually high extent of reduction of GO sheets, not
reported earlier. These RGO sheets exhibit Raman G-peak at
~1585 cm1, a single and sharp G0 -peak (FWHM ~80 cm1), low
I(D)/I(G) ratio and high I(G0 )/I(G) and I(G0 )/I(S3) ratios, indicating a
drastic de-oxygenation and restoration of graphitic network, dur-
ing the reduction process. The reduction process carried out at
900
C or lower temperatures, results in a substantially lesser
extent of reduction. Reduction carried out at 1100
C causes
noticeable morphological damage of RGO sheets and a lesser extent
of reduction. If the reduction process is carried out without graphite
powder inside the sealed enclosure, only a marginal reduction of
GO sheets is found to take place. The effective graphite mediated
reduction of GO sheets at 1000
C inside a sealed enclosure is
attributed primarily to the formation of CO which after reaction
with GO produces CO2, which in turn, undergoes Boudouard re-
action with graphite to establish a self-sustained cyclic production
of CO, which appears to be responsible for the exceptional reduc-
tion of GO and restoration of graphitic network.
Valence band electronic structure studies have shown that a
substantial increase of DOS near the Fermi level and a decrease in
work function take place for the GO sheets reduced at 1000
C. The
RGO sheets display a relatively high conductivity in the range of
(2e3)  103 S/cm, not reported earlier for RGO sheets. The bottom
gated FET employing these RGO sheets exhibits ambipolar behavior
with charge neutrality point at a positive gate voltage, indicating p-
type nature, consistent with the UPS studies. These devices exhibit
field effect mobility in the range of (20e45) cm2/Vs, which are
substantially higher than those reported for RGO sheets obtained
by chemical reduction followed by heat treatment. This work
demonstrates a simple, low cost and single-step method for
obtaining large area, highly reduced GO sheets on solid substrates,
making them an attractive alternative to graphene for large scale
applications.
Acknowledgements
The authors would like to thank FIST (Physics)-IRCC Central SPM
facility, IIT Bombay for AFM measurements, Central Surface
Analytical Facility, IIT Bombay for UPS measurements, Centre for
Research in Nanotechnology and Science (CRNTS), IIT Bombay for
SEM and Raman spectroscopy measurements and Centre for
Excellence in Nanoelectronics (CEN), IIT Bombay for XPS and
electrical measurements.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.carbon.2015.08.067.
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