Carbon 184 (2021) 437e444

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

Research Paper ISSN 0008-6223 I.F: 11.3

Temperature dependent Raman modes of reduced graphene oxide:
Effect of anharmonicity, crystallite size and defects
Meenu Sharma a, Sonam Rani a, Devesh K. Pathak b, Ravi Bhatia a, Rajesh Kumar b, c, **,
I. Sameera a, *
a
Department of Physics, Guru Jambheshwar University of Science & Technology, Hisar, 125001, India
b
Materials and Device Laboratory, Department of Physics, Indian Institute of Technology Indore, Simrol, Indore, 453552, India
c
Centre for Advanced Electronics, Indian Institute of Technology Indore, Simrol, Indore, 453552, India

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

Article history: A consolidated effect of anharmonicity, crystallite size and defects has been studied using temperature
Received 19 April 2021 dependent Raman spectroscopy of reduced graphene oxide (rGO). The micro-Raman spectra obtained
Received in revised form over a wide temperature range of 173e723 K (below and above room temperature) indicate linear shifts
24 June 2021
in the peak position of G- and D- modes, with negative temperature coefficients of
0.009 and
Accepted 7 August 2021
Available online 18 August 2021

0.010 cm
1 K
1, respectively. The average crystallite size and defect density were calculated and their
correlation with the temperature coefficient of G-peak position and line width were discussed. Further,
contributions from true-anharmonic and quasi-harmonic parts in shifting the G- and D- peak positions
Keywords:
Reduced graphene oxide
were estimated using theoretical models, which indicate the dominance of true-anharmonic part. Role of
Raman spectroscopy electron-phonon, anharmonicity and defect contributions to the temperature dependent variation of line
Phonon anharmonicity width of G-peak have been discussed.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction potential applications of rGO along with its composites include

flexible photo-detectors, batteries, supercapacitors, solar cells, light
Reduced graphene oxide (rGO), also known as chemically emitting diodes, thermal imaging and sensors [1,2,7e11].
derived graphene, is a competitive candidate to graphene, because Traditionally, Raman spectroscopy has been employed as non-
of its good electrical and thermal conductivities and ease of syn- destructive probe to investigate vibrational properties and as a
thesis [1e3]. Enormous amount of research efforts, at par with handy tool to distinguish among the different carbon allotropes. For
graphene, has been dedicated in the past few decades to tune the graphitic carbon materials, specific Raman bands and their in-
optical, thermal and electrical properties of rGO [1e3]. These tensity ratios (IG/ID and I2D/IG) are helpful to quantify the purity,
properties are largely dependent on the synthesis process, as it defects, doping, strain and atomic arrangements [12,13]. Further,
controls the extent of reduction, number of layers, doping level etc Raman spectroscopy is a convenient technique in comparison to
[3e5]. The synthesis methods of rGO include chemical, thermal, electron and atomic force microscopy to identify the number of
electro-chemical, microwave- and photo- assisted routes [3e7]. layers of graphene and estimating the graphitic crystallite size
Among them, chemical reduction (modified Hummers’ method) [12,14]. In case of rGO, Raman spectroscopy has been evolved as a
has attracted considerable attention due to the possibility of mass specialized probe to monitor the extent of oxidation/reduction,
production of rGO from inexpensive graphite powder, thus making defect density, sp3 content, doping etc [15,16]. Raman modes’
it an alternative material to graphene in device applications. The response to temperature provides insights on the anharmonic
phonon-phonon (ph-ph) interactions and electron-phonon (e-ph)
coupling effects [17,18]. For graphitic carbon materials, studies have
* Corresponding author. Department of Physics, Guru Jambheshwar University of shown that temperature dependent Raman spectra is helpful in
Science & Technology, Hisar, 125001, India. probing the thermal expansion, charge doping, thermal conduc-
** Corresponding author. Materials and Device Laboratory, Department of Physics, tivity and specific heat [19e21].
Indian Institute of Technology Indore, Simrol, Indore, 453552, India. Many reports have presented detailed studies on shift in peak
E-mail addresses: [email protected] (R. Kumar), [email protected]
position and peak width of G-mode with the temperature, pressure,
(I. Sameera).

https://doi.org/10.1016/j.carbon.2021.08.014
0008-6223/© 2021 Elsevier Ltd. All rights reserved.
M. Sharma, S. Rani, D.K. Pathak et al. Carbon 184 (2021) 437e444

gate biasing and laser wavelength for both exfoliated and substrate 3. Results and discussion
grown graphene [12,22e25]. However, for the case of rGO most of
the studies are limited to room temperature, and only a few studies Chemically derived rGO is poly-crystalline in nature, which
are available on the temperature dependent evolution of charac- consists of crystallites that define the smallest coherent volume of
teristic Raman modes. Allen et al. [26] observed nearly linear the material, as revealed using X-ray diffraction (XRD) and Raman
variation in the G-peak position with a negative temperature co- spectroscopy, powerful non-destructive techniques to determine
efficient (TC) of
0.0267 cm
1 K
1 (22e400 K), and have shown the average crystallite size of the material. From XRD, average
that D-band does not show any obvious trend with temperature. crystallite size along the plane (La) and perpendicular to the plane
Bhaskaram et al. [27] reported the change in LD (distance between (Lc) of graphitic lattice, can be calculated from (100) and (002)
defects) values, as a function of temperature. Late et al. [14] has peaks [28]. The obtained XRD pattern for the rGO obtained at room
shown peak position of G-mode exhibits negative linear TC temperature is shown in Fig. 1(a). The most intense peak at ~20
(
0.029 cm
1 K
1, 77e573 K), while the peak widths of G- and 2D- corresponds to C (002) of rGO whereas, the other small peak at
modes exhibit positive TC. These studies have also established the ~11.8 denotes the (002) planes of graphene oxide (GO) [29], indi-
variation of TC of peak position (G-peak) with the number of layers cating the partial reduction of GO to rGO. Reduction of GO to rGO
of rGO, and concluded that the TC decreases with an increase in decreases the interlayer spacing (d), and the calculated values of
number of layers. However, these studies have not discussed the d002 from Bragg's law are 4.4 Å and 7 Å for rGO and GO, respectively.
effect of crystallite size and defect density on the observed values of The larger value of d002 for rGO than that of graphite (~3.4 Å) is due
TC. Anharmonic terms (consists of 3-ph and 4-ph scattering) and to the presence of residual functional groups such as carbonyl,
thermal expansion mainly contribute to the shift in peak position of hydroxyl, epoxy and carboxylic groups, attached to graphitic carbon
Raman modes with temperature, for both graphene and graphite lattice even after reduction [5,11]. The crystallite thickness (Lc)
[17,22,25]. Thus, the role of ph-ph contribution, the relation of calculated using Scherrer equation is ~20 Å, which corresponds to
average crystallite size and defect density, on the temperature 4e5 layers (Lc/d002) of rGO [28]. Further, the SEM micrograph dis-
dependence of various Raman modes of rGO needs to be investi- plays (Fig. 1 (b)) the morphological information of the rGO, with the
gated in detail. Understanding the phonon anharmonicities of rGO exfoliated graphene layers spreading in few hundreds of nm.
can be useful in evaluating thermal management and carrier The average in-plane crystallite size (La) can be calculated from
transport, and comparison with that of graphene and graphite will Raman spectra, using Eq. (1), given by Tuinstra and Koenig, and
be important, as rGO being a potential candidate to the former in others (for 514 nm) [30],
device applications.
In this study, the temperature dependent shifts for the charac- ID 4:4
¼ ; (1)
teristic peaks of rGO have been studied in the range of 173e723 K IG La ðnmÞ
(below and above room temperature range). The crystallite size and
morphological information have been extracted using X-ray where, I denotes the intensity of the corresponding band. Cançado
diffraction (XRD), Raman spectroscopy and electron microscopy. et al. [31] has provided a general equation for determining the La
The experimentally observed line-shifts of G- and D- peaks of rGO value, for any laser-wavelength, and has the form shown in Eq. (2).
have been explained using established theoretical models involving
phonon anharmonicities. Raman modes’ peak shifts and line 560 1
La ðnmÞ ¼ ; (2)
widths of rGO were discussed in comparison with that of graphite El4 IID
G
and graphene, to get the holistic picture of different interactions
taking place at microscopic level. where, El is excitation energy of laser (in eV), ID and IG are in-
tensities of D- and G- peaks, respectively. In the present study, ID/IG
2. Experimental details ratio, which corresponds to the peak intensity ratio of D- and G-
peaks has been utilized, following Cançado et al. [12]. The tem-
Powder form of rGO was purchased from Sigma-Aldrich (cat. no. perature dependent variation of ID/IG is shown in Fig. 1(c), and the
777684) and the as-obtained powder was dispersed in ethanol with calculated values of La lie in the range of 16e21 nm. According to
the help of ultrasonicator. Thereafter, the solution was dried at Ferrari et al., La follows linear variation with inverse of ID/IG for
70  C for 15 min and the obtained powder was used for the further larger crystallites (>2 nm), while for smaller crystallites (La < 2 nm),
study. The crystallinity of the powdered sample was studied with the linear relation breaks down, and ID/IG varies quadratically with
Rigaku Miniflex-II X-ray diffractometer using Cu Ka (1.54 Å) radia- crystallite size [32]. Considering rGO as a material with crystallites
tion with 2q ranging from 10 to 80 and with a scanning rate of 4 and having point defects (with LD as average distance), as depicted
per minute. NOVA Nanosem 450 field emission scanning electron by Cançado et al. [33] for graphene based materials, distance be-
microscopy (FESEM) was used to investigate the morphological tween the defects (LD) and defect density (nD) were calculated using
information of the sample. The temperature dependent Raman following Eq. (3) and Eq. (4) [12],
spectroscopy was carried out using a HORIBA Jobin Yvon micro-
Raman spectrometer, equipped with Linkam temperature

1
ID
controller set up and 633 nm laser excitation. All the spectra were L2D ðnmÞ2 ¼ ð1:8±0:5Þ  10
9 l4L ; (3)
IG
collected in ambient air on a heating and freezing stage in the
temperature range from 173 to 723 K. The heat rate was kept !

constant with steps of 10  C per minute with 120 s holding time at ð1:8±0:5Þ  1022 ID
each fixed temperature value to settle the respective temperature
nD ðcmÞ
2 ¼ ; (4)
l4L IG
throughout the sample. Raman spectra at each temperature value
were obtained after taking the average of four consecutive recorded The calculated values of LD lie between 11 and 13 nm for the
spectra. Each spectrum was recorded for 30 s of integration time. whole temperature range. Cançado et al. [12] reported that, for a
The spot size of the laser beam was ~2 mm, and the measurements specific LD, ID/IG depends on the excitation laser wavelength (lL ) (in
were taken from same point on the sample to study the tempera- the visible range), and Eq. (3) is valid for quantifying defects in
ture effects only. graphene-like samples for LD > 10 nm. The calculated values of nD
438
M. Sharma, S. Rani, D.K. Pathak et al. Carbon 184 (2021) 437e444

Fig. 1. (a) X-Ray diffraction pattern at room temperature, (b) FESEM micrograph of rGO, (c) Variation of intensity ratio (ID/IG), defect density (nD) and inverse of crystallite size (La) as
a function of temperature (red lines are guide to eyes), (d) Raman spectra at 323 K showing peak fits for D- and G- bands (inset). (A colour version of this figure can be viewed
online.)

for rGO, lie in the range 2.0e2.6  1011 cm
2 for the whole tem-
perature range (Fig. 1(c)).
The Raman spectra of rGO consist of two main bands at
~1320 cm
1 (D-band) and ~1580 cm
1 (G-band), as shown in
Fig. 1(d). These bands were further fitted using combination of
Gaussian and Lorentzian peaks (inset, Fig. 1(d)) [15,34. The various
deconvoluted peaks are centred at ~1320 cm
1 (D), ~1500 cm
1
(D”), ~1570 cm
1 (G) and ~1600 cm
1 (D0 ). The D” peak is related to
amorphous carbon present in the sample [15]. The disorder-
induced D-peak is a double resonant Raman mode of graphitic
carbon atoms, which involves the inelastic inter-valley scattering
by iTO phonon (near K-point) with a photo-excited electron (to K
′-point), followed by elastic back-scattering of the electron (from K′
to K) by a defect [13]. D-peak arises due to the presence of defects
such as vacancies, grain boundaries, and edges present in the car-
bon lattice. The position of D-peak is strongly dispersive with the
variation of excitation energy, with a slope of ~50e100 cm
1eV
1
[35,36]. The dispersive behaviour of D-peak position with excita-
tion energy can be seen from Fig. S1 of the supplementary infor-
mation. The position of D-peak with 532 nm excitation is observed
around ~1350 cm
1, whereas in the present study, for 633 nm
excitation, the position shifts to ~1320 cm
1, which is consistent Fig. 2. Temperature dependent Raman spectra of rGO with normalized intensities
with the reported dispersive behaviour. The origin of D0 -peak is plotted via y-axis off-sets as a function of Raman shift and phonon energy. (A colour
similar to that of D-peak, however D0 -peak arises from “intra-val- version of this figure can be viewed online.)
ley” scattering around K point (rather than “inter-valley” scat-
tering) [12]. The G-peak is a signature of graphitic carbon phase,
which arises from the in-plane tangential stretching of carbon peak, but here the backscattering of electron is by another iTO
atoms (E2g mode), and is due to the phonons at the centre of the phonon [32,35]. The profile of 2D mode is strongly dependent on
Brillouin zone (G-point) [30,32,35]. The proper deconvoluted fits the number of layers in case of graphene [13]. But for the case of
for D- and G- bands for various temperatures, and their corre- rGO, the relative stacking of graphene layers is random, and the
sponding parameters are shown in Fig. S2, Tables S1 and S2 in the peak widths of all the modes increase as function of disorder, which
supplementary information. There is a broad bump like feature leads to overlapping of 2D mode with other modes (D þ D0 and 2D0 ),
indicating 2D-band (~2700 cm
1), arising from a two-phonon resulting in a broad bump-like feature in ~2500e3200 cm
1 range
scattering process, which also involve the mechanism same as D- (Fig. 1(d)) [15].

439
M. Sharma, S. Rani, D.K. Pathak et al. Carbon 184 (2021) 437e444

Fig. 3. Temperature dependent variation of (a) peak position and (b) line width for D (black squares), D” (blue circles), G (magenta triangles), and D’ (green stars) peaks. Red lines
indicate the linear fits for peak position and line width with temperature. (A colour version of this figure can be viewed online.)

Table 1 for all the modes (Fig. 3 (a)). The value of J for D- and D0 - peaks is
Parameters obtained by linear fits to shift in peak position and line width for various small and positive, while JG is nearly zero (Fig. 3 (b)). Late et al. [14]
modes.
has reported positive value of JG for chemically reduced rGO,
Peak c (cm
1K
1) J (cm
1K
1) negative value of JG for thermally exfoliated GO, and nearly zero
D
0.010 0.005 for the mechanically exfoliated graphite. It is to be mentioned that
D”
0.050
0.013 most of the studies have reported on the c for G-peak only, and
G
0.009 ~0 have not reported the value of JG.
D0
0.008 0.016
It is interesting to compare cG and line widths of rGO, to that of
other carbon based materials. All the reported results show an
overall negative value of cG for graphene and rGO, which indicates
The normalized intensity vs. Raman shift (and energy) at the softening of phonon modes with the increasing temperature
different temperatures from 173 to 723 K is shown in Fig. 2, dis- [14,22,25,26]. Table 2 reflects the variation in the value of cG and
playing the red-shift of D- and G- bands with increasing tempera- line width as an effect of substrate, doping, defects, and the fabri-
ture. The change in peak position (displayed in Fig. 3) reflects the cation process of graphene based materials. Though the previous
overall softening of phonon modes for the characteristic modes of studies [14,26,27] reported cG for rGO, the comparison is not trivial,
rGO. The observed values of TC for D- and G- peaks are as the defects, doping, and reduction level vary depending on the

0.010 cm
1 K
1 and
0.009 cm
1 K
1, respectively. The down- synthesis process. The attempts to quantify the disorder, crystallite
ward shift in G-peak position with temperature is very well re- size, defect density and relating with cG for rGO were also lacking in
ported for graphitic carbon materials such as carbon nanotubes, the literature. Hence, calculating La, LD and nD, and correlating with
graphene etc. [14,17,18]. The variation of peak position and line values of TC is very much required, in order to understand the
width for D- and G- peaks (discrete points) were fit with a linear relation among the different values of cG reported in the literature.
relation (solid lines in Fig. 3), and the corresponding first order TCs Further, the change in phonon frequency of Raman mode as a
denoted with symbol c (peak position) and J (line width) are listed function of temperature is an effect of anharmonic terms in the
in Table 1. The peak position exhibits softening with temperature lattice potential energy and thermal expansion of the crystal. At

Table 2
A comparison of cG and line width of G-peak (at room temperature) for various graphene based materials.

Carbon materials Temperature range (K) cG ðcm
1 K
1 Þ FWHM ðcm
1 Þ Reference

Graphene doped with 100e850
0.044 Cu [37]

 (m-DIB)@
0.061 Cu
 (3,5-DBP)&
0.048 Cu
 (2,4-DBP)&
Vertical Graphene nanosheets 100e500
0.015 SiO2/Si 34 [23]
Graphene 20e294
0.076 Cu (grown) 12 [25]

0.028 Cu (transferred) 25

0.018 SiO2/Si 18

0.011 Al2O3 27

0.023 SiO2/Si (doped) 12
1L-Graphene 78e318
0.016 SiO2/Si 9 [38]
 Defect free
0.025 SiO2/Si 11
 Defective
1L-Graphene 83e373
0.016 SiO2/Si 13.5 [39]
2L-Graphene 113e373
0.015 SiO2/Si 18.2
Graphite 300e500
0.017 12 [17]
Plasma treated Multilayer graphene sheets 78e573
0.015 7.6 [40]
Graphene nanoplatelets 100e680 0.0005 20 [41]
Graphene sheet 79e400
0.020 SiC 17.5 [42]
400e773
0.022 SiC 21
1L-rGO 77e573
0.029 75 [14]
2L-GNR!
0.030 38
N-doped 3L-Graphene
0.022 30
rGO 22e400
0.027 SiO2/Si 90 [26]
rGO 123e423 46 [27]
rGO 173e723
0.009 60 Present study
@
Di-iodobenzene, &Di-bromopyridineand, !Graphene nanoribbons.

440
M. Sharma, S. Rani, D.K. Pathak et al. Carbon 184 (2021) 437e444

constant pressure, shift in peak position of Raman mode consists of where, A, B are anharmonicity constants, x ¼ ZkuT0 , u0 is the phonon
B
implicit (quasi-harmonic) and explicit (true-anharmonic) contri- frequency at 0 K, kB is Boltzmann constant, and
butions. The quasi-harmonic contribution arises from thermal fan ðxÞ ¼ 1=ðexpðxÞ
1Þ describes phonons occupation at tempera-
expansion, which is due to the change in force constant of the ture T, in Bose-Einstein distribution. The first and second terms on
material with volume. True-anharmonic contribution is a result of the right side of Eq. (8) represent cubic and quartic anharmonic-
self-energy shift arising from phonon-phonon coupling. This can be ities, which arise from the decay of a single optical phonon into
simply described using the thermodynamic relation given in Eq. (6) two- and three- low energy phonons, respectively.
[18,42], as follows, The variation in the peak position of G-mode for rGO has been
  presented in Fig. 4(a). The temperature dependent peak shift of G-
1 dui  1 vui 
¼
gi a; (5) and D- modes has been estimated using Eq. (6). Total theoretical
ui dT P ui vT V contribution, individual contributions by thermal expansion and
anharmonic interactions, are depicted in Fig. 4 (a) and 4(b), by
where, P stands for the pressure, V for the volume, gi is the mode
offsetting the curves over y-axis. Thermal expansion part gives rise
Grüneisen parameter and a ¼ V
1 ðvV∕vTÞ is coefficient of thermal
to blue shift (hardening of modes), while anharmonic term leads to
expansion. The left side of Eq. (5) represents temperature depen-
red shift (softening of modes) in peak position with increasing
dent isobaric wavenumber shift of Raman mode, also known as
temperature. This behaviour is completely consistent with the re-
total anharmonic shift. The first part on the right side represents
sults reported for graphite and graphene [17,42]. The estimated
the “true-anharmonic” contribution and the second one represents
values of coefficients for cubic and quartic terms, from the linear
“quasi-harmonic” part. The true-anharmonic part represents the
variation of G (D) peak positions are
0.6 (
1.8) cm
1 and
3.4
degree of anharmonicity of the various modes. The total anhar-
(
2.4) cm
1, respectively. These fits describe the approximate
monic, true-anharmonic and quasi-harmonic parts for the peak
behaviour of anharmonicity contribution to the variation of peak
shifts of G- and D-peaks were calculated using Eq. (5) and are
position, as the contribution from thermal expansion term is not
displayed in Table 3. The overall red-shift of D- and G- peaks results
exact, due to the values of a and gi adopted from literature, and
in the negative value of total anharmonic contribution. Quasi-
their temperature variation has not been considered. A comparison
harmonic term contributes to the positive shift, which causes
of anharmonicity constants of different carbon materials is shown
hardening of modes. The larger negative value of true-anharmonic
in Table S3 (supplementary material). The anharmonicity constants
term results in the overall softening of modes.
vary for graphene samples grown on various substrates and syn-
Further, temperature dependent shift in the peak position of
thesized in different processes (Table S3). The values of A and B of
Raman mode can be decoupled into two main parts [17,25,42], as
the present study are in agreement with those reported by Lin et al.
given below in Eq. (6),
[42].
Furthermore, the variation of line width for the characteristic
DuðTÞ ¼ DuT ðTÞ þ DuA ðTÞ; (6)
modes of rGO with temperature is shown in Fig. 3 (b). According to
theoretical models, line width consists of two main contributions
where, first and second terms show contributions to peak shift
arising from ph-ph and e-ph interactions. Along with these, there is
arising from the thermal expansion and anharmonic effects,
one more contribution arising from defects, which affects the line
respectively. The shift in peak position, as a result of thermal
width of the Raman modes [22,45].
expansion of lattice is given by the following Eq. (7) [42],
8 2 3 9
< ðT = GðTÞ ¼ Gdefect þ Ge
ph þ Gph
ph ; (9)
Du ðTÞ ¼ u0 exp4
gi aðT ÞdT 5
1 ;
T 0 0
(7)
: ; The e-ph contribution (Ge
ph ) is due to phonon decay into
0
electron-hole pairs, and the ph-ph contribution (Gph
ph ) results
where, gi is Grüneisen parameter, and a ¼ 2aa þ ac , with ac and aa from anharmonic phonon interactions in phonon self-energy.,
are linear thermal expansion coefficients along and perpendicular Bonini et al. [22] has theoretically predicted the behaviour of
to c-axis. Here, the contribution from ac to the peak shift is being Ge
ph as an effect of rise in temperature for graphene and graphite.
neglected, due to a large spacing in between the graphitic planes of The change in line width due to e-ph interactions depends on the
rGO. The value of a  2aa with aa z-1.3  10
6 K-1 [43] has been difference between the occupation of states above and below Fermi
used. The values of gD and gG reported in the literature are ~2.7 [44] energy (eF) (as reported by Eq. (2) in Ref. [22]). An increase in
and ~1.8 [43], respectively, have been utilized. temperature provokes the occupancy of empty states above eF,
The variation of peak position with temperature by considering resulting in the decrease of line width with temperature. However,
3-ph and 4-ph terms was described by Balanski et al. [45] and is as ph-ph interactions, having similar form given by Eq. (8), results in
follows, broadening of line width with temperature, having cubic (3-ph)
h  x i h x  i and quartic (4-ph) terms exhibiting nearly linear and quadratic
2 x
DuA ðTÞ ¼ A 1 þ 2fan þ B 1 þ 3fan þ 3fan ; (8) temperature dependencies, respectively, in the high temperature
2 3 3 limit [42,45]. Temperature dependent shift in the line width of G-
peak for rGO is shown in Fig. 5. There are only few reports available
in the literature, which inspect the temperature variation of line
width of G-mode. For instance, Kolesov et al. [25] reported tem-
Table 3
perature dependent variation of line width and concluded insen-
Total anharmonic, true-anharmonic and quasi-harmonic contributions for the peak
shifts of G- and D- peaks. sitive or nearly positive temperature dependencies for the as-
  grown, transferred and doped graphene on various substrates.
Mode 1 dui  1 vui 
gi a  10
5
 10
5  10
5 Yang et al. [38] has reported the insensitive behaviour of line width
ui dT P ui vT V
for mono- to 10- layer defect free and defective graphene as a
G
0.59
1.06 0.47 function of temperature. Graphene exhibits decrease in line width
D
0.75
1.45 0.70
(G-peak) with the variation in temperature, as a result of the
441
M. Sharma, S. Rani, D.K. Pathak et al. Carbon 184 (2021) 437e444

Fig. 4. The variation in peak position for (a) G-peak, (b) D-peak of rGO as a function of temperature. The solid orange lines represent theoretically predicated behaviour of peak
position using Eq. (6). The individual contributions from thermal expansion (dashed lines) and anharmonicity (dash-dotted lines) are shown by offsetting the curves, appropriately.
(A colour version of this figure can be viewed online.)

Pardanaud et al. [46], has shown the line width of G-peak scales
with crystallite size (La) following the relation, G ¼ B1 þ A1 =La ; this
relation is valid for disorder carbon materials having crystallite size
>2 nm, calculated by using Eq. (2). In the above mentioned studies,
samples with different La values were obtained by probing wide
range of carbon materials, from nano-crystalline graphite to a-C,
synthesized from various approaches.
In the present work, for rGO, the intensity ratio (ID/IG) and
crystallite size (La) vary with temperature (Fig. 1 (c)). The variations
in ID/IG can be attributed to the thermally induced structural
changes such as creation of defects, exhaustion of residual func-
tional groups attached to carbon lattice etc [16,47]. The variations in
ID/IG (there by in La) can result in the temperature dependent
variation of Gdefect , as discussed above. However, further experi-
mental/computational investigations relating Gdefect and La (over a
wide range of La values) are required, in order to calculate Gdefect ðTÞ
quantitatively. Thus, the observed variation of line width as a
function of temperature (Fig. 5), can be a consolidated effect of all
Fig. 5. The variation in line width of G-peak for rGO as a function of temperature.
the contributions arising from Gdefect ðTÞ, Ge
ph ðTÞ and Gph
ph ðTÞ.

4. Summary
dominant contribution from e-ph term [42]. For the case of
graphite, line width decreases till ~500 K due to e-ph contribution. Temperature dependent evolution of Raman modes for rGO has
As the temperature increases anharmonic contribution fully com- been studied above and below room temperature (173e723 K), to
pensates e-ph contribution resulting in nearly temperature inde- reveal that rGO having crystallites with average size (La) varying
pendent behaviour of line width (~500e700 K), and afterwards from 16-21 nm, and defects density (nD) in the range
anharmonic term starts dominating over e-ph term, resulting in 2.0e2.6  1011 cm
2, as estimated from ID/IG, as a function of
broadening of line width [17]. In the present case, the variation of temperature. The temperature dependence of peak position for G-
line width for rGO (Fig. 5) is nearly independent of temperature, and D- peaks was explained based on the theoretical models. The
similar to the previous reports [25,38]. Unlike the case of crystalline line width of G-peak for rGO has been compared with that graphite,
graphite, the variations induced by e-ph and anharmonicity con- in order to estimate the broadening due defects. The temperature
tributions to the line width are not clearly distinguishable, as the variation of line width was interpreted qualitatively, by taking in all
defect induced broadening Gdefect ðTÞ overlaps with Ge
ph ðTÞ and possible contributions (anharmonicity, crystallite size and defects).
Gph
ph ðTÞ.
In order to estimate the defect contribution, the line-width of CRediT authorship contribution statement
rGO has been compared to that of graphite. Line width of graphite
at low temperature, is nearly ~12 cm
1 (with Ge
ph and Gph
ph Meenu Sharma: Investigation, Data curation, Formal analysis,
values ~10 cm
1 and ~1.6 cm
1, respectively, at 0 K) [17]. In the Writing e original draft. Sonam Rani: Investigation, Data curation.
present study, line width of G-peak (rGO) at 0 K is ~58 cm
1, by Devesh K. Pathak: Investigation, Data curation. Ravi Bhatia:
comparison with the values of graphite [17], contribution from Conceptualization, Funding acquisition, Project administration,
Gdefect has been estimated as ~46 cm
1. Similar value of Gdefect Resources, Supervision, Writing e review & editing. Rajesh Kumar:
(~35 cm
1) for rGO was reported by Bhaskaram et al. [27], by Investigation, Data curation, Funding acquisition, Project adminis-
comparing the line width with single layer graphene. tration, Resources, Supervision, Writing e original draft, Writing e
In their seminal works, Cancado et al. [31,33], and Ferrari et al. review & editing. I. Sameera: Investigation, Data curation, Formal
[32], have established relation between intensity ratio (ID/IG) and analysis, Funding acquisition, Project administration, Supervision,
crystallite size (La) for carbon materials. Following these studies, Writing e original draft, Writing e review & editing.
442
M. Sharma, S. Rani, D.K. Pathak et al. Carbon 184 (2021) 437e444

Declaration of competing interest 751e758, https://doi.org/10.1021/nl904286r.

[14] D.J. Late, U. Maitra, L.S. Panchakarla, U.V. Waghmare, C.N.R. Rao, Temperature
effects on the Raman spectra of graphenes: dependence on the number of
The authors declare that they have no known competing layers and doping, J. Phys. Condens. Matter 23 (2011), 055303, https://doi.org/
financial interests or personal relationships that could have 10.1088/0953-8984/23/5/055303.
appeared to influence the work reported in this paper. [15] A. Kaniyoor, S. Ramaprabhu, A Raman spectroscopic investigation of graphite
oxide derived graphene, AIP Adv. 2 (2012), 032183, https://doi.org/10.1063/
1.4756995.
Acknowledgements

[16] X. Díez-Betriu, S. Alvarez-García,

C. Botas, P. Alvarez,
nchez-Marcos,
J. Sa
C. Prieto, R. Mene
ndez, A. de Andre
s, Raman spectroscopy for the study of
reduction mechanisms and optimization of conductivity in graphene oxide
M. Sharma, is grateful to UGC, New Delhi (India) for financial aid. thin films, J. Mater. Chem. C 1 (2013) 6905e6912, https://doi.org/10.1039/
Authors, I. Sameera & R. Bhatia are thankful to Department of Sci- C3TC31124D.
ence and Technology (DST), New Delhi (India) for the financial [17] H.-N. Liu, X. Cong, M.-L. Lin, P.-H. Tan, The intrinsic temperature-dependent
Raman spectra of graphite in the temperature range from 4K to 1000K, Car-
support in the form of Inspire Faculty Awards [DST/INSPIRE04/ bon 152 (2019) 451e458, https://doi.org/10.1016/j.carbon.2019.05.016.
2017/002776 &DST/INSPIRE/04/2015/000902]. We thank DST, New [18] M. Sharma, S. Rani, D.K. Pathak, R. Bhatia, R. Kumar, I. Sameera, Manifestation
Delhi for providing XRD facilities (FIST scheme, grant number SR/ of anharmonicities in terms of phonon modes' energy and lifetime in multi-
wall carbon nanotubes, Carbon 171 (2021) 568e574, https://doi.org/10.1016/
FST/PSI-089/2005). R. Kumar is thankful to Science and Engineering j.carbon.2020.09.018.
Research Board (SERB), Govt. of India, for the funding received [19] S. Linas, Y. Magnin, B. Poinsot, O. Boisron, G.D. Forster, V. Martinez,
(grant no. CRG/2019/000371). D.K. Pathak acknowledges Council of R. Fulcrand, F. Tournus, V. Dupuis, F. Rabilloud, L. Bardotti, Interplay between
Raman shift and thermal expansion in graphene: temperature-dependent
Scientific and Industrial Research (CSIR) (India), for financial measurements and analysis of substrate corrections, Phys. Rev. B 91 (2015),
assistance (file number 09/1022(0039)/2017-EMR-I). Facilities 075426, https://doi.org/10.1103/PhysRevB.91.075426.
received from DST, Govt. of India, under FIST scheme (grant number [20] M. Hulman, M. Haluska, G. Scalia, D. Obergfell, S. Roth, Effects of charge im-
purities and laser energy on Raman spectra of graphene, Nano Lett. 8 (11)
SR/FST/PSI-225/2016) are highly acknowledged.
(2008) 3594e3597, https://doi.org/10.1021/nl8014439.
[21] Q.-Y. Li, K. Xia, J. Zhang, Y. Zhang, Q. Li, K. Takahashi, X. Zhang, Measurement
Appendix A. Supplementary data of specific heat and thermal conductivity of supported and suspended gra-
phene by a comprehensive Raman optothermal method, RSC Nanoscale 9
(2017) 10784e10793, https://doi.org/10.1039/C7NR01695F.
Supplementary data to this article can be found online at [22] N. Bonini, M. Lazzeri, N. Marzari, F. Mauri, Phonon anharmonicities in graphite
https://doi.org/10.1016/j.carbon.2021.08.014. and graphene, Phys. Rev. Lett. 99 (2007) 176802, https://doi.org/10.1103/
PhysRevLett.99.176802.
[23] K.K. Mishra, S. Ghosh, R.R. Thoguluva, S. Amirthapandian, M. Kamruddin,
References Thermal conductivity and pressure dependent Raman studies of vertical
graphene nanosheets, J. Phys. Chem. C 120 (43) (2016) 25092e25100, https://
[1] Y. Chen, K. Fu, S. Zhu, W. Luo, Y. Wang, Y. Li, E.M. Hitz, Y. Yao, J. Dai, J. Wan, doi.org/10.1021/acs.jpcc.6b08754.
V.A. Danner, T. Li, L. Hu, Reduced graphene oxide films with ultra-high con- [24] K.T. Nguyen, D. Abdula, C.-L. Tsai, M. Shim, Temperature and gate voltage
ductivity as Li-ion battery current collectors, Nano Lett. 16 (6) (2016) dependent Raman spectra of single-layer graphene, ACS Nano 5 (6) (2011)
3616e3623, https://doi.org/10.1021/acs.nanolett.6b00743. 5273e5279, https://doi.org/10.1021/nn201580z.
[2] Y. Zeng, T. Li, Y. Yao, T. Li, L. Hu, A. Marconnet, Thermally conductive reduced [25] E.A. Kolesov, M.S. Tivanov, O.V. Korolik, O.O. Kapitanova, H.D. Cho, T.W. Kang,
graphene oxide thin films for extreme temperature sensors, Adv. Funct. Mater. G.N. Panin, Phonon anharmonicities in supported graphene, Carbon 141
29 (2019) 1901388, https://doi.org/10.1002/adfm.201901388. (2019) 190e197, https://doi.org/10.1016/j.carbon.2018.09.020.
[3] S. Pei, H.-M. Cheng, The reduction of graphene oxide, Carbon 50 (2012) [26] M.J. Allen, J.D. Fowler, V.C. Tung, Y. Yang, B.H. Weiller, R.B. Kaner, Temperature
3210e3228, https://doi.org/10.1016/j.carbon.2011.11.010. dependent Raman spectroscopy of chemically derived graphene, Appl. Phys.
[4] D. Voiry, J. Yang, J. Kupferberg, R. Fullon, C. Lee, H.Y. Jeong, H.S. Shin, Lett. 93 (2008) 193119, https://doi.org/10.1063/1.3011030.
M. Chhowalla, High-quality graphene via microwave reduction of solution- [27] D.S. Bhaskaram, G. Govindaraj, Carrier transport in reduced graphene oxide
exfoliated graphene oxide, Science 353 (6306) (2016) 1413e1416, https:// probed using Raman spectroscopy, J. Phys. Chem. C 122 (19) (2018)
doi.org/10.1126/science.aah3398. 10303e10308, https://doi.org/10.1021/acs.jpcc.8b01311.
[5] B. Lesiak, G. Trykowski, J. To
th, S. Biniak, L. Ko
€ ve

r, N. Rangam, L. Stobinski, [28] R. Sharma, N. Chadha, P. Saini, Determination of defect density, crystallite size
A. Malolepszy, Chemical and structural properties of reduced graphene oxi- and number of graphene layers in graphene analogues using X-ray diffraction
deddependence on the reducing agent, J. Mater. Sci. 56 (2021) 3738e3754, and Raman spectroscopy, Indian J. Pure Appl. Phys. 55 (2017) 625e629. http://
https://doi.org/10.1007/s10853-020-05461-1. nopr.niscair.res.in/handle/123456789/42780.
[6] B. Xue, Y. Zou, Y. Yang, UV-assisted reduction of graphite oxide to graphene by [29] H.-H. Huang, K.K.H. De Silva, G.R.A. Kumara, M. Yoshimura, Structural evo-
using a photo initiator, J. Mater. Sci. 52 (2017) 4866e4877, https://doi.org/ lution of hydrothermally derived reduced graphene oxide, Sci. Rep. 8 (2018)
10.1007/s10853-016-0721-y. 6849, https://doi.org/10.1038/s41598-018-25194-1.
[7] T. Purkait, G. Singh, D. Kumar, M. Singh, R.S. Dey, High-performance flexible [30] F. Tuinstra, J.L. Koenig, Raman spectrum of graphite, J. Chem. Phys. 53 (1970)
supercapacitors based on electrochemically tailored three-dimensional 1126, https://doi.org/10.1063/1.1674108.
reduced graphene oxide networks, Sci. Rep. 8 (2018) 640, https://doi.org/ [31] L.G. Cançado, K. Takai, T. Enoki, M. Endo, Y.A. Kim, H. Mizusaki, A. Jorio,
10.1038/s41598-017-18593-3. L. Coelho, R. Magalhaes-Paniago, M. Pimenta, General equation for the
[8] Y. Mussa, F. Ahmed, M. Arsalan, E. Alsharaeh, Two dimensional (2D) reduced determination of the crystallite size La of nanographite by Raman spectros-
graphene oxide (RGO)/hexagonal boron nitride (h-BN) based nanocomposites copy, Appl. Phys. Lett. 88 (2006) 163106, https://doi.org/10.1063/1.2196057.
as anodes for high temperature rechargeable lithium-ion batteries, Sci. Rep. [32] A.C. Ferrari, J. Robertson, Interpretation of Raman spectra of disordered and
10 (2020) 1882, https://doi.org/10.1038/s41598-020-58439-z. amorphous carbon, Phys. Rev. B 61 (2000) 14095, https://doi.org/10.1103/
[9] L.-S. Lin, X. Yang, G. Niu, J. Song, H.-H. Yang, X. Chen, Dual-enhanced photo PhysRevB.61.14095.
thermal conversion properties of reduced graphene oxide-coated gold super [33] L.G. Cançado, M. Gomes da Silva, E.H. Martins Ferreira, F. Hof, K. Kampioti,
particles for light-triggered acoustic and thermal theranostics, RSC Nanoscale K. Huang, A. Pe
nicaud, C.A. Achete, R.B. Capaz, A. Jorio, Disentangling contri-
8 (2016) 2116e2122, https://doi.org/10.1039/C5NR07552A. butions of point and line defects in the Raman spectra of graphene-related
[10] S. Suragtkhuu, O. Tserendavag, U. Vandandoo, A.S.R. Bati, M. Bat-Erdene, materials, 2D Mater. 4 (2017), 025039, https://doi.org/10.1088/2053-1583/
J.G. Shapter, M. Batmunkh, S. Davaasambuu, Efficiency and stability aa5e77.
enhancement of perovskite solar cells using reduced graphene oxide derived [34] D. Lopez-Diaz, M.L. Holgado, J.L. Garcia-Fierro, M.M. Velazquez, Evolution of
from earth-abundant natural graphite, RSC Adv. 10 (2020) 9133e9139, the Raman Spectrum with the Chemical Composition of Graphene Oxide,
https://doi.org/10.1039/D0RA01423K. J. Phys. Chem. C 121 (2017) 20489e20497, https://doi.org/10.1021/
[11] P. Sehrawat Abid, S.S. Islam, P. Mishra, S. Ahmad, Reduced graphene oxide acs.jpcc.7b06236.
(RGO) based wide band optical sensor and the role of Temperature, Defect [35] A.C. Ferrari, J. Robertson, Resonant Raman spectroscopy of disordered,
States and Quantum Efficiency, Sci. Rep. 8 (2018) 3537, https://doi.org/ amorphous, and diamond like carbon, Phys. Rev. B 64 (2001), 075414, https://
10.1038/s41598-018-21686-2. doi.org/10.1103/PhysRevB.64.075414.
[12] L.G. Cançado, A. Jorio, E.H. Martins Ferreira, F. Stavale, C.A. Achete, R.B. Capaz, [36] S. Krause, M.H. Overgaard, T. Vosch, Photon energy dependent micro Raman
M.V.O. Moutinho, A. Lombardo, T.S. Kulmala, A.C. Ferrari, Quantifying defects spectroscopy with a continuum laser source, Sci. Rep. 8 (2018) 11621, https://
in graphene via Raman spectroscopy at different excitation energies, Nano doi.org/10.1038/s41598-018-29921-6.
Lett. 11 (8) (2011) 3190e3196, https://doi.org/10.1021/nl201432g. [37] Y.-R. Lee, J.-X. Huang, J.-C. Lin, J.-R. Lee, Study of the substrate-induced strain
[13] M.S. Dresselhaus, A. Jorio, M. Hofmann, G. Dresselhaus, R. Saito, Perspectives of as-grown graphene on Cu(100) using temperature-dependent Raman
on carbon nanotubes and graphene Raman spectroscopy, Nano Lett. 10 (2010) spectroscopy: estimating the mode Grüneisen parameter with temperature,

443
M. Sharma, S. Rani, D.K. Pathak et al. Carbon 184 (2021) 437e444

J. Phys. Chem. C 121 (2017) 27427e27436, https://doi.org/10.1021/ [43] N. Mounet, N. Marzari, First-principles determination of the structural,
acs.jpcc.7b08170. vibrational and thermodynamic properties of diamond, graphite, and de-
[38] M. Yang, L. Wang, X. Qiao, Y. Liu, Y. Liu, Y. Shi, H. Wu, B. Liang, X. Li, X. Zhao, rivatives, Phys. Rev. B 71 (2005) 205214, https://doi.org/10.1103/
Temperature dependence of G and D’ phonons in monolayer to few-layer PhysRevB.71.205214.
graphene with vacancies, Nanoscale Res. Lett. 15 (2020) 189, https:// [44] N. Ferralis, Probing mechanical properties of graphene with Raman spec-
doi.org/10.1186/s11671-020-03414-w. troscopy, J. Mater. Sci. 45 (2010) 5135e5149, https://doi.org/10.1007/s10853-
[39] I. Calizo, A.A. Balandin, W. Bao, F. Miao, C.N. Lau, Temperature dependence of 010-4673-3.
the Raman spectra of graphene and graphene multilayers, Nano Lett. 7 (2007) [45] M. Balkanski, R.F. wallis, E. Haro, Anharmonic effects in light scattering due to
2645e2649, https://doi.org/10.1021/nl071033g. optical phonons in silicon, Phys. Rev. B 28 (1983) 1928e1934, https://doi.org/
[40] A.S. Pawbake, K.K. Mishra, L.G.B. Machuno, R.V. Gelamo, T.R. Ravindran, 10.1103/PhysRevB.28.1928.
C.S. Rout, D.J. Late, Temperature and pressure dependent Raman spectroscopy [46] C. Pardanaud, C. Martin, P. Roubin, Multiwavelength Raman spectroscopy
of plasma treated multilayer graphene nanosheets, Diam. Relat. Mater. 84 analysis of a large sampling of disordered carbons extracted from the Tore
(2017) 146e156, https://doi.org/10.1016/j.diamond.2018.03.021. Supra tokamak, Vib. Spectrosc. 70 (2014) 187e192, https://doi.org/10.1016/
[41] I. Efthimiopoulos, S. Mayanna, E. Stavrou, A. Torode, Y. Wang, Extracting the j.vibspec.2013.12.004.
anharmonic properties of the G-band in graphene nanoplatelets, Phys. Chem. [47] A.V. Dolbin, M.V. Khlistyuck, V.B. Esel'son, V.G. Gavrilko, N.A. Vinnikov,
C 124 (8) (2020) 4835e4842, https://doi.org/10.1021/acs.jpcc.9b10875. R.M. Basnukaeva, et al., The effect of the thermal reduction temperature on
[42] J. Lin, L. Guo, Q. Huang, Y. Jia, K. Li, X. Lai, X. Chen, Anharmonic phonon effects the structure and sorption capacity of reduced graphene oxide materials,
in Raman spectra of unsupported vertical graphene sheets, Phys. Rev. B 83 Appl. Surf. Sci. 361 (2016) 213e220, https://doi.org/10.1016/
(2011) 125430, https://doi.org/10.1103/PhysRevB.83.125430. j.apsusc.2015.11.167.

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