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Synthesis of Graphene and Graphene Films with Minimal Structural

Defects
Minh-Hai Tran, Ian Booth, Arash Azarakhshi, Peter Berrang, Jeremy Wulff, and Alexandre G. Brolo*

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ABSTRACT: Graphene is a carbon material with extraordinary properties that has been drawing a significant amount of attention
in the recent decade. High-quality graphene can be produced by different methods, such as epitaxial growth, chemical vapor
deposition, and micromechanical exfoliation. The reduced graphene oxide route is, however, the only current approach that leads to
the large-scale production of graphene materials at a reasonable cost. Unfortunately, graphene oxide reduction normally yields
graphene materials with a high defect density. Here, we introduce a new route for the large-scale synthesis of graphene that
minimizes the creation of structural defects. The method involves high-quality hydrogen functionalization of graphite followed by
thermal dehydrogenation. We also demonstrated that the hydrogenated graphene synthesis route can be used for the preparation of
high-quality graphene films on glass substrates. A reliable method for the preparation of these types of films is essential for the
widespread implementation of graphene devices. The structural evolution from the hydrogenated form to graphene, as well as the
quality of the materials and films, was carefully evaluated by Raman spectroscopy.

■ INTRODUCTION
Graphene, a monolayer of delaminated graphite, is a two-
Therefore, bulk graphene materials and films consist of a
distribution of exfoliated graphitic forms with an average
dimensional material of sp2-bonded carbon that has remarkable “small” number of stacked layers. The production of large
electronic, optical, and mechanical properties due to its special amounts of these materials either in bulk or as large area films
electronic semimetal band structure in which conduction and of high quality is very challenging. Although significant
valence bands meet at the Dirac point.1−5 In particular, this advances on the various graphene fabrication methods,
electronic condition confers the high mobility of charge including mechanical exfoliation, liquid-phase exfoliation,
carriers with unique electrical conductivity properties com- bottom-up synthesis, and reduction of graphene oxide, are
bined with optical transparency. These characteristics of constantly being reported,13−18 there has not yet been a
graphene have attracted tremendous interest for applications universal method that can meet the industrial requirements
in electronics, photonics, and energy storage.6−11 criteria in both material quality and fabrication yield.19
In principle, graphene can be fabricated by simply According to a 2021 review on graphene synthesis by
delaminating a single graphite layer, one of the cheapest and Santhiran et al.,15 there are several limiting aspects to large
most abundant resources in the world. This type of single-layer industrial production through the current graphene prepara-
graphene is useful for specialized fundamental research, such as tion routes. Those limitations are relative to costs, availability
investigations of the quantum properties of the material.5,6,10 of resources, and the requirement for complex technologies.
Nevertheless, industrial applications require bulk graphene
materials and high-quality films. It is important to emphasize
that the standalone single-layered graphene cannot resist Received: July 4, 2023
aggregation due to the van der Waals interactions between Accepted: September 7, 2023
carbon rings. This effect and further instabilities due to thermal Published: October 18, 2023
fluctuations have led to the conclusion that long-range
crystalline order in graphene is impossible to maintain at
room temperature.12,13
© 2023 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsomega.3c04788
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For instance, the exfoliation route, either the mechanical or In contrast, graphene oxide has different BDEs for the various
liquid phase, does not scale-up. Furthermore, some bottom-up oxygen functional groups. Some of the approximated values are
methods, including chemical vapor synthesis and epitaxial 6.0, 4.8, and 10.5 eV for C−OOH, C−OH and C−O−C,
growth, require complex facilities to deal with high vacuum, respectively.38 Thus, while thermal reduction of graphite oxide
heating requirements, and complex gas systems.15 requires high temperatures of about 1000 °C,39 hydrogenated
The production of graphene-like materials through graphene graphite (HG) should be thermally stripped of hydrogen
oxide reduction is the most common route for large-scale functional groups at lower temperatures, around 500−600 °C.
fabrication. In this case, the production cost for graphene oxide An attempt to overcome the current limitations of
is low, and the reaction can be processed under 100 °C in traditional Birch reduction is reported in this work. A modified
ambient conditions.15,16 Unfortunately, large-scale graphene route to graphite hydrogenation is suggested, leading to both
oxide production involves strong oxidation precursors, such as high quality and quantity of the obtained product. It is also
fuming nitric acid and potassium chlorate, leading to a high shown that thermal dehydrogenation leads to good-quality
risk of explosion.15,16 Moreover, the subsequent reduction graphene films on glass substrates, which is an important step
processes lead to the rupture of the graphene lattice via for the implementation of devices. The dehydrogenation of
formation of CO2, leaving permanent vacancy and hole defects graphane can then be considered a better route for bulk
in the resulting materials or films.20,21 The presence of a high graphene production compared with the graphene oxide
density of defects influences not only the electrical and thermal method. The dehydrogenation route is amenable to scale-up,
conductivities of the material but also the mechanical strength and it also maintains the sp2 structure of the final graphene
that relies on the sp2 lattice structure of graphene.20,21 product better than the oxidation process, due to the low
It is then important to consider alternative synthetic temperature requirements.
methods that can produce graphene materials and films on a
large scale while minimizing the defects in the structure of the
product. In this contribution, we report on a new route for the
■ EXPERIMENTAL SECTION
Sample Preparation. Warning: The ingredients in the
synthesis of graphene that follows hydrogen functionalization Birch reduction include liquid ammonia and alkali metals,
of graphite instead of oxidation. The method described here requiring considerable safety awareness due to the risk of
allowed the coating of large-area glass substrates with a good explosion. The use of face shield, blast shield, and fume hood
level of chemical homogeneity. The structure of fully are essential requirements. This reaction should only be
hydrogenated graphene, known as graphane, was predicted performed by adequately trained personnel and monitored at
theoretically in 2007.22 Afterward, since 2009, there have been all the times.
several attempts to fabricate hydrogenated graphene by Graphite powder (synthetic, 20 μm diameter) from Sigma-
microwave discharge,23 plasma,24 chemical vapor deposition25 Aldrich was used for the Birch reduction method.32,36
or using super critical hydrogen at high pressure and high Typically, a mixture of dry ice and acetone (−78 °C) was
temperature in a diamond anvil cell.26 However, those used to cool a three-neck flask fitted to a condenser. Liquid
methods are suitable only on a small scale in microgram ammonia (150 mL) was condensed into the flask followed by
quantities or for the formation of graphane films. Although the slow addition of sodium (20 g) and graphite powder (5 g).
electrochemical reduction has shown the ability to hydro- The mixture was stirred for 1.5 h, and then a protonation step
genated bulk quantities of graphene, this method still has the was initiated by the dropwise addition of 200 mL of butanol
drawback of unexpected chemical functionalizing from the and methanol to the reaction for more than 3 h. The ammonia
electrolyte and typically produces a low hydrogenation was then allowed to evaporate overnight. The samples of
ratio.27,28 The hydrogenation of carbon materials through carbon materials produced by this procedure were rinsed three
solvated electrons from dissolved alkali metals in ammonia, times with methanol, deionized water, and dilute sulfuric acid
also known as the Birch reduction,29 is considered the most followed by sonication and vacuum filtering to remove any
capable of producing bulk quantities of graphane. However, remaining sodium impurities. The sample was then dried in an
safety considerations are an important concern, since lithium is oven at 125 °C for 24 h. The dried powder of HG materials
the most common metal used for that reaction.30−32 Although obtained by this procedure will be termed HG throughout this
the hydrogenation efficiency obtained by Birch reduction is manuscript. The dehydrogenation step of the processes was
generally higher compared to either physical or electro- accomplished by thermal annealing at either 500 °C (for 3 h)
chemical methods, this method still has a disadvantage in or 600 °C (for 3 h). In both cases, the temperature was
that the residues from lithium salt are hard to remove due to increased at a 10 °C/min rate in Argon gas. The samples
the strong interactions between lithium atoms and graphene obtained after annealing are referred to as HG500 and HG600.
layers33 which can be seen in Fourier transformed infrared Characterization. Microscale images of the powder
absorption spectroscopy (FTIR) by the sharp peak at about samples were obtained by scanning electron microscopy
3600 cm−1.30 A few groups tackled this challenge by replacing (SEM, Hitachi S-4800 FESEM). The extent of the chemical
lithium with sodium in Birch reduction, but only micrograms functionalization of the samples was inferred by FTIR
of hydrogenated carbon was produced34,35 due to the violent (PerkinElmer Spectrum Two). The component phase purity
reaction. Morse et al.36 have reported a more practical route to and the crystalline structures of the samples were obtained by
scale-up the production of hydrogenated carbon, but the XRD (Panalytical Empyrean X-ray diffractometer) of 2θ with
degree of hydrogenation needed improvements since a residual CuKa radiation λ = 0.1542 nm, 40 kV tube voltage, 40 mA
graphite crystalline peak was present in the X-ray diffraction tube current with scanning range of 10−60°.
(XRD) of their product. Raman spectroscopy was performed using a Renishaw 1000
Density functional theory calculations were used to model Raman microscope. The samples were excited using a 532-nm
graphane. The computational data indicated a C−H bond laser focused to ∼2 μm diameter spot with a 50× (NA = 0.75)
dissociation energy (BDE) in the range of about 3.5−4.0 eV.37 objective lens. The laser intensity was adjusted between 300
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and 500 μW to minimize any adverse heating effect. The laser that is assigned to the sp3-hybridized C−H stretching
light was rejected by a bandpass filter, and the Raman vibration.32 The presence of that peak is a strong indication
scattering was measured in a spectrograph equipped with a of successful hydrogen functionalization of the original
CCD camera. Samples for the Raman measurements were graphitic structure. The FTIR spectra of the thermally treated
prepared by drop coating a (1 wt %) methanol solution of the samples, HG500 and HG600, shown in Figure 1c,d, do not
carbon material (sonication was required to ensure dispersion) present any characteristic peak, consistent with a functional
on a glass slide. The glass slide was dried at room temperature group-free structure. The disappearance of the C−H stretching
before the Raman measurements. Spectra were recorded from band in the FTIR spectra of the HG carbon material after the
5 to 10 spots randomly chosen from each sample. moderate annealing process demonstrates effective dehydro-
Raman mappings were utilized to verify the homogeneity of genation at relatively mild temperatures.
the chemical characteristics of graphene films formed through The degree of graphitization and the crystallinity parameters
the thermal reduction of HG. The films were prepared as were characterized by XRD. Figure 2a presents a XRD pattern
follows: The dispersion of hydrogenated graphene in deionized
water was dropped on a glass substrate, and then the films were
heated at 600 °C for 3 h in Argon gas (HG600 films). The
Raman maps were obtained over an area of 32.5 μm by 32.5
μm (0.5 μm step) using 532 nm laser, 1.75 mW for 5 s and 3
accumulations. Several areas, chosen randomly, were mapped
in a given film to provide statistics of long-range chemical
homogeneity. A MATLAB code employed a 2 Gaussian
method to fit the Raman bands. All spectra were corrected by a
linear baseline between 1050 and 1800 cm−1. The hydrogen
content (H[atom %]) was estimated based on the slope of the
linear baseline (m) divided by G-band intensity (I(G)),
according to eq 1 below.40,41
l
o m |
o
H[atom %] = 21.7 + 16.6logm
o [ m]}
o
o
n I ( G ) o
~ (1)

This Raman method for the determination of H[atom %] Figure 2. XRD analysis of (a) graphite, (b) hydrogenated graphite,
was shown to be accurate in determining hydrogenated carbon and (c) and (d) samples thermal annealed at 500 and 600 °C,
material for H[atom %] > 20%. respectively. The diffractograms on the right show a magnified image
of the XRD spectra in the range about 40−50°.

■ RESULTS AND DISCUSSION

Figure 1 shows the representative FTIR spectra of the samples
produced in this work. Figure 1a corresponds to the spectra that is characteristic for graphite, with a peak at 26.5° of the
from the precursor graphite (PG), Figure 1b is the HG lattice (002) and the derivative interlayer spacing (d002) of 0.34
material, and Figure 1c,d are spectra of the HG material after nm calculated using Bragg’s law.42,43 The graphite (PG) XRD
thermal treatment at 500 and 600 °C, respectively. The HG at 26.5° shifts to 18.9° for HG, as shown in Figure 2b. The
sample in Figure 1b has a significant sharp peak at 2850 cm−1 interlayer distance calculated from the pattern in Figure 2b was
0.47 nm. That is smaller than the 0.8 nm layer distance
typically obtained from XRD of graphene oxide43 and larger
than pristine graphite (PG) (0.34 nm). It is possible to
attribute the difference in layer distances to the presence of
covalently bound hydrogen atoms on the surface of exfoliated
graphene.32 The XRD patterns of the thermally treated
samples HG500 and HG600 are shown in Figure 2c,d,
respectively. The main peaks for Figure 2c,d are closer to those
observed for graphite in Figure 2a. The approximately 26.0°
diffraction feature observed in Figure 2c,d, relative to the 26.5°
observed in Figure 2a, suggests dehydrogenation and
restoration of sp2-conjugated domains. These results indicate
the restacking in a turbostratic carbon structure which is less
dense than the graphite precursor.44
The diffraction peak in Figure 2 at around 44°, assigned to
(004) planes, indicates that both the number of parallel carbon
layers and the order of aromatic carbon grid has recovered
after thermal reduction.42 It is important to note that the (004)
peak was not recovered in graphene films produced by
thermally reduced graphene oxide.43,45 On the other hand, that
Figure 1. FTIR spectra of (a) precursor graphite (PG), (b) feature clearly starts to emerge in Figure 2 after a relatively
hydrogenated graphite (HG), and thermally treated samples at (c) mild thermal treatment of 500 °C. These results suggest that
500 °C (HG500) and (d) 600 °C (HG600) samples. both crystallinity and ordering layers were recovered more
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efficiently by following the annealing of hydrogenated materials

than from the oxide reduction route.
The crystalline structure parameters of the samples were also
calculated based on two specific planes, (002) and (100),
corresponding to XRD peaks at around 26 and 42°,
respectively.42,51
The interlayer spacing (d002) was determined by Bragg’s eq
2, the graphitization degree (g) by Franklin’s eq 3, the
crystallite size (La) and stacking height (Lc) from Scherrer’s eq
4, and the number of layers (n) were determined by eq 5.
d002 = /2sin 002 (2)

g = [(0.3440 d002)/(0.3440 0.3354)] × 100% (3)

La = k1 /[ 100cos 100 ] and n = Lc = k 2 /[ 002 cos 002 ]

(4) Figure 3. SEM images of samples: (a) PG, (b) HG, (c) HG500, and
(d) HG600.
n = Lc /d002 (5)
where k is the Scherrer parameter (k1 = 1.84, k2 = 0.94), β and Figure 3 demonstrate that the dehydrogenation process,
θ represent the full width at half-maximum (fwhm) and the followed by thermal treatment, significantly reduced the
Bragg angle of the diffraction peak, respectively. The values of thickness of the bundle of graphite layers in the material.
0.3440 and 0.3354 are assumed as the carbon layer spacing Raman spectroscopy is the most commonly used technique
(nm) of the original carbonaceous materials and of an ideal for the characterization of graphene-type materials. It is a well-
graphite crystal.42 known versatile tool for the determination of the number and
The summary of the structural parameters of all samples is orientation of graphene layers, as well as the level of disorder
displayed in Table 1. Table 1 shows that hydrogenation and functionalization in graphene-based materials.46−51 The
characteristic Raman G-band (at ∼1600 cm−1) is assigned to
Table 1. Crystallinity Properties Calculated from XRD the E2g phonon at the Γ-point of the Brillouin zone, while the
Spectra of Pristine Graphite and Hydrogenated Graphene 2D-band at the second phonon zone (∼2700 cm−1) is due to
Derivatives transverse optical (TO) phonons around the K-point in the
Brillouin zone.52 The D-band (at ∼1300 cm−1) arises from an
sample d002 (nm) g (%) La (nm) Lc (nm) n
excitation of a phonon induced by a defect in the double
PG 0.335 100 86 742 2215 resonance process around the K-point.53,54 The 2D band,
HG 0.467 13.7 30 146 313 which is a second-order overtone of the D-band, is a Raman
HG500 0.343 13.1 56 298 869 feature induced by defects. However, it does not originate from
HG600 0.342 22.2 68 466 1363 defects and, as a result, does not serve as an indicator of defect
presence.53 Instead, the Raman 2D-band shape is used as a
affected approximately 80% of the stacked structure of fingerprint for the number of graphene layers and it is very
graphitization (g). However, up to 79% of the graphene dependent on the electronic band structure of graphene.55,56
crystallinity was recovered in HG600 based on the values of Accordingly, based on the characteristics of the peaks in both
crystalline size (La). In contrast, similar quality graphene regions of the first and second phonon Raman scattering (D
obtained from the thermal graphene oxide route requires and 2D), the defects and graphitic structure quality can be
thermal conditions above 1000 °C.43 These are expected evaluated.
results, since the favored energetics allow the recovery of the Figure 4 shows the evolution of the Raman signature from
crystallinity of graphene structure by thermal treatment at the precursor material PG (Figure 4a), through the hydro-
lower temperature for the hydrogenated route compared to the genation product HG (Figure 4b) to the thermally
oxidized material. Table 1 also shows that the number of layers dehydrogenated samples HG500 and HG600 (Figure 4c,d,
(n) of HG decreased almost seven times from the PG material, respectively).
suggesting an increase in detached graphene sheets promoted The interpretation of the Raman features of the hydro-
by the inserted hydrogens. The thermal reduction toward genated and dehydrogenated materials presented in Figure 4
graphene leads to an increase of the numbers of layers (n) in takes into account the Raman signatures for tetrahedral
HG500 and HG600 (Table 1) to approximately half of the amorphous carbon59,60 compared to the Raman of function-
value in the graphite precursor (PG). The variation in the alized carbon species, such as graphene oxide.58,61
values of n indicated in Table 1 is supported by the scanning The Raman spectrum for PG in Figure 4a is typical for
electron micrographs presented in Figure 3. graphite, with prominent features assigned to the G-band
Representative SEM images of the samples in Figure 3 show (∼1580 cm−1) and the 2D-band (∼2700 cm−1) characteristic
that the original graphite material (PG) was mainly composed for sp2 carbon networks. A weak D-band that originates from
of large particles with a significant number of stacked layers the edge of the graphite domains is also present in Figure 4a.54
(Figure 3a). Clearly separated layers with porous structures Other minor peaks that originate from the combination of
can be observed in Figure 3b for the HG sample. The phonon and overtones are assigned to the D + D″ (∼2400
thermally treated (500 and 600 °C) samples, HG500 and cm−1) and 2 D′ (∼3200 cm−1) which are related to two
HG600, present similar appearance in Figure 3c,d, with more phonon scattering processes that do not require defects for
wrinkled and thinner-layered structures. Overall, the results in activation.50,63,64
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Figure 4. Raman spectra of (a) pristine graphite (PG) (b) hydrogenated graphite (HG), (c, d) baked sample at 500 °C (HG500) and 600 °C
(HG600), respectively; (e, f) deconvolution of 2D peak of PG and HG600, respectively.

After hydrogenation, the Raman features of the HG sample, to an intravalley double resonance process which is activated
displayed in Figure 4b, are significantly different in terms of by the presence of defects.61 The defects allow combination of
featured bands and spectral shape relative to the PG shown in intervalley phonon processes that produces the D+ D′-band.50
Figure 4a. The Raman photoluminescence background in The small band at around 1000 cm−1 in Figure 4c is labeled as
Figure 4b is a typical signature of hydrogenated carbon a D*-band, representing a disordered graphitic lattice involving
samples and it is assigned to the hydrogen saturation of a mixture of sp2 and sp3 carbons.58 The thermal treatment
nonradiative recombination centers.42,65 The magnitude of the removed the photoluminescence background and increased the
background is related to the hydrogenation levels; for instance, intensity of the 2D-band. The increase of the 2D peak activity,
samples with less than 20 atom % of hydrogenation were around 2700 cm−1, compared to the other peaks in the second
shown to not exhibit a photoluminescent background.42 Figure phonon region (∼ 2300 to 3300 cm−1) strongly supports the
4b shows the appearance of a new D** band at ∼1500 cm−1, decrease in the density of hydrogen groups on the graphitic
which possibly can be assigned to the contribution of C−H structure, since that band is sensitive to π-structure of
vibrations in hydrogenated carbons58 or to the reduction in the graphene.57
number of layer66 due to the intercalation of hydrogen A typical Raman spectrum of the carbon sample
functionalization. Considered as a whole, the Raman features dehydrogenated at a higher temperature (HG600) is presented
in Figure 4b are signatures of a hydrogenated graphene in Figure 4d. Overall, the Raman features of the HG600
structure. The Raman data corroborate the FTIR and XRD product (Figure 4d) present characteristics similar to those of
results discussed in Figures 1 and 2, respectively. Furthermore, the precursor graphite (Figure 4a). Most of the defect-induced
the hydrogenation promoted an increase in the defect-induced bands are not present in the spectrum of Figure 4d, which is
D-band, as shown in Figure 4b. The double-phonon area has dominated by major peaks in the G- and 2D-band regions.
also changed from a high-intensity 2D band observed in Figure This result proves the recovery of the graphitic structure after
4a to triple bands assigned to 2D (∼2650 cm−1), D+ D′ thermal treatment of the HG samples. The shape and position
(∼2900 cm−1) and G+ D′ (∼3130 cm−1) in Figure 4b. The of the 2D-band are sensitive to the number of graphene layers.
triple bands in the second-phonon region (between ∼2650 and Figure 4e and f present an expanded view of the 2D region for
3131 cm−1) are similar to some Raman features reported for precursor PG and HG600 sample, respectively. The peaks in
graphene oxide, where those peaks illustrate the disruption of the 2D region were fitted by Lorentzian line shapes. The 2D-
the graphitic structure and the D+ D′ (also assigned as D + G band in bulk graphite (PG, Figure 4e) consists of two
band) and G+ D′ band that arise due to lattice disorder and components: 2D1 and 2D2, at approximately 2695 and 2735
defects.61,63,67 A broad feature in that region was also proposed cm−1, respectively. Compared to the graphite peak in Figure
as evidence that nanocrystalline graphite had been transformed 4e, HG600 has the component peak of 2D1 that is more
into low sp3 amorphous carbon.59 dominant exhibiting in Figure 4f. It has been demonstrated
The Raman spectrum of the HG500 sample in Figure 4c that as the number of graphene layers decreases to below 5, the
presents features previously assigned to graphene or nano- relative intensity of the lower frequency peak, 2D1, increases
crystalline graphene structure.60,67 There are several defect- progressively relative to the 2D2-peak.56,68 The deconvolution
induced bands including the D-band (∼1350 cm−1), the D′- of the contribution from the 2D1 to the overall 2D-band,
band (∼1615 cm−1) and their combination, and the D+ D′- presented in Figure 4e,f, indicates that thermally treated
band (∼2970 cm−1). In particular, the D-band is assigned to a hydrogenated graphene sample HG600 has fewer stacked
breathing mode at the K-point while the D′-band corresponds layers than PG. Furthermore, the restored graphitic structure
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after dehydrogenation of the HG product (HG600) can be evidenced by the decreasing intensities of both D- and D′-
classified as restacked graphene layers with random stacking bands in HG600, suggesting that the reduction process is more
known as turbostratic graphite.69 The absence of an interlayer efficient at higher temperatures. The HG sample in Figure 4a
interaction between the graphene planes in turbostratic exhibits a D**-band around 1500 cm−1 that is related to sp3
graphite yields a Raman signature that is similar to that carbon hybridization.58
observed from a monolayer graphene but with larger line The well-known Tuinstra and Koenig relation (ratio of the
width.70 This is consistent with the more symmetric shape of D- to G-band intensities (ID/IG))51 is commonly used to
the broad feature in Figure 4f compared to that in Figure 4e quantify disorder or determine the crystalline quality of
due to the blue shift of the 2D band. graphene. The ID/IG-value is expected to vary inversely with
While the changes in the Raman spectrum of graphene oxide the crystallite size (La) or the distance between the defects
under the reduction are normally considered in the first (LD). These are opposite trends in terms of quality.51,62
resonant range, the Raman spectra of hydrogenated graphene However, second-order bands can be used to supplement the
before and after the reduction process have significant crystalline quality information for graphene-based materials.62
differences in the second resonance range. It should be In particular, the ratios of the second phonon bands (2D, D+
noted that the 2D band is sensitive to the π-band structure.57 D′) to the G-band change in the opposite way; I2D/IG show an
The oxidation process normally causes ring opening and increase for increased crystallinity, while ID+D′/IG show a
formation of carboxylic groups resulting in the destruction of decrease as demonstrated by Vollebregt.62 The various ratios
the conjugated system.20,57 This means that graphene of the Raman spectra of the HG samples in Figure 4 are listed
synthesized through the reduced graphene oxide route inherits in Table 2. The resulting trends demonstrated an increase in
in-plane vacancy defects from the graphene oxide precursor. crystalline structure quality of HG samples after thermal
These defects are readily evident in the Raman signature of the annealing, particularly at higher temperature.
material by the suppressed 2D band.58
In summary, graphene oxide and hydrogenated graphene Table 2. Comparison of Ratios of Raman Peaks of Pristine
have quite similar Raman bands except for the fluorescence Graphite and Hydrogenated Graphene Derivatives
effect observed for the hydrogenated case. The intensity ratio
of the D- and G-bands is about 1 and the triple bands are in sample
2D
I(G) I(
D+D
)
G
the second resonance range for both materials. The HG PG 0.3 0
samples produced here are well functionalized on graphene HG 0.2 0.3
sheets and lead to disordered graphene structures upon HG500 0.3 0.1
annealing. HG600 0.5 0
Raman spectroscopy was used to characterize defects and
crystalline structures in the hydrogenated graphene derivatives.
Three distinct kinds of defects, namely on-site defects, The results from Raman and XRD data presented in Figures
hopping, and Coulomb defects, are possible in the electron- 2 and 4 indicate that the HG route is more viable for the
defect scattering model.53 Specifically, hydrogen bonding to a preparation of graphene-like materials than the graphene oxide
carbon atom in the graphene sheet is considered as a type of approach, since it allows for large-scale graphene synthesis with
on-site defect, while hopping defect is described as vacancies in lower temperature and less disordered structure. Hydrogen can
the graphene structure.48,49,53 The main defect-induced Raman intercalate into graphene layers and break van der Waals forces
features are the D-band at 1350 cm−1 and the D′-band at 1625 (as oxygen does), but the hydrogenated material can be
cm−1. The characteristics of those features were proved to be reduced more efficiently than oxygen functional groups to yield
proportional to the concentration and type of defects.49,53 The graphene sheets.
Coulomb defect, also referred to as charged impurities, is not Finally, the HG samples were coated on glass substrates to
expected to exert the same influence on the D- and D′-bands.48 obtain graphene-like films upon annealing. The films were
In fact, the intensity of the D-band is expected to increase with Raman mapped (196 Raman spectra each); i.e., the laser was
the defect density while the D′-band intensity stays constant.48 rastered across the film. The mappings were used to obtain
Therefore, the ratio of the integrated intensities from the D- some information about the chemical homogeneity resulting
and D′-bands can be used to define the origin of the defects.48 from both the hydrogenation and annealing processes. Figure 5
The convergence of the D′-band with the G-band is observed shows the results of Raman mapping distribution histograms of
at elevated levels of defect concentrations.48 This phenomenon hydrogen content, calculated using eq 1, from individual
accounts for the nonexistence of a distinct D′-band in the Raman spectra for HG films deposited on glass substrates. The
HG600 sample depicted in Figure 4d. On the other hand, both Raman mapping results in Figure 5a,b exhibit a uniform color,
the D- and D′-bands are present in Figure 4c for the HG500 demonstrating that the HG films adhered well before and after
sample. The integrated intensity ratio of D and D′ (ID/ID′) annealing on a glass substrate, maintaining a relatively uniform
calculated from Figure 4c was 11.8. This value is close to the spatial composition. Figure 5c shows that the distribution of
ID/ID′ = 13 expected for sp3 defect type as described by hydrogen contents for the HG film was about 45% with a
Eckmann et al.48,63 In the case of graphane (HG), shown in spatial variation of about 3−5%. On the other hand, the
Figure 4b, the D-band is attributed to the stretch motion of the histogram for the annealed sample, HG600, showed a sharp
C(sp3)−C(sp3) bonds or the wagging motion of the C(sp3)− peak of 20%. Notice that Raman spectroscopy is used in Figure
H bond and the D′-band is due to the wagging motion of 5 to determine the level of hydrogenation of the films based on
C(sp3)−H bonds on hydrogenated graphene.46 The analysis of a method that correlates hydrogenation with the background
the Raman data suggests a partly dehydrogenated process for fluorescence in hydrogenated materials.42 That method,
the HG samples annealed at 500 °C. A more efficient however, has a minimum limit of hydrogenation level
dehydrogenation occurred at higher temperature (600 °C), as estimation at ∼ 20 atom %, i.e., films with H% ≤ 20% are
40392 https://doi.org/10.1021/acsomega.3c04788
ACS Omega 2023, 8, 40387−40395
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Advanced Materials and Related Technologies, University of

Victoria, Victoria, BC V8W 2Y2, Canada; orcid.org/
0000-0003-4658-4956
Ian Booth − XlynX Materials Inc, Sidney, BC V8L 3R6,
Canada
Arash Azarakhshi − Center for Advanced Materials and
Related Technologies, University of Victoria, Victoria, BC
V8W 2Y2, Canada; Department of Physics and Astronomy,
University of Victoria, Victoria, BC V8W 2Y2, Canada
Peter Berrang − XlynX Materials Inc, Sidney, BC V8L 3R6,
Canada
Jeremy Wulff − Department of Chemistry, University of
Victoria, Victoria, BC V8W 3 V6, Canada; Center for
Advanced Materials and Related Technologies, University of
Victoria, Victoria, BC V8W 2Y2, Canada; orcid.org/
0000-0001-9670-160X
Figure 5. Raman mapping of (a) HG and (b) HG600. Comparisons
of hydrogen content (%) relative to (c) normalized frequency and (d) Complete contact information is available at:
area fraction. https://pubs.acs.org/10.1021/acsomega.3c04788

Notes
indistinguishable. The results for the annealed sample, Figure The authors declare no competing financial interest.
5d, imply then that ∼98% of the film coated on a glass
substrate contains less than 20% H content after annealing.
These results, combined with the features discussed in Figure
4, point toward very effective dehydrogenation and graphene-
■ ACKNOWLEDGMENTS
This work was funded by the MITACS Accelerate Program.
like characteristics for annealed graphene (HG) films coated
on glass substrate. The uniformity of HG and HG600 samples
on the glass can be explained by the fact that the polar surface
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