RAMAN CHARACTERIZATION OF STRUCTURAL

PROPERTIES OF THERMALLY MODIFIED NANOGRAPHITE.

Muhammad Ali

Supervisor: Tatiana Makarova

Master’s Thesis in Physics, Department of Physics, Umeå University

I
Department of Physics
Linnaeus väg 20
901 87 Umeå
Sweden
www.physics.umu.se

II
ABSTRACT
Raman spectroscopy is highly sensitive to study the structural properties of nanographite
(NG) materials. An experiment was conducted to assess the spectrum of multi-shell
nanographite at different temperature and laser treatments. Four samples with different
temperature were used. The range of temperature used was 1500-1650 oC. All samples
were subjected to different laser treatments like 488, 514, 633 and 785 nm respectively.
The spectrum of nanographite was observed by using the Raman spectroscopy. The 1st
and 2nd order spectra of NG were evaluated by using the Voigt analysis. The variations in
the intensities of D and G bands were analyzed. The decrease of D band width with heat
treatment was observed. The peak 1523 cm-1 exhibited more and more reduction with
increase in temperature treatments. Temperature induced the conversion of nanodiamond
to nanographite.

III
 TABLE OF CONTENTS

Sr. No. Contents Page No.

Abstract III
Acknowledgements V
1 Introduction 1
2 Theory 3
2.1 Graphite 3
2.2 Hexagonal Graphite 5
2.3 Rhombohedral (beta) Graphite 5
2.4 Polycrystalline Graphite 5
2.5 Nanographite 6
2.6 Raman Spectroscopy 8
2.7 Raman Spectroscopy For characterizing sp2 and sp3 nanocarbons 11
2.8 The dispersion of D and G bands 16
3 Experimental Section 18
3.1 Sample Synthesis 18
3.2 Experimental Work 19
4 Results and Discussions 21
5 Summary and Conclusions 45
6 References 46

IV
 ACKNOWLEDGEMENTS

If all infinite resources of water are turned in ink and all the wood turned in to pens even then it is impossible
to express His affections, generosity, bounteous blessings and neutifulness, because the words are bound,
knowledge is finite and time is limited. I must bow my head to offer my humblest and sincerest thanks to
″Almighty Allah″ Who enabled me to perceive and persue higher ideas of life.

I do offer the earnest reverences for the Holy Prophet (PBUH) who is embodiment of knowledge and
sages for whole mankind.

I feel heartiest end ever burning flame of my gratitude and deep sense of devotion to my respected
worthy supervisor Tatiana Makarova, Department of Physics, Umeå University, Sweden whose auspices I
took intride the completion of this work, Her thorough analysis and rigorous critique improved not only the
quality of this dissertation but also opened an avenue for the understanding of Physics, I am obliged and
grateful deeply for his sympathetic and inspiring guidance, keen interest his enlightened approach and
affectionate behavior throughout the course of my research work.

I am also greatly thankful to my examiner, Thomas Wågberg, Department of Physics, , Umeå

University, Sweden for their guidance and kind cooperation provided during the course of my study.

I am very thankful to the teachers of the Department of Physics, Umeå University, Sweden for
providing me a peaceful working environment.

Last but not least, I feel helpless in searching words to pay tribute to the personalities my Fathar and
Mother for their day and night prayers which boosted my moral to fly high to accomplish my goal

I am thankful to my wife Sidra Jamil for her encouraging behavior which proved a solid foundation
during my period of education.I am feeling short of words to express my heartiest feelings to my brothers,
Ahmad Hussain, and Mahmood ul Hassan for their nice and encouraging behavior throughout the duration
of my study. Sweet wishes for my kind and loving sisters Saima Azeem and Zahra Noreen for their love and
encouraging behavior which proved a solid foundation during my period of education.

Muhammad Ali

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1. INTRODUCTION
The carbon nanostructure with a well developed π-electron system like nanotubes, nanographite
and turbostractic carbons has been a subject of special interest. Nanofibers, nanoribbons,
nanohoops, nanocones, nanohorns, nanoonions and graphene are regarded as carbons structure
with nanometer size. It is generally accepted that the ability of multishell diamond like carbon to
maintain the exceptionally high charge/discharge rates without a considerable loss of capacitance
is due to its hexahedral structure and small particle size, resulting in a high curvature. The
increased capacitance achieved are related to the moderately high surface area of curved graphic
shells, combined with the high charge–discharge rate capabilities and high electrical conductivity
makes diamond like carbon attractive for high-power applications[47]. In graphite, atoms are
strongly bonded within the sheet but the layers can slip easily over each other due to weak force
between them. Therefore the graphite is used as a dry lubricant, as pencil or standard material for
scanning probe in microscopy etc. When the large numbers of defects are introduced in the
graphite then it behaves like hard material. The pyrolytic graphite and carbon fibers are
extremely strong and heat resistant (about 3000 oC) materials. Such types of materials are used
for jets and missiles, high temperature reactors, electric motor brushes, reinforced plastics etc.
Due to this wide range of applications graphite has been studied for last sixty years [5].

Graphite and diamond are the most naturally occurring chemical elements of carbon. There are
many forms of carbon known as allotropes that can be considered as pure forms of carbon but
arranged in a different crystal lattice. These forms include hexagonal graphite, rhombohedral
graphite, diamond, buckminsterfullerene and amorphous carbon. The chemistry of graphite and
diamond is same but with different crystalline structure (polymorphs) [1]. Diamond like Carbon
(DLC) is a metastable form of amorphous carbon. It contains a significant fraction of sp2 and sp3
type C bonds. The DLC can be insulator with high resistivity if it is structurally very close to the
tetrahedral amorphous carbon or ta-C on plots of bonding ratio with hydrogen content. It is very
interesting that if DLC prepare in the medium cobblestone version then electricity can pass
through it (Conductor). This process results in the formation of DLC which behaves like a
semiconductor [1,3].

1
The multishell nanographite (MSNG) particles are usually produced by the annealing of
detonation nanodiamonds (grain size ~5 nm) in inert atmosphere or in vacuum causing the
transformation of nanodiamond to multishell nanographite. Nanodiamond begins to graphitize at
about 1500 oC. The MSNG were obtained by the heat treatment at 1500, 1550, 1600 and 1650 oC
of nanodiamond particles lead to their conversion to the mixture of quasi-spherical carbon onion
and multishell polyhedron nanographite [6].

Raman effect was discovered by an Indian Physicist Chandrasekhara Venkata Raman who won
the Nobel Prize in 1928. Raman spectroscopy is powerful technique that can be used for
characterization of carbon nano materials. Raman is suited to detect the small change in the
structural morphology of the carbon nano materials. Raman spectroscopy is also used to
characterize the material composition and to analyze the specific phonon mode energy. It is
traditionally carried out at wavelength in blue 488 nm and green 514 nm spectral regions but
multi-wavelength Raman studies are increasingly used. It has been a considerable improvement
in the field of multi-wavelength Raman spectroscopy in carbon systems. Raman measurement
needs very little sample preparation and rapid nondestructive spectrum can be easily achieved.
Raman spectroscopy is very good to investigate the crystallinity of micro and nano materials
through the phonon confinement effect. The phonon confinement effect occurs with the lifting of
phonon momentum selection rule q=0 for the Raman scattering process. This phenomenon
occurs when the crystalline domain becomes very small and it effects as both the frequency shift
and an asymmetrical broadening of phonon modes. The intensity of Raman scattering is
proportional to the number of density of interacting media.

In this thesis chapter 2 presents the theoretical information about graphite, nanographite and
Raman spectroscopy for characterization of sp2 and sp3 nanocarbons. Additionally the
information about the dispersion of D and G band are also expressed in this chapter. In chapter 3
sample synthesis and experimental work is described. All the results and discussion are
expressed in chapter 4 and chapter 5 gives the summary and conclusion about this thesis.

2
2. THEORY
2.1 Graphite:

Carbon is an element of group IVA in the periodic table having the electronic configuration 1s2,
2s2, 2p2. Graphite is the most stable allotrope of carbon materials. The graphite is very fine
conductor of heat and electricity and has highest natural strength and stiffness as compared to
any other material. It is one of the lightest in all reinforcing agents and has high natural lubricity.
The sp2 hybridization undergoes due to one s-orbital and two p-orbitals in the carbon atom [7].
One electron in 2s2 state is stimulated and combines with the 2p orbital to form the 3sp2 orbital
and one unhybridized delocalized (free) p-orbital electron (Fig. 2.1).

1s2 2s2 2px 2py 2pz

Ground state

1s2 2s2 2px 2py 2pz

Promoted

1s2 2sp2 2sp2 2sp2 2p

Sp2 Hybridized

Figure 2.1: sp2 hybridization of carbon atoms.

3
The sp2 bonded carbon atoms are densely packed in the planar hexagons sheet. This planar
atomic sheet is called the graphene. The carbon-carbon bond length in the graphene is about
0.142 nm. The graphene sheet stacks to form the graphite with the interplanar spacing of 0.335
nm as shown in figure 2.2. These graphene layers loosely bonded and have the twice spacing
distance than the Vander Waals radius of carbon. This bonding arrangement results due to the sp2
hybridization of carbon electronic orbitals. The hybridized fourth valence electron is paired with
another delocalized electron to the adjacent plane from Vander Waals bond. Graphite can
conduct the electricity due to the vast electron delocalization within the layers of graphite. The
valance electron is freely moved within the planes of layers, so electricity can conduct within the
planes of the layers of graphite. It means that phonon can propagate very quickly along the
tightly bonded planes but slower to move along one plane to another plan. [8].

Figure 2.2: Structure of graphite and graphene [49].

4
Graphene layers stack in different ways to form the graphite hexagonal lattice and rhombohedral
lattice.
2.2 Hexagonal graphite:

The hexagonal graphite is formed by the stacking layers of graphene in sequence of ABABAB.
The planar layers are stacked in such a way that the atoms of hexagon lie exactly above or below
of nearest atoms and the center of the hexagons in the neighboring atoms. It belongs to the
P63/mmc (D46h) space group. Such type of graphite is bulk or flat and thermodynamically
stable form of graphite. By using the mechanical treatment, the hexagonal shape can be
converted to rhombohedral form and this form can be return to hexagonal structure when it is
heated to above 1600 K [8].

2.3 Rhombohedral (beta) graphite:

The rhombohedral has stacking order of ABCABC. This type of graphite does not exist in nature
in pure form. It is found only in combined form with the hexagonal graphite and it is
thermodynamically unstable form of graphite [8].

2.4 Polycrystalline graphite:

Hexagonal graphite which described above has no defect and naturally this form of graphite is
seldom. But in case of polycrystalline different forms like Pyrolytic graphite, carbon fiber,
carbon matrix composites, carbon black and vitreous carbon are all reported. They graphite can
exhibit a random orientation, more or less preferred orientation, or a highly oriented texture as in
some pyrolytic graphites. Their planar may not be perfectly to each other as compared to the
hexagonal graphite. The large cluster type is often found in pyrolytic graphite that is more
uniformly ordered, free of defects and planar layers are more parallel to each other [8].

5
Figure 2.3: Structure of (a) Hexagonal and (b) Rhombohedral graphite crystal. The view is
perpendicular to the basal plane [8].

2.5 Nanographite:

The term nanodiamnod is used for a variety of diamond based materials at nanoscale.
Nanodiamonds are produced by the explosive detonation and have mean size distribution about 5
nm. The natural diamond is hydrophobic but nanodiamond is hydrophilic. Nanodiamond core
comprises of sp3 orbital structure and it is surface contain sp2 orbital structure. Therefore the
surface also has dangling [9]. Nanographite samples are prepared by the heat treatment of
nanodiamond. The nanodiamond particles (5 nm) are heated at different temperatures i.e., 1500
o
C, 1550 oC, 1600 oC and 1650 oC leads to their conversion of mixture quasi-spherical carbon
onions and multi-shell polyhedral nanographites.

6
 Figure 2.4: Chemical formula of trinitrotoluene (TNT) and hexogen structure [48].

This heat treatment changes the structural properties of the materials. The quasi-spherical and
polyhedral nanographite structures initially found in the detonation-synthesized nanodiamond
heat-treated at high temperatures. The nanodiamond to nanographite transformation starts from
the surface of nanodiamond layers. Then graphitization front propagates into the diamond core.
The annealing temperature and time duration determines how much amount of carbons atoms
transferred from sp3 to sp2 hybridization [6].

7
2.6 Raman Spectroscopy:
Raman spectroscopic techniques are used to study the vibrational, rotational and other low
frequency modes. The shift in wavelength is unique for every material that is called as
fingerprints of materials. Raman affect is due to the interaction of electromagnetic field of
incident beam with the sample material. When a laser beam falls or strikes on the sample
material it may interact with it in different form like an absorption, scattering or reflection. Here
Raman affects deal with the scattered situation [10].

Figure 2.5: Schematic diagram of Raman spectrometer showing essential features [11].

When the laser light is incident on the molecule or atom, the incoming phonon interacts with the
phonon in the atom or molecules. The laser beams scattered from the molecules or atom can
suffer the Rayleigh scattering, Stokes scattering or Anti-stokes scattering. A large fraction of
laser light scattered that is called Rayleigh scattering. In Rayleigh the emitting photon has same
energy as an incident photon. The inelastic scattering of photon known as the Raman effect. A
few are shifted to higher energy wavelengths (Anti-stokes scattering) but most are shifted to
lower frequencies (stokes scattering) [10]. When the phonons in molecule or atom are in ground
state, they interact with the incident phonon and excited into the virtual or the real transition state
at high energy. Due to instability, phonon tends to back its initial state and emitting a photon of
same energy (Rayleigh scattering). A few electrons fall back to the higher energy state just above
the ground state by emitting the photon of lower energy that is called stokes scattering. The
incident laser beam may be also excited the phonon from the above state of their ground state. In

8
this situation electron falls back to the ground state emitting a photon having more energy than
the incoming photon. This process is rare and called as anti-stokes scattering [12].

Stokes scattering is most common than anti-stokes scattering because mostly electrons exist on
the ground state at normal temperature. In Raman spectroscopy, stokes scattering is used mostly
because anti-stokes scattering is less intense than stokes scattering. The shift in wavelength of
stokes and anti-stokes scattering compared to the incoming photon wavelength to vibrational
energies of molecules that is called Raman shift [12].

Virtual states
Energy

Vibrational states

Ground states
Rayleigh Stokes Anti-Stokes
Scattering Scattering Scattering

Figure 2.6: Raman transitional diagram.

In Raman spectroscopy scattering is possible when a photon can interact with the vibration of
molecules. The polarization of molecules with an electric field will change during the interaction
of incident light on the molecules or atoms. The dipole moment P is induced in molecule by
external electric field E with frequency ω.

P E (1)

Where α is the polarizability of the molecules. If a molecule is vibrating then polarizability

depends on the vibrational frequency of molecules. In classical mechanics E and P of the

9
molecules are oscillating during the interaction process. The oscillating function of electric field
depends on the frequency of light,

E = Eo cos 2πνo t = Eo cos ωot (2)

Where νo is the frequency of light and Eo is an interacted electric field with the molecules in time
t. Putting value of E in the equation (1), new equation will be

P = α Eo cos ωot (3)

The polarizability changes due to motion of nuclei in the molecules [13]. This term can be shown
by an expression depending on the internal vibrational mode q that is equation as

q = qo cos π νvib t (4)

Where νvib presents the eignfrequancy of nuclei. The equation for series α is presented as


  0  ( )q  higherorderterms (5)
q

Now inserting the equation (5) into (3), the new complex equation for dipole moment is
produced that is

1 
P  ( 0 E0 cos 0t )  E0 q [cos(0  vib )t  cos(0  vib )t ] (6)
2 q

In this equation the first term represents the equilibrium condition of the molecules and second
term ω0 ˗ ωvib and ω0 + ωvib expression are the stokes and anti-stokes shifts respectively [14].

10
2.7 Raman spectroscopy for characterizing sp2 and sp3 nanocarbons:

Graphite and diamond are the famous allotropes of carbon with wide range of disordered forms.
Raman spectroscopy is quite sensitive to these structures in which the translation symmetry takes
place in polycrystalline or grain size. It is powerful method to describe the characterization of
carbon material that needs little or no sample preparation becomes a suitable choice for Raman
spectroscopy [15]. It is very sensitive to short range disorder carbon material and can also expose
the different forms of amorphous carbons. Carbon materials itself from different compounds
undergo different structural changes in the original material due to rearrangement of the atoms
through different hybridization. The carbon materials are integrated with the linear chain of C-C
atoms forming the monomers and polymers. This type of homonuclear bonds show very weak or
no polarization due to high symmetry mostly found in the polymer system. The vibrational mode
will be symmetrical if molecules contains the centre of symmetry and infra red forbidden. The
existence of π-states in carbon materials with the sp2 bonds have very long range polarizability,
leading to a large Raman cross section making Raman spectroscopy a suitable choice [16].

Diamond is the crystalline form of carbon and belongs to the face centered cubic lattice. Its
Raman active phonon is a single, triply degenerate zone centered vibrational mode which is
attributed to C-C single bonds between sp3 hybridized carbon atoms in the cubic structure. This
mode is only Raman active with first order band appearing at 1332 cm-1 as a sharp line.

Graphite is the stacked sheet of carbon atoms in the basal planes arranged in the sp2 tetragonal
configuration. Graphite has two dimensional hexagon shapes with the fourth electron in the π-
orbital and perpendicular to the weakly bonded hexagon sheets [15]. Graphite has a high degree
of disorder due to strong C-C bonding. It will be sufficient to consider the graphene layers for the
physical properties of graphite because of weak interaction between the layers. The symmetry of
graphite is shown in figure 2.7.

11
 Figure.2.7: Graphite lattice in (a) top and (b) side view. α1, α2and α3 span the unit cell of
graphite [17].

The graphite has the six normal modes at q=0, these modes can combined in phase ( vib, 2 D  A1g

) or out of phase ( vib, 2 D  B1u ) to obtain the phonon vibration symmetry of graphite [17]. The

phonons vibration symmetry of graphite are given by

vib,3D  2 A2u  2B2 g  2E1u  2E2 g (7)

How the graphite modes split into higher frequency out of phase and lower frequency in phase
vibration are shown in figure 2.8.

The irreducible representation for the brillouin zone (BZ) center optical modes can be
decomposed into

  A2u  2B2 g  E1u  2E2 g (8)

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 E1u IR 1582cm 1
B2 g
B2 g
A2u
E2 g
E2 g
IR 1582cm 1

IR 868cm 1
B2 g
A2u E1u
R 42cm 1
127cm 1
E2 g

Figure 2.8: Phonon eigenvectors of graphene and graphite. Every phonon eigenvector of
graphene gives rise to two vibrations of graphite. For example, the in-phase combination of the
two layers for the E2g optical mode of graphene yields E2g  A1g= E2g and the out-of-phase
combination E2gB1u= E1u. Next to the graphite modes we indicate whether they are Raman (R)
or infrared (IR) active and the experimentally observed phonon frequencies [17].

The Raman active modes are 2E2g were observed at 42 and 1582 (G) cm-1 (Nemanich and Solin
1979). The maids at A2uand E1u have been observed at 867.8 and 1588 cm-1 (Nemanich et al.
1977) and one of the two optically inactive B2g modes were observed at 127 cm-1 by neutron
scattering (Nicklaus et al. 1972). The other B2g mode corresponds to out of plane atomic
displacement observed in the Raman spectrum of pyrolytic graphite edge planes. The peak is
possible when the Raman inactive mode B2g becomes Raman active due to crystalline point
group symmetry by a slight rearrangement of the lattice structure near the edge (Kawashima and
Katagiri 1999). According to these results, a sharp peak observed at 864 cm-1 for He-Ne laser
(633 nm) excitation and 864 cm-1 in the case of 780 nm laser excitation when an incident photon
is polarized at 90 degrees to the basal plane [18].

Raman spectroscopy of nanographite structure increased due to the measles relativistic properties
of electron conduction in a single layer of graphite [19, 20]. The plane size La of crystallites can
be determined by using the Raman spectrum of nanographite. The local arrangement of atoms in

13
nanographite has defined the edges as an armchair or zigzag shape. This local arrangement of
atoms can determined by the disorder induced bands in the Raman spectrum of nanographite.
This spectrum can be used if the nanographite sample presents the stacking order or turbostratic
structure.

The Raman spectrum of nanographite is divided into first and second order spectrum. The first
order spectrum lies in the range of 200-2000 wave number (cm-1), where the 200-900
wavenumber (cm-1) is the low energy region. The second order spectrum lies in the range of
2000-3400 wavenumber (cm-1).

The first order spectrum is characterized by the D-band at 1350 cm-1. This D-band is related to
the disorder induced in the nanographite and it is assigned to the k point of A1g symmetry. [21].

Figure 2.9: The Raman spectroscopy to characterize the diamond like carbons [22].

The first allowed band at 1580 cm-1 is called the G band that is originated from doubly
degenerated vibrational mode E2g. It occurs in the first Brillouin zone at the cross of (iLO) and
(iTO) phonon branches at the  point. [21].

14
 Figure 2.10: First order Raman spectrum of nanographite [22].

The intensities of Raman spectra of nanographite are dependent on the ratios of D (1350 cm-1)
and G (1580 cm-1) band intensities and structural properties of nanographite. The D and G band
ratio can be used to measure the crystalline size La of nanographite. This ratio is inversely
proportional to the crystalline size La of nanographite [23]. The Raman spectrum can be used to
measure the order occurring along the c axis and second order D and G-band is sensitive to the
degree of graphitization of the material [23].

According to the Tuinstra and Koenig relation with the coefficient belonging to Knight and
White:

La(nm) = 4.4 nm ID / IG (at green laser 514nm)

The crystalline size can also calculated by using the Cancado formula at different laser energy.

La (nm) = 560/ E4 (ID / IG)-1

Where E is the excitation laser energy used in the Raman experiment in eV units.

The D band mode also appears in the second order spectrum of nonographite at about 2700 cm-1
and has the double peak structure. The shape and position of the 2D peak is very good tool for
analyzing the stacking sequence of nanographite. The difference in the peak position in the
second ordered spectrum of single or multilayer graphene is useful to how many layers of
graphene are in the stacking sequence [24].

The 2450 cm-1 band and the 2D band corresponds to q=0 and fully dispersive q=2k respectively.
This band is assigned to an overtone mode of longitudinal optical phonon (LO) from the dispersion

15
and frequency of phonons [25] G+D at 2940 cm-1. The 2936 cm-1 is assigned to a combination of
the zone centre mode 1592 cm-1 and the zone boundary mode at 1358 cm-1 [26]. The 2960 cm-1 is a
band that becomes more intense with decreasing crystalline size [27]. The C-H stretching at 2925-
2970 cm-1 are absorption peaks in the C-H vibration region. The 2925 cm-1 is assigned to sp3-CH2
bonds that are asymmetrically Raman active. The 2970 cm-1 corresponds to CH3 bond
asymmetrically Raman active. 3000 cm-1 is assigned to sp2 C-H bonds [28]. The 2D´ band at 3250
cm-1 is suppressed with decreasing crystallite size [29]. The 3480 cm-1 maybe assigned to O-H
stretching of surface of hydroxyls generated from absorption of the trace of amount of moisture
[30].

2.8 The dispersion of D and G bands:

A variety of foure different excitaion energies are used to charactarize the Raman spectra of
nanographite. The Raman modes are assigned on the double resonance Raman effect. In many
Raman modes of nanographite there is presence of frequency inconsistency between the stokes
and anti-stokes lines. These frequency inconsistency values are highly dependent on the
excitation energy in which the D band values are change from positive to negative. The
frequency of the D band shows two important spectral features. First, the frequency of the D
band is highly dispersive for different sp2 carbon materials and shift with excitation energy at a
rate of 44 to 53 cm-1over wide excitation energy (ɛL). Secondly the stokes (ωs) and anti stokes (
ωAs) component of the D band in graphite materials have different frequency and this difference
in frequency is equal to the product of the phonon energy (ħωs) of D band and its laser energy
difference. The similar spectral property exists for the overtone of D band is called the 2D or
G´mode and other dispersive mode [7, 13].

The dispersion modes may have different values for different graphite materials. For example, by
1.96 eV excitation, the frequency of D modes in graphite whisker and single wall carbon
nanotubes are 1333 and 1323 cm-1 respectively. The stokes Raman spectra can provided the
probe of first order dispersive modes, because the frequency of higher order modes are the sum
of frequency of its fundamental modes. The frequency ωs of the first order or higher order stokes
mode can be detected by the frequency ωAs of the corresponding anti-stokes mode by the
excitation ɛL. For example, the anti-stokes frequency of the 2D´ mode by 2.54 eV excitation is
3235 cm-1, then can get the stokes frequency of the 2D´ mode by the 2.94 eV (2.54 eV + ħω2D´)

16
excitation is 3235 cm-1. Therefore the anti-stokes modes provide us more information on the
excitation energy dispersion properties of dispersion Raman modes. So, the dispersion properties
of anti-stokes Raman modes allow us to probe the phonon dispersion relation of the graphite
materials by using the double resonance anti stokes process.

17
3. EXPERIMENTAL SECTION

3.1 Sample synthesis:

Multishell nanographite (MSNG) particles were produced by the annealing of detonation
nanodiamonds (grain size ~5 nm) in argon flow. The MSNG nanogaraphite is prepared by the
heat treatment of nanodiamonds. This was done in the Department of Technology, Tokyo
Institute of Technology, Enoki Laboratory, and described in the paper “Magnetic and EPR
studies of edge-localized spin paramagnetism in multi-shell nanographites derived from
nanodiamonds” by V.Yu. Osipov, A.I. Shames, T. Enoki, K. Takai, M. Endo, T. Hayashi, Y.
Kaburagi, A.Ya. Vul. Diamond and Related Materials, 18, 220. Below are the main points of this
paper.

Prolonged (up to 2 h) heat treatment at 1500, 1550, 1600 and 1650 °C of nanodiamond particles
(5 nm) leads to their conversion to the mixture of quasi-spherical carbon onions and multi-shell
polyhedral nanographites. This treatment changes structural properties of nanodiamonds.

Figure 3.1: The HRTEM images of nanographite with quasi-spherical carbon onions shape [6].

According to the high-resolution transmission electron microscopy (HRTEM) observation, the

annealing at T>1600 oC transfers the nanodiamond particles into the quasi-spherical carbon

18
onions after the few minutes of process (Fig 3.1a) and no traces of nanodiamond cores were
detected in the sample. Some onion-like particles which made up to 6-8 defective quasi-spherical
graphitic shells are enclosed into one another with an average inter shell spacing of 0.34−0.39
nm. One of such particle is marked by arrow in figure 3.1 a. The smallest diameter 0.83 nm of
the shell indicated by an arrow in figure 3.1 (a) that is as the small as the diameter 0.71 nm of the
C60 molecules. Further graphitization produces the polyhedral multi shell nanographite particles
with an empty core as the heat-treatment temperature or annealing time were increased (Figure
3.1d) [6].

3.2 Experimental work:

The experiment was conducted in physics department of Umea University. The samples were
studied by the Renishaw1000 micro-Raman spectrometer by using the three different lasers;
green, red and infrared laser.
Table.3.1 Lasers available in the Raman spectroscopy

Color Laser wavelength Energy

Green Argon ion 514 nm 2.41eV
Green Argon ion 488nm 2.54 eV
Red Helium-Neon 633nm 1.96 eV
Infrared Diode 785nm 1.57 eV

Raman spectrometer has the 5x, 20x, 45x and 50x lenses. In this experiment mostly 20x and 50x
lens were used for the characterization of nanographite. Raman spectrometer was calibrated with
Si wafer at about wavelength 520 cm-1.

19
 Figure 3.2: Renishaw1000 micro-Raman spectrometer in department of chemistry Umea
University.

All the samples were placed on the Si substrate for measurements. Each sample was measured at
three different points to get the structural information of nanographite by using the argon laser.
Similarly also measurements were done with Helium-Neon and diode lasers. The origin 8.5 and
PeakFit software was used for analysis of spectra. In the PeakFit software the Voigt function was
used to analyze the peaks in the spectra of samples.

20
4. RESULTS AND DISCUSSION
The D and G band at ~1350 cm-1 and ~1590 cm-1 indicates the presence of sp2 phase. The D
band is the disordered graphitic lattice (graphene layer edges) with the A1g symmetry. The
presence of D peak is defined as the rate of the disorder and shape. The G peak reflects more
graphitic planes [31]. Here disorder means the presence of elastic scattering sources for phonon
and electron systems. The perfect crystal with finite size (with size smaller than the mean free
path of electrons or phonons) shows the D band, here the domain boundaries can be considered
as the defects or disorder that is scattering the phonon and electron. The G peak is shifted to
~1582 cm-1 at temperature 1650 oC that is graphitic lattice with E2g symmetry. The D´ peak at
~1618 cm-1 is also produced in sample 1650 oC. The dispersion peak at ~1360 cm-1 is the extra
peak in first order spectra of nanographite [32].

The 1st order Raman spectra of nanographite approximately have the same result of green laser at
energy 2.41 eV as explained at energy 2.54 eV. The D peaks (disordered induce band) appeared
at ~1343 and ~1345 cm-1 respectively and bands at ~1596 and ~1595 cm-1 were very closed to
the G band for nanocrystalline graphite as shown in figure 4.2. This G band has a higher
frequency than the G peak of oriented pyrolytic graphite at ~1582 cm-1 as produced in sample
1650 oC. This means that sample 1650 oC has more planner, oriented and more graphite like
structure. At temperature 1650o C, the D´ peak was ~1612 and ~1615 cm-1 at 488 and 514 nm
respectively. The presence of D peak determined the amount of disorder and G peak determined
perfection of graphene layers. Both temperatures (1500 and 1600 oC) showed different
increasing and decreasing trend in both bands at different laser treatments (i.e. 488 and 514.5
nm). However, more intensity was observed in D band when subjected to wavelength of 514 nm
laser treatment under both temperatures. But under influence of 488 nm laser treatment both
peaks behave differently on above mentioned temperatures. So in this regard G peak showed
higher intensity at 1500 oC while at 1600 oC, no significant difference in both bands was
recorded. Under 1550 and 1650 oC, both peaks also behave differently when subjected to 488
and 514 nm. At 1550 oC both peaks were at same level by applying laser wavelength 488 nm
while a little bit increase was observed in G peak. However, when material was subjected to 514
nm laser treatment, a little bit more intensity in G band was recorded under both (1550 and 1650

21
 o
C) temperatures. This means that there is higher perfection of graphene layers present. So,
overall it was concluded that the graphene bands are temperature as well as laser dependent.

Table 4.1 Crystalline sizes La according to Tuinstra and Cancado at different laser energies

Samples Green (2.54 eV) Green (2.41 eV) Red (1.96 eV) Infrared (1.57 eV)

Ratio Cancado Ratio Tuinstra Cancado Ratio Cancado Ratio Cancado

(ID / IG ) (nm) (ID / IG ) (nm) (nm) (ID / IG ) (nm) (ID / IG ) (nm)

1500 1.78 7.5 0.99 4.3 16.76 0.63 59.94 0.50 184.32

1550 1.26 10.62 1.60 7 10.29 0.56 67.53 0.40 230.40

1600 1.36 9.81 0.94 4.1 17.59 0.63 59.94 0.38 239.61

1650 1.38 9.68 1.35 5.9 12.28 0.46 82.32 0.37 248.83

The results calculated by using the Tuinstra and Cancado formulas gave quite different values.
The green laser exhibited different values of La at different temperatures. It was suggested that
ID/IG depends strongly on the excitation laser energy used in the Raman experiment. Tuinstra
formula is only valid when we conduct an experiment by using the laser level 514 nm (2.41 eV)
[33, 34]. The green laser (514 nm) shows that the samples at 1500 and 1600 oC have small
crystalline size as compared to samples at 1550 and 1650 oC. It is related to the large sp2
hybridization in samples at both (1550 and 1650 oC) temperatures. The green laser has shorter
wavelength that can only probe the surface of the materials. The red and infrared laser gave the
larger crystalline size values because they can probe the depth of nanographite due to larger
wavelength.

22
 0 500 1000 1500 2000

1050 1650

Counts
700

350

1260 1600

840
Counts

420

2430 1550

1620
Counts

810

3300 1500
Counts

2200

1100

0 500 1000 1500 2000

-1
Raman Shift cm

Figure 4.1 The 1st order spectra of all samples with the blue laser (488nm).

23
 4000
G D G
1500o C 1595
2500 1351
1591
3500
488nm 1550o C
3000 488nm
D 2000 1377

1351
2500
1376
1500
2000

Counts
1542
Counts

1527

1500
1000
1000
500
500 1183 1187
470 630 842 470 631 832
0
0
-500
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
-1
Raman Shift cm Raman Shift cm-1

1400 D 1200
G G
1351 1591 1582
1200 D
1600o C 1000 1650o C 1350
1372
488nm 488nm
1000
800
1369
800
1524 600
Counts

Counts

600 1618
400
400 1523

200
200 1181 470 638
829 1175
633 845
470

0 0

-200 -200
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
-1
Raman Shift cm Raman Shift cm-1

Figure 4.2 1st order spectra of samples after peak analysis in the PeakFit at1500-1650 oC.

24
 0 500 1000 1500 2000

1020 1650
Counts

680

340

1290 1600
Counts

860

430

1950 1550
Counts

1300

650

1680 1500
Counts

1120

560

0 500 1000 1500 2000

-1
Raman Shift cm

Figure 4.3 The 1st order spectra of all samples with the Green laser (514nm).

25
 1800 D
o
1343
2000
G
1600 1500 C 1595
1550o C D
514nm
1400 514nm 1343
1370
G
1596 1500
1200
1374

1000
Counts

1526

Counts
800 1518
1000

600

400 500
1185
1188 624
200 470 823
470 628 825

0 0

-200
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
-1
Raman Shift cm Raman Shift cm-1

1400 D G
1345
1582
o 1000
1200 1600 C 1650o C D
514nm 1370
514nm
1345
G
1000 1595 800

800
600
1366
Counts
Counts

600 1524
1615
400
400
1525

200 1187 200

633 820 1181
470
472 635 824
0
0

-200
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200

Raman Shift cm-1 Raman Shift cm-1

Figure 4.4 1st order spectra of samples after peak analysis in the PeakFit at 1500-1650 oC.

26
 0 500 1000 1500 2000

1530 1650

Counts
1020

510

5100 1600
Counts

3400

1700

540 1550

360
Counts

180

3600
1500
Counts

2400

1200

0 500 1000 1500 2000

-1
Raman Shift cm

Figure 4.5 The 1st order spectra of all samples with the Red laser (633 nm).

27
 4000 600
D D
1309 1319
3500 o
o
500 1550 C
1500 C 633nm
3000
633nm
1352 400
2500
G
1590
1363
G
2000 300 1597
Counts

Counts
1532
1500
200 1538

1000
1180 100 1172

500 457 625

823

453 629 830

0
0

-500 -100
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
-1
Raman Shift cm Raman Shift cm-1

6000 D
D 1600 1321

1316 1650o C
5000 1600o C 1400 633nm
633nm
1200
4000 1344
1000 1351
G
1587 G
3000
Counts
Counts

800 1592

600 1619
2000 1533 1536

400
1185
1000 1175
200
470 625
828
472 823
0
0
-200
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
Raman Shift cm-1 Raman Shift cm-1

Figure 4.6 1st order spectra of samples after peak analysis in the PeakFit at 1500-1650 oC.

28
 0 500 1000 1500 2000

5100 E

3400
Counts
1700

15300 D

10200
Counts

5100

4800 C

3200
Counts

1600

2100 B

1400
Counts

700

0 500 1000 1500 2000

-1
Raman Shift cm

Figure 4.7 1st order spectra of all samples with the infrared laser (785 nm).

29
 2500
D 5000 1550o C D
1300
1500o C 1300
785nm
2000 785nm
4000

1500

Counts
1351
1352 3000
Counts

G
1000 1598 G
1598
2000
1527
1188
500 1183 1525
1000
520*
470
621 850 470
624 855
0 0

0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
-1
Raman Shift cm Raman Shift cm-1

D 6000
16000 o 1299 D
1600 C 1301
14000 785nm 1650o C
5000
785nm
12000
4000
Counts

10000
Counts

8000 1350 G 3000 1348 G

1598
1597
6000
2000
4000 1192
1527
1195 1523
2000 520* 1000
625 858
473
473 624
0 853
0
-2000
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
-1
Raman Shift cm Raman Shift cm-1

Figure 4.8 1st order spectra of samples after peak analysis in the PeakFit at 1500-1650 oC.

30
 Table 4.2 The FWHM of D and G bands at different laser energies

Samples Blue (2.54 eV) Green (2.41 eV) Red (1.96 eV) Infrared (1.57 eV)

Band width (FWHM), cm-1 for D band

1500 104 50 68 80
1550 73 89 62 73
1600 55 51 88 75
1650 56 41 61 69
Band width (FWHM), cm-1 for G band

1500 70 78 80 61
1550 78 81 63 68
1600 72 76 69 67
1650 40 43 61 60

The full wave half maximum (FWHM) of D bands behave differently at 514 nm. A variation in
FWHM at different temperature was noticed at different laser treatments as shown in above
table. However, more decrease in FWHM of D band was recorded at 1650 oC. The decrease in
FWHM of D band means that there is less disorder in the material. The nanographites at this
temperature (1650 oC) behave in same manners at all laser treatments. The FWHM of G band
also decreases and this decrease ranges from 78 cm-1 to 43 cm-1 at 514 nm. This decreasing trend
in FWHM of G band was similar under all laser treatments which are mentioned in the above
table. In basal planes the characterization level of graphitization is linked with specific
parameters of nanocarbons like FWHM of both D and G bands. This means that there is a higher
degree of graphitization if D and G bands are more constrict. The FWHM of G-band and ID/IG
ratio for multi-shell nanographites are almost highest compared to other graphitic materials with
well developed π-electronic system. The crystalline sizes of the nanographites at different
temperatures are extremely small as compared to other graphitic materials with well-developed
π-electronic network [1].

The dispersion peak of D band on red laser (633nm) was produced at ~1309, ~1319, ~1316 and
~1321 cm-1 as mentioned in figure 4.4. These disorders induced peaks are slightly lower than the

31
~1329 cm-1 as observed by Tan et al. (2011) for turbostractically stacked structures (TS). The G
band peak positions are different in all samples but they are very close to the ~1590 cm-1. The D
and G band positions are changed on red laser (633 nm). It is related to the change of wavelength
of the laser treatments and temperature variations. At 1650 oC red laser induced D´ peak was at
~1619 cm-1 that is strongly referred to the more oriented and microcrystalline graphite structure
[35].

Raman spectrum of nanographite with infrared laser (785nm) is shown in figures 4.8. The D and
G bands appeared at ~1300 cm-1 and ~1598 cm-1 respectively. The spectra with the infrared laser
(785 nm) of all samples showed similar trend with a little bit differences in peaks. For example,
the D peaks of have the lowest peaks value than the D peaks at green (488 nm and 514 nm) and
red laser (633 nm). But the trends of G bands were approximately same at all mentioned laser
treatments. Here the intensity of D band is also greater than the intensity of the G band in all
samples of nanographite (figures 4.8). The peaks related to nanodiamonds are very well seen in
Raman measurements. They are not only seen at the green laser line and also observed at red and
infrared laser.

The peaks around 470 and 625 cm-1 were observed in turbostratic stakes. In the nanographite
these peaks belongs to the density of phonon states (PDOS) in the LA and TA mod branches
[36]. The peak position 620 cm-1 has shifted upward by 8 cm-1, 4 cm-1, 13 cm-1and 15 cm-1 at
temperature 1500 oC, 1550 oC, 1600 oC and 1650 oC respectively as it was observed at 620 cm-1
by Osipov et al. (2011). The appearance of dispersion peaks around 830 cm-1was described as
PDOS. It is assigned to the intra-valley out of plane tangential optical (oTO) phonon branches, it
is counterpart with the auto phonon close to the Γ point and its activity is due to the plane
curvature [37]. This peak has shifted downward by 15, 17, 20 and 16 cm-1 in samples at 1500,
1550, 1600 and 1650 oC respectively as was presented at 840 cm-1by the Osipov et al. (2011).
These peaks in the lower region frequency have very weak intensities. The first peak has higher
frequency while the second and third peaks have lowest frequency that is observed in the carbon
onions. These peaks are related to the relaxation of the Raman selection rule that might be
caused by the curvature of graphene planes in the shell [38].

32
 350 o 600
1500 C o
2680 1550 C 2679
514 nm
300 514 nm
500
2757 2749
250
2941 400 2612
2931
200 2607 2848
2839
300
Counts

Counts
150
3122 3124
200
100 2489 3253
2487 3223

100
50

0 0

-50 -100
2000 2500 3000 3500 4000 2000 2500 3000 3500 4000
-1
Raman Shift cm Raman Shift cm
-1

500 o
700 1650 C
2699
o 514 nm
1600 C 2686
400 514 nm 600

500
2773
300 2749
2645
400
2614
Counts

2819
Counts

200 2932 300

3123 2863
200
100
2482 3231 2947 3242
100 2489
3175
0
0

-100 -100
2000 2500 3000 3500 4000 2000 2500 3000 3500 4000
-1 -1
Raman Shift cm Raman Shift cm

Figure 4.9 Second order Raman spectra at energy 2.41 eV.

33
 800 1000
2693

o
1500 C 2733
2692

488 nm 2836 2934 800

600 o
1550 C
2627
488 nm 2761

600
2917
400 2631 2939
Counts

Counts
3072
400
2485

200 3147

200 2488 3238

0
0

-200 -200
2000 2500 3000 3500 4000 2000 2500 3000 3500 4000
-1 -1
Raman Shift cm Raman Shift cm

600
1600
2693 2705

500 1400
o
1600 C o
1650 C
488 nm 1200 488 nm
400 2791
2761
2647 1000
2906 2643
300
Counts
Counts

800 2870
2962

200 600

3128
2463 400
100 3235 2945
3247
200 2459 3144
0
0

-100 -200
2000 2500 3000 3500 4000 2000 2500 3000 3500 4000
-1 -1
Raman Shift cm Raman Shift cm

Figure 4.10 Second order Raman spectra at energy 2.54 eV.

34
 200
600 1500o C 2616 1550o C 2633
633nm 633nm
500
2677 2698
2565
400 2561
2850
2899 100 2922
300
Counts

2823

Counts
3146
2460 3294
3157
200
2456
3230
100
0
0

-100
2000 2500 3000 3500 4000 2000 2500 3000 3500 4000
-1 -1
Raman Shift cm Raman Shift cm

1000
1600o C 1650o C
2622 500
633nm 633nm 2648
800
2717
400
2625
2825
600 2527 2907
300
Counts

Counts

2862
400
200
2431 3139 2925
200 3239 2459
100 3046
3239

0 0

-200 -100
2000 2500 3000 3500 4000 2000 2500 3000 3500 4000
-1 -1
Raman Shift cm Raman Shift cm

Figure 4.11 Second order Raman spectra at energy 1.96 eV.

35
The second ordered Raman spectra of four different samples of nanographite at energy 2.41 eV
and 2.54 eV are shown in figures (4.9, 4.10) respectively. These spectrums are to the overtone
caused by the defects resulting from double resonance Raman process. It was fitted by several
Voigt curves. The 2D band originates from a two phonon double resonance Raman process [39].
Sometimes the 2D band is also named as G band as it is a second most well-known band of
graphite [40]. Here it is referred as 2D band because it is the second order overtone of the D
band. The 2D band at 2680 cm-1 and 2679 cm-1 was recorded as overtone of the disorder induced
band at 1343 cm-1 in sample at temperature 1500o C and 1550o C. The peaks 2686 cm-1 and 2699
cm-1 which were produced are the overtone of the disordered at 1345 cm-1 at temperature 1600
o
C and 1650 oC respectively. The D+G modes were observed at 2941 cm-1, 2931 cm-1, 2932 cm-1
and 2947 cm-1 at previously nominated temperatures. The presence of D+G bands indicates the
structural disorder in the sample as well [31].

The peak at 2489 cm-1 (at 2.41eV) linked to the blend of oTo phonon and iLo phonon near the Г
point by a strong curvature of graphene sheet in the study of nanographite particles. This band
shifted upward 13 cm-1and 18 cm-1 in samples at 1500 oC and 1600 oC respectively and 20 cm-1
in materials at 1550 oC and 1650 oC as observed by Osipov et al. (2011) in diamond related
materials at 2469 cm-1. The strong curvature of graphene sheets was also observed at other (2.54
eV and 1.96 eV) laser treatments but the peaks showed a little bit deviation from peak which
produced at 2.41 eV. The 2D´ bands were also studied there at different points 3223, 3253, 3231
and 3242 cm-1 at different temperatures as shown in figure 4.9. These modes are related to
scattering of non center optical phonons in the brillioun zone. It has a mixed character as it is
neither longitudinal nor transverse optical or acoustic [41]. The 2G bands were produced at 3122,
3124, 3123, and 3175 cm-1. The modes at 2848, 2839, 2819 and 2863 cm-1 are natural with
positive dispersion can be assigned to the combination of D and 1518, 1526, 1524 and 1525 cm-1
peaks respectively.

The peak at 1172-1195 cm-1 can be certified to hexagonal diamond or sp3 rich phase. The
structure consists of both sp2 and sp3 bonding diamond like structure connected by the chain of
different length and composition [31, 42]. As our samples are produced from nanodiamonds, this
band may be due the disordered graphitic lattice, poylenes, ionic impurities and can be assigned
to the C=C and C-C stretching vibrational modes of a polyene like structure [43].

36
 1500
1195 1550
1600

1190

Peak Positions (cm-1)

1185

1180

1175

1170
1.4 1.6 1.8 2.0 2.2 2.4 2.6
Laser Energy

Figure 4.12 The 1172-1195 band position at different laser energies.

The bands were shifted in all samples to the higher position as observed at 1170 cm -1 by Osipov
et al. (2011). Then the 1170 cm-1 band can be assigned to a local vibration mode of TPA-like
chains which is most likely, weakly coupled with other phonon modes of the NG particle [31].
The bands of these peaks also become wider than observed by Osipov et al. (2011). All the peaks
showed positive dispersion at different laser photon energies. However, these peaks are laser
specific. It means peaks centered at different points at different laser photon energies. As
mentioned above that these peaks showed variations at different laser treatments. For example,
sample which has temperature 1550 oC showed increasing and decreasing trend in peak with
respect to different laser treatments. An increasing trend in peak was noticed at 1.57, 2.41 and
2.54 eV energy levels respectively. While at 1.96 eV a significant decrease in peak was recorded.
But the other peaks having temperature 1500 oC and 1600 oC showed a little bit opposite trend as
compared to peak with 1550 oC. Such as both peak showed increasing trend at 1.57 and 2.41 eV
energies respectively. While a decreasing trend was observed at 1.96 and 2.54 eV energies levels
respectively.

37
 1500
1360 1550
1600
1650
1350

D Peak position (cm-1)

1340

1330

1320

1310

1300

1290
1,4 1,6 1,8 2,0 2,2 2,4 2,6
laser Energy

Figure 4.13 The variation of D band values with respect to laser energies.

The D bands depicted approximately a linear positive dispersion relation. At energies 1.57, 2.41
and 2.54 eV the peaks levels were approximately at same points while at energy 1.96 eV peaks
range was 1309-1321 cm-1. Such as the lowest peak was observed at 1500 oC and highest peak
was produced at 1650 oC. All of this it is concluded that the ranges of peaks are temperature
specific at laser photon energy 1.96 eV. At 1650 oC another band which we called D´ band was
also noticed at all given treatments of laser. It may be due to the defects that is why D´ band is
produced only in this sample. The large amount of disorder and resultant decrease in plain
domain size (La) of the sp2 could give rise to the D bands.

38
 1500
1550
1600
2700 1650

2680

2D Peak position (cm-1)

2660

2640

2620

2600
1,9 2,0 2,1 2,2 2,3 2,4 2,5 2,6
Laser Energy

Figure 4.14 The 2D band position with respect to laser energies.

The 2D band showed positive dispersion relationship. An increasing trend was observed in
bands. At 1.96 eV peaks range was 2616- 2648 cm-1. The ranges of peaks were 2680-2699 cm-1
and 2693-2705 cm-1 at 2.41eV and 2.54 eV respectively.

In second order spectra it was concluded that the peaks were laser as well as temperature
specific. Remarkable variations in levels of bands were also recorded with respect to different
temperatures. At 1.96 eV, the peak with 1500 oC centered at lowest value while sample with
temperature 1650 oC centered at highest peak level. The peaks with temperature 1500 oC and
1550 oC exhibited the lower most peak points at laser energy 2.41 eV. However, at laser energy
2.54 eV all peaks were originated at same point except the peak having temperature 1650 oC. It
was noticed that peak with temperature 1650 oC occupied highest peak values in the graph. The
graph of second order spectra showed the variations in peaks with respect to temperature but this
trend was clearly observed at 2.41 eV. Such as at this level of laser energy, the peak points
showed increasing trend with an increase in temperature.

39
 1500
2970 1550
1600
1650
2960

2950

D+G peak position (cm-1)

2940

2930

2920

2910

2900

1,9 2,0 2,1 2,2 2,3 2,4 2,5 2,6

Laser Energy

Figure 4.15 The D+G band position with respect to laser energies.

The structural disorder can be indicated additionally by the presence of D+G bands. The graph in
the figure 4.15 shows different pattern of D+G peaks at different laser photon energies and
different temperatures. The band with temperature 1650 oC presented the highest peak values at
1.96 eV and 2.41 eV. While at 2.54 eV energy level, a deviation in trend of peaks was noticed.
At this energy level (2.54 eV) the band with 1600 oC exhibited the maximum peak value. The
overall pattern of the D+G bands in graph showed that the bands are temperature specific at
different laser photon energies.

Table 4.3 The amorphous carbon ratios in nanographite at laser energy 2.41eV and 2.54 eV

Samples 1500 1550 1600 1650

Laser energy 2.41 eV I1518s/ID I1526/ID I1524/ID I1525/ID
Ratio 0.31 0.57 0.26 0.08
Laser energy 2.54 eV I1542/ID I1527/ID I1524/ID I1522/ID
Ratio 0.68 0.27 0.18 0.14

The dispersion peak 1525-1542 cm-1 can be assigned to the amorphous carbon. It exists in the
form of interstitial defects outside the planes of aromatic rings with sp3 links or to odd-membered

40
ring structures which are also expected in the nanographite particles [31]. According to the
Dallas the presence of five membered or seven membered rings with vibration modes at 1529
cm-1 and 1531 cm-1 linking the nanocrystalline aromatic regions is explanation for this band
appearance [44]. The ratio of this band and relative intensity of D or G band peaks indicated the
relative contact of amorphous carbon in the disordered graphite. The values of ratio I1518-1542/ ID
for different samples presented in table 4 indicate the reduction of amorphous carbon contact
with increasing of temperature 1500 to 1650 oC with heat treatment detonation nanodiamonds.
The downward shift is caused by bond angle disorder present in the sp3 bonded fractions, which
forces the graphene sheet to be nonlinear or it may be due to the decrease of holes carriers in the
sample [45].

1540

1538
1550
1536
1600
1650
1534
Peak position (cm-1)

1532

1530

1528

1526

1524

1522

1.4 1.6 1.8 2.0 2.2 2.4 2.6

Laser Energy

Figure 4.16 The band positions between1525-1542 at different laser energies.

The figure 4.16 shows the ratio of amorphous carbons at different temperatures with respect to
laser treatments. The peaks with temperature 1550 and 1600 oC showed variations in the level of
peaks at different laser photon energies. The peak with temperature 1550 oC exhibited the
maximum value at laser energies 1.96, 2.41 and 2.54 eV. But at energy 1.57 eV highest value
was observed in peak of 1600 oC. While an opposite trend was noticed in peak with temperature
1600 oC. However, peak with 1650 oC exhibited a different trend. It showed the minimum peak
values at all laser treatments except the 1.96 eV. These lowest peak intensities indicated that

41
higher temperature improved the perfection of graphene sheets and reduced the concentration of
point like defects in nanographite.

G 1500
2000 1550
514 nm D
1600
1650
1500
Counts

1000

500

0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200

Raman Shift cm-1

1500
4000 G 1550
1600
3500 1650
488 nm D
3000

2500

2000
Counts

1500

1000

500

-500
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200

Raman Shift cm-1

Figure 4.17 Raman spectra of D and G bands of nanographite at 514 and 488 nm.

42
 1500
D
1550
16000 1600
1650
14000
785 nm
12000

10000 G
Counts

8000

6000

4000

2000

-2000
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200

Raman Shift cm-1

1500
1550
5500 D 1600
5000
1650
633 nm
4500

4000

3500 G
3000
Counts

2500

2000

1500

1000

500

-500
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
-1
Raman Shift cm

Figure 4.18 Raman spectra of D and G bands of nanographite at 785 and 633 nm.

43
The figure 4.17 and 4.18 shows the pattern of D and G bands at laser wavelength 514 nm, 488
nm and 633nm, 785 nm respectively. At 514 and 488 nm the width of D bands constricts more
and more from lower to higher temperature. Such as the peak with temperature 1500 oC was less
narrow as compared to peak at 1650 oC. The constriction of the peak at higher temperature
showed the more perfection of particles of nanographite. The peaks at 785 and 633 nm also
showed the deep valley but the behavior was irregular with respect to temperature.

44
 5. SUMMARY AND CONCLUSIONS
Raman spectroscopy is a very useful technique to characterize the structural properties of
nanocarbons. This experiment was conducted to analyze properties of nanographite. The
structural properties of nanographite were noticed at different temperature as well as laser
treatments. Different laser treatments were applied to nanographite to assess the structural
properties and perfection of nanographite. Positive results were observed by
characterizing the nanographite. The range of perfection varies with variations in the
temperatures. However, more perfect form of nanographite with well arranged graphene
sheets was gained at highest temperature treatment. So from this experiment it was
concluded that more perfection in nanographite could be acquired by giving heat
treatments.
It was concluded:
I. Temperature-induced changes from nanodiamonds to nanographite at all temperature,
particularly observed in sample with temperature 1650 oC which showed more planner,
oriented and graphite like structure.
II. Temperature-mediated reduction in integrated intensity of 1523 cm-1 strongly linked with
the improvement of crystal perfection of graphene sheets near the edges and mitigation of
point like defects.
III. Slight decrease of D band width with heat treatment temperature was resulted which
means that particles become less defective and more crystalline.
IV. The strong curvature of graphene sheets in second order spectra were additionally noticed
at different temperatures.

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