Phys. Scr. 98 (2023) 095030 https://doi.org/10.

1088/1402-4896/acf07b

PAPER

Fabrication of tunable band gap carbon based zinc nanocomposites

RECEIVED
20 April 2023
for enhanced capacitive behaviour
REVISED
23 July 2023
ACCEPTED FOR PUBLICATION
Dipti, Peeyush Phogat , Shreya , Deepa Kumari and Sukhvir Singh∗
15 August 2023 Research Lab for Energy Systems, Department of Physics, Netaji Subhas University of Technology, New Delhi, India
∗
PUBLISHED Author to whom any correspondence should be addressed.
31 August 2023
E-mail: [email protected]

Keywords: nanospheres, nanocomposites, thin films, bandgap, capacitor

Abstract
This manuscript highlights the tunable properties of carbon nanospheres by controlling the
concentration of zinc nitrate in them. Zinc nitrate has converted the phase of carbon spheres, which
has also altered the optical, structural and electrochemical properties of carbon nanospheres by
forming nanocomposites. Carbon nanospheres and their nanocomposites have been synthesized by
using a two-step hydrothermal method. X-ray diffraction analysis of the as synthesized material
revealed the formation of carbon spheres and their nanocomposites. It is also observed that the
crystallinity of the as synthesized material increases as the concentration of Zn(NO3)2.6H2O increases.
UV- visible measurements revealed a blue shift in the as-synthesized samples. With the increase in the
concentration of zinc, the band gap was also found to increase from 0.6 eV to 4.7 eV. The
morphological and microstructural analysis of the as-synthesized samples showed the formation of
nanospheres for as-synthesized carbon, and nano flakes for carbon nanocomposites. Fourier-
Transform Infrared Spectroscopy (FTIR) measurement provided the information about the molecular
structure and vibrational bands present in the samples. Electrochemical analysis of the thin film
revealed the capacitive behaviour of the material. The aerial capacitance and Nyquist plot represents
the capacitive properties of the material. The present study on carbon nanospheres and their
nanocomposites showed that the material is a potential candidate for the application in capacitors,
supercapacitors and energy storage devices.

1. Introduction

The limitations of traditional batteries in terms of energy density, power density, cycle life, environmental
impact and charging time have led to the exploration of more efficient storage device. In response, researchers
have turned their focus towards supercapacitors as a promising alternative since they are highly durable, have a
fast charging–discharging rate and are eco-friendly [1, 2]. Electric double-layer capacitors (EDLC) and pseudo-
capacitor (PC) are the two categories of supercapacitors. Porous carbon [3, 4], carbon nanofibers [5], graphene
[6, 7] and activated carbon [8] can be used for manufacturing EDLC electrodes because they have high specific
surface area. Among various potential materials for supercapacitors, the focus of the present research work is to
explore carbon and zinc-based nanocomposites along with their structural, optical and electrochemical
properties.
Carbon nanospheres have emerged as promising candidates for supercapacitors due to their unique
properties and structural characteristics which include high surface area, porous structure, electrical
conductivity, structural stability, scalability and environmental sustainability [9, 10]. Carbon nanospheres are
formed as a result of the pairing of pentagonal and heptagonal carbon rings which form circular concentric
graphite layers and are called carbon nanospheres. They can be synthesized by a variety of methods including
chemical deposition method (CVD), hydrothermal method and by usage of hydrocarbons and biomass [11–18].
They can be used in a variety of applications viz. adsorbents for dye removal, photovoltaics, gas sensing, etc [19].

© 2023 IOP Publishing Ltd

Phys. Scr. 98 (2023) 095030 Dipti et al

Table 1. The list of chemicals and analytical reagents used for the synthesis.

Chemicals used Company

Glucose (C6H12O6) M/s Thermo Fisher Scientific

Potassium Hydroxide (KOH) M/s Thermo Fisher Scientific
Zinc Nitrate Hexahydrate Zn (NO3)2 .6H2 O M/s Loba Chemicals
Sodium Hydroxide (NaOH) M/s Thomas Baker
Acetonitrile (C2H3N) M/s Thomas Baker

It is due to their excellent mechanical, chemical and optical properties that they can be used for fabricating
electrodes of supercapacitors [20, 21]. They also offer tremendous potential for improving the performance of
lithium-ion batteries since they have low mass density and are excellent charge transporters [22].
Nanocomposites are heterogeneous multiphase solid materials with at least one phase of the order of
dimension in nano-range and as a result they exhibit unique chemical properties, high surface areas, high
electron mobility and active functional groups. Due to these properties, nanocomposites show better adsorption
capacity and stability towards toxic pollutants than nanoparticles [23]. They can be synthesized by several
synthesis routes like sol–gel method, CVD, solvothermal/hydrothermal process, etc[24]. Bio renewable
nanocomposites can be synthesized by using cellulose, starch, vegetable oils, natural rubber etc [25]. Addition of
nanoparticles in polymers results in the formation of polymer nanocomposites which have higher conductivity
and thermal stability than their components [26]. Nanocomposites find applications in optical fibres, FET,
microelectronics, drug delivery, food packaging etc [23, 24]. Furthermore, carbon-based nanocomposites have a
variety of applications from photovoltaics, energy storage to electromagnetic interference shielding (EMI) [27].
Zinc (Zn) is a transition metal which forms oxides and hydroxides with various elements. Zn-based
nanocomposites can be used as an electrode material for supercapacitors because they have excellent
electrochemical properties and are inexpensive [28, 29]. To remove toxic gases, zinc carbonate compounds are
used in respirators [30]. Zinc hydroxide nitrate is a layered compound which finds applications in intercalations
and immobilization anion exchanges [31]. The thin films of the Zn-based nanocomposites can be synthesized by
various techniques like PVD, CVD, sputtering, spin coating etc [32]. Due to their mechanical properties, thin
films can be used as coating materials for wear and corrosion protection. They find applications in the
photovoltaic sector, electronics and optoelectronics [32].
In the present investigation, carbon nanospheres and carbon-based zinc nanocomposites have been
synthesized via hydrothermal route. Although, the carbon-based nanocomposites have been extensively studied
for various applications, including energy storage, catalysis, and sensing, there is still a research gap when it
comes to exploring carbon zinc-based nanocomposites. There is a need for reliable and scalable synthesis
methods for fabricating carbon zinc-based nanocomposites with controlled structure and composition. The
synthesis in the present manuscript enables the precise incorporation of zinc-based compounds into the carbon
matrix while preserving the desirable properties of both the materials. Another research gap includes the
electrical and electrochemical properties of carbon zinc-based nanocomposites. This includes evaluating their
electrical conductivity, charge storage capacity, and cyclic stability. The manuscript discusses the charge storage
capacity and cyclic stability of the as-synthesized materials in detail.

2. Experimental section

2.1. Chemicals used

The list of the chemicals and reagents used for the synthesis is presented in table 1. All solutions have been
prepared in ELIX Milipore’s DI water (>5 MΩ). Absolute Ethanol and Acetone from Changshu Hongsheng
Fine Chemical Co. Ltd has been used for cleaning purposes.

2.2. Synthesis of carbon nanospheres

0.5 M D-glucose solution has been prepared in 100 ml DI water and stirred for 30 min at room temperature.
Afterwards, the solution has been transferred to a 200 ml stainless-steel autoclave and placed in a hot air oven at
200 °C for 6 h. The solution has been then left to cool down naturally to room temperature. The obtained
precipitates have been centrifuged and washed with absolute ethanol and DI water several times. The as-
synthesized material has been then dried in a vacuum oven at 60 °C for 24 h. After drying, the sample has been
collected and ground till the fine powder is obtained and is coded as CSD.

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2.3. Synthesis of nanocomposites

60 mg of as-synthesized carbon nanospheres coded as CSD have been added in 1, 3 and 5 M solutions of sodium
hydroxide (NaOH) each. The solutions have been stirred continuously for 4 h at room temperature which
facilitates the adsorption of hydroxyl ions at a significant concentration on the surface of carbon spheres. The
solutions have been then centrifuged and the collected precipitates have been mixed with 1, 3 and 5 M solutions
of Zn (NO3)2.6H2 O. The obtained solutions have been stirred followed by ultrasonication for half an hour. The
solutions have been then transferred to 100 ml stainless-steel autoclaves and placed in a hot air oven at 200 °C for
12 h. Afterwards, the autoclaves have been left in the oven and allowed to cool naturally. The precipitates formed
have been further collected by centrifuging at 8000 RPM and washed twice with both ethanol and DI water. The
collected samples have been placed in a vacuum oven for drying at 60 °C for 18 h. After drying the samples in the
vacuum oven, the samples have been ground to obtain the fine powders. The samples of 1, 3 and 5 M are coded
as CSZD1, CSZD3 and CSZD5 respectively. For a better explanation of our analysis, the samples’ results are
colour coded as orange for CSD, blue for CSZD1, green for CSZD3 and pink for CSZD5.

2.4. Deposition of thin films (working electrodes)

Pre-cleaned fluorine doped tin oxide (FTO) glass substrates have been used for thin film deposition by using spin
coating technique. 400 μl solutions of respective samples have been dispensed on the FTOs using micropipette.
The FTOs have been then spun at 1500 RPM for 40 s and heated at 70 °C for 5 min. This process has been
repeated several times to get the uniform thin films of all of the as-synthesized materials. These have been kept in
a vacuum oven for drying at 70 °C for 15 h.

3. Characterisation

XRD spectra have been obtained by using XPERT-PRO Diffractometer PANalytical with Cu kα- radiation
(where λ = 1.54 Å) to analyse the crystal structure and composition of the samples. The optical behaviour along
with the bandgap has been determined by using UV–vis spectroscopy (make: Shimadzu 2006i UV visible
spectrometer). Microstructural features associated with the material have been investigated by using high
resolution transmission electron microscope (HRTEM, make: TECNAI) operated at 200KV. Surface
morphological investigations of the as synthesized samples have been done by using FESEM (make Jeol, model:
70106 F plus).
Spectroscopically parameters have been performed by using FTIR (make: Perkin Elmer) to determine the
vibrational bands in the samples. CV and PEIS studies have been performed using the EC-Lab Biologic SP-240
instrument.

3.1. XRD
The structural analysis of the as-synthesized samples has been determined by recording the XRD spectra in the
range from 5° to 90° for 2θ. The diffraction pattern of CSD revealed that the amorphous nature of the material
with a broad peak near 24°. The presence of broad peak shows a match with JCPDS file 01-075-2078 [33–35].
The as synthesized material reveals a rhombohedral crystal structure of carbon with characteristic peaks
corresponding to (111) and (010) planes as shown in figure 1(a). As Zn(NO3)2.6H2O is introduced into the
carbon matrix, the crystallinity of the samples increased. CSZD1 shows partially amorphous nature which shows
a match with JCPDS file 01-072-1100 confirming the formation of zinc hydroxide carbonate. Additionally,
broad peaks of carbon are also found to be present in this sample. It infers that the as-synthesized material is a
composite of zinc hydroxide carbonate with a monoclinic crystal structure and carbon with a rhombohedral
structure. The observed diffraction peaks corresponding to zinc hydroxide carbonate are (200), (020), (311),
(021), (510) and (−602) planes. These planes provide clear information about the crystal lattice.
The XRD spectra of as synthesized samples CSZD3 and CSZD5 revealed high crystallinity and showed a
match with JCPDS file 00-045-0593 confirming the formation of zinc ammine hydroxide nitrate with a
monoclinic crystal structure. The planes corresponding to diffraction peaks are (200), (−110), (310), (−111),
(−510), (−401), (020), (−511), (511), (020), (−601) (−112), (−402), (312), (−602) and (621). Along with highly
crystalline zinc ammine hydroxide nitrate some peaks of carbon are also present revealing the formation of
nanocomposites as shown in figure 1(b). The formation of amines is due to high presence of Zn (NO3)2.6H2 O in
CSZD3 and CSZD5 which has resulted in the reduction of nitrate into amines. The high concentration of 3 M
and 5 M Zn (NO3)2.6H2 O causes the introduction of amine in the material. The XRD patterns shown in
figure 1(b) clearly reveals that CSZD3 and CSZD5 are more crystalline than CSZD1 as they possess sharp
diffraction peaks. This increase in crystallinity is due to increase in concentration of Zn (NO3)2.6H2O.

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Figure 1. XRD pattern for (a) CSD & CSZD1, (b) CSZD3 & CSZD5 with their respective miller indices and crystal systems.

Table 2. Lattice parameters, size strain and stacking faults of as synthesized CSZD1, CSDZ3 and
CSDZ5.

Parameters CSZD1 CSZD3 CSZD5

a 16.5 Å 22.41 Å 22.42 Å

b 6.29 Å 6.31 Å 6.33 Å
c 5.46 Å 5.04 Å 5.05 Å
Debye Scherer Size 29.8 nm 15.9 nm 17.2 nm
W-H Plot Size 21 nm 35.9 nm 42.1 nm
Strain 3.27 ´ 10-4 5.87 ´ 10-3 4.91 ´ 10-3
Dislocation Density, δ 2.26 ´ 10-3nm-2 7.75 ´ 10-4nm-2 5.63 ´ 10-4nm-2
Stacking Fault, σ 3.2 ´ 10-3 5.1 ´ 10-3 4.3 ´ 10-3

The crystallographic parameters of the as synthesized samples are calculated using equation-1 [36] .
1 h2 k2 l2 2hl cosb
= + + - (1)
d 2 a sin b
2 2 b 2 c sin b
2 2 ac sin2 b
Where a, b, c are lattice parameters, h, k, l are Miller indices and d is lattice spacing. The calculated values are
summarised in table 2.
The crystallite size of the samples is calculated by using two approaches- Debye Scherer equation and
Williamson-Hall plot (W-H plot). While using Debye Scherer equation as given in equation (2), it is assumed
that there is no strain present in the material [37]. The calculated crystallite size for as synthesized samples are
approximately 29, 15 and 17 nm for CSZD1, CSZD3 and CSZD5 respectively as shown in table 2.
Kl
D= (2)
b cosq
Where D is crystallite size, K is Scherer’s Constant (0.9), l is wavelength of Cu source, b is Full Width at Half
Maxima (FWHM) and θ is peak position.
However, the deviation of lattice parameters from its standard value indicates that there is strain present in
the as synthesized materials. W-H plot takes into account the strain present in the material and thus, the
crystallite size and strain are calculated with more precision using this. Equation (3) known as Williamson Hall
equation [38] which is used to get the W-H plots.
Kl
b cosq = e (4sinq ) + (3)
D
Here D is crystallite size, K is Scherer’s Constant (0.9), l is wavelength of Cu source, b is Full Width at Half
Maxima (FWHM) and θ is peak position and ε is strain. W-H plots for as synthesized samples CSZD1, CSZD3
and CSZD5 are shown in figure 2 with their respective intercept value and slopes determined by linear fitting.
The slope and intercept values of all the samples are compared to W-H equation to calculate the values of
crystallite size and strain and are presented in the table 2. For CSZD1, the crystallite size is 21 nm and strain

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Figure 2. W-H Plot for CSZD1 (blue), CSZD3 (green) and CSZD5 (pink) with their respective slope and intercept values and error
bars.

present is 3.27 × 10−4.; in case of CSZD3, the crystallite size is 35 nm and strain present is 5.87 × 10−3; in case of
CSZD5, crystallite size is 42 nm and strain is found to be 4.91 × 10−3. W-H plot analysis depicts that strain
present in the material is very low and thus, the dislocation density of the samples is determined. Dislocation
density is the number of dislocations per unit volume and found to be low due to low strain value. Calculated
values of dislocation density for CSZD1, CSZD3 and CSZD5 are 2.26 × 10−3 nm−2, 7.75 × 10−4 nm−2 and
5.63 × 10−4 nm−2 respectively which are calculated by using equation (4), given as [39].
1
d= (4)
D2
Here D is the crystallite size as calculated by using Debye Scherer equation.
This plot gives information about the crystallite size, lattice strain, and microstructural defects in the
material. In the present work of Zinc based carbon nanocomposites, carbon nanospheres show amorphous
nature. The nanospheres do not show well-defined Bragg peaks in the XRD pattern, instead, they exhibit broad
humps indicating a disordered arrangement of atoms. Due to the hybridisation of amorphous and crystalline
materials in nanocomposites, high strain and dislocation density is observed. Thus, these factors are responsible
for the randomness in W-H plot [40, 41].
Stacking faults for CSZD1, CSZD3 and CSZD5 are also calculated using equation (5) and the values for
stacking faults are summarized in table 2. Stacking faults for CSZD1, CSZD3 and CSZD5 are 3.2 × 10−3, 5.1 ×
10−3 and 4.3 × 10−3 respectively [39].
2p 2
Stacking Fault, s = ´b (5)
45(3tanq )1 / 2

Here b is Full Width at Half Maxima (FWHM), θ is peak position and σ is Stacking Fault. Table 2 summarizes all
the above-mentioned results.

3.2. UV–vis spectroscopy

The optical properties of the samples have been studied by this technique and absorbance spectra have been
obtained in a wavelength range of 190 nm to 850 nm. The absorbance spectra of the samples are shown in
figure 3. CSD shows absorbance in both UV and Visible regions varying from 240 nm to 384 nm for UV region
and from 417 to 841 nm in the visible spectrum. The most intense absorbance peaks of CSD are observed at
wavelengths 374 nm, 378 nm and 384 nm. The formation of zinc hydroxide carbonate and carbon
nanocomposites caused the shifting in absorbance peak towards UV region. The absorbance of CSZD1 is from
191 nm to 397 nm for the UV region and from 402 nm to 666 nm for the visible region of electromagnetic
spectrum. The maximum absorbance shows a blue shift and is observed at 310 nm.
Further increase in concentration of Zn (NO3)2.6H2 O causes the shifting of absorbance towards UV region.
Sample CSZD3 shows absorbance in a range from 192 nm to 399 nm, which is entirely in UV region. The
maximum absorbance peak of CSZD3 is observed at 225 nm. Similarly, for CSZD5 sample, absorbance is
present only in UV spectrum from 191 to 286.5 nm with maximum peak at 191 nm. The peaks are completely

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Figure 3. Absorbance spectra of CSD (orange), CSZD1 (blue), CSZD3 (green) and CSZD5 (pink) with their respective maximum
absorbance peaks.

Table 3. Shows the Bandgap and refractive index for as synthesized

samples.

Parameters CSD CSZD1 CSZD3 CSZD5

Bandgap 0.6 eV 1.6 eV 3.2 eV 4.7 eV

Refractive Index 3.24 2.03 2.00 1.76

shifted to the UV region due to very high concentration of Zn (NO3)2.6H2 O and also the presence of amines in it
which has resulted in negligible absorbance of CSZD5 in the visible region.
Tauc and Davis-Mott relation [42] as given in equation (6) below is used to calculate the bandgap of as
obtained samples which are shown in table 3.

(ahv )n = A (hv - Eg ) (6)

where, a = absorbance coefficient, hv = incident photon energy, A = Energy independent constant,

Eg = Bandgap, n = exponent representing the nature of transition (for direct bandgap n is given as 2, whereas for
indirect bandgap, n = 1/2).
The above relation is used to obtain Tauc plots of the samples which are shown in figure 4. The bandgap of
CSD as obtained by extrapolating the linear part of the Tauc plot is found to be 0.6 eV. The standard value of the
band gap for carbon nanospheres is 2 eV to 3.3 eV depending on the particle size which varies from 1 micro to
15 nm respectively [43]. However activated carbon shows a narrow band gap of 0.9 eV which is close to the as-
synthesized carbon nanospheres [44]. The bandgap suggests that the material can be used in the solar cell
applications but, since it is amorphous in nature as revealed by XRD results, it is less preferred. As zinc nitrate is
introduced in the matrix of carbon spheres, the bandgap of CSZD1 is perceived to be 1.6 eV. The standard band
gap for zinc hydroxide carbonate is approximately 3 eV, however due to the presence of carbon, the band gap is
found to reduced to 1.6 eV [45]. The band gap of CSZD3 sample is shifted to a larger value i.e., 3.2 eV as the
concentration of Zn (NO3)2.6H2 O is increased. This band gap value is close to the bandgap of zinc oxide (ZnO).
The increased bandgap of CSZD3 makes it a candidate for UV applications such as space shuttles. With further
increase in the concentration of zinc nitrate hexahydrate, the value of bandgap is increased to 4.7 eV for CSZD5
which means the bandgap is shifted to insulator range now. This suggests that the saturation point is observed at
5 M concentration and CSZD5 can definitely be not used for semiconductor applications. This tuning of
bandgap is due to the change in concentration of zinc nitrate hexahydrate in the carbon matrix. The standard
band gap of zinc amine hydroxide nitrate is not found in the earlier studies and as far as authors have explored,
there are no texts available for the material. The increase in the band gap of the synthesized material is due to the
increase in the amount of Zn(NO3)2.6H2O as well as the formation of multiple phases forming at different
concentrations. The introduction of higher energy levels in pre-existing carbon spheres causes the band gap to

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Figure 4. Tauc plots showing the band gaps of CSD (orange), CSZD1 (blue), CSZD3 (green) and CSZD5 (pink).

rise. The synthesis route provides the breakage of carbon HOMO LUMO level and transitioning it to create
energy levels with zinc creating larger band gap.
The refractive index is an important property of a material which is calculated by using equation (7) [46].

h2 - 1 Eg
=1- (7)
h2 + 1 20

Here, Eg is the bandgap of as synthesized samples and η is the refractive index. The calculated values of refractive
index for as synthesized samples are 3.24, 2.03, 2 and 1.76 for CSD, CSZD1, CSZD3 and CSZD5 respectively.
Bandgap and refractive index of all the as synthesized samples are summarized in table 3.

3.3. Microstructural analysis

The microstructural properties and elemental compositional analysis of the as-synthesized samples have been
studied by using HR-TEM and energy dispersive spectrometer (EDS). Figures 5(a) and (b) reveal that sample
CSD has spherical particles of size approximately 200 nm. No lattice fringes of carbon nanospheres are observed
due to its amorphous nature. After the introduction of Zn(NO3)2.6H2O, the TEM images of sample CSZD1 are
shown in figures 5(c) and (d) in which the formation of round shaped particles of carbon along with irregular
nanosheets are observed. With further increase in the concentration of zinc nitrate hexahydrate in CSZD3, nano
flakes of size lying between 50 to 200 nm are visible. At higher magnification, TEM micrographs revealed the
presence of sheet with smaller particle size as shown in figures 5(e) and (f). On analysis of selected area electron
diffraction pattern (SAEDP) of sample CSZD3, the rings are found corresponding to (021) and (−820) planes
(figure 5(g)) which is in good agreement with the XRD data as analyzed in figure 1(b). Figure 5(h) shows the
formation of smaller nanosheets of approximately 100 nm on the surface of larger sheets with no formation of
spherical particles in CSZD5 because of the very high concentration of amines in the as synthesized sample.
Energy dispersive spectroscopy (EDS) has also been used for the elemental analysis of the samples. EDS
spectra of CSZD1, CSZD3 and CSZD5 are shown in figures 6(a)–(c). EDS pattern of CSD is not recorded because
it is pure carbon and since all the sample are loaded on a carbon coated copper grid, the presence of carbon and
copper peaks are natural. CSZD1 reveals peaks of O (oxygen), C (carbon) and Zn (zinc) which confirms the
presence of zinc hydroxide carbonate in it (figure 5(a)). Both CSZD3 and CSZD5 have peaks of Zn (zinc), N
(nitrogen) and O (oxygen) which indicates the formation of amine in the as synthesized materials (figures 5(b)
and (c)).

3.4. Morphological analysis

The morphology of the as synthesized samples has been analyzed by using FE-SEM. Figures 7(a) and (b) clearly
depicts the formation of carbon nanospheres for CSD sample. These nanospheres have raspberry like surface as
shown in figure 7(b). The same morphology has also been observed in the TEM image as shown in (figure 5(b)).
As Zn(NO3)2.6H2O has been introduced in the matrix of carbon spheres, the sample CSZD1 reveals the
formation of nano-flakes as depicted in (figures 7(c) and (d)) which may be due to the formation of zinc

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Figure 5. TEM micrographs for (a) & (b) CSD, (c) & (d) CSZD1, (e) & (f) CSZD3, (g) SAED pattern for CSZD3 and (h) HR-TEM Image
for CSZD5.

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Figure 6. EDS Patterns of sample (a) CSZD1, (b) CSZD3 and (c) CSZD5.

hydroxide carbonate. As the concentration of Zn(NO3)2.6H2O further has been increased resulting in the
formation of amines, the morphology reveals nanoflakes with some nano sheets. Figures 7(e) and (f) depicts the
morphology for CSZD3 revealing flakes/sheet like structures. Figures 7(g) and (h) shows agglomeration of
nanosheets in the sample CSZD5. The change in the morphology is due to the varying concentration of
Zn(NO3)2.6H2O. The introduction of zinc nitrate causes the formation of nanoflakes in the carbon
nanospheres’ matrix and as its concentration increases, some broken parts of flakes in nano range are observed
in CSZD3. As the concentration is further increased, it is observed that the sample CSZD5 show agglomeration
of thin flakes/sheets (figures 7(g) and (h). Energy dispersive spectroscopy (EDX) analysis revealed the presence
of carbon and oxygen for the CSD sample as depicted in figure 8(a). The presence of oxygen peak is due to the
adsorption of oxygen on the surface of carbon due to the hydrothermal synthesis method. The EDX spectra of
CSZD1 (figure 8(b)) contains high intensity peaks of zinc (Zn), carbon (C) and oxygen (O) which confirm the
formation of zinc hydroxide carbonate. The EDX spectra of samples CSZD3 and CSZD5 show peaks of Zn, O
and carbon (figures 8(c) and (d)) confirming the presence of these elements.

3.5. FTIR
The vibrational modes of as-synthesized samples have been studied by FTIR spectra as shown in figure 9. The list
of observed vibrational bands are listed in table 4. The peaks at wavenumbers 3449 cm−1, 3327 cm−1, 3473 cm−1
and 3473 cm−1 correspond to O-H bond [47–50]. It is observed that CSD has C–O, C=O, C–H, C=C bonds
present at 1217 cm−1, 1715 cm−1, 790 cm−1 and 1026 cm−1 positions, respectively [51]. The presence of C, O
and H elements in CSD indicates the formation of pure carbon. The presence of O–H bond at 1366 cm−1, C=O
bonds at 1511 cm−1 and 1741 cm−1 and Zn-O bonds at 584 cm−1 and 468 cm−1 [52–54] confirms the
formation of zinc and oxygen bond in the as synthesized material CSZD1 [55–57]. Both CSZD3 and CSZD5 have
O–H bonding at 1371 cm−1, C=O bonding at 1748 cm−1, C=C bonds at 888 cm−1and 762 cm−1 [58–60]. The

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Figure 7. Shows (a) & (b) carbon nano spheres for CSD samples, (c) & (d) nano flakes morphology for sample CSZD1, (e) & (f) broken
nanoflakes and sheets morphology for CSZD3, (g) & (h) nano sheet for CSZD5.

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Figure 8. EDX spectra of (a) CSD, (b) CSZD1, (c) CSZD3 and (d) CSZD5 with corresponding area of SEM images as inset.

Figure 9. FTIR spectra of CSD, CSZD1, CSZD3 and CSZD5 samples.

peaks for Zn–O bonds are present at 637 cm−1 and 463 cm−1 for both the samples, whereas a peak at 1632 cm−1
is corresponding to NH2 bond [38, 61, 62] which confirms the formation of amine in them.

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Figure 10. Nyquist plot with their equivalent circuit as an insert for (a) CSD, (b) CSZD1, (c) CSZD3 and (d) CSZD5 samples.

Table 4. Vibrational Bands for as synthesized CSD, CSZD1, CSZD3 and CSZD5.

Functional Groups/ CSD Wavenumber CSZD1 Wavenumber CSZD3 Wavenumber CSZD5 Wavenumber
Bonds (cm-1) (cm-1) (cm-1) (cm-1)

O-H (broad) 3449 3327 3473 3473

O-H (sharp) 1363 1366 1371 1371
C=O 1715, 521 1741, 1511 1748 1748
C-O 1217 — — —
C-H 790 821, 700 — —
C=C 1026 1038 888, 762 888, 762
Zn-O — 584, 468 637, 521, 463 637, 463
NH2 — — 1632 1632

3.6. Electrochemical impedance spectra (EIS)

The electrochemical performance of the synthesized samples has been studied using potentio electrostatic
impedance spectroscopy (PEIS) and cyclic voltammetry (CV). The three-electrode set-up contains a standard
calomel electrode (SCE) as a reference, a platinum electrode as a counter electrode and synthesized thin films as
working electrode in 1 M KOH solution for the creation of a working system.

3.6.1. PEIS
EIS has been performed in the frequency range of 100 kHz to 10 MHz. The Nyquist plot of the as-synthesized
films CSD, CSZD1, CSZD3 and CSZD5 along with their respective equivalent circuit is shown in figures 10(a)–
(d). The plot is drawn between imaginary impedance and real impedance for both the raw data and the data
fitted using EC-Lab software. Sample CSD shows a semicircular curve with Warburg impedance. The presence
of Warburg impedance confirms that the exchange of ions between the electrolyte and thin film is happening at a
higher rate creating a infinite layer of electron on the surface of thin film. The plot for CSD shown in figure 10(a)
suggests that CSD is a potential candidate for solar cell applications but it cannot be used in such applications

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Phys. Scr. 98 (2023) 095030 Dipti et al

Figure 11. Bode plot for (a) CSD, (b) CSZD1, (c) CSZD3 and (d) CSZD5 samples.

Table 5. Shows the values of components of equivalent circuit.

Parameters CSD CSZD1 CSZD3 CSZD5

R1( Resistance offered by electrolyte, Rs) 15.77 Ω 138045 Ω 136688 Ω 16.27 Ω

C1 17.97 ´ 10-6F 24.21 ´ 10-6F — —
R2(Resistance offered by thin film, Rf) 2174 Ω — 57.81 Ω 1.424 ´ 106W
C2 10.98 ´ 10-6F — 22.56 ´ 10-6F —
R3(Charge transfer resistance, Rct) 150455 Ω — — —
W(Warburg Impedance) 12639 Ws-1 / 2 — — —
Q1(Phase change element) — — — -0.632 ´ 10-6Fs (a - 1)
Q2(Phase change element) — — — 22.57 ´ 10-6Fs (a - 1)

because it’s amorphous nature. The values of R1 (Resistance offered by the electrolyte, Rs), C1, R2 (Resistance
offered by thin film, Rf), C2, R3 (Charge transfer resistance, Rct) in the equivalent circuit of CSD are provided in
table 5. After the addition of Zn(NO3)2.6H2O in carbon the nature of thin film changes altogether showing
charging behaviour which makes the material a potential candidate for capacitor application. The Nyquist plot
with its Randle’s circuit as shown in figure 10(b) reveal that the material shows a high charging behaviour with
ow resistance presented by electrolyte only. The equivalent circuit of CSZD3 shown in figure 10(c) is also a
parallel combination of resistances and capacitances. However, the circuit reveals that there are multiple
resistance offered either by electrolyte or thin film. The values of the equivalent circuit of CSZD1 and CSZD3 are
provided in table 5. For sample CSZD5 the material provides no behavior of capacitance or charging. The
equivalent circuit reveals only presence of resistance present in the circuit. The values of the components of
equivalent circuits are also listed in table 5.
The Bode plots of the as synthesized samples have also been plotted which exhibits the change in impedance
and phase angle with log frequency [63]. The Bode plot shows stability in system setup. Figures 11(a)–(d) show
that CSD has stability along two maxima which are at zero and two log frequency range, with a straight
depression in log of amplitude. As for CSZD1 and CSZD3, both has one maximum across mid frequency range

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Phys. Scr. 98 (2023) 095030 Dipti et al

Figure 12. CV Cycle for (a) CSD, (b) CSZD1, (c) CSZD3 and (d) CSZD5 samples.

and depressing curve which end across lower amplitude. The stability for CSZD5 is very high as it has straight
maximum along maximum of the curve which shows high stability.

3.6.2. Cyclic voltammetry studies

CV has been performed at five different scan rates of 20, 40, 60, 80 and 100 mV s−1. The voltammograms of all
the samples are shown in figures 12 (a)–(d). The scans have been performed in a potential window of −1.5 V to
+1.5 V. The curves of CSD, CSZD1, CSZD3 and CSZD5 samples show that at a higher scan rate, the cathodic
peak current increases with increasing scan rate value. The cathodic part of all the curves shows a wider part
whereas the anodic part of the material is quite linear. CSD shows low increase in peak currents across cathodic
part, whereas CSZD1, CSZD3 and CSZD5 reflect high increase in peak current shift. The current anodic
maximum for CSD is very high and around 23 mA (figure 12(a)) when compared to CSZD1 and CSZD3
(figures 12(b) and (c) which are around 17 mA (figure 12(d)) respectively. CSZD5 again shows a high current
of 20 mA.
The degradation study of CV has been conducted to know the stability of the as synthesized thin films on the
surface of FTO. 21 Scan rates have been performed for all the as synthesized samples. CSD and CSZD1 show little
to no degradation along a steady scan rate of 60 mV s−1 as shown in figures 13(a) and (b). CSZD3 and CSZD5
both show high degradation for initial cycles but after that the stability is flowing as depicted in figures 13(c)
and (d).
The electrochemical reaction has two mechanisms either diffusion controlled or capacitive behaviour.
Equation (8) is used to know the dominating phenomena [64],
I = n (J )m (8)
Here, I stand for current; ν is the scan rate and n, m is positive constants. Taking logarithm on both sides we
have,
log (I ) = mlog (J) + log (n) (9)
where m is the slope that is required for understanding the behaviour of the synthesized thin films. So, taking log
of scan rate along x-axis and log of peak current along y-axis, we have figure 14. CSD has a slope of 1.6 which
indicates capacitive behaviour as the slope is near 1 value. This is very common as carbon sphere can be used for
supercapacitors [3, 4]. The value of slope keeps on increasing, as for CSZD1 and CSZD3 shows a slope of 1.3 and

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Phys. Scr. 98 (2023) 095030 Dipti et al

Figure 13. Degradation Cycles for (a) CSD, (b) CSZD1, (c) CSZD3 and (d) CSZD5.

Figure 14. Graph for log of peak current Vs log of scan rate for CSD (orange), CSZD1 (blue), CSZD3 (green) and CSZD5 (pink) with
their respective slopes.

1.6, which are also a capacitive behaviour reaction. The highest slope is for the material CSZD5 which is nearly
equal to 1.9. All the as synthesized materials show capacitive behaviour and hence can be used in charging
materials like battery and capacitor.
As discussed above, the peak current increases with scan rate, it is confirmed by analysing the variation of
scan rate versus peak current. The as-synthesized materials show a linear relationship between scan rate and
peak current, it indicates that the peak current is increasing with increase in scan rate and thus showing

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Phys. Scr. 98 (2023) 095030 Dipti et al

Figure 15. Plots representing relationship between peak current and scan rate for CSD (orange), CSZD1 (blue), CSZD3 (green) and
CSZD5 (pink).

capacitive behaviour of the materials [65]. This behaviour is shown in figure 15 for CSD, CSDZ1, CSDZ3 and
CSZD5.
The specific capacitance for the as synthesized materials has been calculated and studied by using
equation (10) [46],
V2 V2
òV1 I (J) dJ = òV1 ( Cp ´ m ´ k) dJ (10)

Where I (J) is the area of the CV curve, Cp represents the specific capacitance in F/g. m is the mass of the active
material and k is the scan rate of CV. The specific capacitance for CSD shows a slight decrease and then increase
in the figure 16(a). The highest value for specific capacitance for the material is at 60 mV s−1 scan rate. For
CSZD1, the specific capacitance increases till 60 mV s−1 and then there is a slight decrease (figure 16(b)). For this
material also, the highest specific capacitance is at 60 mV s−1. CSZD3 shows a shift in the maximum capacitance
towards 40 mV s−1 and for CSZD5, the value for maxima is at 60 mV s−1 (figures 16 (c) and (d)). The plot for
CSZD5 shows a plateau at a scan rate of 50 mV s−1 with a highest value of 0.34 F g−1 for specific capacitance
(figure 16(d)).

4. Conclusion

Carbon nanospheres and C-Zn based nanocomposites have been synthesized successfully using two-step
hydrothermal method. The crystallinity is found to be increased with the introduction of zinc in the carbon
matrix. Absorbance plot shows that carbon spheres show absorbance in both UV and visible spectrum, however
for high concentration of Zn(NO3)2.6H2O the absorbance shows a blue shift with presence only in UV region.
Similarly, the band gap increases from 0.6 eV for CSD to 1.6 eV, 3.2 eV and 4.7 eV for CSZD1, CSZD3 and
CSZD5 respectively. HR-TEM micrographs for the samples show that CSD contains nanospheres of particle size
lying around 200 nm. The morphology of the particles are found to changed significantly from spheres to nano
flakes with the increase in amount of Zn(NO3)2.6H2O. The change in morphologies of particles are found to be
responsible for changes in physical parameters. FTIR results have confirmed the bond formation of zinc and
oxygen also carbon and amines. It is observed that using Nyquist plot that carbon can be used in solar cells as
indicated by the presence of Warburg impedance but the zinc-based carbon nanocomposites show charging
behavior with low resistance. The saturation of zinc causes the material to show resistance only with no charging.
The result is verified with CV showing capacitance behavior for all the as synthesized material. PEIS and CV
studies have confirmed that the as-synthesized samples can be used for supercapacitor application.

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Phys. Scr. 98 (2023) 095030 Dipti et al

Figure 16. Specific Capacitance curves for (a) CSD, (b) CSZD1, (c) CSZD3 and (d) CSZD5 samples.

Acknowledgments

The authors are thankful to the honourable Vice-Chancellor, Netaji Subhas University of Technology, Delhi,
India for providing the essential resources for the present research work. The authors also acknowledge the
support of H.O.D Department of Physics, Prof. Ranjana Jha for providing the essential facilities during this
research.

Data availability statement

All research data is included in the manuscrip. The data that support the findings of this study are available upon
reasonable request from the authors.

Compliance with ethical standards

Conflict of interest. The authors have no conflicts of interest to declare that are relevant to the content of this
article.

ORCID iDs

Peeyush Phogat https://orcid.org/0000-0002-3858-6233

Shreya https://orcid.org/0000-0002-4339-1756
Sukhvir Singh https://orcid.org/0000-0003-3770-0265

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