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Materials Today: Proceedings 3 (2016) 2450–2456 www.materialstoday.com/proceedings

Recent Advances In Nano Science And Technology 2015 (RAINSAT-2015)

Synthesis and characterization of NiO nanoparticles by thermal

oxidation of nickel sulfide nanoparticles
V.P. Muhammed Shajudheena, M. Sivakumarb, S. Saravana Kumarc,*
a
Department of Physics, Karpagam University, Coimbatore, 641021, Tamilnadu, India
b
Department of Sciences, Amrita School of Engineering, Amrita Vishwa Vidya Peetham, Coimbatore, 641112, Tamilnadu, India
c
Department of Physics, NSS College Pandalam, 689501, Kerala, India

Abstract

In the present work, nanoparticles of nickel sulfide were synthesized using chemical precipitation method with tri ethanol
ammine (TEA) as a capping agent. The nickel sulfide nanoparticles were characterized using X-ray diffraction technique and
were found to be in orthorhombic Ni9S8 phase. The thermogravimetric (TG) and differential thermal curves of the samples were
recorded and the phase transformation temperature of nickel sulfide (Ni9S8) to NiO was found to be at 6000C. The as prepared
nickel sulfide nanoparticles were annealed at 700oC to obtain NiO nanoparticles. The grain size of nanoparticles of NiO was
obtained from XRD pattern and was found to be approximately 10 nm. The micro raman, UV-Visible absorption and
photoluminescence spectrum of NiO nanoparticles were recorded and analyzed.

© 2015Elsevier Ltd.All rights reserved.

Selection and Peer-review under responsibility of [Conference Committee Members of Recent Advances In Nano Science and
Technology 2015.].

Keywords:nickel sulfide nanoparticles; nickel oxide nanoparticles;micro raman, UV Visible absorption, Photoluminescence

* Corresponding author. Tel.: +91-9447625367; fax: +91-4734-252240.

E-mail address:saravanks80@gmail.com
2214-7853© 2015 Elsevier Ltd.All rights reserved.
Selection and Peer-review under responsibility of [Conference Committee Members of Recent Advances In Nano Science and Technology 2015.
].
 V.P. Muhammed Shajudheen, et al./ Materials Today: Proceedings 3 (2016) 2450–2456 2451

1. Introduction

The synthesis and characterization of nanoparticles of transition metal oxides have been widely reported in the
literature due to their versatile applications, such as, fabrication of microelectronic circuits, sensors, piezoelectric
devices, fuel cells, coatings for the passivation of surfaces against corrosion, and as catalysts [1-5]. Nickel oxide is a
versatile wide band gap semiconductor material with band gap ranging from 3.6 to 4.0 eV [6]. Nanoparticles of
nickel oxide find wide range of applications including the fabrication electrochromic films[7], fuel cell
electrodes[8], gas sensors [9],battery cathodesetc [10-16].Synthesis of NiO nanoparticles by various chemical
methods, mostly through hydroxide route, is extensively reported in the literature [17-26]. Niasari et al. [21]
reported the synthesis of nanoparticles of NiO using nickel oxalate and oleylammine as precursors. Dharmaraj et al.
[22] and Tao et al. [23] reported the synthesis of NiO nanoparticles keeping reaction temperature above 600 K.
Synthesis of nanoparticles of NiO by heat treatment of a new precursor nickel octanoate was reported by Niasari et
al.[24]. In all these methods, nickel oxide nanoparticles were synthesized using either hydroxyl route or keeping
reaction temperature above room temperature. Synthesis of nanoparticles of nickel oxide by thermal oxidation of
nickel sulfide is scarcely reported. In the present work, nanoparticles of nickel oxide are synthesized bythermal
oxidation of nickel sulfide nanoparticles prepared by chemical precipitation method at room temperature. The
samples are characterized using X-ray diffraction, micro raman, UV-Visible absorption and photoluminescence
techniques.

2. Experimental

Nanoparticles of nickel sulfide were synthesized as free standing powder by wet chemical synthesis method. 10
ml of 1M nickel acetate and 2 ml of 0.1 M tri ethanol ammine is taken in a beaker. To this solution, 10 ml of 1M
Na2S is added dropwise while the reactants are continuously stirred. The precipitate formed is centrifuged, washed
several times with water and finally with acetone, and then air dried to obtain nano powders of nickel sulfide. The
samples were annealed at 700o C to obtain nanoparticles of NiO. The oxidation mechanism of nickel sulfide from
ambient up to 1000 °C was investigated by thermogravimetric (TG) and differential thermal analysis (DTA). The
scanning electron microscope images of nickel sulfide and nickel oxide nanoparticles were recorded using Carl
Zeiss Sigma HD FESEM.X-ray diffraction patterns of the nickel sulfide and nickel oxide samples were recorded
using a Philips Xpertpro diffractometer and using CuKα radiation over the diffraction angles (2θ) from 10 to 900.
The micro Raman spectrum of nickel oxide nanoparticles were recorded using Horiba Labram-HR with an
excitation at 514.5 nm. UV- Visible absorption and photoluminescence spectra of nanoparticles of NiO were
recorded using Varian, Cary 5000 spectrophotometer and JASCO FP 8200 Spectrofluorometer respectively.

3. Results and Discussion

3.1. Scanning Electron Microscope studies

The scanning electron microscope images of nanoparticles of NiS and NiO are shown in the figures 1 and 2
respectively. The SEM image of NiS reveals that the nanoparticles show a large size distribution due to
agglomeration. This may be due to the presence of the tri ethanol ammine, the capping agent. The SEM image of
NiO shows a narrow size distribution with average particle size between 20-30 nm.
2452 V.P. Muhammed Shajudheen, et al./ Materials Today: Proceedings 3 (2016) 2450–2456

Fig. 1. SEM imageof nanoparticles of Ni9S8

Fig. 2. SEM imageof nanoparticles of NiO

3.2. X-ray Diffraction Studies

The X-ray diffraction (XRD) patterns of nanoparticles of nickel sulfide and nickel oxide are shown in the figures
3(a) and (b) respectively. The figure 3 (a) shows diffraction peaks at 2θ values of19.6, 20.7, 26.1, 30.4, 33.1, 35.1,
38.9, 42.1 and 52.30. A detailed review on existing literature suggests that, depending on the synthetic process, a
variety of compositions of nickel sulfide can be obtained, including Ni3S2, Ni3+xS2, Ni4S3+x, Ni6S5, Ni7S6, Ni9S8,
Ni3S4, Ni9S8 and NiS. The XRD pattern of samples of present study were compared with standard JCPDS values
(JCPDS card No.22-1193) and the peaks can be indexed as orthorhombic phase of Ni9S8.
 V.P. Muhammed Shajudheen, et al./ Materials Today: Proceedings 3 (2016) 2450–2456 2453

Fig. 3. XRD pattern of nanoparticles of (a) Ni9S8 and (b)NiO

The thermo gravimetric (TG) and differential thermal curves of the samples were recorded and the phase
transformation temperature of nickel sulfide (Ni9S8) to NiO was found to be at 6000C. The samples of present study
were annealed at 700oC in a muffle furnace to synthesize NiO nanoparticles. The figure 3 (b) shows diffraction
peaks at 2θvalues of 36.9, 42.9, 62.3, 74.9 and 78.70. The peaks are identified to originate from (110), (200), (220),
(311) and (222) planes of the cubic phase of NiO [JCPDS card No.78-0643]. The average crystallite size is
calculated from the full width at half maximum (FWHM) of the diffraction peaks using the Debye-Scherrer formula
[27] D = kλ/βcosθ where D is the mean grain size, k is a geometric factor (equal to 0.89), λis the X ray wavelength, β
is the FWHM of diffraction peak and θ is the diffraction angle. The grain size of the NiO particles calculated from
the most intense peak is approximately 10 nm.

3.3. UV-Visible absorption studies

The UV-Visible absorption spectrum of nanoparticles of NiO of present study is shown in the figure 4. The
spectrum shows two absorption peaks around 302 and 420 nm corresponding to the energy values of 4.1 and 2.95
eV respectively. In bulk NiO, exciton is not detectable at room temperature. However, for nanocrystals of grain size
comparable to that of bulk Bohr exciton radius, the overlap of the electron and the hole wave functions is enhanced
increasing the excitonic binding energy. Thus even at the room temperature, the excitonic peak can be observed in
the optical absorption spectra of nanocrystals. The peak observed at 302 nm in the absorption spectrum of the NiO
samples of the present study can be attributed to the excitonic transition between 1Se – 1Sh levels. The peak at 420
nm can be attributed to absorption due to oxygen related defects [28].
2454 V.P. Muhammed Shajudheen, et al./ Materials Today: Proceedings 3 (2016) 2450–2456

Fig. 4. UV-Visible absorption spectrum of nanoparticles of NiO

Fig. 5.. Photoluminescence spectrum of nanoparticles of NiO

3.4. Photoluminescence studies

The photoluminescence spectrum of nanoparticles of NiO excited at 280 nm is shown in the figure 5. The
spectrum shows two broad emission peaks around 340 and 425 nm. Anand et al [29] reported an emission peak
around 345 nm in NiO nanoparticles synthesizedby CTAB assisted solvothermal process. They attributed the peak
to electronic transition of the Ni2+ ions. Adler and Feinleib [30] reported a series of absorption peaks below 4 eV as
purely intraionic 3d8-3d8 transitions of Ni2+. The study of electron energy loss spectroscopy (EELS) and spin
polarized electron energy loss spectroscopy (SPEELS) also confirm the existence of this kind of transition of the 3d8
electrons in NiO [31]. The presence of peak around 340 nm in the PL spectrum can be attributed to electronic
transition of Ni2+ ions.
A peak at 420 nm was observed in the absorption spectrum of NiO particles of present study was attributed to
oxygen related defects. The emission peak at 425 nm can be attributed to the radiative recombination of charge
carriers from the defect levels and valence band.
 V.P. Muhammed Shajudheen, et al./ Materials Today: Proceedings 3 (2016) 2450–2456 2455

3.5. Micro Raman studies

The micro Raman spectrum of nanoparticles of NiO excited at 514.5 nm is shown in the figure 6. The figure
shows peaks around 516, 997, 1130 and 1256 cm-1. The room temperature Raman spectrum for bulk NiO consists
of several bands: a one-magnon (1M) band at ~34 cm-1 ; five vibrational bands – one-phonon (1P) TO at 440 cm-1
and LO at 560 cm-1 modes, two-phonon (2P) 2TO at 740 cm-1, TO+LO at 925 cm-1 and 2LO at 1100 cm-1 modes; a
one-magnon (M) band at ~40 cm-1 [32-34]. The peak observed at 516 cm-1 in the Raman spectrum of present study
can be attributed to 1TO+1M mode. The peaks at 997, 1130 and 1256 may be attributed to TO+LO, 2LO and
LO+2TO modes of NiO. The shifts in the Raman peaks compared to bulk NiO can be ascribed to the combined
effect of phonon confinement effect,(ie the relaxation of k = 0 selection rule and the scattering by phonons existing
in the region bounded by 2π/d, where d is the size of nanocrystal, around the center of the first Brillouin zone) and
defect induced Raman scattering.

Fig. 6. Raman spectrum of nanoparticles of NiO

4. Conclusion

In the present work, nanoparticles of NiO were synthesized by thermal oxidation of nickel sulfide nanoparticles.
The nickel sulfide nanoparticles (Ni9S8) synthesized by chemical precipitation method were annealed at 700oC to
synthesize nanoparticles of NiO. The XRD pattern of nanoparticles of NiO showed cubic phase of NiO and the grain
size estimated using Debye Scherrer equation was approximately 10 nm. The UV-Visible absorption spectrum
showed peaks around 302 and 420 nm, which were attributed to the absorption of excitonic energy levels and defect
levels due to oxygen vacancies respectively. The peak at 420 nmin the PL spectrum of the samples also indicated the
presence of oxygen related defect levels. The shift of peaks in the micro Raman spectrum of the NiO nanoparticles
was attributed to the combined effect of phonon confinement effect and defect induced Raman scattering.

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