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Sol-gel synthesis and characterization of α-Fe2O3 nanoparticles

K. Raja1, M. Mary Jaculine2, M. Jose3, Sunil Verma4, A.A.M.Prince5, K. Ilangovan1,
K. Sethusankar1, S. Jerome Das2,*

1 Department of Physics, Ramakrishna Mission Vivekananda College, Chennai-600 004, India

2 Department of Physics, Loyola College, Chennai-600 034, India
3 Department of Physics, Sacred Heart College, Tirupattur-635 601, India
4 Laser Materials Development and Devices Division, Raja Ramanna Centre for Advanced
Technology, Indore- 452 013, India
5 Department of Chemistry, Ramakrishna Mission Vivekananda College, Chennai-600 004, India
*Corresponding Author: [email protected] Mobile No.: +91-93811 90314

Abstract
The α-Fe2O3 nanoparticles have been successfully synthesized via sol-gel technique. The
lattice parameters, the lattice strain and crystallite size were investigated by X-ray diffraction
(XRD) analysis. Fourier transform infrared spectroscopy (FT-IR) analysis has been carried out to
confirm the presence of functional groups. Using UV-visible spectrum, the optical band gap
energy is estimated as 2.55 eV. The morphology and chemical composition of the α-Fe2O3
nanoparticles were examined by high resolution scanning electron microscopy (HR-SEM) and
energy dispersive X-ray diffraction (EDX) analysis respectively. The hysteresis loop was traced
out using vibration sample magnetometer and the values of coercivity and saturation
magnetization are found out to be 3891 G and 0.4193 emu/g respectively.
1.Introduction
Magnetic nanomaterials have been in the trajectory for scientific and technological
interests due to their strong influence on physical and chemical properties. Iron oxide
nanoparticles are widely used in data storage devices, electrodes, magnetic fluids and bio-
medicines [1-7]. The iron oxide exhibited variety of crystalline structures such as hematite (α-
Fe2O3), akaganeite (β- Fe2O3), maghemite (γ- Fe2O3) and magnetite (Fe3O4) [8-9]. Among these,
the eco-friendly, economically flexible, thermally stable, abundant and non-toxic α- Fe2O3
nanoparticles have been towed the methodical attention in recent years [10-12]. They are
extensively used as red pigments [13], catalysts [14], anticorrosive agents [15], high density

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magnetic recording media [16], printing ink [17], magnetic resonance imaging (MRI) contrast
agents [18] and nanofillers [19]. The promising applications of α- Fe2O3 nanoparticles are also in
nonlinear optics [20], gas sensors [21,22], lithium ion batteries [23] and dye sensitized solar cells
[24]. Various techniques available to prepare α-Fe2O3 nanoparticles like forced hydrolysis [25],
hydrothermal technique [26], micro-emulsion technique [27], sol-gel process [28], template
assisted synthesis method [29], vapor–solid growth technique [30], high energy ball milling [31]
and thermal decomposition technique [32]. Review of literature reveals that the size and
morphology of α-Fe2O3 nanoparticles strongly depend on the composition of precursors, pH of
the solution and rate of heating/cooling during synthesis. Thus a considerable attention must be
paid on the optimization of experimental parameters to avoid the formation of undesired
products [33-35]. This manuscript presents the synthesis of α-Fe2O3 nanoparticles using ethylene
glycol with ferric nitrate crystals and their interesting structural, optical and magnetic properties.
2.Experimental
A 0.15 M of ferric nitrate (Fe (NO)3·9H2O) was dissolved in 50 ml of ethylene glycol
(C2H6O2) at 50 °C. The solution was vigorously stirred at this temperature using magnetic stirrer
for 90 minutes to make stable sol. The sol was further heated and maintained at 80 °C under
continuous stirring until a brown semi-solid (gel) is formed. This was followed by aging about 5
days for the condensation and polymerization reactions, and then dried in a hot air oven at 100
°C for 5 hours. This xerogel was annealed under air atmosphere at 800 °C for 150 minutes and
the final product was crushed to powder form, which was reddish in color.

3. Results and discussion

3.1 Structural analysis by X-ray diffraction

The phase formation and crystallinity of synthesized α-Fe2O3 nanoparticles were
identified using BRUKER DRX500 X ray diffractometer with CuKα radiation of wavelength
1.5406 Å through the angular range 20-70° by scanning at the step of 0.04° per minute. Fig.1
shows the powder X-ray diffraction pattern of α-Fe2O3 nanoparticles recorded at room
temperature. All diffraction peaks are in excellent agreement with JCPDS card number 86-0550.
The strong peaks are indexed and the absence of additional peaks suggests the definite yield of
α-Fe2O3 nanoparticles excluding impurities. X-ray diffraction data reveals that α-Fe2O3
nanoparticles are crystallized in hexagonal crystal system with rhombohedral lattice structure
(space group: R 3 c) whose lattice parameters are a =5.035 Å and c=13.74 Å. The peak intensity
of (104) plane is stronger than (110) plane which implies that the sample has the preferential
growth along (104) plane. The average crystallite size was calculated by measuring the full width
at half maximum of all the reflections based on Scherrer formula, which is close to 35 nm. The
sharp peaks indicate that the synthesized sample is highly crystalline in nature. Table1 shows the
variation in crystallite size of α-Fe2O3 nanoparticles for different 2θ values ranging from 12 to 56
nm. The increase in crystallite size may be due to Ostwald ripening. It is a thermodynamically
driven spontaneous process occurs because larger particles are more energetically stable than
smaller particles [36-38]. The lattice strain and the crystallite size were calculated by
Williamson-Hall (W-H) plot using the relation [39],

--------------- (1)

The W-H plot of α-Fe2O3 nanoparticles is shown in Fig.2 and the determined values of lattice
strain and mean crystallite size are -0.04036 and 30 nm respectively which is very well in
agreement with the XRD results. The negative slope indicates that strain broadening must be
small [40-42]. The relations obtained from powder XRD profile are graphically represented in
Fig.3.
Fig.1. Powder X-ray diffraction pattern of α-Fe2O3 nanoparticles

0.64

0.62
β cosθ / λ

0.60

0.58

0.56

0.15 0.20 0.25 0.30 0.35

sinθ / λ

Fig. 2. Williamson-Hall plot of α-Fe2O3 nanoparticles

Table 1: Variation in crystallite size of α-Fe2O3 nanoparticles

2θ (degree) Intensity β (2θ) Crystallite

(a.u.) (radians) size (nm)
24.16 17 0.0054 26.2570

25.28 06 0.0054 26.3135

33.16 64 0.0028 51.6687

35.68 53 0.0028 52.0215

40.88 16 0.0084 17.6163

43.44 06 0.0028 53.3039

46.08 06 0.0056 26.9068

49.48 30 0.0054 28.2720

54.08 32 0.0028 55.5959

57.68 09 0.0134 11.8120

62.64 25 0.0084 19.3216

64.00 24 0.0056 29.1977

 70 0.014

(a) (b)
60
0.012

50
0.010

Peak broadening
Intensity (a.u.)

40
0.008
30

0.006
20

10 0.004

0 0.002
25 30 35 40 45 50 55 60 65 25 30 35 40 45 50 55 60 65
Glancing angle (2θ) Glancing angle (2θ)

60
(c)

50
Crystallite size (nm)

40

30

20

10
25 30 35 40 45 50 55 60 65

Glancing angle (2θ)

Fig.3. (a) Glancing angle Vs Intensity, (b) Glancing angle Vs Peak broadening and (c)
Glancing angle Vs Crystallite size

3.2 FT-IR analysis

FT-IR is an important tool to identify the functional groups present in a material. Fig.4
shows the FT-IR transmittance spectrum of α-Fe2O3 nanoparticles recorded in the frequency
range 400-4000 cm-1 using Perkin Elmer FTIR spectrometer at room temperature. The
characteristic absorption bands (Fe-O bonds) occur at 470 cm-1 and 554 cm-1. The broad peak
around 3300 cm-1 is due to O-H stretching vibration and 1399 cm-1 corresponds to O-H
deformation band. The peak at 1565 cm-1 is attributed to the presence of adsorbed water
molecule (H-O-H) in the sample [43,44].

100

90

80

470
% Transmittance

70

60

50

40
1399

554
1565

30

20
4000 3600 3200 2800 2400 2000 1600 1200 800 400

-1
Wave number (cm )

Fig. 4. FT-IR spectrum of α-Fe2O3 nanoparticles

3.3 UV-Vis analysis

The absorption of electromagnetic wave excites the electrons from the highest occupied
molecular orbital (HOMO) in the valence band to the lowest unoccupied molecular orbital
(LUMO) in the conduction band. The wavelength absorbed between bonding and anti-bonding
orbitals explains the band gap energy of the material. The possible electronic transitions between
200-1000 nm are n→σ*, n→π and π→π*. The optical absorbance of α-Fe2O3 nanoparticles was
investigated using Perkin Elmer Lambda 35 UV-Vis spectrophotometer in the wavelength region
of 200 to 800 nm at room temperature and the corresponding spectrum is shown in Fig.5a. The
characteristic absorption peak is found near to the visible region at around 400 nm and thereafter
the absorption increases gradually. The optical band gap energy of α-Fe2O3 nanoparticles was
evaluated using the Tauc relation,

= C( – Eg) --------------- (2)

Where, h is Planck’s constant, υ is frequency of vibration, C is proportional constant, α is
absorption coefficient, Eg is the average band gap energy and n depends on the type of transition.
Fig.5b shows the Tauc plot (the linear extrapolation of (αhυ)2 versus hυ to the energy axis ) of α-
Fe2O3 nanoparticles for the direct allowed transition. The average band gap energy has come out
from the Tauc plot as 2.55 eV which is larger than the value reported for bulk counterpart of
hematite. This is due to the quantum confinement effect where delocalized electronic states close
to the Fermi level [45,46].

0.40 1.60E+009
(b)
(a)
0.38 1.40E+009

0.36 1.20E+009
Absorbance (a.u.)

0.34 1.00E+009
2
(α hν) ( eV/cm)

0.32 8.00E+008
2

0.30 6.00E+008

0.28 4.00E+008

0.26 2.00E+008

0.24 0.00E+000
200 300 400 500 600 700 800 1 2 3 4 5 6 7
hν (eV)
Wavelength (nm)

Fig.5. (a) UV-Visible absorption spectrum of α-Fe2O3 nanoparticles and (b) Tauc plot of

α-Fe2O3 nanoparticles

3.4 Morphological and Elemental analyses

The surface morphology and the elemental composition of α-Fe2O3 nanoparticles were
recorded using FEI Quanta FEG 200 model scanning electron microscope equipped with energy
dispersive X-ray instrument. Fig.6(a and b) represents the surface morphology of α-Fe2O3
nanoparticles at two different magnifications. The SEM images show the agglomerated form of
α-Fe2O3 nanoparticles. The nanoparticles become tend to agglomerate and grow into larger
assemblies as they possess high surface energies. The increase in particle size of α-Fe2O3
nanoparticles is in the range of 1-1.3 μm. The agglomeration can be caused due to Van der Waals
force and magnetic interactions among the particles [47-51]. However, no unique shape and size
distribution of α-Fe2O3 particles found out of SEM images.

Fig.6(a) & (b) High resolution scanning electron microscopy images and (c) EDX spectrum
of α-Fe2O3 nanoparticles
 The peaks appear in EDX spectrum (Fig.6c) confirm the presence of Iron and Oxygen.
Their atomic and weight percentages are 45.16 and 54.84, 74.19 and 25.81 respectively. There is
no peak observed as unidentified in the spectrum which demonstrates the purity of the sample.

3.5 Magnetic measurements

Magnetic behavior of α-Fe2O3 nanoparticles was investigated using VSM (Lakeshore VSM
7410) with a maximum applied field up to 15000 G. Hematite (α-Fe2O3) nanoparticles often
display the unusual magnetic behavior. Tadic et al., reported that the Hysteretic behavior is a
consequence of surface spin disorder, while the linear part of the M(H) dependence represents
the influence of the particle’s antiferromagnetic core [52]. According to Vallina et al. α-Fe2O3
nanoparticles exhibit temperature-dependent magnetic coercivity values in the range of 289 to
5027 Oe. The origin of high coercivity values is a consequence of the slower growth rate of
crystallite size during the heating process [53]. In addition to the temperature, morphology also
plays an important role in the magnetic properties and the increase in coercivity value is
attributed to the orientation of magnetic spins along the easy axis of magnetization [54-57]. Fig.7
shows magnetic hysteresis loop of α-Fe2O3 nanoparticles traced at room temperature. The
synthesized sample presents weak ferromagnetic behavior which is almost same as the one
reported by Zhang et al. The magnetic parameters such as coercivity, retentivity and saturation
magnetization of the sample are measured as 3891 G, 0.1617 emu/g and 0.4193 emu/g
respectively. The sample shows a considerably broadened hysteresis loop and does not level off
to the saturation magnetization.
 Fig.7: Hysteresis loop of α-Fe2O3 nanoparticles

Conclusions
The hexagonal α-Fe2O3 nanoparticles were successfully synthesized using sol-gel
technique. The average crystallite size of the synthesized particles was 35 nm. The band gap
energy Eg associated with α-Fe2O3 nanoparticles was 2.55 eV. SEM image shows that the
nanoparticles are composed of several randomly assembled and irregular shaped nanoparticles.
VSM measurements revealed α-Fe2O3 possesses broadened hysteresis loop and does not level off
to the saturation magnetization.
Acknowledgements
The authors gratefully acknowledge the scientific support rendered by Department of
Nuclear Physics, University of Madras, Chennai, by providing X-ray diffraction analysis and
SAIF, IIT Madras, for recording SEM, EDX and VSM analyses. They extend their gratitude to
Instrumentation centre, St. Joseph’s College, Trichy, for recording FT-IR and UV spectra. They
are grateful to Dr. A. Jeya Rajendran, Associate Professor of Chemistry and Dr. J. Mary Linet,
Assistant Professor of Physics, Loyola College, Chennai, for their valuable suggestions. They are
also thankful to Mrs. Sheeba Anu Jacob and Mr. L. Allwin Joseph, Research scholars of
Department of Physics, Loyola College, for their support throughout this work.
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