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Synthesis and characterization of mesoporous α-Fe2O3 nanoparticles and

investigation of electrical properties of fabricated thick films

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DOI: 10.2298/PAC1604209M

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Processing and Application of Ceramics 10 [4] (2016) 209–217
DOI: 10.2298/PAC1604209M

Synthesis and characterization of mesoporous α-Fe2O3 nanoparticles

and investigation of electrical properties of fabricated thick films
Ali Mirzaei1,∗, Kamal Janghorban1, Babak Hashemi1 , Seyyed Reza Hosseini1 ,
Maryam Bonyani1 , Salvatore Gianluca Leonardi2, Anna Bonavita1, Giovanni Neri2
1 Department of Materials Science and Engineering, Shiraz University, Shiraz, Iran
2 Department of Electronic Engineering, Chemistry and Materials Engineering, University of Messina, Italy
Received 18 August 2016; Received in revised form 16 October 2016; Accepted 3 November 2016

Abstract
In this work, α-Fe2 O3 nanoparticles (NPs) have been synthesized by using a simple Pechini sol-gel method from
iron nitrate, citric acid as complexing agent and ethylene glycol as polymerization agent. The calcined α-Fe2 O3
NPs were fully characterized by different techniques. It was confirmed that ultrafine and highly crystalline α-
Fe2 O3 NPs with high purity and mesoporous nature can be obtained after calcination at 550 °C for 3 h. In
addition, the results of electrical resistance measurements of the fabricated Fe2 O3 thick films showed that α-
Fe2 O3 thick films have stable electrical properties which are beneficial for electrical applications such as gas
sensing and field effect transistors.
Keywords: α-Fe2 O3 , Pechini sol-gel, structural characterization, electrical resistance

I. Introduction α-Fe2 O3 crystalline nanostructures including nanocrys-

tals, nanocubes, nanorods, nanowires, nanotubes, hol-
Iron (III) oxides have been one of the most ex- low structures, nanoflakes, nanofibers, and so on, have
tensively investigated transition metal oxides. Besides been fabricated through different techniques, such as
the amorphous phase, Fe2 O3 has four polymorphs: i) chemical vapour deposition, hydrothermal synthesis
α-Fe2 O3 ; ii) β-Fe2 O3 ; iii) γ-Fe2 O3 ; and iv) ε-Fe2 O3 . [12], sonochemical technique, chemical precipitation
While the highly crystalline α-Fe2 O3 and γ-Fe2 O3 oc- [13], sol-gel technique [14], microemulsion technique
cur in nature, β-Fe2 O3 and ε-Fe2 O3 are generally syn- [15], hydrolysis [16] ball milling [17], laser ablation,
thesized in the laboratory [1]. Each polymorph pos- sputtering, and spray pyrolysis [18].
sesses peculiar crystal structures and physical proper-
Since most of these reported methods either demand
ties, i.e. electrical, optical, and photoelectrical. Among
sophisticated instrumentation or require elevated tem-
them hematite (α-Fe2 O3 ) has many peculiar properties,
perature, the preparation of α-Fe2 O3 NPs at low cost at
such as low precursor and synthesis cost, low toxic-
the industrial scale is a challenge. Therefore, using the
ity, abundance, environmental friendly nature, easy pro-
cheap starting materials, simple fabrication processes
duction and storage, high corrosion resistance, chem-
and suitable conditions of synthesis are the main re-
ical inertness, biocompatibility and excellent substrate
quirement for low cost/facile synthesis procedures. In
adherence [2,3]. These features make α-Fe2 O3 very in-
this context, it is practically significant to obtain α-
teresting for researchers and have led to intense inves-
Fe2 O3 NPs using a facile, cheap, and effective way such
tigation of this material for applications in many ar-
as Pechini sol-gel method. Pechini et al. [19] intro-
eas such as water treatment [4], contrast reagents/drug
duced a polymerizable complex route, referred to as Pe-
delivery [5], sensor technology [6,7], optical coatings,
chini method, to serve as an important supplement for
magnetic materials [8], field effect transistor [9], cata-
the conventional sol-gel method and due to its cheap-
lysts [10], pigments [11], etc. As a consequence, various
ness, handiness, good stoichiometric control, low toxi-
∗
Corresponding author: tel: +9837131984, city, low cost and insensitivity to water existence, this
fax: +9837131984, e-mail: alisonmirzaee@yahoo.com method has been used rather extensively in synthesis of

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 A. Mirzaei et al. / Processing and Application of Ceramics 10 [4] (2016) 209–217

different materials. Moreover the highly branched poly- ing at 200 kV and equipped with Gatan 794 Multi-Scan
mer can reduce the cation mobility during heat treat- CCD camera. Room-temperature micro-Raman spec-
ment, so that the product with a good dispersion could troscopy (µRS) was used to get information about the
be prepared [20]. In a typical Pechini process, com- material quality, the phase and purity. Raman spec-
mon metal salts are dissolved in a solution using an trum was recorded at room temperature using micro-
α-hydroxy carboxylic acid, such as citric acid (CA) as Raman spectrometer (Renishaw, Great Britain) in the
chelating agents of metal ions, then a poly hydroxyl al- back scattering geometry with 514.5 nm Ar+ laser as an
cohol, such as ethylene glycol (EG) or polyethylene gly- excitation source and data were collected in the range
col (PEG) is introduced as a crosslinking agent to form of 150–1550 cm-1 . The molecular structure of iron ox-
a polymeric resin on molecular level, thus, segregation ide NPs was studied by using Fourier transform in-
of particular metal ions is reduced and compositional frared spectrometer (Nicolet FTIR Impact 400D), with
homogeneity is guaranteed. the frequency ranging from 400–3500 cm-1 . Optical ab-
The goal of this work is to synthesize mesoporous sorbance of iron oxide was recorded with a 1 cm path
iron oxide by a Pechini route using iron nitrate as pre- length quartz cell using a UV-Vis spectrophotometer
cursor, citric acid as chelating agent and ethylene gly- as a function of wavelength in the range from 200
col as crossing-linking agent. Afterwards, the aim is to to 800 nm. X-ray photoelectron spectroscopy (XPS)
fully characterize synthesized powders using different was employed to determine the surface component
techniques and finally to study electrical properties and and composition of the prepared nanoparticles. XPS
effect of UV light on the electrical resistance of meso- was performed on ESCALAB MKII X-ray photoelec-
porous α-Fe2 O3 NPs. tron spectrometer (VG Instruments, CA, USA), using
non-monochromatized Mg-Kα X-rays as the excitation
II. Experimental source. The binding energies for the samples were cal-
ibrated by setting the measured binding energy of C1s
2.1. Synthesis of α-Fe2 O3 NPs to 284.60 eV. Thermal analysis was carried out on Met-
Hydrated iron nitrate (Fe(NO3 )3 ×9 H2 O), citric acid tler Toledo thermal gravimetric analyser and Perkin
(C6 H8 O7 ×H2 O), poly(vinyl pyrrolidone) and ethylene Elmer differential thermal analyser. The analysis was
glycol (C2 H6 O2 ) were purchased from Merck. All the performed in air flow, in the temperature range be-
chemicals were used as received and without further tween 25 and 600 °C, with heating rate of 10 °C/min.
purification. Double distilled water was used to pre- Brunauer-Emmett-Teller (BET) surface area and pore
pare precursor solutions. First, Fe(NO3 )3 ×9 H2 O was size distribution of the samples were measured by ni-
dissolved in distilled water at 70 °C for 1 h under mag- trogen adsorption-desorption analyser (Quantachrome
netic stirring to make 0.5 M Fe+3 solution. In a sepa- Autosorb-1C). All the particles were degassed under
rate beaker citric acid (CA) was dissolved in distilled vacuum at 150 °C for 2 h before the measurements, and
water at 70 °C for 30 min. Subsequently, the CA solu- the nitrogen gas adsorption at 77 K was measured us-
tion was added slowly to the Fe+3 solution with stir- ing a continuous flow method with nitrogen and he-
ring ([CA]/[Fe+3 ] = 2). Then the esterification agent, lium mixture as the carrier gas. Specific surface area
i.e. ethylene glycol (EG), was added with a molar ra- (SBET) was calculated by using the BET method, and
tio [CA]/[EG] = 2, while stirring and heating the solu- pore size distribution was determined by applying the
tion. The final solution was reflux at 120 °C for 2 h. The Barrett-Joyne-Halenda (BJH) model.
generated precursor resin was dried at 120 °C for 12 h 2.3. Electrical measurements
to obtain the precursor powders. Finally, the amorphous
powders were calcined at 550 °C in air atmosphere for For electrical measurements, α-Fe2 O3 thick films
3 h using a muffle furnace to obtain iron oxide NPs. were prepared by drop cast method on the Pt-electroded
alumina substrate equipped with Pt heater and electri-
2.2. Characterization of synthetized nanopowders cal resistance was studied by means of Agilent 34970A
Characterization of α-Fe2 O3 NPs was achieved by multimeter using the two point method.
different techniques. X-ray diffraction analysis (XRD)
was performed using Philips X-Pert diffractometer op- III. Results and discussion
erating with monochromatic CuKα (λ = 1.54056 Å)
radiation at 40 kV and 30 mA. The XRD pattern was 3.1. Mechanisms in Pechini sol-gel preparation
recorded at room temperature at a scan rate 0.05°/sec The Pechini method used in the present work allowed
and 2θ from 10° to 70°. Morphological analysis was obtaining of the homogeneous metal-organic polymer in
carried out using scanning electron microscopy (SEM) which the iron ions were randomly distributed along the
by using JEOL 5600 LV instrument operating with a backbone of the polymer. During the heat treatment at
20 kV accelerating voltage and equipped with EDS de- 120 °C, this polymeric precursor method goes through
tector (Oxford instruments). Morphological studies of two main stages: the first one is the reaction mechanism
synthesized powders were performed with JEOL JEM of esterification of citric acid with ethylene glycol as in-
2010 electron microscope (LaB6 electron gun) operat- dicated in Fig. 1a, and the second one, the chelation of

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 A. Mirzaei et al. / Processing and Application of Ceramics 10 [4] (2016) 209–217

the iron nitrate by the formed esters as shown in Fig. 1b. 3.2. Structural and morphological studies
Citric acid and ethylene glycol generate a reaction of
esterification, and the formed ester acts as complexing Figure 3 shows thermo-gravimetric (TGA) and dif-
agent of the iron cations forming a polymer network that ferential thermal analysis (DTA) of the dried iron ox-
is resin-like or solid as viscosity increases. At this point, ide gel. According to TGA curve of amorphous iron
it is necessary for the exchange reaction of the iron ni- oxide, decomposition proceeds with thermal treatment
trate with the acid group to proceed until its comple- through three steps. Initially, at a temperature below
tion. If this exchange reaction is not driven to comple- 100 °C, a small weight loss is observed, probably due to
tion, precipitation of unreacted iron nitrate would occur the evaporation of humidity adsorbed during storage is
in the resin on cooling and this may lead to gross segre- observed. Two other large weight losses are observed at
gation of the iron in the ceramic. In the considered sys- temperatures higher than 150 °C, starting at about 185
tem, the polymer solidified to a clear resin on cooling, and 250 °C, respectively. These are due to the decom-
implying that all of the iron nitrate had reacted with the position of organic species from citric acid and ethylene
polymer [21]. Figure 2 shows Fe+3 -citric acid complex glycol. No further weight loss is observed above 350 °C,
and polyesterification process. thus indicating that the organic material was completely

Figure 1. Reaction mechanism for esterification of citric acid with ethylene glycol (a) [21] and reaction mechanism of chelation
of iron nitrate by polymer (b)

Figure 2. Chelating process (formation of metal citrate complexes) and polyesterification during Pechini process [22]

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 A. Mirzaei et al. / Processing and Application of Ceramics 10 [4] (2016) 209–217

The lattice constants a and c of α-Fe2 O3 were evalu-

ated according to Bragg law:

n · λ = 2d · sin θ (1)
where n is the order of diffraction, λ is the X-ray wave-
length, and d is the spacing between planes of given
Miller indices h, k, and l. In the hexagonal structure of
α-Fe2 O3 , the plane spacing is related to the lattice con-
stant a, c, and Miller indices by the following formulas:
!2 !2
1 4 h2 + hk + k2
!
l
= + (2)
d 3 a2 c
!2 
λ2  4 h2 + hk + k2
 !
2 l 
sin θ = + (3)
4 3 a2
 
Figure 3. TGA/DTA curves of amorphous iron oxide c 
According to the above formulas, for the (110) plane
with diffraction peak at 2θ = 35.64°, the lattice constant
a was calculated by:
λ
a= (4)
sin θ
and for (104) plane with diffraction peak at 2θ = 33.15°,
the lattice constant c was calculated by:
s
12a2 · λ2
Figure 4. X-ray diffraction pattern of α-Fe2 O3 NPs c= (5)
3a2 sin2 θ − λ2
eliminated at this temperature. DTA profile shows two The lattice parameters for the hexagonal phase of α-
peaks which are associated with exothermic reactions. Fe2 O3 using Eq. (5) have been calculated to be a =
On the basis of these experimental evidences and lit- 0.50 nm and c = 1.39 nm, which are in close agreement
erature data, the peak at 220 °C is related to the trans- with the reported data.
formation of amorphous phase to crystalline γ-Fe2 O3 , Figure 5a shows TEM micrograph of iron oxide pow-
whereas the second peak at 350 °C is likely attributed to der calcined at 550 °C for 3 h. Very fine particles with
its transformation to α-Fe2 O3 [23]. sizes between 10–30 nm are observed. Figure 5b shows
Figure 4 shows the XRD pattern of the calcined iron SEM micrograph of α-Fe2 O3 thick film on the alumina
oxide powder. All the diffraction peaks can be assigned substrate. As clearly observed, it has quite porous struc-
to the hexagonal α-Fe2 O3 phase and are consistent with ture that renders a high surface area for these particles.
those reported in the literature and with the respective Porous structure is the result of the burning of polymeric
JCPDS card no. 89-596. species from ethylene glycol.

Figure 5. TEM (a) and SEM (b) micrographs of iron oxide NPs calcined at 550 °C for 3 h

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 A. Mirzaei et al. / Processing and Application of Ceramics 10 [4] (2016) 209–217

independent constant, m is a constant which determines

type of the optical transition (m = 1/2 for allowed direct
transitions and m = 2 for allowed indirect transitions)
and E gOpt is the optical band gap. It is evaluated that the
optical band gap of the α-Fe2 O3 has a direct optical tran-
Opt
sition. The optical band gap (E g ) could be obtained by
the extrapolating method using the (α · h · ν)1/2 vs. h · ν
plot. Inset in Fig. 7 shows plot of (α · h · ν)1/2 vs. h · ν
for the α-Fe2 O3 . Value of E gOpt obtained by this method
Figure 6. EDS analysis of iron oxide sample 550 °C for 3 h is 2.4 eV.
The Raman spectroscopy technique has been exten-
sively used for structure, composition, and phase char-
acterization of materials [25]. A Raman analysis was
also carried out. α-Fe2 O3 belongs to the crystal space
group D63d . Since the primitive cell contains six atoms,
there are 18 modes of vibration divided into 15 optical
mode and 3 acoustic modes. According to the group the-
ory of hematite, the following normal vibrational modes
are predicted and represented by the hematite’s irre-
ducible vibrational mode at the first Brillouin zone cen-
tre [26]:

Γvib = 2A1g ⊕ 2A1u ⊕ 3A2g ⊕ 2A2u ⊕ 5E g ⊕ 4E u (7)

The acoustic 2A1u and 2A2u modes are optically silent

because they are inactive in Raman. As for the optical
Figure 7. UV-Vis spectrum of α-Fe2 O3 NPs. (inset) Tauc plot modes, they are 2A1g , 5E g , 3A2g , 4E u , in which the 2A1g ,
of α-Fe2 O3 NPs
5E g modes are active in Raman and the 3A2g , 4E u modes
are inactive [27]. So it has seven characteristics Raman-
active vibrations. The Raman spectrum of the sample
is given in Fig. 9. This spectrum exhibit seven spectral
signatures that are indicative for hematite, and do not
contain any peaks associated with any maghemite.
Figure 8 shows characteristic bands of hematite
which can be assigned to 2A1g (222 and 498 cm-1 ) and
5E g (243, 290, 408 and 608 cm-1 ). Besides the typ-
ical 2A1g and 5E g symmetry phonon modes (below
620 cm-1 ), a very strong feature at 1315 cm-1 and a
very weak peak at 657 cm-1 are detected. Hematite is
Figure 8. Raman spectrum of α-Fe2 O3 NPs
an antiferromagnetic material and the collective spin
movement can be excited in what is called a magnon.
Figure 6 shows EDS analysis of iron oxide calcined
The intense feature at 1315 cm-1 is assigned to a two-
at 550 °C for 3 h. It reveals the presence of O and Fe ele-
magnon scattering which arises from the interaction of
ments and no significant signals of other elements from
two magnons created on antiparallel close spin sites.
starting materials, which indicates that the synthesized
The peak at 657 cm-1 , which is typical of nanocrys-
iron oxides are pure.
talline hematite, originates from the presence of surface
The UV-Vis spectrum of the calcined α-Fe2 O3 NPs
defects and/or reduced grain size [28,29].
is presented in Fig. 7. For recording of UV-Vis spectra,
This result confirms that the calcined product is
the sample of α-Fe2 O3 solution was prepared in abso-
α-Fe2 O3 . No other iron oxides such as magnetite or
lute ethanol dispersed by ultrasonic bath. The absorp-
maghemite were detected indicating high purity of the
tion peak in Fig. 7 corresponds to α-Fe2 O3 nanopow-
final product. Also the large line widths and the low
ders showing the strong absorption in the wavelength of
wave number shifts of the Raman peaks could be due
∼400 nm.
to the phonon confinement effects in the nanocrystals.
From these spectral data, the absorption coefficient
To obtain further information about surface area and
was calculated using the following relationship [24]:
the distribution of pores in the NPs, BET N2 adsorption-
 Opt m
 desorption analysis was performed. The adsorption-
α · h · ν = A h · ν − Eg (6)
desorption isotherm and the corresponding BJH pore
where α is absorption coefficient, A is an energy- size distribution plot (inset) of the α-Fe2 O3 NPs are

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 A. Mirzaei et al. / Processing and Application of Ceramics 10 [4] (2016) 209–217

shown in Fig. 9. According to the IUPAC classifica- The primary difference between the EDS and XPS
tion, the loop observed is ascribed to type H3 loops and techniques is that EDS could be used to determine the
the BET surface area of the material was calculated to composition of several different particles individually,
be ∼30 m2 /g. BJH plot indicates the existence of meso- then an average could be taken of the composition,
pores (pores 2–50 nm in diameter) in the α-Fe2 O3 NPs. while for XPS which is a surface sensitive technique
The size of mesopores in the architecture was not uni- (it can only detect the element no more than 10 nm in
form and most of the pores fall into a size range from 5 the depth [30]), a relatively large analysis area results in
to 30 nm in diameter. simultaneous analysis of several particles.
Figure 10 shows survey of XPS spectrum of calcined
(550 °C/3 h) iron oxide. It shows the presence of Fe
and O elements. The peak observed at 711.1 eV is at-
tributed to Fe 2p3/2 and the peak at 725.08 eV is at-
tributed to Fe 2p1/2. The shake-up satellite line is char-
acteristic of Fe+3 in Fe2 O3 . The Fe 2p spectra of α-
Fe2 O3 and γ-Fe2 O3 are almost identical with each other.
In both cases, the main peaks maximum of 2p3/2 and
2p1/2 have the shake-up structures at their higher bind-
ing energy side at about 8.0 eV. In the present case, this
value is found to be ∼8.0 eV, which confirms the for-
mation of Fe(III) oxide. However, the marked differ-
ence in these XPS spectra is that the binding energy
of the main peak, 2p3/2 is slightly higher in the case
of α-Fe2 O3 (711.3 eV) compared to γ-Fe2 O3 (710.7 eV)
Figure 9. BET curve of Fe2 O3 NPs. (inset) BJH plot showing [31]. Also appearance of Fe+3 cations (711.1 eV) rather
distribution of pores
than Fe+2 cations (709 eV) indicates the presence of the
Fe2 O3 phase [32].
The FTIR spectroscopy was utilized to detect the
presence of functional groups adsorbed on the surface
of the synthesized α-Fe2 O3 particles. Figure 11 shows
the FTIR spectrum of α-Fe2 O3 powder acquired from
Pechini sol-gel route calcined at 550 °C for 3 h. The
band at ∼3350 cm-1 is assigned to the stretching vibra-
tion of water, indicating the existence of a little water
absorbed on the sample. Two absorption bands below
1000 cm-1 represent characteristic features of α-Fe2 O3
and are assigned to metal oxygen stretching frequencies.
The high frequency band ∼560 cm-1 refers to Fe–O de-
formation in the octahedral and tetrahedral sites while
the low frequency band ∼462 cm-1 is attributed to Fe–O
Figure 10. XPS survey of Fe2 O3 NPs 550 °C/3 h deformation in the octahedral site of hematite [31]. The
intensity of absorption band at 560 cm-1 is stronger than
that at 462 cm-1 . It gives further evidence for the forma-
tion of α-Fe2 O3 and this is in agreement with the XRD
measurement. There is no peak at 2900 cm-1 indicating
the C–H stretching band, which means all organic com-
pounds are removed from the samples after calcinations
at 550 °C.
The DC electrical resistivity of the iron oxide thick
film was measured as a function of temperature in the
range of 483–673 K using DC two-probe method. Be-
cause resistance of the film at room temperature was
very high and exceeds the limit of the used instrument
(120 MΩ), it could not be measured using the experi-
mental setup. However at higher temperatures, the resis-
tance fall within readable value, and the electrical prop-
erties of α-Fe2 O3 NPs were evaluated in dry air in the
range of 483–673 K. Figure 12 shows electrical resis-
Figure 11. FTIR spectrum of α-Fe2 O3 calcined at 550 °C/3 h tance change of the sensor during heating and cooling

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 A. Mirzaei et al. / Processing and Application of Ceramics 10 [4] (2016) 209–217

Thus, for a given material with constant l and A, if nb

increases R will decrease. For semiconductor materials,
there is an exponential relationship between nb and tem-
perature:
!
p Eg
nb = Nc · Nv exp − (12)
2k · T
where Nc and Nv are the effective density of states in
the conduction band and valence band, respectively. Ac-
cording to above equation as temperature increases, nb
will increase. In case of α-Fe2 O3 as a semiconductor,
with increase of temperature more electrons transfer to
conduction band and consequently nb increases and the
Figure 12. Heating-cooling curves showing electrical resistance will decrease [34]. It is worthy to note that as
resistance of α-Fe2 O3 NPs as a function of temperature (inset
- variations of ln R versus (1/T) for the α-Fe2 O3 NPs) Fe2 O3 is a narrow band gap semiconductor and mobility
of ions at tested temperatures are much lower than the
cycles. As it clearly could be seen, resistance of sensor mobility of electrons and it is supposed that electrical
on heating and cooling is approximately the same. This conductivity is dominant in this material [35].
means that sensor resistance is very stable upon heating Temperature coefficient α(T ) can be written as follow
and cooling cycles. The relationship between the resis- [36]:
tance and temperature is as follows: 1 dR
α(T ) = (13)
Eg
! R dT
RT = R0 exp (8) If temperature change is not significant as in our case, it
2k · T
can approximately be written as:
where R0 is the pre-exponential factor, k is the Boltz-
mann’s constant, E g is bulk electrical band gap. From
the plot of ln R against 1/T the band bending of the ∆R = α · R · ∆T (14a)
sensing layer can be determined. The plot of resistance or
versus inverse temperature, shown in inset of Fig. 12, 1 ∆R 1 RT2 − RT1
shows that the temperature dependent resistance values α= = (14b)
R ∆T R T2 − T1
obey the Arrhenius relation (a linear trend) and a linear
decrease of the ln RT with increase in the temperature The variation of the electrical resistance as a func-
is observed. The estimated value of electrical band gap tion of the temperature was characterized by a nega-
was found to be ∼2.47 eV. It is worthy to note that for tive temperature coefficient of electrical resistance. As
individual particles, there is a relationship between elec- with increase of temperature the resistance decreases,
trical band gap (E gEl = E gbulk,el +E ee ) and optical band gap so α has a negative value, which is consistent with a
(E gOpt = E gbulk,el + E ee − E eh , where E ee and E eh are the semiconducting-type behaviour.
electron-electron and electron-hole interaction energies, Figure 13 shows a schematic diagram of the photo-
respectively [33]). However, for most inorganic semi- excitation in semiconductors. When UV radiation falls
Opt
conductors the values of E gEl and E g of particles are on the metal oxide, the absorption of a photon with
almost the same. enough energy promotes an electron in conduction band
After heating to high temperatures, the resistance de- and it generates a hole in the valence band; the photo-
creased strongly. The resistance of a layer with length l generated holes recombine with electrons trapped on the
and cross section A is defined as: surface causing desorption of the adsorbed oxygen ions.
This results in the conductivity increase due to the in-
l creased free electrons density.
R=ρ (9)
A The required energy for band to band excitation de-
where ρ is the resistivity of the layer. Conductivity (in- pends on the band gap energy of semiconductors. Ac-
verse function of resistivity, σ = 1/ρ) can be expressed cording to band gap determined from Tauc plot band
by the product of the charge q, the effective mobility µ gap of α-Fe2 O3 NPs was about ∼2.4 eV. The photon en-
of the layer and the electron concentration nb : ergy is determined by light wavelength (E = h · c/λ).
This means that the photon energy of 400 nm (3.1 eV) is
σ = q · µ · nb (10) sufficient for band to band excitation of α-Fe2 O3 NPs.
Figure 14 shows effect of UV light on the resistance
Combining the latter three expressions one obtains: change of α-Fe2 O3 NPs. As it can be observed, UV light
has little effect on the resistance of α-Fe2 O3 NPs. Before
l UV light irradiation, large amount of O2– is absorbed on
R= (11)
q · µ · nb · A

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 A. Mirzaei et al. / Processing and Application of Ceramics 10 [4] (2016) 209–217

tion of hematite at 550 °C. Also XPS, FTIR and EDS

results proved the formation of desired chemical com-
position and purity of synthesized NPs. Furthermore
BET results showed a high surface area which origi-
nated from nanosize nature of synthesized NPs. Thick
films of Fe2 O3 NPs prepared on the interdigitated alu-
mina substrates and the electrical resistances at differ-
ent temperatures were studied. It was found that the
prepared α-Fe2 O3 thick films had very stable electrical
properties which are especially good for gas sensing ap-
plications. Moreover, the effect of UV light on the elec-
trical resistance of sensor was studied and it was found
that UV light had no significant effect on the change of
Figure 13. Schematic representation of the photo-excitation electrical resistance of Fe2 O3 thick films.
in semiconductors [37]
Acknowledgement: This work was partially supported
by Iran Nanotechnology council.

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