Materials Characterization 178 (2021) 111269

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Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Review

Ferrite application as an electrochemical sensor: A review

Rohit Ranga a, Ashok Kumar b, Parveen Kumari a, Permender Singh a, Vasundhara Madaan a,
Krishan Kumar a, *
a
Department of Chemistry, Deenbandhu Chhotu Ram University of Science & Techonology, Murthal, Sonepat 131039, Haryana, India
b
Department of Physics, Deenbandhu Chhotu Ram University of Science & Techonology, Murthal, Sonepat 131039, Haryana, India

A R T I C L E I N F O A B S T R A C T

Keywords: Nano-ferrites are one of the extensively explored sensing materials for the detection and quantification of the
Ferrites evolution of toxic gases from industries, vehicle exhaust and biological wastes. It can be further utilized for the
Sensor monitoring and regulation of environmental pollution. This review article reports the literature available on
Nanomaterials
ferrite with single metal ion dopant, mixed ferrite materials (multi-ion doping), ferrite-based composites with
Spinel
Gas sensing
another metal oxide, polymer and carbon material /ferrite-based core-shell structures. It is reported that the
Doping ferrite with a single metal ion dopant exhibits a better response for gas sensing than pure Fe3O4. Also, by doping
Ferrite synthesis the La ions in Mg-ferrite the sensitivity increases many times at lower operating temperature and similar is the
case with Ce ion doping to Co-ferrite. Nanocomposite of PANI (Polyaniline) with Cu-ferrite reports higher
response for NH3 gas at room temperature than pure Cu-ferrite and the selectivity of NiO/Ni-ferrite changes for
HCHO than the pure Ni-ferrite. In general, ferrites possess characteristic porosity, physical and chemical ab­
sorption properties which are easily optimized by choosing appropriate synthesis routes and parameters like pH
of the solution, temperature, sintering temperature, nature and concentration of doping/co-doping ions, nano-
composites and morphology. This paper consolidates the available literature over the last three decades on
the development of ferrites as a gas sensing material.

1. Introduction
Over the past decades, few oxide complexes have attracted the
ability to optimize the physical and chemical properties of the gas de­
tector [1,2]. Some of the work on structural and magnetic properties has
also been done by our group [3–6]. Spinel ferrites having the formula
AB2O4 unit (B = Fe3+ and A = M2+) are complex oxides with the
promising application of gas sensing. Ferrites based gas sensors have
also been used for the qualitative and quantitative estimation of haz­
ardous and pungent/odorless gases to check their optimum permissible
levels in the surrounding environment and prevent accidents with an
inbuilt alarm system to save workers lives. Sometimes spinel ferrites are
also referred to as magnetic materials. In the case of the pure ferrite gas
sensor which is having low selectivity for a certain gas, their selectivity
can be improved by doping them with one dopant/co-doping with
different suitable metal ions as dopants and also by selecting appropriate
synthesis route [7]. The increased selectivity and sensitivity with
dopant/co-doping have been reported by many researchers [8–14]:
Cadmium ferrite (CdFe2O4) shows high selectivity and sensitivity for
C2H5OH vapor detection [8]. Other reported ferrites which are used for
detections are: ZnFe2O4 [9], Ni-ZnFe2O4 [10], MFeO3 (M = Ln, Gd, La,
Ni) [11,12] Mn-ZnFe2O4 [13]. Depending upon the gas concentration
the corresponding potential difference is developed by the change in
resistance of ferrite used for the sensing electrode and can be measured
by applying fixed voltage for these sensors [14,15]. Therefore, by using
this resistance value from the calibration plot generated by the different
concentrations of the same gas under investigation, the concentration
and type of gas used can be determined. When the gas concentration
exceeds the threshold, the digital value then starts flashing and in analog
meter needle position on the scale indicates the gas concentration. So
herein, we reported the review of ferrites as a gas sensing material over
the last few decades. Fig. 1 represents the number of publications of
ferrite sensors as per google scholar till the year 2020.
1.1. Goal of the review
The leading objective of the review is to emphasize the sensing
application of ferrites along with their synthesis method and

* Corresponding author.
E-mail address: krishankumar.chem@dcrustm.org (K. Kumar).

https://doi.org/10.1016/j.matchar.2021.111269
Received 27 April 2021; Received in revised form 14 June 2021; Accepted 16 June 2021
Available online 18 June 2021
1044-5803/© 2021 Elsevier Inc. All rights reserved.
R. Ranga et al. Materials Characterization 178 (2021) 111269

1.3. Reason to prefer ferrite

Ferrites are preferred over other materials because of their wider

range of applications, their low cost, high sensitivity where high sensing
is required and selectivity for particular gases. Ferrites find usage in
variety of applications in the fields like sensors [19], transformer cores
[20], chip inductor [21], electromagnetic wave absorber [22], data
storage [23,24], drug delivery [25], ferrofluids [26,27]. Also, ferrites
have received huge attention because of their extensive applications
such as power applications [28,29], application in hyperthermia [30],
biomedicines [31], catalysis [32], etc. Many constant efforts are under
process to control the size, shape, magnetic and morphological proper­
ties of ferrites by different types of methods of synthesis of ferrites.
Ferrite based gas-sensors are mechanically robust and relatively inex­
pensive and provide excellent detection capacity. When a chemical re­
action occurs on ferrite surfaces, there will be an electron transfer
process between gas molecules and ferrite surfaces, with the consequent
variation of electrical conductivity/resistivity. This repositions the
spinel ferrites as an alternative material for the gas sensor market.

Fig. 1. Number of publications since last two decade containing “Ferrite

1.4. Synthesis method to prepare ferrites
sensor” as per Google scholar.

Synthesis of the nanoparticle can be achieved by two approaches:

characterizations. Ferrites in particular constitute a particular niche for
bottom to top and top to bottom. In the bottom to top (bottom-up)
nanoparticles because the scientific community shows great interest in
method small scale atomic blocks combine to form nanoparticles. This
ferrite for detection application. In addition, this review article critically
process is the most successful method to produce narrow sized, pure and
analyzes the selection of the method to synthesize the ferrites and their
homogenous nanoparticles. In top to bottom approach material in bulk
applications in the sensing along with different parameters such as
form breaks down to nanoscale to get the nanoparticles. This approach
operating temperature, particle/grain size, response and recovery time.
was not preferred because the products are not homogenous and
generally metal-oxide requires quite a high temperature for reaction also
1.2. Morphology of ferrite
the presence of the crystal defects and impurities along with imperfec­
tion in surface and the size distribution. Solid-state reaction [33], co-
Generally, spinel is a cubic crystal system in structure constituting 64
precipitation method [34–36], combustion method [37], hydrother­
tetrahedral (Td) and 32 Octahedral (Oh) sites. Electrical neutrality in
mal method [38], sol-gel method [39–41], low-temperature chemical
ferrite occurs when divalent (M2+) ionsoccupy 8 Td sites and trivalent
methods [42] etc. are the various techniques that can be used for ferrite
(Fe3+) ions occupy 16 Oh sites [16]. Four oxygen atoms surround A-site
nano-particles synthesis shown in Fig. 3. Some of the synthesis tech­
and the six closest oxygen atoms around B-site are as shown in Fig. 2.
niques for ferrite synthesis are shown in Fig. 4.
Depending on site occupancy ferrite structure can be normal, inverse
and mixed. When divalent ions occupy Td sites and trivalent ions occupy
2. Different types of gas sensors
Oh sites then ferrite is known as normal spinel (e.g. ZnFe2O4). If all the
divalent cations and half of the trivalent cations occupy Oh sites and the
The six different types of gas sensors have been reported based on the
remaining half of trivalent cations occupy Td sites then ferrite is said to
sensing materials used for detection and the principle on which they
be inverse (e.g.: Fe3O4). When cations occupy sites randomly then mixed
work. Different kinds of gas-detector can be obtained from the market e.
ferrite is formed. Factors that affect the occupancy of the cations in the
g. metal-oxide based gas sensor (change in resistance) [43], capacitance
lattice are Crystal field effect, cation charge, cation radii, electrostatic
gas sensors (change in capacitance) [44], electrochemical gas sensors
force and lattice energy [17,18].
(Redox reaction) [45], optical gas sensors (IR) [46], calorimetric gas
sensor (color change) [47] and acoustic gas sensor (ultrasonic technol­
ogy) [48]. The electrochemical sensors are used for the detection of toxic

Fig. 2. Unit cell of the spinel structure. Fig. 3. Techniques to synthesize ferrite nanoparticles.

2
R. Ranga et al.
Fig. 4. Method of synthesis of ferrite nanoparticles.
gases. They respond when gas flows between electrodes to complete the
electrical circuit through the generated electrical signals. The infrared
sensor works when gas interferes with the transmitter and receiver
signal by altering the state of light. The thin films of metal-oxide based
sensor work exploit the semiconducting properties of sensitive films.
Fig. 5 represents the schematic of these gas sensor categories.
3. Fabrication of gas sensor
The metal-oxide based gas sensors consist of the following four
components as [13,14]
Fig. 5. Classification of Gas Sensor.
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Materials Characterization 178 (2021) 111269
3.1. Metal-oxide as a sensing layer
The gas on exposure to metal oxide sensing layer surface undergoes
chemical absorption reaction by either oxidation or reduction reaction
and adsorbs on its surface physically. This chemical absorption or
desorption and physical adsorption, of the gas on the metal oxide
changes either the conductivity or resistivity and can be easily measured
by electronic setup. They exhibit a linear and proportional relationship
with gas concentration which helps in establishing a simple calibration
curve between resistivity/conductivity change and gas concentration.
3.2. Heating coil
Heater coil has been used to heat the sensing electrode to remove
adsorbed gas molecules from the sensing electrode to revive sensitivity,
efficiency and fast recovery of the sensing element. Normally, Nickel-
Chromium has been used as a heating element because of its high
melting point to withstand high temperatures.
3.3. Electrode layer for electrical connection
It is defined as the junction in which the output of the sensing layer is
connected to the electronic circuit. So that the output current can be
passed to the electrode terminal. This electrode can be made of vacuum
evaporated gold layer, silver paste electrode or one can also use indium
tin oxide coated glass plate for base electrode connection. These elec­
trode materials are very good conductor.
R. Ranga et al.
3.4. Tubular ceramic for countering high temperature
Tubular ceramic made up of Al2O3 has been used in between the
heating coil and sensing layer to maintain pre-heating of the sensing
layer which increases the reactivity of the detecting layer to achieve
sufficient output current.
3.5. Mesh over the sensing element
For the protection of the setup and sensing elements, a metal mesh is
used over. This also limits/restrains the dust particles or impurities that
enter the mesh prevent from corrosive particles in the atmosphere to
damage the gas sensing layer.
4. Working of the gas sensor
The gas sensor detects the gases with the help of a chemiresistor for
the conduction of the current. Frequently used chemiresistor is SnO2
(Tin Dioxide is a semiconductor of n-type), which has free electrons
(termed as donor electron). In the atmosphere, the O2 content is higher
than the combustible gases. The free electrons that exist on the metal-
oxide surface layer are attracted by oxygen. Hence no donor electron
is available and the output result is zero. When the combustible or toxic
gas present in the environment, the gas reacts with oxygen which is
adsorbed and breaks the bond present between free electron and oxygen
thus sets electrons free. With the help of this free electron conduction
takes place. The conduction is directly proportional to the number of
free electrons in the metal oxide layer, a large number of free electrons
are available for interaction with toxic gas. It means the gas sensor plays
a crucial role in a variety of applications and developed for vast range of
combustible and toxic gases during the past few decades. Fig. 6 illus­
trates the setup for gas sensing.
5. Gas sensing parameters
The following are the desired parameters that are taken into account
to develop the resistive gas sensor: resistance of a sensor for gas, sensi­
tivity, selectivity, pore structure, surface area, adsorption and gas
sensing mechanism, operating temperature, dopants, hysteresis, for­
mation of phase, particle size, and crystallite size
5.1. The resistance of a sensor for a gas
The function of gas sensing is detected via an electrode signal and
will vary with different gases. Thus, conductance change is the funda­
mental factor that affects the performance of the gas. The resistance of a
Fig. 6. Schematic Representation of Gas Sensing Setup.
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Materials Characterization 178 (2021) 111269
sensor for a gas explains the effect of gas concentration on the resistance
of the sensor. At fixed constant temperature and given concentration,
the conductivity (G) is given by equation [49]:
G s = K Cg α (1)
In the above equation terms α, K is constant and Cg denotes gas
concentration parameter in air.
5.2. Sensitivity
It is the influence on the detector by the particular gas to a certain
extent. It is given by Ra (resistance in the air) to Rg(resistance with
sample gas) [50].
( / )
(%) Sg = Ra Rg × 100 (2)
It is a function of the detection material and the concentration of the
gas. “Sensitivity (S) was calculated with the help of relation at a certain
temperature” [51].
/ ( )/
S = ∆R Ra = Ra –Rg Ra (3)
It depends on the gas concentration and the nature of the detection
material.
The resistance of the gas sensor in the reducing gas medium de­
creases and in the oxidizing gas atmosphere it increases. Therefore, for
oxidizing gases the value of the sensitivity is less than 1 and greater than
1 for reducing gases. This line leads to few conclusions-.
1) Within the different limits, it is difficult to compare the parameters of
sensors when resistance changes, considering the air resistance to be
the fundamental one.
2) The given sensitivity specifies the sensor at a fixed concentration of
gas (it is not a universal parameter but a function of the
concentration).
3) The α index in Eq. (3) is constant during the measurement and is
much more of the universal sensor parameter.
4) The resistance of the air to gas arises due to the interaction of the gas
with the oxygen ion.
Alteration in a specific area, pore size and porosity alter the sensi­
tivity. These parameters cause problems in the manufacturing of
ceramic gas sensors because they need to be controlled. The problems of
controlling these parameters can be resolved by bringing up appropriate
additives which provoke pore formation and by choosing a suitable
temperature range. Up to a certain limit, the high sensitivity is deter­
mined by a large specific surface area.
R. Ranga et al.
5.3. Selectivity
The sensor can detect a distinct gas from the gas mixture. The sensor
has to be selective as a variety of gases is present in the atmosphere. It is
the process in which the sensing material surface is covered (adsorbed)
with gas. Selectivity and sensitivity are interrelated parameters. These
can be monitored and improved by temperature control [52], use of
dopant [53], special additives [54] and filters. Selectivity can also be
improved by the method of synthesis, thickness of the sensing layer and
the distance between the electrodes [55]. Porosity was determined using
relation [56].
P = 1 − d/dx (4)
d = m/V (5)
where d = bulk density, m = mass and V = volume.
/
dx = 8 M Na3 (6)
where terms signify dx = theoretical density, a = lattice parameter, M =
molecular weight and N = Avogadro's number.
The response of the sensor for the particular gas in presence of
various other gases is considered as selectivity. It is much more corre­
lated with the working temperature condition along with the effect of all
the other gases present. Therefore, a sensor has to be selective along
with a quick response for a particular gas. The reactions of the sensor to
affect a gaseous atmosphere possessing gases of several chemical con­
figurations can be explained as a collective result of the effects expressed
by all the present gases. Therefore, the selectivity of a sensor is essential
i.e., it must show the response for a specific gas only. The molecules of
gas are adsorbed on the exterior of the grains which is a step-in gas
detection process. Along with the adsorption, the surface chemical re­
action is also occurring. A high temperature range is required for the
sensor to be effective because at the higher temperature the energy
required to initiate the chemical reaction becomes lower. The temper­
ature range, selectivity and sensitivity of a sensor are interrelated and
overcome at the same time. Also, by using the appropriate thickness,
electrode gap, distance between electrodes of the sensing layer, selec­
tivity can be improved further. Fig. 7 shows the selectivity of ZnFe2O4
for gas sensing with variation in the temperature. It can also be seen
from Fig. 7 that at an operating temperature of 250 ◦ C sample show
selectivity for the acetone vapors when tested with other gases. The
same sample but at the higher operating temperature of 375 ◦ C shows
higher selectivity for the LPG gas.
Fig. 7. Histogram showing response for the ZnFe2O4 sensor at (a) 375 ◦ C and
(b) 250 ◦ C towards 2000 ppm of various gases. Adapted from Patil et al. [57]
with License number 5046000012615.
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Materials Characterization 178 (2021) 111269
5.4. Pore structure
A pore is the minute opening on the surface. Pores are of three types.
1) Open End Pores – pores that go via bulk from one surface to another
or certain volume depth and re-emerge to the same surface. 2) Closed-
end pores – pore originates starting from surface to a certain depth. 3)
Sealed pores – which exist inside the bulk and don't have an opening to
the surface. Based on cross-section view pores can be square, oval, cy­
lindrical, etc. On the base of pore size, they can be macropores (cross-
section diameter about 200 nm), mesopores (2–200 nm), micro-pores
(≥2 nm) [58,59].
Porosity = Total pore Volume/Body Volume.
( / )
P = Vp V (7)
where term Vp = pore volume in total and V = body volume.
The specific surface (s) = Total Surface/Mass.
s = S/M (8)
where S = (surface total area + surface of internal pores). The large
specific surface results in an increase of sensitivity within limits [60].
5.5. Surface area
Surface to volume ratio drastically improves gas sensitivity. In
nanostructure material, the presence of a high surface to volume ratio
helps in improved reaction time for specific gases [61]. Using the
equation, the specific surface area (A) was determined as [62,63].
A = s/(v × d) = 6/(d × Dm ) (9)
were symbols as follows s = particle surface, v = volume, Dm = average
grain size and d = bulk density. The numeric 6 denotes shape factor.
‘A’ (specific surface area) is measured using the BET method [47] at a
temperature of liquid N2, utilizing N gas as an adsorbent. The size of the
particle is determined by utilizing the equation [64].
dBET = 6/(surface area × density of sample) (10)
A large surface area helps to detect the gas at low temperatures.
Fig. 8 shows that the uniform nanorod morphology of the zinc ferrite
sample with a diameter of 300 nm and length of 10 μm, exhibits a large
number of pores on the nanorod surface and Fig. 9 shows the tetrahe­
dron morphology of the cobalt ferrite sample with a mixture of the small
rhombohedral system (trigonal). The nanocrystal of the synthesized
sample is much larger in size, after calcination the nanocrystal size
Fig. 8. SEM images of ZnFe2(C2O4)3 (a–b) and ZnFe2O4-Ns (c–d). Adapted from
Li et al. [64] with License Number 5045900666031.
R. Ranga et al.
Fig. 9. FESEM images of CoFe2O4 synthesized at 200 ◦ C, 5 h before (a,b) and
after (c,d) calcination. Adapted from Xu et al. [65] with License number
5054710097892.
decreases and showed a large Oh space in the spinel structure.
5.6. Adsorption and gas sensing mechanism
5.6.1. Adsorption
Adsorption is the ability of all solids to attract the surface gas
molecule or solutions with which they are in contact [66]. Solid that are
used to adsorb gases is called adsorbate. It is a surface phenomenon and
is the consequence of surface energy. It is a process in which an atom,
ion or molecule enters a material in a solid, liquid or gaseous phase via
chemical or physical phenomenon [67]. The term sorption encompasses
both processes, chemical and physical processes by which a substance
gets adsorbed on another surface.
Two Types of sorption:
(i) Physisorption: The procedure in which a molecule or atom is
barely perturbed (electronic structure) at the time of adsorption.
The cause of physisorption is the “Van der Waals” force. Due to
the fluctuation of charge among two interacting molecules or
atoms attractive force originates. Adsorbed molecules can form
multi-layers.
(ii) Chemisorption: It occurs due to strong binding interaction of
chemical bond present between molecule and atom with crystal
[68]. The bonding is partially ionic and mainly covalent. Mole­
cules are absorbed on the surface forming a monolayer only.
Desorption is the process in which species of molecule or atom leave
the surface of the solid and break free into the environment [69].
5.6.1.1. Surface states. At the surface of materials there are the surface
states which are constrained state energy levels. The sharp transition
from solid material ending with a surface is the reason for the existence
of these surface states. These states exist only at atom layers nearest to
the surface. Alteration of the electronic bond structure from bulk ma­
terial to vacuum is caused by the termination material with a surface. In
ionic crystals namely semiconducting metal oxide, these states are
categorized into two types [70].
1) Intrinsic surface states: - These are the surface states which come
into existence by the deformation of lattice periodicity at the surface.
Intrinsic constrained electronic energy states are determined by
Tamm by considering the interruption in periodicity of a crystalline
lattice which is called a Tamm state [71]. A Tamm state especially
comes to light for anionic crystal, when substantial divergence exists
6
Materials Characterization 178 (2021) 111269
in the power of accepting an external electron in the isolated gaseous
state between the bulk species and surface species. Tamm states are
appropriate in expressing the wide-gap semiconductors and transi­
tion metal [72,73]. Intrinsic surface states for covalent material are
described by Shockley too, where dangling bonds are formed by the
atoms at the surfaces. These states are calculated in the framework of
the nearly free electron approximation for cleansed and systematic
surfaces. This point of view is convenient for describing some narrow
gap semiconductors and normal metal [74,75].
2) Extrinsic states: These states are generally determined states which
do not arise from a cleansed and systematized surface. It is the
adsorption of contamination and gases on the surface which leads to
a rise in the extrinsic states. These states are comprised of the
defected surface with adsorbate interfaces connecting two sub­
stances namely interface between liquid-solid phases and semi­
conductor–oxide or semiconductor–metal. The extrinsic states may
also come into existence due to a fault on the surface interface con­
necting two materials viz. an interface between liquid and solid
phases and semiconductor–oxide or semiconductor–metal [73,74].
5.6.2. Gas sensing mechanism
Gas sensing occurs when oxygen gets chemisorbed on ferrite thus
trapping electron and layer formation occurs, where electron got
depleted on the n-type surface of particle or layer of conduction form via
hole accumulation on the p-type surface. In n-type, an increase in con­
ductivity is observed due to an increase in charge (electron) carrier. On
the other hand, in p-type decreases in conductivity are observed due to
hole recombination. This process changes the resistance of the oxide.
Electrons are released when a molecule of gas reacts with chemisorbed
oxygen to oxide as per reaction Gas(ads) + O− → Gas(ads)O + e− . This free
electron causes change in conductivity. At surface oxygen molecules
(O2)adsorbed are not fully ionized into O−2 , O-ve or O2− ions via attracting
an electron from the valence band with varying temperatures. At a
higher temperature O− is more occurring as compared to another oxy­
gen adsorbate [76–83].
(O2 )gaseous ⟷(O2 )adsorbed (11)
(O2 )adsorbed + e− ⟷(O2 − )adsorbed (12)
(O2 − )adsorbed + e− ⟷(2O− )adsorbed (13)
( )
(O− )adsorbed + e− ⟷ O2− adsorbed (14)
On the surface of the sensor, the reducing gases (R) may get absorbed
as.
R⟷Radsorbed (15)
Adsorbed oxygen and adsorbed gas species reaction as follows, for
example (O-ve)adsorbed and (O2− )adsorbed are oxygen species which
advance as [84,85].
Radsorbed + O− adsorbed ⟷ROadsorbed + e− (16)
Radsorbed + O2− adsorbed ⟷ROadsorbed + 2e− (17)
ROadsorbed ⟷ROgaseous (18)
Adsorption depends upon detector material and the test gases which
affect reaction time and sensitivity. A large quantity of test gas shows
high sensitivity and reaction among oxygen and reducing species is
expected to be easy. The difference in gas sensing occurs due to the
difference in reaction and adsorption process for different gases. The
quantity of oxygen adsorbed plays a crucial role in providing sufficient
reactants for the reaction. Fig. 10 shows the mechanism for reducing gas
with ferrite. The incorporation of catalyst improves the gas sensing
property [86]. Catalyst improves the rate of reaction occurring at the
surface sites, thus increasing the oxygen content at the surface which
R. Ranga et al.
Fig. 10. Gas sensing mechanism for ferrites.
leads to rapid response for the detection of the gas.
5.7. Operating temperature
It is one of the main conditions which rule the sensitivity of the de­
tector. The variation in resistance for gas depends on the activation
process at the adsorbed site and the rate at which gas molecules diffuse.
The rates at which gas molecules adsorbed (dispersed) and the chemical
reaction become almost equal at a moderate temperature [87]. At this
point, the response is maximum. There is a certain temperature for every
gas at which maximum sensitivity is observed. Fig. 11 shows the
sensitivity of nickel ferrite for various gases at different temperatures.
The sensitivity for most of the sensors shows an increase in the ten­
dency for maximum decay for various gases with increasing tempera­
ture. The interaction between the sensor exterior and target gas
determines the sensitivity of metal-oxide semiconductor sensors. Suffi­
cient thermal energy is not available for the gas molecule to react with
absorbed oxygen species O− at the surface under low operating tem­
perature. Therefore, at low operating temperature, the speed of reaction
between absorbed oxygen species and the target gas is generally low and
its consequences the low sensitivity. Enhancement in sensitivity can be
attributed to with increasing temperature by the following facts:
1) Sufficient activation energy due to high thermal energy which helps
to overcome the energy barrier.
2) Change of the adsorbed oxygen species O2− to O− which increases the
concentration of electrons at higher temperature due to reaction
between the oxygen species and the target gas.
After achieving the maximum sensitivity, the reduction is observed
due to the difficulty in adsorption at elevated temperatures. Hence, a
suitable temperature must be considered to achieve maximum
Fig. 11. Plot of sensitivity verses temperature for nickel ferrite for various
gases. Adapted from Patil et al. [88] with License number 5046000012615.
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Materials Characterization 178 (2021) 111269
sensitivity.
5.8. Dopants
These are used to alter the selectivity, reactivity and reaction time of
a sensor [89]. They can be transition metal ions, alkali metals, alkali
earth metals or rare earth metal ions [90]. Also, sensitivity can be
modified by varying the doping concentration. Fig. 12 shows the vari­
ation of gas response with different concentrations of the same dopant.
5.9. Hysteresis
“Hysteresis can be defined as the lack of re-traceability of the
magnetization curve, which may be related to the existence of magnetic
domain in bulk ferromagnetic material” [91]. It is also defined as a
difference in the output of the sensor when input is varied. A good sensor
has negligible resistance [92]. The hysteresis loop is used to identify the
type as hard, soft and superparamagnetic ferrite. Fig. 13 shows the
hysteresis curve of the iron and its oxide without doping of different
elements.
5.10. Formation of phase
Various types of phases can exist depending upon temperature and
composition. Ferrite exists in various phases at different temperatures.
Fig. 14 shows the iron-oxygen phase diagram with restect to tempera­
ture and percentage of oxygen. Depending on the phase present at that
temperature the property is different from the other phase and how the
phase arranges also affects its property. This led to various structural
possibilities in size and shape. Fig. 15 shows the magnetite undergoes
the Verwey transition (Tv) at ambient pressure where there occurs
structural, charge ordering, and metal-insulator transitions. From the
figure, it is concluded that there is a decrease in temperature for the
metal-insulator transition and the distorted structural transition with
increasing pressure, while the temperature increases with increasing
pressure for the charge ordering transition.
5.11. Crystallite size and particle size
It is expressed as the size of a single crystal inside the particle.
Several crystals combine to form a single grain. Grain size is the particle
size or we can say the diameter of a single grain. An increase in hardness
and strength causes grain size reduction [95,96]. The smaller the grain
(large surface area) shows the high sensitivity [97].
6. Results and discussion: (i) ferrite with single metal ion
dopant
Simple ferrite may or may not show sensing efficiency for gas
sensing. Therefore, an efficient method is to dope the nanoparticle of
Fe3O4 with other transition metal ions, which help in increase of charge
carriers or generation of holes. There have been many studies done in
MFe2O4 (M = Co, Ni, Zn, Cd, Al, Mn, Al, Sr, Bi, Sr, Ba, Ca, Mg Li). These
(s, p, d-block) metal ion substitutes Fe ion coordination at Td and Oh site
in the crystal lattice of Fe3O4, resulting in alteration of the holes and
charges which allows the electron to move more freely in the lattice and
reacts with the reducing gas. In presence of reducing gases, various
ferrites can directly respond to gases like C2H5OH, LPG, NO2, H2,
CH3OH, (CH3)2O and various other gases as given in Table 1. While
preparing and optimizing doped ferrites, the factors that affect their
activity must be taken into consideration. Since the activity depends on
several factors, including the precursors of the metals, the type and
concentration of surfactants used in their synthesis. There are many
other factors reported that affect the activity and detection efficiency of
these ferrites. For example, changing the weight or type ratio of one of
the two or three precursors produced different detection responses.
R. Ranga et al. Materials Characterization 178 (2021) 111269

Fig. 12. Effect on gas response at different operating temperature with varying Sm3+ concentration. Li0.5Fe2.5-ySmyO4 (y = 0 (L1), 0.05 (L2), 0.1(L3), 0.2(L4).
Adapted from Rezlescu et al. [61] with license number 5045911275124.

Fig. 13. B-H curve shows (a) Fe3O4 and (b) Fe nanowires adapted from Han
et al. [93].
Fig. 14. Iron‑oxygen phase diagram adapted from Han. et al. [94].

Therefore, the difference in detection behavior between different ferrite-

highly sensitive to ethanol at a temperature of 290 ◦ C. As per grain size,
doped metal ions indicates that the incorporation of an additional
reported sensitivity for C2H5OH increases in order ZnFe2O4 < CuFe2O4
element can play an important role in improving detection efficiency.
< MgFe2O4 < CdFe2O4.Tao et al. [84] reported CuFe2O4 using the
Chen et al. [9] reported MFe2O4 (M = Zn, Cu, Cd and Mg) using the
synthesis method of co-precipitation. Morphology with tetragonal phase
co-precipitation technique and tested with CO, C2H2, LPG, H2, and
was obtained at 90 ◦ C and sintered done at 800 ◦ C. The sample was
C2H5OH for gas sensing. The result shows high sensitivity for C2H2, for
tested with various test gases. At a concentration of 1000 ppm,
C2H5OH the sensitivity is 28 at 2000 ppm concentration. TEM analysis
maximum sensitivity of 7.5 for C2H5OH was reported with an average
reveals that particle size lies within 50 nm. The result shows CdFe2O4 is

8
R. Ranga et al. Materials Characterization 178 (2021) 111269

particle size of 22 nm. The conductance of the sample is almost the same,
above 350 ◦ C for N2 conductance increases in comparison to air. Liu
et al. [98] reported n-type MgFe2O4 by solid-state reaction technique
sintered at 700 ◦ C for 1 h. The result shows that nano-material is sen­
sitive for both the H2S and C2H5OH. At a temperature near 160 ◦ C
product is sensitive for H2S but at a higher temperature around 335 ◦ C
sample is sensitive for C2H5OH at a concentration of 50 ppm. The re­
ported average grain size is 15–30 nm. Xiangfeng et al. [99] synthesized
n-type CoFe2O4 by hydrothermal synthesis and investigated for gas
sensing property for C2H5OH, petrol, triethylamine. CoFe2O4 shows a
good response, high selectivity to the low C2H5OH vapor concentration
at 150 ◦ C. Sample can detect 10 ppm of C2H5OH with recovery time and
response time is 100 s. and 50 s. respectively. This sensor can be used to
detect triethylamine in the absence of C2H5OH. Zhang et al. [100] re­
ported ZnFe2O4synthesized using the PVA Xerogel technique and tested
for C2H5OH, CH3OH, (CH3)2 CO, HCHO and petrol. XRD confirms the
Fig. 15. Phase diagram of Fe3O4 at extreme pressure and temperature Adapted presence of a cubic phase with an average crystallite size of 5–13 nm.
from Lin et al. [82]. (Tv) is Verwey transition. Sample shows better sensitivity for C2H5OH in comparison to other
gases. The synthesized product exhibits better sensitivity because of its
hollow structure and thin walls which leads to a decrease in optimum
Table 1 working temperature and response time as compared to the sensor made
Analysis of gas sensing for ferrite with single metal ion dopant. of particles.
Sample Gas tested Selectivity Sensitivity Response Lou et al. [101] reported nano-sized CdFe2O4 synthesized by utiliz­
time (s) ing the sol-gel citrate method and sintered at 700 ◦ C. The maximum
ZnFe2O4 C2H2, CO, LPG, H2, C2H2 19 15 sensitivity for the sample was reported for C2H5OH at an operating
C2H5OH temperature of 250 ◦ C with a reaction time of 18 s. and the recovery time
CuFe2O4 C2H5OH, gasoline, C2H5OH 7.5 – of 54 s. at a concentration of 100 ppm. The reported average crystallite
C2H2, H2, CO, LPG
size was 20–60 nm. Sun et al. [102] reported CuFe2O4 using the solid-
MgFe2O4 CH4, H2S, LPG, C2H5OH 13 –
C2H5OH state reaction method. The precursor was mixed and ground using
CoFe2O4 C6H6, C2H5OH, petrol, C2H5OH 70 50 agate mortar. Then powder was dried and annealed for 2 h at 900 ◦ C to
C6H5CH3, (C2H5)3N obtain the final desired product. At an operating temperature of 700 ◦ C,
ZnFe2O4 C2H5OH, CH3OH, C2H5OH 11 22 the reactivity for C2H5OH is 7.5 at a concentration of 700 ppm. With an
HCHO, petrol,
(CH3)2CO
increasing calcination temperature, the crystallite size increases.
CdFe2O4 C2H5OH, NH3, H2S, C2H5OH 55 – Tudorache et al. [103] reported MFe2O4 (M = Cd, Cu and Zn) synthe­
gasoline, C6H6, sized using the sol-gel technique. The palletized sample was annealed at
(CH3)2CO 1000 ◦ C for 30 min. The maximum sensitivity for C2H5OH is near 42% at
CuFe2O4 C2H5OH, H2, NH3, C2H5OH 7.5 5
300 ◦ C for a 150 ppm concentration. The reported average grain size is
(CH3)2CO
Cu/ MFe2O4 C2H5OH, (CH3)2CO, LPG 45 – 700 nm and the porosity percentage is 32.8 with the specific surface area
(M =Cd, LPG of 2.4 g/m3. For NiFe2O4 the sensitivity for ethanol is 19% at 250 ◦ C and
Cu,Zn) the porosity of the sample was 35.2% with a specific surface density of
ZnFe2O4 C2H5OH, (CH3)2CO, C2H5OH 38 120 8.6 g/m3 having an average grain size of 200 nm. ZnFe2O4 is highly
LPG
sensitive for C2H5OH with 38% sensitivity at a concentration of 150 ppm
MgFe2O4 LPG, H2S, C2H5OH, Petrol 3 –
NH3, (CH3)2CO, H2, with the specific surface area of 22.2 g/m3 having an average grain size
CH3OH, petrol, NOx, of 100 nm and a porosity value of 48.4. Rezlescur et al. [104] reported
CO MFe2O4 (M = Zn, Cu and Cd) synthesized using the combination of sol-
MgFe2O4 LPG, NH3 C2H5OH, LPG 71 51
gel and combustion technique followed by sintering at 1000 ◦ C. The
(CH3)2CO
ZnFe2O4 C2H5OH, (CH3)2CO, C2H5OH 23 – sample was tested with LPG, C2H5OH and (CH3)2 CO. Sensitivity
isopropanol, xylene, response of 43 for C2H5OH was reported at an operating temperature of
toluene, heptane, C6H6 350 ◦ C for CdFe2O4 and good sensitivity for ZnFe2O4 with porosity of
ZnFe2O4 C2H5OH C2H5OH 1.1 – 45.5 and 32.2 respectively. The sample exhibits good stability for a
ZnFe2O4 C2H5OH, (CH3CH2)O, C2H5OH 21.5 4
certain time and then remains almost constant. The particle size ob­
H2, HCHO, NH3, H2S,
LPG, gasoline, tained was smaller than obtained with the ceramic method.
C6H4(CH3)2 Hankare et al. [105] reported spinel structured MgFe2O4utilizing the
NiFe2O4 NH3, LPG, C2H5OH, LPG 142 – method of co-precipitation and studies for various gases like H2, LPG,
(CH3)2CO
SOx, H2S, NOx, C2H5OH, CH3OH and acetone. At 900 ◦ C the product was
ZnFe2O4 NH3, LPG, C2H5OH, i) LPG i) 55 –
(CH3)2CO ii) ii) 57
sintered for 4 h. The operating temperature for sensing was 250 ◦ C. The
CH3COCH3 product was found sensitive to petrol. It shows maximum sensitivity for
SrFe12O19 LPG, C2H5OH, NH3, LPG 0.7 – petrol and less for ethanol. For C2H5OH at a temperature of 250 ◦ C the
NO reactivity was 1.5. An increase in resistivity of the sample was observed
ZnFe2O4 C2H5OH, CH3OH, H2, (CH3)2CO 54 Short
with an increasing temperature. Patil et al. [106] prepared MgFe2O4 by
(CH3)2CO, CO, NH3,
DyFeO3 (CH3)2CO, NH3, CH3COCH3 3.8 48 utilizing the glycine-combustion method. The sample was sintered at
HCHO, C2H5OH, 973 K. With the rise in sintering temperature, an increase in average
CH3OH, acetylacetone particle size was observed and hence the porosity decreases. The grain
LaFe3O4 O2 O2 8.3 15
size obtained by this method was <1 μm. The sample exhibits the n-type
semi-conduction. Maximum sensitivity was shown for LPG. At a tem­
perature of 598 K the sample sensitivity is 71 at a concentration of 1000

9
R. Ranga et al.
ppm. Reaction and recovery time are 51 s. and 94 s. respectively. Sutka
et al. [107] reported ZnFe2O4 synthesized by sol-gel technique followed
by the combustion method. The gas sensing result shows that the sample
was most sensitive for C2H5OH. To initiate combustion the gel was
heated up to 240 ◦ C. The sample was sintered at 800 ◦ C for 1 h and made
into pallets. Sensitivity increases up to 300 ◦ C then a decrease in
sensitivity was observed. The sample shows a large recovery and
response time. He also synthesized n-type ZnFe2O4 [85] using the spray
pyrolysis technique and tested for C2H5OH vapors. The thickness of the
layer is 30 nm. With an increasing operating temperature, an increase in
sensitivity is observed. The sensor shows good sensitivity at a very low
concentration of C2H5OH.
Cao et al. [108] reported ZnFe2O4 synthesized using solid-phase
synthesis method and tested with C2H5OH, HCHO, H2, H2S, LPG, NH3,
xylene, gasoline and ethoxy-ethane. At a temperature of 240 ◦ C, the
sample shows high reactivity for C2H5OH at a concentration of 100 ppm.
Reaction and recovery time are 4 s. and 14 s. respectively were reported.
This method is a one-step process and yields a high quality product with
great sensitivity and selectivity along with better reaction and recovery
time. Patil et al. [109] reported NiFe2O4 synthesized by glycine com­
bustion method. The sample was calcined for 2 h at 500 ◦ C. The sample
was palletized and calcined at 700 ◦ C. The response was tested for
C2H5OH, LPG, NH3 and (CH3)2CO at a temperature of 350 ◦ C. The
sample was most sensitive for LPG. For C2H5OH response was reported
108%. For LPG it is above 140% at a concentration of 100 ppm. It shows
a p-type semi conductance. He also reported ZnFe2O4 [110] by using the
glycine combustion method. The average particle size of 33 nm was
reported. At an operating temperature of 250 ◦ C reactivity for C2H5OH is
13% at 100 ppm concentration. Singh et al. [111] reported SrFe12O19
synthesized using the method of co-precipitation and annealed for 2 h at
900 ◦ C. The result shows high sensitivity for LPG gas. For C2H5OH
sensitivity was less around 0.35. Pore size lies in 0.1–0.5 μm range grain
size is 20 nm is reported with hexagonal structure. Li et al. [112] re­
ported ZnFe2O4 nanorods synthesized by hydrothermal method and
heat-treated at 350 ◦ C for half hour. At a temperature of 260 ◦ C, the
reactivity for C2H5OH is 16.3 at a concentration of 100 ppm was re­
ported. The length of the nanorod is 10 μm and a diameter of 300 nm
was reported. The reactivity of the detector increases with the increasing
concentration of gas.
Cao et al. [113] reported rare earth ferrite DyFeO3 with ortho­
rhombic structure using sol-gel method and studied for acetone gas
sensing with good response and recovery time at 190 ◦ C. Sample shows
high selectivity for acetone and shows promising material for the sensor
in the medical and industrial fields. An average grain size of 55 nm was
reported on analysis with FE-SEM. Mun et al. [114] reported lanthanum
ferrite nanostructure using sol-gel and electrospinning method for oxy­
gen sensing. Sample shows fast response and recovery time due to the
presence of mixed particle and nanofiber structure. Sample film
response for oxygen is 2.6 times that of powder sample with the stability
of more than 100 h. The result shows that control on morphology can
refine the performance of the sensor.
Since in Table 1 we have summarized the analysis performed along
with gas sensing for ferrite with single metal ion dopant. From Table 1 it
can be concluded that the doping of the single ion specifically Mg, Zn.
which belongs to the category of soft ferrites greatly enhances the
sensitivity, selectivity and lowers the operating temperature and it can
be pointed out that maximum sensitivity is shown by sample NiFe2O4 for
gases NH3, LPG, C2H5OH,(CH3)2CO is 142. Similar behavior is also
observed when the doping of the rare-earth elements is done resulting in
detection capability at a much lower concentration limit of the test gas.
As we can observed that very nice work was performed by many re­
searchers, however In order to further improve the sensitivity, many
researchers preferred with the multi-ion doping after ferrite with single
metal ion dopant.
10
Materials Characterization 178 (2021) 111269
6.1. Mixed ferrite materials (multi-ion doping)
Researchers have prepared multi-doped nano-ferrites i.e., doping of
multiple metal ions replacing the ions at the Td or Oh site. This concept
provides the property of two different materials which can respond at a
much faster rate than pure ferrite. The enhanced response is due to the
increases in the movement of electrons through the lattice which occurs
due to the lowering of the conduction band by multiple doping. On
fabricating these have combined characteristics of the metal ion and
ferrite conduction energy level. It is observed that by changing the metal
ion and its concentration desired response can be achieved. The doping
can be of s, p, d, f block element. Mostly for sensing, desired doping is
from transition and lanthanum series elements. Dororftei et al. [66]
synthesized magnesium ferrite doped with tin and molybdenum using
an auto-combustion method (Mg1–xSnxFe2–yMoyO4) with different
compositions. At x = 0.1 and y = 0 sample was analyzed for C2H5OH and
(CH3)2CO. It was found to be more sensitive for (CH3)2CO and exhibits
the maximum resistance at this composition. At 380 ◦ C maximum
sensitivity for C2H5OH is observed. When the sample is doped with only
Sn, it exhibits the minimum grain size. On the other hand, Rezlescu et al.
[115] reported (Ni0.99Co0.01Mn0.02Fe1.98O4) synthesized by the method
of combustion sintered at 1270 K. Sample was tested with C2H5OH,
(CH3)2CO, LPG and CH4. It shows high reactivity for (CH3)2CO at an
operating temperature of 488 K and shows 3 min reaction time. For
C2H5OH, it shows a sensitivity of 0.9 at a temperature of 450 K. Sensi­
tivity increases with an increase in temperature but above 488 K it de­
creases. Lattice constant was found to be higher than pure nickel ferrite.
Liu et al. [116] reported perovskite-type LaMgxFe1− xO4 synthesized
using the sol-gel method utilizing citric acid. The precursor (nitrate of
lanthanum, magnesium and ferric) was mixed in ratio and solution was
prepared. Then citric acid was mixed in a ratio of 1:2. After that PEG
(polyethylene glycol) was added to the sol and dried to obtain gel, fol­
lowed by drying and grounding. The obtained product was analyzed for
C2H5OH vapors. With the increase of Mg content, the average grain size
decreases. Also, an increase in resistance was observed with the
increasing Mg content. Rezlescu et al. [61] reported Li-SmFe2O4 using
the method of sol-gel self-combustion and tested with NH3, LPG,
CH3OH, and C2H5OH. Sample shows better sensitivity for C2H5OH and
CH3OH vapors. With an increasing doping of Sm2+ content response for
C2H5OH vapor increases due to the increase in porosity of structure.
Also, with increase of Sm2+ content, the increase in resistivity and
reduction in average particle size was observed due to the dispersion of
agglomeration. At a concentration of 0.05 of Sm2+, the sample shows the
maximum response for C2H5OH. It can detect 50 ppm of C2H5OH with a
response of above 70% at a temperature of 340 ◦ C. Kapse et al. [117]
reported zinc doped nickel‑zinc ferrite synthesized using citrate sol-gel
method and tested with NH3, H2S, LPG and C2H5OH. The reactivity
for C2H5OH is 0.6 at 300 ◦ C with a concentration of 100 ppm. Further
incorporation of 1 mol% of Pd the sensitivity for C2H5OH increases
around 0.8. With the increase in nickel content, reduction in lattice
parameter is observed with increases of average size increases. The
average size and lattice parameter increase with Zn content. Zn1-
xMnxFe2O4 was reported by Kadu et al [13] utilizing the sol-gel citrate
method and tested with LPG, C2H5OH, CO, and CH4. At a temperature of
300 ◦ C maximum response for C2H5OH was reported. ZnFe2O4 shows
less reactivity for C2H5OH before the doping of Mg. The selectivity and
sensitivity were further increased by the doping of 1.5 weight percent­
age of Pd. With doping decrease in operating temperature to 230 ◦ C was
observed. The reactivity increases up to 0.97. A decrease in sensitivity is
observed with a further increase of Pd content. The result shows that it
has a spinel structure having a spherical shape with good crystallinity.
Devi et al. [118] reported (Mn-doped CoFe2O4) synthesized using the
chemical precipitation method. The sample shows an increase in reac­
tivity for the Manganese-doped sample than pure CoFe2O4. With an
increase of Mn content in the sample, lattice constant increases and a
reduction in the average size of the particle was reported. The sensitivity
R. Ranga et al.
of 12 for C2H5OH was reported with an average size of particle ranges
from 14 to 17 nm. At room temperature, a short recovery time was re­
ported. Khandekar et al. [119] reported Ce-CoFe2O4 synthesized by
using the molten salt method and tested with LPG, (CH3)2CO, C2H5OH,
and NH3. Polyvinyl acetate was used as a binder to prepare pellets and
sintered at 700 ◦ C for 2 h. Sample shows better sensitivity for (CH3)2CO
and less for C2H5OH. After the incorporation of the cerium, a decrease in
particle size was observed from 20 nm to 10 nm. For C2H5OH at 100 ppm
concentration, its sensitivity is 112% with a working temperature of
200 ◦ C. They also reported Ce-CuFe2O4 [120] using a molten salt
method and tested with the same gases. The sample shows better
sensitivity for LPG and less for C2H5OH. The average particle size of the
sample was reported as 26 nm. Kumar et al. [121] reported manganese
doped copper ferrite (Mn0.4Cu0.6Fe2O4) synthesized using an auto
combustion technique. Sample shows an excellent gas sensing property
towards LPG. The sensor response for the C2H5OH was around 0.04 at a
concentration of 1000 ppm. An increase in the size of the particle is
observed with increasing temperature. Using the TEM result, the re­
ported shape of the particles is spherical with 40 to 60 nm in size. The
dielectric property of the sample decreases with a decrease in sample
size. Vasambekar et al. [122] reported Nd3+-ZnFe2O4 synthesized using
the method of oxalate co-precipitation and sintered at 1000 ◦ C. XRD
reveals that it has a cubic spinel structure. With increasing incorporation
of Nd3+ the grain size decreases. The sample was tested with C2H5OH,
Cl2 and LPG. The result shows better sensitivity for C2H5OH. At a tem­
perature of 337 ◦ C, the reaction and recovery time are 85 s. and 109 s.
respectively. Tudorache et al. [123] reported Ni1-xCoxFe2O4 synthesizes
using spin coating technique and tested for CH3COOH, LPG, C2H5OH
and CH3OH. It shows better sensitivity for C2H5OH over other gases, at a
value of x = 0.75. Also, a decrease in lattice parameter was reported with
an increase of Ni2+ in Cobalt ferrite. 10–15 nm average crystallite size is
reported for the sample.
Karmakar et al. [124] reported Zn1-xMgxFe2O4 synthesized using the
wet chemical method and followed by auto-combustion. The product
was calcined for 2 h at 750 ◦ C and tested for C2H5OH and (CH3)2CO
vapors. It was found to be more sensitive for (CH3)2CO vapors. At a
temperature of 325 ◦ C the reactivity is 29 with a concentration of 20
ppm for C2H5OH. The reaction and recovery time for C2H5OH is 61 s.
and 65 s. respectively. Dong et al [77] reported Bi0.9Ba0.1FeO2.95 pre­
pared utilizing the sol-gel technique. A stable sol precursor is obtained
by aging it for 24 h at 100 ◦ C. The obtained gel was calcined at 2 h at
450 ◦ C and finally annealed for 2 h at 850 ◦ C. At a temperature of 400 ◦ C,
the sensitivity for C2H5OH was found to be 16 for 100 ppm. The reaction
time and recovery time are 3 s. and 10 s. respectively for the sample.
With the incorporation of Bi3+ ion, grain size decreases and shows p-
type conduction. Joshi et al. [125] reported Co1-xNixFe2O4 using the
method of wet chemical co-precipitation with cubical spinel structure
and tested with CO and C2H5OH. The reactivity for ethanol was very
high at a concentration of 1500 ppm at operating temperature of 400 ◦ C.
15–25 nm average crystallite size was reported. With the incorporation
of the Co2+ ion the average size of the particle increases. With
increasing, Ni2+ concentration sensitivity is observed. Dalawai et al.
[126] synthesized Ni–Zn ferrite sensor using oxalate co-precipitation
method followed by thin film method. The product was sintered for 2
h at 450 ◦ C. With an increasing nickel content, the crystallite size in­
creases. The sample was tested for LPG, Cl2 and C2H5OH. At a temper­
ature of 177 ◦ C, the sample show reactivity for C2H5OH is 58% and the
reaction and the recovery time are 30 s. and 40 s. respectively. On
comparing with pure nickel and zinc ferrite the Ni–Zn ferrite shows less
sensitivity for ethanol. Sen et al. [127] reported BaCa2Fe16O27 utilizing
the sol-gel technique and annealed at 950 ◦ C for 4 h. The average
crystallite and average grain size were determined to be 20 nm and 200
nm respectively. The sample was tested with C2H5OH, CO, (CH3)2O, and
CH4. The sample shows the highest sensitivity 55% for C2H5OH at a
concentration of 100 ppm. Fast response and recovery time are exhibited
by the sample. Rao et al. [128] reported Cu-NiFe2O4 by dual-mode spray
11
Materials Characterization 178 (2021) 111269
pyrolysis technique. A temperature of 350 ◦ C was maintained during the
deposition of the film. At a temperature of 650 ◦ C for 3 h thin film ob­
tained via spray pyrolysis method is sintered. Then thin films were
analyzed for gases like ethanol, LPG, CH3OH and H2S. It was found that
the films are more sensitive towards C2H5OH around 320–375 ◦ C. With
the incorporation of Cu, the particle size slightly decreases. The best
result was shown when the incorporation of 1 wt% of Cu. Further with
the rise in doping amount results in a decrease in sensitivity for ethanol.
Wei et al. [129] reported Ag-LaFeO3 synthesized by the electro-spinning
method. The sample was tested with various sample gas (NH3, C2H5OH,
HCHO, C6H6). For C2H5OH, it shows a response of 0.6. Fibrous shape
product was observed with a diameter of 80–150 nm.
Mutkule et al. [130] reported CoBi0.1Fe1.9O4 synthesized via sol-gel
technique and calcined at 100 ◦ C. The sample was tested with
C2H5OH, CH3OH, NH3, H2S and NO2. Using the result from the HRTEM
sample exhibits the crystallite size of 5–90 nm with irregularity in
structure. The sensitivity for ethanol is around 13% at a temperature of
200 ◦ C. The sample shows a good reaction and recovery time. Man­
ikandan et al. [131] reported a thin film of indium-substituted copper
ferrite. Crystallite size of 30 nm was reported using XRD and 50 nm
using TEM analysis. Sample shows the high response for LPG gas on
testing. UV–Visible spectroscopy at 450 nm revealed the bandgap of
1.54 eV showing semiconductor behavior. The sensor shows result
reproducibility of 96%. The sample shows a quick response for lower
concentration and decreases with increasing concentration. He also re­
ported a thin film of cubic phase lithium doped copper ferrite [132] with
irregular polyhedron shape size for LPG gas sensing. The Crystallite size
of 17 nm having a bandgap of 1.15 eV with repeatable sensing behavior.
Chethan et al. [133] synthesized nickel doped cadmium ferrite using the
sol-gel auto combustion method. The sample was tested for humidity
and a good response with recovery time was reported. The material
shows stability over a long period. Reddy et al. [134] reported a nano­
composite of yttrium-oxide doped copper ferrite and tested for humidity
sensing with excellent response and recovery time with good stability.
Synthesized material shows a potential application in electronic devices
in industries where humidity sensor is important. Nano-composite
shows a high response in comparison to undoped copper ferrite.
Deepty et al. [135] reported polycrystalline MnxZn1-xFe2O4 using co-
precipitation and sol-gel auto combustion method and high sensitivity
for LPG gas was observed. A decrease in dielectric constant is observed
with a decrease in Mn2+ concentration. Sample prepared using copre­
cipitation method shows lower operating temperature. The presence of
multiple phases is observed in the sample prepared using the sol-gel
method and this causes in low sensing behavior than a coprecipitation
sample. Hao et al. [136] reported microspheres of Ni-LaFeO3 perovskite
using the hydrothermal method showing high sensitivity for acetone
vapors with quick response and recovery time. Ni doping improves the
sensing property of LaFeO3.LaFe0.98Ni0.02O3 shows the maximum
response for acetone at 100 ppm at an operating temperature of 220 ◦ C
along with quick response and recovery time with excellent stability.
Srinivas et al. [137] reported NixZn1-xFe2O4 using the co-
precipitation method and test for various gases. No particular selec­
tivity is shown for a particular gas. Maximum response for 1000 ppm
LPG gas was reported at an operating temperature of 200 ◦ C. Waghmare
et al [138] reported nano-cubes and nano-plates palladium-doped
perovskite bismuth ferrite synthesized using sol-gel method and tested
for NO2 gas sensing. As synthesis sample shows the better response with
high sensitivity with a repeatable result which is due to high surface area
and active sites provided by the obtained morphology. Manikandan
et al. [139] reported Ruthenium doped nickel ferrite synthesized using
co-precipitation method followed by annealing at different tempera­
tures. The sample was tested with various gases and the maximum
response for H2 was reported at 100 ◦ C with a selective response and
thus shows potential for durable sensor material. The sample shows
coercivity of 99.26 G with retentivity of 6.76 G. He also reported Va­
nadium doped nickel ferrite [140] using co-precipitation and tested for
R. Ranga et al. Materials Characterization 178 (2021) 111269

sensing performance for NO gas. The doped sample shows super­
paramagnetic nature and better response.
As Table 2 contains analysis performed along gas sensing for multi-
ion doped mixed ferrites which shows that multi-ion doping greatly
increases the sensitivity of the ferrite sample and maximum sensitivity
shown by Y-CuFe2O4 is 4895. For example, doping of the rare-earth
element to soft ferrite such as La to Mg-ferrite, Ce to Co-ferrite greatly
enhances the sensitivity of the pure single ion doped ferrite. Also, in few
cases rare-earth doping drastically reduces the operating to nearby room
temperature for detection of gases such as Yt3+ doped to Cu-ferrite
lowers the operating temperature to 32 ◦ C showing very high sensi­
tivity for humidity. Other ferrite doping such as doping of soft ferrite
with other soft ferrite metal ions such as Ni to Co-ferrite, Mg to Zn-ferrite
increases the sensitivity of the sample. Although sensitivity have
increased many folds in this case as compared to the single metal ion
doping but for the further scope of enhancement, many researchers
[141,142] tried ferrite base composites with other metal oxide, polymer
and carbon materials after multi-ion doping.
6.2. Ferrite based composites with other metal oxide, polymer and carbon
material
Ferrite and its composites with various metal oxides are highly
studied for sensing application. Composite material doped sensing has
been synthesized to take advantage of two different energy level sys­
tems, so that alteration can be done in charge carriers to achieve
desirable sensing activity. Some systems were successfully synthesized
such as ferrite/semiconductor, ferrite/metal-oxide, ferrite/polymer.
Based on these, many researchers have synthesized coupled systems
such as CdO-Fe2O4, NiO/Fe2O4, CuO-Fe2O4, NiO-NiFe2O4, polymer
based are ZnFe2O4@ polyindole, PANI/CuFe2O4 carbon based
MgFe2O4/g-C3N4 [141,142].
Tianshu et al. [141] reported CdO-Fe2O4 synthesized using the co-
precipitation method, using CdCO3 as a precursor. The sample was
sintered at 650 ◦ C. The sample was tested with C4H10, H2 and C2H5OH at
a temperature of 380 ◦ C. Maximum reactivity for C2H5OH was observed
at a 200 ppm concentration. The reported recovery and the reaction time
are 35 s. and 15 s. respectively. Sample detects the minute amount of
C2H5OH vapor present in the air. Pure Fe3O4 has an inverse spinel
structure with CdO doping multi-phase are formed which leads to a
decrease in conductance till 350 ◦ C. Under dry N2 the conductance in­
creases with increases in temperature. Liu et al. [142] reported n-type
CdO-Fe2O4 using co-precipitation process and tested for ethanol,
Hydrogen, CO, LPG and petrol. At a temperature of 300 ◦ C reactivity for
C2H5OH is 50 at a concentration of 800 ppm. 2 s. and 3 s. are the reaction
and recovery time respectively. In presence of oxygen, the sample shows
low conductance hence good for sensing reducing gases. During the first
10 days, the sample shows an increase in reactivity for C2H5OH. After
70 days the sample shows no change in selectivity and sensitivity. Reddy
et al. [143] reported (Fe2O3 (0.9) – SnO2 (0.1)) synthesized utilizing hy­
drazine technique (tin chloride + ferric nitrate + hydrazine mono­
hydrate). The obtained product was tested with C2H5OH, CH4, CO and
H2. It was found to be the most sensitive for C2H5OH as compared to
others gases at an operating temperature of 400 ◦ C sensitivity is near
1100. Sensitivity is further increased with doping of 1 wt% Pt around
1547. With the increase in sintering temperature, the sensitivity de­
creases after 400 ◦ C. Zhang et al. [144] reported MgFe2O4/g-C3N4
nanocomposite synthesized using the solvothermal method. The sample
was tested for C2H5OH vapor. The result shows better sensitivity as
compared to pure MgFe2O4 with the incorporation of 15 wt% of g-C3N4.
At a temperature of 300 ◦ C, the reactivity of 112 at 500 ppm concen­
tration was reported. The reaction and recovery time for the sensor is 10
s. and 47 s. respectively. Anjitha et al. [145] synthesized nano-
composite of zinc ferrite and polyindole using the sol-gel auto-com­
bustion method. AC conductivity increases for nano-composite in com­
parison to zinc ferrite. Sample shows maximum sensing with 7 wt%
doping of polyindole for ammonia gas. Synthesized material shows a
potential application for sensors and electronic devices. Also,
Hernández et al. [146] reported NiFe2O4/NiO using levitation-jet syn­
thesis method and characterized by using XRD, TEM, XPS, VSM, Raman

Table 2
Analysis of gas sensing for multi-ion doped mixed ferrites.
Sample Gas tested Selectivity Sensitivity Response time (s) Recovery time (s)

Mg1–xSnxFe2–yMoyO4 (CH3)2CO, C2H5OH (CH3)2CO 0.83 – –

Ni0.99Co0.01Mn0.02 Fe1.98O4 LPG, CH4, (CH3)2CO, C2H5OH (CH3)2CO 4.5 – –
LaMgxFe1− xO4 C2H5OH, HCHO, NH3, gasoline, heptane C2H5OH 130 128 –
Li-SmFe2O4 C2H5OH, CH3OH, NH3, LPG C2H5OH 80 80 360
Ni0.6Zn0.4Fe2O4 LPG, H2S, C2H5OH, NH3 C2H5OH 0.6 0.6 –
Mn-Zn CH3OH, CO, LPG, CH4 CH3OH 0.8 10 20
Mn-CoFe2O4 C2H5OH C2H5OH 0.12 Short Short
Ag-NiFe2O4 LPG, CO, CH4, toluene, C2H5OH, (CH3)2CO (CH3)2CO 42 – –
Ce-CoFe2O4 C2H5OH, (CH3)2CO, NH3, LPG (CH3)2CO 138 – –
Ce-CuFe2O4 NH3, LPG, C2H5OH, (CH3)2CO LPG 70 – –
Mn0.4Cu0.6Fe2O4 NH3, LPG, C2H5OH, (CH3)2CO, CO, H2 LPG 0.28 – –
Nd3+-ZnFe2O4 LPG, C2H5OH, Cl2 C2H5OH 85 85 109
Ni1-xCoxFe2O4 C2H5OH, (CH3)2CO, NH3, CH3OH C2H5OH 66 – –
Mg0.5Zn0.5Fe2O4 C2H5OH, (CH3)2CO CH3COCH3 60 61 65
Bi0.9Ba0.1FeO2.95 C2H5OH, (CH3)2CO, CH3OH, gasoline, HCHO, NH3,Toluene C2H5OH 14 3 10
Co1-xNixFe2O4 C2H5OH C2H5OH 42 – –
Ni-Zn LPG, Cl2, C2H5OH C2H5OH 82 30 40
BaCa2Fe16O27 C2H5OH, CH3OH, (CH3)2CO, CO C2H5OH 55 – –
Cu-NiFe2O4 LPG, H2S, C2H5OH, (CH3)2CO C2H5OH 3.2 …… …..
Ag-LaFeO3 C2H5OH, NH3, C7H8, HCHO, (CH3)2CO, C8H10 HCHO 20 7.5 –
Li-CuFe2O4 NH3, LPG, C2H5OH, (CH3)2CO (CH3)2CO 1.82 162 1162
CoBi0.1Fe1.9O4 CH3OH, C2H5OH, H2S, NH3, NO2 NO2 20 – –
In-CuFe2O4 LPG, CO2, humidity LPG 25 37.15 –
Ni-CdFe2O4 Humidity H2O – 30 45
Y- CuFe2O4 Humidity H2O 4895 9 23
MnxZn1-xFe2O4 LPG, CO, NH3, H2 LPG 1.7 50 45
Ni-LaFeO3 (CH3)2CO, NH3, HCHO, C2H5OH, CH3OH CH3COCH3 82.7 3 11
NixZn1-xFe2O4 CH3COCH3, NH3, H2, LPG LPG 0.75 40 20
Pd-BiFe3O4 NO2 NO2 75 60 100
Ru-NiFe2O4 H2, NH3, C2H5OH H2 1.36 – –
V-NiFe2O4 NO NO 43 5 –

12
R. Ranga et al. Materials Characterization 178 (2021) 111269

and UV–Visible spectroscopy. The sample was also tested for gas sensing
for various gases and found high sensitivity for ethanol gas in compar­
ison to other gases. While Wang et al. [147] reported nano-composite
film of polyaniline/copper ferrite hybrid sensor using polymerization
method and tested for a variety of gases and the maximum response was
reported for NH3 gas with short response and recovery time. NH3 alarm
circuit shows good response over a wide range of concentrations fabri­
cated using prepared nano-composite. The band at 1491.44 cm− 1 in
Raman spectra indicate band shift resulting in increased disorder on the
sample surface.
Xu et al. [148] reported nano tetrahedrons of NiO/NiFe2O4 nano­
composite synthesized using the hydrothermal method and tested with
various gases but for HCHO response is quite high in comparison to
others with quick response and even more recovery time with the con­
centration of sample gas in part per billion at an operating temperature
of 240 ◦ C. Particular selectivity for gas was not reported and can be
further researched with potential sensor material. Arshak et al. [149]
reported NiO/Fe2O3 synthesized using the thin-film method and heated
treated for 5 h at 1250 ◦ C. The sample was tested for C2H5OH, CH3OH
and THF. For ethanol, the sensitivity is around 11 at a concentration of
10,000 ppm of ethanol. De et al. [150] reported CuO–CuFe2O4 using a
thin-film method and calcined for 12 h at 550 ◦ C. The sample was tested
with C2H5OH and H2. The result shows that the sample was more sen­
sitive to C2H5OH. At the concentration of 500 ppm, the sensitivity for
ethanol was 130% at 450 ◦ C. The reaction and recovery time was 450 s.
and 90 s. respectively.
Table 3 categories the ferrite nanocomposites (metal-oxide, polymer,
carbon) which shows that the composite of metal-oxide with ferrite
enhances the response time in comparison to the ferrite material. In the
case of tin oxide sensitivity is enhanced accompanied by increasing the
sensitivity at a lower concentration. Carbon based graphene and poly­
mer increase the sensitivity when ferrites are with composites. In the
case of PANI polymer composite with copper ferrite, lowers the oper­
ating temperature to room temperature and detected the lower con­
centration of the test gas. Also it is concluded from the data that
maximum sensitivity shown is 220 in case of sample Fe2O3 (0.9) – SnO2
(0.1) when tested for different gases like C2H5OH,CH4, CO, H2. After
ferrite nanocomposites, ferrite based core-shell structures were studied
by scientists [151–154].
method for the synthesis of homogeneous core-shell structure of MFe2O4
(M = Ni, Cd, Co, Zn) using monospheres as a template of carbonaceous
saccharide. On changing the concentration of the metal precursor
thickness and size manipulation of the core-shell structure was achieved.
Using this method binary, ternary metal oxide core-shell microspheres
can be synthesized. Hu et al. [154] synthesized litch shaped ZnO/
ZnFe2O4 core-shell using the solvothermal method. Using SEM images, it
is reported that the sample shows the core-shell morphology and tested
with acetone vapors at 100 ppm with an operating temperature of
280 ◦ C. The sample shows a higher sensitivity than pure ZnO and
ZnFe2O4 respectively having an average size of 2.5 μm and a pore size of
8.8 nm.
7. Future requirements of sensors
Globally various volatile liquids and gases are increasing in the
environment day by day. For a developing country like India, the
ethanol market alone is around $ 3 billion in the year 2018 and is
estimated to hike even more around $ 9 billion by the year 2025 because
of the increasing application of C2H5OH as beverages, fuel additives,
disinfectants and fragrance. Governments in various countries are trying
to decrease the dependency on crude oil and investing in biofuels.
Methylated spirits (industrial) are derived with the aid of C2H5OH for
chemical industries and domestic burners. LPG is another gas which is
needed to monitor, it was around a 14 billion-dollar market per year and
increasing with steady growth in the Indian economy. Worldwide also
the demand for biofuels is emerging rapidly. Developing countries like
India and Brazil are researching C2H5OH, H2 as a biofuel. Sensor plays
an important role in such a process by detecting the amount of gas in fuel
injection system to maintain the ratio of additives. The sensor used by
traffic police to detect C2H5OH consumption in case of drink and drive

6.3. Ferrite based core-shell structures

This type of morphology is started to gain researcher interest from

the last two decades. As it possesses a variety of applications in the field
of catalysis [151], supercapacitor electrode [152] and sensors [153]. As
the structure of the core-shell is derived from the nanospheres which
include a hollow structure causes increase in the surface area (porous
surface and double shell structure) and reduces the distance for charge
transfer by providing more active sites. It is considered as the morpho­
logical impact which enhances the electrical and other properties
leading to the core-shell structure to a more suitable form for the
Fig. 16. Demand of sensor in various fields.
detection of the various gases. Li et al. [153] developed a general

Table 3
Ferrite nanocomposites (metal-oxide, polymer, carbon).
Sample Gas tested Selectivity Sensitivity Response time (s) Recovery time (s)

CdO-Fe2O4 C2H5OH, petrol, LPG, H2, C4H10, C2H5OH 53 2 3

CdO-Fe2O4 C2H5OH, CO, H2, C4H10 C2H5OH 90 15 35
Fe2O3 (0.9) – SnO2 (0.1) C2H5OH, CH4, CO, H2 C2H5OH 220 – –
MgFe2O4/g-C3N4 C2H5OH C2H5OH 115 10 47
ZnFe2O4@ polyindole NH3 NH3 – 200 –
NiFe2O4/NiO C2H5OH, (CH3)2CO, toluene, CO, NO2, C2H5OH 23 – –
PANI/CuFe2O4 NH3, HCHO, C2H5OH, CH3OH, (CH3)2CO, C6H6, CH4 NH3 27.3 84 54
NiO/NiFe2O4 (CH3)2CO, NH3, HCHO, C2H5OH, CH3OH, C6H6, CH3CHO, (C2H5)2O HCHO 17.5 9 3
NiO/Fe2O3 (CH3)2CO, THF, CH3OH, C2H5OH C2H5OH 11 – –
CuO–CuFe2O4 C2H5OH, H2 C2H5OH 130 90 450

13
R. Ranga et al.
and also to check the fermentation in various food processes. The de­
mand for the sensors in various fields is illustrated in Fig. 16. In the
future sensors may be developed to detect the change of molecular and
supramolecular interacting with gas in the biological environment.
8. Conclusion
This review article primarily examines the literature available on the
ferrite sensor. From the literature of ferrite with single metal ion dopant,
it can be concluded that the doping of the single ion specifically Mg, Zn
which belong to the category of soft ferrites that greatly enhances the
sensitivity, selectivity and lowers the operating temperature. Similar
behavior is also observed with the doping of the rare-earth elements.
While the study of the mixed ferrite materials (multi-ion doping) reveals
that multi-ion doping greatly increases the sensitivity of the ferrite
sample. Also, in few cases rare-earth doping drastically reduces the
operating to nearby room temperature for detection of gases and in case
of doping of soft ferrite with other soft ferrite metal ions such as Ni to Co-
ferrite, Mg to Zn-ferrite increases the sensitivity of the sample. In the
case of ferrite-based composites with other metal oxides, polymer and
carbon material it is reported that composite of metal-oxide with ferrite
enhances the response time in comparison to the ferrite material. Carbon
based graphene and polymer increase the sensitivity when ferrites are
used with composites. Also, in the case of polymer composites with
copper ferrite, lowers the operating temperature to room temperature
and detected the lower concentration of the test gas.
Declaration of Competing Interest
None.
Acknowledgements
One of author Mr. Rohit Ranga is gratefully acknowledges financial
support for the work by government of India through Council of Sci­
entific & Industrial Research (CSIR-HRDG), New Delhi, India (letter no.
17/06/2018 (i) EU-V dated 19.03.2019).
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