Physica B: Physics of Condensed Matter xxx (xxxx) 414409

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Physica B: Physics of Condensed Matter

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Properties of Ti doped ZnO nanoparticles under solid state reaction method
involving vacuum annealing

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Soniya Pauline G a, Kaleemulla S b, *
a Thin Films Laboratory, School of Advanced Sciences, Vellore Institute of Technology, Vellore, 632 014, Tamil Nadu, India
b Thin Films Laboratory, Centre for Functional Materials, Vellore Institute of Technology, Vellore, 632 014, Tamil Nadu, India

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ARTICLE INFO ABSTRACT

Keywords: The present study deals with synthesis of titanium doped zinc oxide (Ti:ZnO) nanoparticles (NP) using solid state
Solid state reaction reaction and subjected to vacuum annealing. The Ti doped ZnO nanoparticles were prepared at different tita-
Vacuum annealing nium concentrations (Ti = 0%,1%, 3%, 5% & 7%) and studied the role of Ti on physical properties of the Ti:ZnO
Crystal structure
nanoparticles. The prepared titanium doped zinc oxide nanoparticles were subjected to various characterization
Semiconductor
techniques such as X-ray diffractometer (XRD), UV–Vis-spectrophotometer (UV–Vis–NIR), scanning electron mi-
Band gap
croscope (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and
D
Keithley source meter to study the structural, optical, surface, spectroscopic, elemental and electrical properties,
respectively. From the XRD studies, it was found that the Ti:ZnO NP were in hexagonal structure with average
crystallite size of 39 nm. The SEM images confirms the formation of the clusters in spherical shape. The EDAX
spectrum confirms the presence of the host (Zn & O) and dopant (Ti) elements in the synthesized nanoparticles.
TE

The functional groups were confirmed from FT-IR spectrum. The valence states of the elements such as Ti, Zn and
O were studied and found as Ti+3, Zn+2 and O−2. The electrical properties of the bulk Ti:ZnO NP were studied us-
ing Keithley source meter.

1. Introduction bring by varying the synthesis parameter or doping with different

EC

Currently, nanostructured semiconductors are extensively studied
by many researchers as the semiconductors play their important role in
many electronic devices, supercapacitors and other optoelectronic ap-
plications. Semiconductors with narrow band gap and wide band gap
are essential for the design and development of new semiconductor de-
RR
dopant elements [2]. ZnO can be made into p-type or n-type ZnO by
doping suitable transition and rare earth elements into the host mater-
ial. It belongs to II-VI semiconductor group compound with n-type con-
ductivity and exhibit a direct wide bandgap 3.4 eV [3]. Further, zinc
oxide exhibits quite different properties when it is prepared at
nanoscale. The properties of nanostructured ZnO find in many applica-

vices and technology. These semiconductors possess unique physical
and chemical properties that help in designing new devices. Many
metal oxides such as tin oxide (SnO2), indium oxide (In2O3), indium tin
oxide (ITO), titanium oxide (TiO2), zinc oxide (ZnO), etc were well
studied to improve their physical properties [1]. Among the different
oxide semiconductors, zinc oxide (ZnO) is the best material due to its
peculiar physical and chemical properties. It exhibits different crystal
CO
tions such as piezoelectric devices, solar cell, transistors, light emitting
diodes (LED), diode laser, chemical and biosensor, transducers [4,5].
Moreover, the properties of ZnO also play their role in bio medical sci-
ence like antibacterial, antifungal resistivity as it is non-toxic to human
cells, abundant material and can be used in nanomedicine [6,7]. In ad-
dition to its chemical, physical, optical and electrical properties, ZnO
was well studied for its magnetic properties. Extensive studies were car-

structure such as wurtzite (hexagonal), rock salt and zinc blende (cu-
bic). The zinc oxide (ZnO) is chemically most stable material, less toxic,
less cost, high transmittance, high conductivity, wide band gap and en-
vironment friendly. Hence ZnO semiconductor is well studied and a
large number of research articles were published on synthesis and novel
properties of zinc oxide. A change in the properties of the ZnO can be
ried out on magnetic properties of ZnO. If ZnO exhibits ferromagnetism,
then it can be used for magnetic applications. Great efforts were put to
make ZnO as a dilute magnetic semiconductor (DMS). Conversion of
non-magnetic semiconductor into magnetic semiconductor is called as
dilute magnetic semiconductors. It can be happened by substitution of a
small quantity of transition metal ions into the host semiconductor. Due

* Corresponding author.
E-mail address: skaleemulla@gmail.com.

https://doi.org/10.1016/j.physb.2022.414409
Received 28 June 2022; Received in revised form 29 September 2022; Accepted 7 October 2022
0921-4526/© 20XX

Note: Low-resolution images were used to create this PDF. The original images will be used in the final composition.
S. Pauline G and KaleemullaS
to different exchange interactions between the electrons of host and
dopants, the semiconductor will exhibit magnetism. Hence different ox-
ide semiconductors were studied to make them as magnetic semicon-
ductors because oxide semiconductors possess high transparency, high
conductivity, high thermal stability and wide band gap. Due to these
reasons, oxide semiconductors such as pure and transition metal doped
In2O3, SnO2, ITO, NiO, CeO2 were investigated. As ZnO belongs to the
wide band gap oxide semiconductors, numerous studies were carried
out to make ZnO as dilute magnetic semiconductor as it can be used for
spintronic applications [8–13].
Doping process plays an important role to develop materials with
novel properties. Notably, transition element doping with semiconduc-
tor materials to convert non-magnetic semiconductor into magnetic
semiconductor. Especially Titanium (Ti), Scandium (Sc), Chromium
(Cr), Manganese (Mn), Cobalt (Co), Nickel (Ni), Vanadium (V), Iron
(Fe) and Copper (Cu) were considered to be the vital dopants for ZnO
host material [14–19]. The flexibility of ZnO include its chemical stabil-
ity, wide band gap, high reactivity at nanoscale and hence find applica-
tions in sensors and solar cells.
The carrier concentration in ZnO can be controlled and hence can be
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converted into p-type or n-type ZnO by adding a suitable dopant. Dop-
ing with transition elements enhances the physical, chemical, optical,
spectral and antibacterial properties such as electrical conductivity, op-
tical transmission & absorption, magnetic properties [20–24].
Here Titanium has been considered as a substitution element into
ZnO host material as anatase form of titanium, is a wide band gap semi-
conductor with excellent optical transmission in the visible and near-
infrared regions, a high refractive index, high dielectric constant, low
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tangential loss and useful photocatalysis properties. In addition, Ti in-
creases the conductivity, sensing property when doped with ZnO. It
provides more carriers than magnetic transition ions and the magnetic
moment shown by Ti is equal when compare with Mn, Co and Ni. Also,
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titanium possess different valence states such as +2, +3 and + 4 and
hence it is available as TiO, Ti2O3, TiO2 and moreover, the ionic radii of
Ti (0.68 Å; Ti+4) is close to the ionic radii of Zn (0.74 Å; Zn+2) and
have four valence electrons. The atomic radius of Ti interstitial found
by theoretical calculation is 1.939 Å. The electronic valence states Tita-
EC
nium doped ZnO forms challenges to the researchers due to formation
of secondary phases ZnTiO3, Zn2TiO4 or Zn2Ti3O8 but provide opportu-
nities due to their potential applications. Various methods have been
developed to produce ZnO nanostructures including sol-gel [25], co-
precipitation [26], thermal decomposition [27], solvothermal [28], hy-
drothermal [29], microemulsion, solid state reaction, polyol synthesis
[30], green synthesis [31–34] Similarly, ZnO thin films were prepared
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by different physical and chemical methods such as thermal evapora-
tion [35], pulsed laser deposition [36,37] molecular beam epitaxy etc.
[38–42], Among all the methods solid state reaction method is simple
method to produce nanoparticles from a stoichiometric product and en-
vironment friendly.
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2. Experimental method
Ti doped ZnO nanoparticles are prepared by standard solid state re-
action. For this the chemicals of high purity titanium dioxide (TiO2)
(99.99%) and zinc oxide (ZnO) (99.999%) were purchased from Sigma
Aldrich company (India). The required quantities of powders were
taken to prepare Ti doped ZnO at Ti concentrations of 0%, 1%, 3%, 5%
& 7%. The required quantities of host (ZnO) and dopant (TiO2) powders
were weighed using 5 digit accurate microbalance and then these pow-
ders were mixed using Agate mortar and pestle and subjected to grind-
ing for 6 h till a homogeneous mixture will form. The ground powders
were taken into a small one end quartz test tube and closed with quartz
wool. This quartz tube that was filled with desired powder was kept in a
bigger quartz tube. The bigger quartz tube was connected with rotary
pump which can create a pressure of 1 × 10−3 mbar. The bigger quartz
2
Physica B: Physics of Condensed Matter xxx (xxxx) 414409
tube was inserted into the carried in horizontal tubular microprocessor-
controlled furnace. Using programmable controlled microprocessor,
the temperature of the furnace was raided 1°/minute and the tempera-
ture the system raised till 800 °C. The powder samples were maintained
at 800 °C for 5 h. Later on, the temperature of the furnace was de-
creased with the same rate (1°/minute) and made to come to room tem-
perature (30 °C). All the powder samples were prepared at the same
conditions. Finally, these powder samples were taken out and again
mixed using Agate mortar and pestle to make fine powder and made
into pellet form. These pellets samples were subjected to different char-
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acterization techniques. For simplicity, the titanium doped zinc oxide
samples at different titanium concentrations is represented as
(x = 0.01, 0.03, 0.05, 0.07).
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A clear view on the structural aspects has been observed by using X-
ray diffraction X-ray diffractometer, D8 Advance, BRUKER method. The
compositional details have been confirmed by Energy dispersive analy-
sis spectroscopy (EDS) (OXFORD instrument inca penta FET ×3).
UV–Vis–NIR Spectrophotometer (JASCO V-670) was utilized to study
the optical and photocatalytic properties. The valence states of the ele-
ments were studied using X-ray photoelectron spectroscope (Kα Ther-
moFisher (NEXSA). The electrical properties such as voltage versus cur-
rent characteristics measurements were carried out using two probe
method (KEITHLEY 2450 SOURCE METER).
3. Result and discussions
3.1. Structural studies
Fig. 2 shows the X-ray diffraction profiles of Zn1-xTixO nanoparti-
cles at different titanium concentrations (x = 0.01, 0.03, 0.05,
0.07). The bottom layer indicates the XRD profile of pure zinc oxide
nanoparticles. All the diffraction peaks that were detected by X-ray
diffractometer were taken into consideration and indexed carefully.
The diffraction peaks are sharp and clear. The diffraction peaks such
as (1 0 0), (0 2 2) (1 0 1), (1 0 2), (1 1 0), (1 0 3), (2 0 0), (1 1 2),
(2 0 1), (0 0 4) & (2 0 2) among which (1 0 1) diffraction peak is
more dominant. All these XRD peaks were exactly coincided with
wurtzite structure of ZnO [ICDD file No. 01-078-3323]. The same dif-
fraction peaks were observed for the Zn1-xTixO nanoparticles at dif-
ferent titanium concentrations (x = 0.01, 0.03, 0.05, 0.07). The in-
tensity of the diffraction peaks in Zn1-xTixO increased till x = 0.05
and it decreased at higher Ti concentration x = 0.07 [43]. But at
higher Ti concentrations, the diffraction peaks such as (2 2 0), (3 1
1), (4 0 0), (4 2 2) & (4 4 0) were also identified in XRD profile
which reflect the formation of zinc titanate (Zn2Ti3O8) [44]. The ad-
ditional peaks in Zn1-xTixO at x = 0.07 might be due to exceeding
the miscibility limit of dopant in ZnO host lattice. Similar results
were also observed in Ti doped ZnO prepared by solution combus-
tion method [45]. But a shift in diffraction peak was observed with
increasing Ti concentrations. The inset of Fig. 1 shows XRD peak
shift in Zn1-xTixO nanoparticles at x = 0.01 & x = 0.07. It may be
due to substitution of Ti+4 into Zn+2 in ZnO host lattice as ionic
radii of Ti (0.68 Å; Ti+4) is less than the ionic radii of Zn (0.74 Å;
Zn+2). Hence the shift in XRD peak towards higher diffraction angle
was noticed. The structure parameters such as crystallite size, lattice
parameter, dislocation density, were also calculated using below rela-
tions.
The crystallite size (G) was calculated by using the Debye-Scherer
formula [46],
(1)
where, k is particle geometry dependent constant (for spherical
shape k ∼1), λ is the wavelength of used (λ = 1.5406 Å), β is the full
width-at-half maximum (FWHM) and θ is the diffracted angle, respec-
tively. The crystallite size was calculated for Zn1-xTixO at different Ti
S. Pauline G and KaleemullaS Physica B: Physics of Condensed Matter xxx (xxxx) 414409

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Fig. 1. Synthesis of Zn1-xTixO nanoparticles.

Table 1
Summary of FWHM, Crystallite size, Dislocation density, Strain, Lattice para-
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meter of Zn1-xTixO nanoparticles at different x.
Zn1-xTixO FWHM Crystallite Dislocation Strain (ε) Lattice
β Size D (nm) Density (δ) 10−4 (lines/ parameter
1014 m2 meter)
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a (Å) c (Å)

x = 0.00 0.2547 40 6.8596 9.75 3.24 5.16

x = 0.01 0.2997 33 9.5113 11.58 3.22 5.12
x = 0.03 0.2665 37 7.535 10.3 3.24 5.14
x = 0.05 0.2341 43 5.881 9.01 3.24 5.16
x = 0.07 0.2342 43 5.865 9.02 3.22 5.14
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3.2. FT-IR analysis

Fig. 3 shows the FT-IR spectrum of pure ZnO nanoparticles . The

spectra were recorded for all Zn1-xTixO nanoparticles in the wavenum-
Fig. 2. XRD profile of Zn1-xTixO nanoparticles at x = 0.01, 0.03, 0.05, 0.07. The
ber range of 4000 cm−1 to 400 cm−1. As no significance peaks were
inset of the figure shows XRD peak shift of Zn1-xTixO NP at x = 0.01 &
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observed in the range of 4000 cm−1 to 1500 cm−1, the spectra in Fig. 2
x = 0.07.
is shown in the range of 1500 cm−1 to 300 cm−1. The bands were de-
tected for all samples in the FT-IR spectrum at 455 cm−1, 435 cm−1,
doping concentrations. The mean crystallite size was found to be
416 cm−1, 457 cm−1, 466 cm−1,651 cm−1, 677 cm−1, 850 cm−1,
39 nm. The dislocation density of the all samples was calculated by
880 cm−1 and 1378 cm−1. From FT-IR spectrum of pure ZnO, strong
Williamson and Smallman's relation [47]. The micro strain (ε) devel-
absorption band at 442 cm−1, 495 cm−1 were identified and these may
oped in films were calculated by using the relation.
be due to Zn–O stretching vibrations. From the reported articles, it was
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The Dislocation density

concluded that the absorption bands in the wavenumber range of
400 cm−1 to 500 cm−1 attributed to ZnO vibration [48]. Further, it
(2)
was reported that the absorption peak at 625 cm−1 is ascribed to MO6
group belongs asymmetric stretching modes and the absorption peaks
where, is the dislocation density, D crystallite size. observed at 455 cm−1 and 457 cm−1 are due to metal oxide (M−O)
The micro strain bending modes [49,50]. FT-IR spectra were recorded for other samples
also and the spectra and absorption peaks are similar as observed in
(3) FT-IR spectrum of pure ZnO.

where is FWHM (full width half maximum) value, is Brags dif-
fraction angle. The dislocation density and micro strains were also in-
creased with the increase of Ti dopant concentration. A summary of
crystallite size, lattice parameter, strain and dislocation densities were
that were calculated using above relations are tabulated in Table 1.
3.3. Microstructural and compositional analysis
Fig. 4 shows the SEM images of the Zn1-xTixO nanoparticles at
x = 0.00 and x = 0.07. From the figure, it is clear that particles are
not in uniform size but most of the particles are in almost in spherical
shape [51,52]. The similar behaviour was observed for the Zn1-xTixO

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S. Pauline G and KaleemullaS Physica B: Physics of Condensed Matter xxx (xxxx) 414409

Fig. 5 shows the EDAX spectra of Zn1-xTixO nanoparticles at

x = 0.00 and x = 0.07. The elemental analysis was carried out using
EDAX to know whether the dopant Ti is substituted in ZnO lattice or
not and moreover, the concentration of the dopant can also be con-
firmed by EDAX spectra. The elements such as zinc (Zn) and oxygen
(O) were present in Zn1-xTixO nanoparticles at x = 0.00 whereas zinc
(Zn), titanium (Ti) and oxygen (O) were present in Zn1-xTixO nanopar-
ticles at x = 0.07. No other impurity elements were found in the spec-
tra except carbon (C). From EDAX spectra, the presence of the dopant
and its percentage is confirmed by the weight percentage. The required

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quantities of Ti, Zn and O were found in the Zn1-xTixO nanoparticles at
x = 0.07.

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3.4. Optical studies

Fig. 6 shows the absorbance spectra of Zn1-xTixO nanoparticles at

x = 0.00, 0.01, 0.03, 005 & 0.07. From the figure it is can be seen
that the absorbance of the Zn1-xTixO nanoparticles increased with in-
crease in wavelength and became maximum at a wavelength of
300 nm and it decreased again at 360 nm. From absorption bands,

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maxima observed at 360 nm is in accordance with the literature [53].
From the spectra it is clear that the Zn1-xTixO nanoparticles possess
more absorption in ultra violet region.
Fig. 7 shows the transmittance spectra of the Zn1-xTixO nanoparti-
cles at x = 0.00, 0.01, 0.03, 005 & 0.07. From the figure it is can be
seen that the transmittance of the Zn1-xTixO nanoparticles increased
with increase in wavelength and became maximum at 420 nm and the
absorption edge noticed between 401 and 418 nm in visible region.
D
Optical transmittance increased between 360 nm and 480 nm after
that it remained constant. a highest transmittance of 88% was ob-
served in Zn1-xTixO nanoparticles at x = 0.07.
Using Tauc's equation, a graph between (αhυ)2 versus the photon
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energy (hυ) was drawn as shown in Fig. 8. The linear region of the
graph was extrapolated such that the absorption coefficient becomes
zero. The optical band gap was estimated using the Tauc's equation
[54].

(4)
EC

Where hν is the photon energy, α is the absorption coefficient. The

Fig. 3. FT-IR spectrum of Zn1-xTixO nanoparticles at x = 0.01 & x = 0.07.
nanoparticles at x = 0.01, 0.03 & 005. They have formed a clusters
and increase in the grain size can be observed with increase in anneal-
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Zn1-xTixO nanoparticles at x = 0.01, 0.03, 005 & 0.07 exhibited band
gap of 3.22 eV, 3.25 eV, 3.26 eV, 3.27 eV, respectively as shown in Fig.
8 and Table 2 However, the bandgap of undoped ZnO was found as
3.25 eV. An increase in optical band gap was observed in the Zn1-xTixO

ing temperature. Elemental analysis by means of the Energy Dispersive nanoparticles with increase in Ti concentration. The increase in optical
X-ray Spectroscopy (EDS) along with surface morphology (SEM-EDS)
mode was carried out to know the elements and their stoichiometry.
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Fig. 4. a & b: SEM images of Zn1-xTixO nanoparticles at x = 0.07.

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S. Pauline G and KaleemullaS Physica B: Physics of Condensed Matter xxx (xxxx) 414409

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Fig. 5. a & b: EDAX spectra of Zn1-xTixO nanoparticles at x = 0.00 and x = 0.07.
D
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Fig. 6. Absorbance spectra of Zn1-xTixO nanoparticles at different x.

Fig. 8. Plots of (αhν)2 Vs hν of Zn1-xTixO nanoparticles at different x.

band gap with dopant concentration might be due to Moss- Burstein ef-
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fect.

3.5. XPS studies

Fig. 9 (a) shows the XPS spectrum of the element zinc. The spec-
trum consists of two peaks at 1023 eV and 1029 eV. These peaks reflect
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zinc in Zn2p which in turn indicate +2 valence state of zinc (Zn+2).

Fig. 9 (b) shows the XPS spectrum of titanium. Here also two peaks
were found at 485 eV and 457 eV that will confirm the existence of
Ti2p1/2 and Ti2p3/2 and these will confirm the valence state of Ti is +4
(Ti+4). The titanium comprised with two peaks, such as 2p1/2 and
2p3/2. The peaks at 458.5 eV and 464. 2 eV denotes the standard bind-
ing energy of Titanium [55]. Fig. 9 (c) show the XPS spectrum of oxy-
gen. The XPS spectrum confirms the valence state of oxygen as −2
(O−2) as one peak was observed 529 eV. The peak at 529 eV corre-
sponding to the characteristic spectra of oxygen in ZnO structure [56].
Fig. 7. Transmittance spectra of Zn1-xTixO nanoparticles at different x.
Finally, Fig. 9(d) shows the survey spectra of Zn1-xTixO nanoparticles
and the elements such as Zn, Ti, O were identified and exists in their re-
spective binding energies. Hence it confirms the presence of Ti along
with Zn, O and the peak positions are in best agreement with the re-
ported binding energies.

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S. Pauline G and KaleemullaS Physica B: Physics of Condensed Matter xxx (xxxx) 414409

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D
Fig. 9. (a) Zn 2p core levels, (b) Ti 2p core levels, (c) O 1s core levels (d) XPS Survey spectrum of Zn1-xTixO nanoparticles at x = 0.07.
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3.6. Electrical studies
The electrical properties of the bulk Zn1-xTixO nanoparticles at dif-
ferent titanium concentrations (x = 0.01, 0.03, 005 & 0.07). A simple
two probe method was used here to know the electron transport mecha-
nism in the prepared nanoparticles. The samples were made into small
EC
lows ohm's Law. It is Linear and resistivity can be calculated using
Ohm's Law (V= IR) with correction factor. From this it can be observed
that tunnelling of current is occurring in nanoparticles even at low ap-
plied potentials and hence showing conducting behaviour. The ob-
served current is in nano ampere. From this linear behaviour of current
and voltage, the resistivity values were tabulated in Table 5. The ob-

pellets. A silver paste was used to connect copper wires and these cop-
per wires used as electrodes for the source meters. Two probe method Table 2
was applied to study the current versus voltage characteristics of the Optical band gap of Zn1-xTixO nanoparticles at different x.
Zn1-xTixO nanoparticles at different Ti concentration. A program was
Zn1-xTixO Band Gap (eV)
executed to take voltage at a step of 0.5 V and it gave the I–V character-
istic as shown in Fig. 10. From the figure, it is clear that the samples ex-
RR

x = 0.00 3.25
hibited Ohmic behaviour. The relation between voltage and current fol- x = 0.01 3.22
x = 0.03 3.25
x = 0.05 3.26
x = 0.07 3.27

Table 3
Elemental analysis of pure ZnO.
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Element Weight % Atomic percentage

Zn 68.43 32.41
O 21.46 41.53
C 10.11 26.06
Total 100

Table 4
Elemental analysis of Zn1-xTixO nanoparticles at x = 0.07
Element Weight % Atomic percentage

Zn 79.85 50.42
Ti 3.95 3.4
O 11.06 28.52
Fig. 10. a: Current vs Voltage characteristics of The Zn1-xTixO nanoparticles at C 5.14 17.66
different x. Total 100

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S. Pauline G and KaleemullaS Physica B: Physics of Condensed Matter xxx (xxxx) 414409

Table 5 392001, https://doi.org/10.1088/1361-6528/ab268a.

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4. Conclusion
Titanium doped ZnO nanoparticles (Zn1-xTixO; x = 0, 0.01, 0.03,
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D
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