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

G. Soniya Pauline, S. Kaleemulla

PII: S0921-4526(22)00694-9
DOI: https://doi.org/10.1016/j.physb.2022.414409
Reference: PHYSB 414409

To appear in: Physica B: Physics of Condensed Matter

Received Date: 28 June 2022

Revised Date: 29 September 2022
Accepted Date: 7 October 2022

Please cite this article as: G.S. Pauline, S. Kaleemulla, Properties of Ti doped ZnO nanoparticles under
solid state reaction method involving vacuum annealing, Physica B: Physics of Condensed Matter
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 Credit Author Statement

G.Soniya Pauline: Conceptualization, Methodology, Writing Manuscript and Invesigation

S.Kaleemulla: Validation, Supervision and Visualization

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 Properties of Ti doped ZnO nanoparticles under solid state reaction
method involving vacuum annealing
G. Soniya Paulinea, S. Kaleemullab,*
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.
*
Corresponding author: [email protected]

Abstract

The present study deals with synthesis of titanium doped zinc oxide (Ti:ZnO)

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nanoparticles (NP) using solid state reaction and subjected to vacuum annealing. The Ti doped

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ZnO nanoparticles were prepared at different titanium concentrations (Ti = 0%,1%, 3%, 5% &
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7%) and studied the role of Ti on physical properties of the Ti:ZnO nanoparticles. The prepared
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titanium doped zinc oxide nanoparticles were subjected to various characterization techniques
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such as X-ray diffractometer (XRD), UV-Vis-spectrophotometer (UV-Vis-NIR), scanning

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electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray

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photoelectron spectroscopy (XPS) and Keithley source meter to study the structural, optical,

surface, spectroscopic, elemental and electrical properties, respectively. From the XRD studies,
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it was found that the Ti:ZnO NP were in cubic 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. The functional groups were confirmed from FT-IR spectrum. The

valance 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 using Keithley source meter.

Key words

Solid state reaction; Vacuum annealing; Crystal structure; Semiconductor; Band gap;

1
1. Introduction

Currently, nanostructured semiconductors are extensively studied by many researchers

as the semiconductors play their important role in many electronic devices, supercapacitors and

other optoelectronic applications. Semiconductors with narrow band gap and wide band gap

are essential for the design and development of new semiconductor devices 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

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physical properties [1]. Among the different oxide semiconductors, zinc oxide (ZnO) is the

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best material due to its peculiar physical and chemical properties. It exhibits different crystal
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structure such as wurtzite (hexagonal), rock salt and zinc blende (cubic). The zinc oxide (ZnO)
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is chemically most stable material, less toxic, less cost, high transmittance, high conductivity,
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wide band gap and environment friendly. Hence ZnO semiconductor is well studied and a
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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 bring by varying the synthesis parameter
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or doping with different dopant elements [2]. ZnO can be made into p-type or n-type ZnO by
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doping suitable transition and rare earth elements into the host material. It belongs to II-VI

semiconductor group compound with n-type conductivity 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 applications 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 science like antibacterial, antifungal resistivity as it is non-toxic to human cells,

abundant material and can be used in nanomedicine [6, 7]. In addition to its chemical, physical,

optical and electrical properties, ZnO was well studied for its magnetic properties. Extensive

2
studies were carried 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 to different

exchange interactions between the electrons of host and dopants, the semiconductor will exhibit

magnetism. Hence different oxide semiconductors were studied to make them as magnetic

semiconductors because oxide semiconductors possess high transparency, high conductivity,

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high thermal stability and wide band gap. Due to these reasons, oxide semiconductors such as

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pure and transition metal doped In2O3, SnO2, ITO, NiO, CeO2 were investigated. As ZnO
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belongs to the wide band gap oxide semiconductors, numerous studies were carried out to make
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ZnO as dilute magnetic semiconductor as it can be used for spintronic applications [8-13].
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Doping process plays an important role to develop materials with novel properties.
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Notably, transition element doping with semiconductor materials to convert non-magnetic

semiconductor into magnetic semiconductor. Especially Titanium (Ti), Scandium (Sc),

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Chromium (Cr), Manganese (Mn), Cobalt (Co), Nickel (Ni), Vanadium (V), Iron (Fe) and
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Copper (Cu) were considered to be the vital dopants for ZnO host material [14-19]. The

flexibility of ZnO include its chemical stability, wide band gap, high reactivity at nanoscale

and hence find applications in sensors and solar cells.

. The carrier concentration in ZnO can be controlled and hence can be converted into

p-type or n-type ZnO by adding a suitable dopant. Doping with transition elements enhances

the physical, chemical, optical, spectral and antibacterial properties such as electrical

conductivity, optical 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 semiconductor with excellent optical

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transmission in the visible and near-infrared regions, a high refractive index, high dielectric

constant, low tangential loss and useful photocatalysis properties. In addition, Ti increases

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, titanium possess different valance 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

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Titanium doped ZnO forms challenges to the researchers due to formation of secondary phases

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ZnTiO3, Zn2TiO4 or Zn2Ti3O8 but provide opportunities due to their potential applications.
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Various methods have been developed to produce ZnO nanostructures including sol-gel [25],
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co-precipitation [26], thermal decomposition [27], solvothermal [28], hydrothermal [29],
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microemulsion, solid state reaction, polyol synthesis [30], green synthesis [31-34] Similarly,
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ZnO thin films were prepared by different physical and chemical methods such as thermal

evaporation [35], pulsed laser deposition [36, 37] molecular beam epitaxy etc., [38-42] Among
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all the methods solid state reaction method is simple method to produce nanoparticles from a
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stoichiometric product and environment friendly.

2. Experimental Method

Ti doped ZnO nanoparticles are prepared by standard solid state reaction. 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 powders were mixed using Agate mortar and pestle and subjected

to grinding for six hours till a homogeneous mixture will form. The grind powders were taken

4
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 1x10-3 mbar. The bigger quartz

tube was inserted into the carried in horizontal tubular microprocessor-controlled furnace.

Using programmable controlled microprocessor, the temperature of the furnace was raided

1o/minute and the temperature the system raised till 800oC. The powder samples were

maintained at 800 oC for 5 hours. Later on, the temperature of the furnace was decreased with

the same rate (1o/minute) and made to come to room temperature (30oC). All the powder

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samples were prepared at the same conditions. Finally, these powder samples were taken out

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and again mixed using Agate mortar and pestle to make fine powder and made into pellet form.
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These pellets samples were subjected to different characterization techniques. For simplicity,
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the titanium doped zinc oxide samples at different titanium concentrations is represented as (x
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= 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
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confirmed by Energy dispersive analysis spectroscopy (EDS) (OXFORD instrument inca penta
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FET X3). UV-Vis-NIR Spectrophotometer (JASCO V-670) was utilized to study the optical

and photocatalytic properties. The valence states of the elements were studied using X-ray

photoelectron spectroscope (K ThermoFisher (NEXSA). The electrical properties such as

voltage versus current characteristics measurements were carried out using two probe method

(KEITHLEY 2450 SOURCE METER)

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3. Result and Discussions

3.1 Structural Studies

Fig. 2 shows the X-ray diffraction profiles of Zn1-xTixO nanoparticles 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),

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(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.

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01-078-3323]. The same diffraction peaks were observed for the Zn1-xTixO nanoparticles at
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different titanium concentrations (x = 0.01, 0.03, 0.05, 0.07). The intensity of the diffraction
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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
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2 2) & (4 4 0) were also identified in XRD profile which reflect the formation of zinc titanate
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(Zn2Ti3O8)[44]. The additional peaks in Zn1-xTixO at x = 0.07 might be due to exceeding the
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miscibility limit of dopant in ZnO host lattice. Similar results were also observed in Ti doped

ZnO prepared by solution combustion method [45]. But a shift in diffraction peak was

observed with increasing Ti concentrations. The inset of the 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 relations.

The crystallite size (G) was calculated by using the Debye-Scherer formula [46],

G = k/cos ---------------------- (1)

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where, k is particle geometry dependent constant (for spherical shape k ~1),  is the wavelength

of used ( = 1.5406 Å),  is the full width-at-half maximum (FWHM) and  is the diffracted

angle, respectively. The crystallite size was calculated for Zn1-xTixO at different Ti doping

concentrations. The mean crystallite size was found to be 39 nm. The dislocation density of

the all samples was calculated by Williamson and Smallman’s relation [47]. The micro strain

(ε) developed in films were calculated by using the relation.

The Dislocation density

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1
𝛿=

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---------------------- (2)
𝐷2

where, 𝛿 is the dislocation density, D crystallite size.

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The micro strain
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𝛽𝑐𝑜𝑠𝜃
𝜀= ---------------------- (3)
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where, 𝛽 is FWHM (full width half maximum) value, 𝜃 is Brags diffraction angle. The
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dislocation density and micro strains were also increased with the increase of Ti dopant
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concentration. A summary of crystallite size, lattice parameter, strain and dislocation densities

were that were calculated using above relations are tabulated in Table 1.
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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 wavenumber range of 4000 cm-1 to 400 cm-1. As no

significance peaks were observed in the range of 4000 cm-1 to 1500 cm-1, the spectra in Fig. 2

is shown in the range of 1500 cm-1 to 300 cm-1. The bands were detected in the FT-IR spectrum

at 455 cm-1, 435 cm-1, 416 cm-1, 457 cm-1, 466 cm-1,651 cm-1, 677 cm-1, 850 cm-1, 880 cm-1 and

1378 cm-1. From FT-IR spectrum of pure ZnO, strong absorption band at 442 cm-1, 495 cm-1

were identified and these may be due to Zn-O stretching vibrations. From the reported articles,

it was concluded that the absorption bands in the wavenumber range of 400 cm-1 to 500 cm-1

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attributed to ZnO vibration [48]. Further, it was reported that the absorption peak at 625 cm-1

is ascribed to MO6 group belongs asymmetric stretching modes and the absorption peaks

observed at 455 cm-1 and 457 cm-1 are due to metal oxide (M-O) bending modes [49,50]. FT-

IR spectra were recorded for other samples also and the spectra and absorption peaks are similar

as observed in FT-IR spectrum of pure ZnO.

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

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almost in spherical shape [51,52]. The similar behaviour was observed for the Zn1-xTixO

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nanoparticles at x = 0.01, 0.03 & 005. They have formed a clusters and increase in the grain
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size can be observed with increase in annealing temperature. Elemental analysis by means of
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the Energy Dispersive X-ray Spectroscopy (EDS) along with surface morphology (SEM-EDS)
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mode was carried out to know the elements and their stoichiometry.
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Fig. 5 shows the EDAX spectra of Zn1-xTixO nanoparticles at x = 0.00 and x = 0.07. The
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elemental analysis was carried out using EDAX to know whether the dopant Ti is substituted
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in ZnO lattice or not and moreover, the concentration of the dopant can also be confirmed 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 nanoparticles at x = 0.07. No other impurity elements were found in the spectra except

carbon (C). From EDAX spectra, the presence of the dopant and its percentage is confirmed

by the weight percentage. The required quantities of Ti, Zn and O were found in the Zn1-xTixO

nanoparticles at x = 0.07.

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3.3 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 increase in wavelength and became maximum at a wavelength of 300 nm and

it decreased again at 360 nm. From absorption bands, 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.

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Fig. 7 shows the transmittance spectra of the Zn1-xTixO nanoparticles 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

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nanoparticles increased with increase in wavelength and became maximum at 420 nm and the
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absorption edge noticed between 401 to 418 nm in visible region. Optical transmittance
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increased between 360 nm and 480 nm after that it remained constant. a highest transmittance

of 88% was observed in Zn1-xTixO nanoparticles at x = 0.07

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Using Tauc’s equation, a graph between (αhυ)2 versus the photon energy (hυ) was
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drawn as shown in Fig. 8. The linear region of the graph was extrapolated such that the
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absorption coefficient becomes zero. The optical band gap was estimated using the Tauc’s

equation [54]

h = A(Eg-h)1/2 --------(4)

Where hν is the photon energy, α is the absorption coefficient. The 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. However, the bandgap of undoped ZnO was found as 3.25 eV.

An increase in optical band gap was observed in The Zn1-xTixO nanoparticles with increase in

Ti concentration. The increase in optical band gap with dopant concentration might be due to

Moss- Burstein effect.

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3.5 XPS Studies

Fig. 9 (a) shows the XPS spectrum of the element zinc. The spectrum consists of two

peaks at 1023 eV and 1029 eV. These peaks reflect zinc in Zn2p3 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 binding

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energy of Titanium [55]. Fig. 9 (c) show the XPS spectrum of oxygen. The XPS spectrum

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confirms the valence state of oxygen as -2 (O-2) as one peak was observed 529 eV. The peak

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at 529 eV corresponding to the characteristic spectra of oxygen in ZnO structure [56]. Finally,

Fig. 9(d) shows the survey spectra of Zn1-xTixO nanoparticles and the elements such as Zn, Ti,
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O were identified and exists in their respective binding energies. Hence it confirms the
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presence of Ti along with Zn, O and the peak positions are in best agreement with the reported
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binding energies.
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3.6 Electrical Studies

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The electrical properties of the bulk Zn1-xTixO nanoparticles at different titanium

concentrations (x = 0.01, 0.03, 005 & 0.07). A simple two probe method was used here to

know the electron transport mechanism in the prepared nanoparticles. The samples were made

into small pellets. A silver paste was used to connect copper wires and these copper wires used

as electrodes for the source meters. Two probe method was applied to study the current versus

voltage characteristics of the Zn1-xTixO nanoparticles at different Ti concentration. A program

was executed to take voltage at a step of 0.5 V and it gave the I-V characteristic as shown in

the Fig. 10. From the figure, it is clear that the samples exhibited Ohmic behaviour. The

relation between voltage and current follows ohm’s Law. It is Linear and resistivity can be

10
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 applied potentials and hence

showing conducting behaviour. The observed current is in nano ampere. From this linear

behaviour of current and voltage, the resistivity values were tabulated in Table.5. The observed

resistance is more when compared with that of the reported resistance of ZnO [57]. Further the

resistance increased with increase of the Ti concentration and it might be due to scattering at

grain boundaries due to Ti atoms.

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4. Conclusion

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Titanium doped ZnO nanoparticles (Zn1-xTixO; x = 0, 0.01, 0.03, 005 & 0.07) were

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prepared by solid state reaction and subjected to vacuum annealing. The synthesized samples
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were studied for their structural, surface, elemental, chemical, optical and electric properties.
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From these results it was found that the ZnO nanoparticles were in wurtize structure and the

mean crystallite size was 39 nm. From the surface topography, it was found that the
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nanoparticles were closely packed and grain size was more when compared with crystallite size
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calculated using XRD results. The valence states were studied and found the host and dopants
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in Zn+2, Ti+4 and O-2 states. The ZnO nanoparticles were found as semiconducting and the band

gap increased with Ti concentration. The electrical properties were studied and found the linear

relationship between current and voltage indicating Ohmic behaviour.

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Figure Captions

Fig.1: Synthesis of Zn1-xTixO nanoparticles

Fig.2: XRD profile of Zn1-xTixO nanoparticles at x = 0.01, 0.03, 0.05, 0.07. The inset of the

figure shows XRD peak shift of Zn1-xTixO NP at x = 0.01 & x = 0.07

Fig.3: FT-IR spectrum of Zn1-xTixO nanoparticles at x = 0.01 & x = 0.07

Fig.4 a & b: SEM images of Zn1-xTixO nanoparticles at x = 0.07

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

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Fig.6: Absorbance spectra of Zn1-xTixO nanoparticles at different x

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Fig.7: Transmittance spectra of Zn1-xTixO nanoparticles at different x
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Fig.8: Plots of (h)2 Vs h of Zn1-xTixO nanoparticles at different x
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Fig. 9: (a) Zn 2p core levels, (b) Ti 2p core levels, (c) O 1s core levels (d) XPS Survey
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spectrum of Zn1-xTixO nanoparticles at x= 0.07

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Fig.10 a: Current vs Voltage characteristics of The Zn1-xTixO nanoparticles at different x

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18
Table Captions
Table.1 Summary of FWHM, Crystallite size, Dislocation density, Strain, Lattice parameter
of Zn1-xTixO nanoparticles at different x

Crystallite Dislocation Strain (ε) Lattice parameter

FWHM
Zn1-xTixO Size D Density (δ) 1014 10-4
𝜷 a (Å) c (Å)
(nm) m2 (lines/meter)

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

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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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Table.2 Optical band gap of Zn1-xTixO nanoparticles at different x
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Zn1-xTixO Band Gap (eV)
x = 0.00 3.25
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x = 0.01 3.22
x = 0.03 3.25
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x = 0.05 3.26
x = 0.07 3.27
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Table.3 Elemental analysis of pure ZnO

Atomic
Element Weight %
percentage

Zn 68.43 32.41
O 21.46 41.53
C 10.11 26.06

Total 100

19
Table.4 Elemental analysis of Zn1-xTixO nanoparticles at x = 0.07

Atomic
Element Weight %
percentage
Zn 79.85 50.42
Ti 3.95 3.4
O 11.06 28.52
C 5.14 17.66

Total 100

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Table.5 Summary of electrical resistivity and conductivity of Zn1-xTixO nanoparticles at
different x

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Resistivity Conductivity
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Zn1-xTixO
(109Ωcm) (10-10S/cm)
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x = 0.00 1.3 7.6

x = 0.01 1.29 7.7
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x = 0.03 1.26 7.9

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x = 0.05 1.27 7.8

x = 0.07 1.29 7.7
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20
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 Pristine ZnO
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320 400 480 560 640 720

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x = 0.03
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300 400 500 600 700 800
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Fig. 7

25
 Pristine ZnO
140 1%
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100
(h) (eV/cm )
2

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 600000 80000
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Intensity (counts/s)

60000
400000
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200000 30000

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1050 1045 1040 1035 1030 1025 1020 1015 475 470 465 460 455 450
Binding Energy (eV) 3000000
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Binding Energy (eV) Binding Energy (eV)
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Fig.9
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28
Declaration of interests

☒The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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