Chapter 4

4.1 Introduction

The controversial new technology of the 21st century, "nanotechnology", has played an
important role in the economy of developing countries and has increased the living standards of
the same people. Nanoscience has developed modern technology and produced many
nanoparticles (NPs) such as metals, metal oxides, doped and undoped nanostructures. Among
nanostructured metal oxide semiconductors, these materials are becoming an important choice
for research due to their special properties such as texture, structure, electrical and optical
properties, leading to various technological applications such as optoelectronic devices, gas
sensors and biomedical applications etc. It has been proven that the use of suitable metal
materials such as Cu2+, Nd3+, Co2+ and V3+ can improve and control the properties of nanometal
iron oxide particles. Therefore, nano metal oxide particles, often called transition metal oxides,
show many advantages, the most commonly used are ZnO, TiO2 and SnO2, etc.

High thermal stability and high conductivity in the visible spectrum region, make these propertie
s the most important for research point of view. Tin oxide (SnO 2) is an n-type semiconductor
material with a tetragonal structure, P 4 ¿2 mnm space group, and a wide range (e.g. 3.6eV) [00].
SnO2 nanocrystalline materials have received more attention due to their quantum confinement
effects, morphology, particle sizes, and large surface areas to volumes ratio that determine their
performance [01]. Microstructure, magnetic, and electrical properties can be adjusted by using
appropriate dopant ion exchange in host SnO 2. The effect of Cu2+ doping in SnO2 causes an
increase in the number of defects but a decrease in the band gap energy value (3.60-3.20 eV).
Increasing the Cu2+ content in the SnO2 main matrix reduces the dielectric constant and the size
of the dielectric loss, but it is considered a potential candidate for optoelectronic devices as it
shows good photon absorption in the UV region [02]. Lee et al. investigated the magnetic and
optical properties of Cu2+ doped SnO2 thin films and established a correlation between the
ferromagnetic order of the donor-acceptor complexes.[03]. Janeway et al. indicate an increase in
crystallite size and a decrease in band gap due to Cu 2+ deposition in host SnO2 and also showed a
high dielectric constant, low dielectric loss and a magnetic moment of about 10-1 emu/g [04].

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Sagadevan et al. Cu2+ doped SnO2 was produced by chemical precipitation and presented its
structure, surface morphology and dielectric properties [05]. Singh et al. showed the moisture
content of Cu-doped SnO2 [06]. Zab et al. It was found that the Cu-doped SnO 2 film had a high
response to ethanol [07]. The above discussion leads to the conclusion that Cu 2+ stands out as a
non-magnetic metal ion that gives rise to electronic bands in wide-band gap oxides and also
exists near the valence band. It results in changing the physical properties of n-type
semiconductor oxides [08]. In this report, pristine and Cu 2+ doped SnO2 nanocrystals were
synthesized using the precipitation method, and their structures, microstructures, and electrical
properties were investigated.

4.2 Results and Discussions

4.2.1 Structural analysis

Refinement of the X-ray diffraction pattern (XRD) using the Rietveld method gives the data such
as lattice constants, unit cell volumes, atomic positions, and circumferential and equatorial
distances of pristine and Cu2+-modified SnO2 nanocrystals [Sn(1-x)CuxO2 NCs, where x = 0, 0.05
and 0.10] [51]. XRD patterns of each composite were recorded at a rate of 1°/min at an angle of
20° ≤ 2θ ≤ 80° at room temperature. As seen in the picture. Figure 4.1(a) shows the Rietveld
refined XRD model of Sn(1-x)CuxO2 NCs with x = 0, 0.05 and 0.10. Absence of secondary or
characteristic impurity indicates pure phase synthesis, all characteristic peaks are written with
Miller plane (110), (101), (200), (211), (220), (002), (310), (112), (301), (202), and (321),
according to [10]. The results are consistent with the current JCPDS data card 41-1445 [11] a.
The polyhedral unit cell sphere model is shown in Figure 4.1(b). The average crystallite size is
calculated by the Debye Scherrer formula [equation (1)] [12] and it is found that the average
crystallite size will decrease as Cu2+ of small cation invades the lattice framework of the host
SnO2.

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 0.9 λ
D= (1)
βcosθ

Figure 4.1(a) Rietveld refined XRD profile of Sn(1-x)CuxO2 NCs and (b) Polyhedral unit cell of pristine
SnO2

4.2.2 Microstructural studies

The particle microstructure and surface morphology of Sn (1-x)CuxO2 NCs with x = 0 and 0.10
were investigated using field emission scanning electron microscopy (FESEM). Figure 4.2(a,b)
shows FESEM micrographs of pristine SnO2 NCs; x = 0, and x = 0.10, . As can be seen from the
pictures, the pristine SnO2 particles are well aggregated and stable, while the Cu 2+ doped
composition shows small particles with small clumping lines. The grain size distribution diagram
was fitted with a Gaussian function to obtain the average grain size, as shown in Figure
4.4.1.2(a) and in the appendix to Figure 4.2(a) and 4.2(b) represent x = 0 and x = 0.10,
respectively. The mean grain size was found to decrease from [30.29 nm (x = 0) to 27.43 nm (x
= 0.10)] with Cu2+ substitution in the SnO2 lattice [55]. Selected area electron diffraction (SAED)
images for x = 0 and x = 0.10 are shown in Figure 4.2(c,d). Composite rings written with Miller
planes (110), (101), (200), and (211) appear to support the XRD study, thus demonstrating the
tetragonal rutile crystal structure of composite nanoparticles [can be seen in Figure 4.2(c)] [56].
High-resolution transmission electron microscopy (HRTEM) images [Figure 4.2(e)] showed the
orientation of the grains along the (110) plane with d = 0.34 nm interplanetary spacing and

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confirmed the tetragonal crystal configuration with x = 0.10. Sharma et al. and Vashisht et al.
also reported similar results for modified SnO2 nanoparticles (NPs) [57, 58].

Figure 4.2 (a) FESEM micrograph of x = 0, (b) x = 0.10, (c) SAED pattern of x = 0 and (d) x =
0.10, (e) HRTEM image of x = 0.10.

4.2.3 Electrical properties

Cu2+ entry into the SnO2 crystal lattice also affects the host's carrier concentration and electron
mobility. Sn(1-x)CuxO2 NCs (where x = 0.05 and 0.10) were found to exhibit 3.42 × 10 16 cm-3 and
1.37 × 1016 cm-3 p-type concentrations, respectively as shown in Figure 4.3. In addition, the
mobility of the compound decreased as the Cu2+ concentration increased [59]. The decreased
mobility due to the incorporation of Cu2+ into the crystal structure of the host SnO 2 can be
explained by the XRD results. Doping of short Cu2+ ions with an ionic radius of 69 pm compared
to Sn4+ reduces the unit cell volume by reducing lattice exclusion from Rietveld purification
studies. Roman et al also reported that the reduction in mobility due to dopant ions may be due to
increased scattering by dopant ions [60] and the induced strain in host SnO 2 due to Cu2+ addition.
It has been reported that pristine CuO 2 exhibits n-type semiconductor behavior, but conductivity
decreases as the host lattice is replaced by Cu2+ ions. Hall effect measurements confirmed the
transition from n-type to p-type with increasing Cu2+ content in the element [61]. Pan et al. found
a similar p-type behavior was observed in nitrogen-modified SnO 2 films [62]. The source of the

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p-type semiconductor behavior can be attributed to the acceptor state of Cu2+ ions replacing Sn4+
in the lattice frame.

Figure 4.3 mobility and carrier concentration of Sn(1-x)CuxO2 NCs, with x = 0, 0.05, and 0.010.

4.3 Conclusions

In summary, polycrystalline pristine and Cu2+ modified SnO2 NCs were synthesized using the
sol-gel reaction method. The XRD patterns of all compounds are poorly fitted with the parameter
(GOF ≈ 1.54) and fit well into the P 4 ¿2 mnm space group with confirmed phase-pure tetragonal
crystallinity. FESEM micrographs showed an uneven grain distribution and the average grain
size was observed to decrease from 30.29 nm to 27.47 nm with Cu 2+ doping. SAED images show
concentric rings of tetragonal crystal symmetry for pristine [x = 0] and Cu 2+ modified SnO2 NCs
[x = 0.10]. HRTEM micrographs show the presence of (110) plane with plane pacing, i.e. d =
0.34 nm is contributed in the rutile crystal structure at x = 0.10. The electron material shows a
decrease in carrier density from 9.47 × 1016 cm -3 to 1.37 × 1016 cm-3 due to the orientation of
the Cu2+ ions in the SnO2 crystal lattice. Hall effect measurements show a decrease in mobility
from 4.27 cm2/Vs to 1.19 cm2/Vs with Cu2+ doping. Cu2+ substitution in the host SnO2 causes a p-
type semiconductor behavior with reduced carrier concentration and mobility, possibly due to the
effect of acceptor type Cu2+ (dopant).

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