Vol. 125 (2014) ACTA PHYSICA POLONICA A No.

Proceedings of the 3rd International Congress APMAS2013, April 2428, 2013, Antalya, Turkey

The Eect of Temperature on Grain Size of SnO2

Nanoparticles Synthesized by SolGel Method
a,∗ a b
H. Köse , A.O. Aydin and H. Akbulut
a
Department of Chemistry, Arts and Sciences Faculty, Sakarya University, 54187, Sakarya, Turkey
b
Department of Metallurgy and Material Engineering, Engineering Faculty, Sakarya University
54187, Sakarya, Turkey
Tin dioxide nanoparticles were synthesized by solgel method and calcined at dierent temperatures in the
range 350750 ◦C. The SnO2 precursor solution was prepared from SnCl2 ·2H2 O (tin (II) chloride dihydrate),
and chloride ions were removed from the solution before the solgel synthesis was applied. SnO2 powders were
characterized by thermal analyses, X-ray diraction, eld emission gun-scanning electron microscopy, and energy
dispersive X-ray spectroscopy, and grain size of nanoparticles were determined by using the DebyeScherrer formula.
DOI: 10.12693/APhysPolA.125.345
PACS: 81.07.Wx, 81.20.Fw, 81.20.Ev

1. Introduction the relationships between the microstructural change and

Tin dioxide (SnO2 ), cassiterite structure, is a typi- the crystal structure with the calcination temperature of
cal wide band gap n-type semiconductor (3.6 eV) and nano-SnO2 .
one of the most widely used semiconductor oxides due 2. Experimental

to its chemical and mechanical stabilities. SnO2 is a The SnO2 precursor sols were prepared by sol
non-stoichiometric structure, and its conductivity mainly gel method after removing chloride ions (Cl− ) of
originates from the oxygen vacancies [1]. The electri- SnCl2 ·2H2 O precursor solution. All chemicals were of
cal and chemical properties of SnO2 have been exten- analytical grade and were used without further puri-
sively studied because of its application as transparent cation. For this process, rstly, 10.0 mmol SnCl2 ·2H2 O
electrodes for solar cells, liquid crystal displays; anti- was dissolved in deionized water and then for removing
static coatings and gas sensors; anodes for lithium ion of chloride ions from tin solution, a stoichiometric ratio
batteries, transistors, catalyst supports; nano and ul- of NH3 (25%) solution was added. After the precipita-
traltration membranes and anticorrosion coatings [2]. tion of tin as hydroxide (Sn(OH)n , n = 2 or 4), the solid
Recently tin oxide-based materials have received con- was ltered and washed with diluted NH3 solution. The
siderable attention as promising anode materials for Li- nal precipitate was dissolved in glacial acetic acid, and
-ion batteries due to their high theoretical capacity with then ethylene glycol was added to solution in order to
1498 mAh g−1 [3]. Previous reports demonstrated that form complex with tin cation. The stirring was contin-
nanomaterials could greatly improve electrochemical per- ued from 50 ◦C to 80 ◦C until the acetic acid was removed
formances by nanometer size eects [4]. from the obtained sol and at the end of stirring; gels were
A variety of techniques have been used to synthe- obtained and dried in an oven at 150 ◦C in air. Finally,
size oxide nanoparticles, including solgel [3], hydrother- precalcination step was performed on dried gels at 300 ◦C,
mal [5], solvothermal [2], precipitation [6], spray pyroly- and samples were calcined in the range of 350750 ◦C in
sis [7] and thermal decomposition techniques [8]. Among air at a heating rate of 2 ◦C/min and held at the same
these techniques, the solgel method attracts the most temperature for 2 h. Produced SnO2 powder samples
attention because of several advantages, such as excel- were coded as A, B, C, D, and E for the applied calci-
lent homogeneity, ease of controlling the doping level, nation temperatures of 350, 450, 550, 650, and 750 ◦C,
ability to coat large areas and complex shapes, simple respectively.
equipment requirements and low-cost processing [1]. Synthesized powder morphologies were analyzed with
In this study, SnO2 nanoparticles were synthesized by eld emission gum-scanning electron microscopy (FEG-
solgel method and calcined at dierent temperatures in -SEM) (FEI QUANTA FEG 450). The composition of
the range of 350750 ◦C. It was aimed to develop the ex- the products was determined by energy dispersive X-ray
perimental parameters for producing nanosized chloride spectroscopy (EDS) attached to the SEM (JEOL-JSM
free SnO2 particles prepared from SnCl2 ·2H2 O (tin(II) 6060LV). The working conditions for EDS analysis in-
chloride dihydrate) for possible application in the sensors clude an accelerating voltage of 15 kV, a beam current of
and Li-ion battery electrodes. It was targeted to reveal 5 nA, a working distance of 15 mm, and a life time of 60 s
for each run. XRD analysis was performed with X-ray
diractometer (Rigaku D/MAX/2200/PC model device)
using Cu Kα radiation (λ = 1.54050 Å) with 1◦ /min
∗ corresponding author; e-mail: [email protected] scanning speed using a grazing angle of 5◦ . The solid was
also characterized with dierential thermal and gravimet-

(345)
346 H. Köse, A.O. Aydin, H. Akbulut

ric analyses (TGA/DTA) (SDT Q600 model of TA) to grown, and the crystal quality has been improved ac-
determine endo- and exothermic events that might take cording to lower temperature calcined samples of A, B,
place during the thermal treatment. Analyses were car- and C [10]. It can be clearly seen that the intensity of
ried out in dry air atmosphere (100 mL/min ow) and diraction peaks reduce with low calcination tempera-
heating rate of 10 ◦C/min with Al2 O3 as reference mate- ture, especially for the sample A. The produced phase
rial from 25 ◦C to 1000 ◦C. is mainly a cassiterite type of SnO2 (JCPDS, 00-041-
-1445) [3]. The strongest peak for each case is the
3. Results and discussion
(110) plane and the peak of SnO2 indicated the broadest
To determine the range of calcination temperature, diraction (110) peak suggesting that the nanoparticles
thermal analysis was performed on the solid sample ob- are very small in size. The similar eect of decreasing
tained from the SnO2 precursor gel. Figure 1a shows the particle size on the peak broadening in tin oxide and tin
TGA/DTA curves of solid sample. On the TGA curve, oxide based nanocomposite materials was also proven by
the weight loss about 58% below 225 ◦C is due to removal Lian et al. [11].
of adsorbed water, physisorbed acetic acid and free ethy-
lene glycol that cannot be removed during the thermal Grain size of SnO2 particles obtained from sols.TABLE
treatment and associated with endothermic peak on the Sample Calcination Lattice parameters Grain
DTA curve. The second weight loss (12%) at 375 ◦C on temperature [Å] size [nm]
TGA curve formed the broad endothermic peak on the
A 350 ◦C a110 = b = 4.6971 15
DTA curve. It may correspond to removing chemically
c101−110 = 3.1984
bonded ethoxy groups from the structure by decomposi-
B 450 ◦C a110 = b = 4.7456 17
tion. From 420 ◦C, no weight loss was observed because of
stable SnO2 structure and DTA peak may be associated c101−110 = 3.1808
with material crystallization [9]. C 550 ◦C a110 = b = 4.7388 22
c101−110 = 3.1776
D 650 ◦C a110 = b = 4.7530 36
c101−110 = 3.1946
E 750 ◦C a110 = b = 4.7562 41
c101−110 = 3.1908
Standard value a = 4.7403 and c = 3.1885
(JCPDS, 00-041-1445)
Scherrer's formula (Eq. (1)) was used to determine the
grain size of the SnO2 samples by using XRD data. As
can be seen from Table, the grain size increased with in-
crease of the calcination temperature [1]. For the sample
A minimum grain size was observed, and maximum grain
size was obtained from the sample E which was calcined
at 750 ◦C
Kλ
D= . (1)
β cos θ
In this formula, K is the shape factor, D is the mean
grain size of crystalline structure. λ is X-ray wavelength,
β is the full width at half maximum (FWHM) or integral
breadth of XRD peak, and θ is the Bragg angle. In Table,
calculated grain size of samples by Scherrer's formula and
lattice parameters can be seen. For the tetragonal struc-
ture, the lattice parameters can be calculated by Eq. (2)
where h, k , and l are all integers, (hkl) is the lattice plane
index, and a and c are lattice constants
Fig. 1. (a) TGA/DTA curves corresponding to solid
sample obtained from SnO2 gel, and (b) XRD analyses
1 h2 + k 2 l2
= + . (2)
of SnO2 samples of A, B, C, D, and E. d2hkl a2 c2
For a real crystal, the calculated values of a and c are
XRD analysis was performed to investigate the crys- the same based on dierent crystal planes. However, the
tal structure of powders. In Fig. 1b, XRD results show presence of a large number of vacant lattice sites and lo-
that there is no signicant preferential nucleation and cal lattice disorders may lead to serious reduction in the
growth by changing the calcination temperature. The intensity (or the nearly disappearance) of the XRD peaks
sharp and narrow diraction peaks are observed at high of the corresponding lattice plane as the sample A. There
temperatures of 650 ◦C and 750 ◦C for sample D and E, are a large number of vacancies of oxygen, vacancy clus-
respectively. This result indicated that the particles have ters, and local lattice disorders, which lead to an increase
 The Eect of Temperature on Grain Size . . . 347

in c and decrease in a and the volume of the unit cell [10], and EDS analysis conrmed that Cl− anions were com-
as can be seen from the values of the sample A in Table. pletely removed from sol, additionally the atomic per-
FEG-SEM micrographs of SnO2 powders obtained centage of Sn and O are suitable with the SnO2 struc-
from prepared sols are given in Fig. 2a. As can be seen ture.
from FEG-SEM image of sample A, the SnO2 powders 4. Conclusions
calcined at 350 ◦C showed very ne grain size of SnO2 SnO2 nanoparticles were synthesized with solgel
with spherical particles. Sample B also showed homoge- method at dierent calcination temperatures from 350 ◦C
neous and spherical nanosized particles for the calcina- to 750 ◦C. Synthesized nanoparticles were characterized
tion temperature of 450 ◦C and sample C showed similar by XRD, FEG-SEM, EDS and thermal analyses were
morphology with ner particles, but agglomeration be- performed for solid sample of SnO2 precursor. Solgel
gan to appear in some locations. After applying higher method was applied with removing the chloride ion of
calcination temperatures of 650 and 750 ◦C, for sample D precursor. EDS analysis shows that chloride anions were
and E, particles became equiaxed coarser grains with completely removed from sol. XRD analysis, lattice pa-
homogeneous distribution and agglomeration can be ob- rameters, and grain sizes yielded coherent results. With
served. As a result, FEG-SEM images of SnO2 samples the increase in the calcination temperature, the grain size
clearly indicated that the grain size of SnO2 powders in- has increased, and the crystallinity has been improved.
creased with increasing in the calcination temperature The smallest grain size obtained from SnO2 sample cal-
and the images showed compatible results with XRD cined at 350 ◦C (15 nm), and calcination temperature of
analyses and Scherrer's formula calculations. 750 ◦C resulted in obtaining maximum grain size (41 nm).
FEG-SEM images conrmed XRD results by indicating
agglomeration and coarsening on spherical nanoparticles
at higher temperatures. The results show that sam-
ple A, which has a large number of vacant lattice sites
and minimum grain size, can be eciently used for Li-
-ion battery applications, since ne nano grains provide
improved charge/discharge ability associated with meso-
porous structure.
Acknowledgments
This work is supported by the Scientic and Techno-
logical Research Council of Turkey (TÜBTAK) under
the contract number 109M464. The authors thank the
TÜBTAK MAG workers for their nancial support.
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