Journal of Thermal Analysis and Calorimetry

https://doi.org/10.1007/s10973-018-7432-3(0123456789().,-volV)(0123456789().,-volV)

Investigation on phase formation of Sr2SnO4 and effect of La-doping

on its structural and optical properties
Upendra Kumar1 • Dharmendra Yadav1 • Anukul K. Thakur2 • Kamal K. Srivastav3 • Shail Upadhyay1

Received: 5 December 2017 / Accepted: 27 May 2018

 Akadémiai Kiadó, Budapest, Hungary 2018

Abstract
The reaction mechanism for the formation of Sr2SnO4 by solid-state reaction between SrCO3 and SnO2 has been inves-
tigated using thermal analysis (TG and DSC) combined with X-ray diffraction (XRD) techniques. It is observed that the
formation of single-phase Sr2SnO4 takes place by reaction between SrO and SrSnO3 at temperatures C 900 C. Based on
these studies, a few compositions of the system Sr2-xLaxSnO4 (x = 0.01, 0.02, 0.04, 0.06 and 0.10) have been synthesized
by calcination at 1000 C for 8 h. Rietveld refinement of the XRD data confirmed that all the synthesized samples have
tetragonal structure, space group (I4/mmm) and symmetry group D17 4h. The crystallite size and induced lattice strain has
been calculated using size strain plot (SSP), varies from 30 to 50 nm and from (3.00 to 6.27) 9 10-3, respectively. Raman
and Fourier transformed infrared (FTIR) spectroscopy techniques have been utilized to ponder local changes in the
structure of Sr2SnO4 with La incorporation. The optical properties of the samples have been studied using UV–Vis
spectroscopy. The systematic shift in the position of the absorption edge (toward the higher wavelength) indicates the
incorporation of La in the lattice of Sr2SnO4. The direct and indirect band gap of the samples calculated through Tauc’s
plot. The variation in the value of direct band gap is attributed to changes in the charge compensation mechanism or/
reduction in particle size.

Keywords Layered perovskite: Sr2SnO4  Core–shell  Rietveld refinement  Raman spectroscopy  UV–Vis absorption

Introduction hyper-stoichiometric oxygen by the oxygen interstitial sites

The ternary oxides A2BO4 belong to the family of Rud-
dlesden D Popper (RP) phase with the chemical formula
An?1BnO3n?1 where n is an integer, for example, n = 1
corresponds to A2BO4 and n = 2 corresponds to A3B2O7,
etc. [1]. The A2BO4 structure consists of stacking of per-
ovskite layers (ABO3) alternately with rock-salt-like layers
(AO) along c-axis. The A2BO4 oxides can accommodate
& Shail Upadhyay
supadhyay.app@itbhu.ac.in
1
Department of Physics, Indian Institute of Technology
(Banaras Hindu University), Varanasi, Uttar Pradesh 221005,
India
2
Nanostructured Composite Materials Laboratory, Department
of Applied Physics, Indian Institute of Technology (Indian
School of Mines), Dhanbad 826004, India
3
Department of Chemistry, D.S. College, Aligarh 202001,
India
in between adjacent rock-salt layers and charge compen-
sated by the B-site transition metal, which exists in a mixed
valence state [2–4]. A2BO4 based mixed ionic-electronic
conductors (MIECs) have received renewed interest due to
their high thermal stability, high oxygen diffusion coeffi-
cient, excellent electronic conductivity and strong electro-
catalytic activity toward oxygen reduction reaction (ORR)
[5]. Mixed oxide ion and electron conducting ceramic
materials A2BO4?d (where A = La3?, Nd3? or Pr3? and
B = Cu2?/3?, Ni2?/3? or Co2?/3? have attracted attention
for intermediate-temperature solid oxide fuel cell (IT-
SOFC) cathodes and ceramic membranes for oxygen sep-
aration as well as applications involving partial oxidation
of light hydrocarbons [6–9]. La2NiO4?d have been studied
for electrolyte application in intermediate temperature solid
oxide fuel cell (IT-SOFC) due to their high oxygen ion
conductivity [10]. The change in oxygen stoichiometry in
La2NiO4?d compounds can be accomplished either by
partial substitution of the alkaline earth (Sr, Ba, Ca) at La

123

site or by the Ni site doping with other transition metals,
typically Cu and Co [6, 9, 11].
The development of flat panel displays, such as field
emission displays (FEDs), plasma display panels (PDPs)
and thin film, electroluminescent devices (TFEL) needs
constant improvements in the phosphors. Efforts have been
made to discover novel host materials as well as activators
with high performance for phosphor applications [12, 13].
Practically, oxide phosphors are more attractive than the
traditional sulfide or halide phosphors due to their resis-
tance to moisture. During the last decade, alkaline earth
orthostannates, M2SnO4 (where M = Ca, Sr and Ba) which
are also members of RP phase have been drawing more and
more attention as a host matrix for new phosphors because
of their stable crystalline structure and high physical and
chemical stability [14]. Incorporation of optically active
lanthanide ions into the stannate host matrix resulted in
phosphors possessing photoluminescence (PL) [12, 15] and
long-lasting phosphorescence (LLP) [16] properties. In
alkaline earth stannates, strontium stannate (Sr2SnO4) has
an ordered tetragonal K2NiF4-type structure with space
group I4/mmm, lattice parameters of a- and c-axis are
4.052 and 12.580 Å [17], respectively. Rare earth metals
such as Eu, Sm, Nd, Tb, Dy doped Sr2SnO4 solid solutions
have shown exciting emission properties [14, 17]. It is
reported that doping of Ti on Sn site of Sr2SnO4 emits blue
light which is suitable for the display devices [18]. Ter-
bium-doped strontium orthostannates system, Sr2Sn1-x-
TbxO4, has been investigated as yellow pigments with high
infrared reflectance for energy saving applications [19].
As mentioned above, Sr2SnO4 structure consists of
layers of cubic perovskite SrSnO3 interconnected with
rock-salt-like layers of SrO along c-axis. Properties of La-
doped on alkaline earth site of perovskite oxides, MSnO3
(M = Ba, Sr and Ca) have been investigated widely. La-
doped SrSnO3 and BaSnO3 have been used for various
applications such as humidity sensor, transparent con-
ducting oxides, proton conducting electrolyte in fuel cells,
etc. [20]. The interesting properties of La-doped perovskite
stannates motivated us to synthesize and study the effect of
La-doping on the properties of layered perovskite RP phase
compound Sr2SnO4 and explore its applications. To the
best of author’s knowledge, this will be the first report on a
study of La-doping at the Sr site on structural and optical
properties of Sr2SnO4. In the literature synthesis of
nanopowders of Sr2SnO4 has been reported by different
chemical routes such as sol–gel [14], combustion [21], gel
polymerization [22], etc. The use of expensive chemicals
and lengthy steps involved in the synthesis mentioned
above routes makes these methods impractical for the bulk
synthesis of the powder required for the industrial appli-
cations. The solid-state reaction method [23] is a simple
method and requires inexpensive chemicals, is still
123
U. Kumar et al.
considered as the preferred choice for the bulk production
of powder for industrial application; therefore, in this
investigation, powders have been synthesized by the solid-
state reaction method.
In the present work, the formation mechanism of Sr2-
SnO4 using raw materials SrCO3 and SnO2 by solid-state
reaction method has been studied extensively. Further-
more, a few compositions of the system Sr2-xLaxSnO4
(x = 0.01, 0.02, 0.04, 0.06 and 0.10) has been synthesized
by calcination at 1000 C for 8 h. The crystal structure and
phase identification of the samples have been investigated
using the Rietveld refinement profile fitting to the powder
X-ray diffraction data. All the La-doped samples are a
single phase with tetragonal crystal structure and space
group D17 4h(I4/mmm) similar to host Sr2SnO4. The crystal-
lite size and lattice strain of the samples were obtained
using the size–strain plot (SSP) of XRD data. The syn-
thesized samples have been additionally analyzed using
Raman and the Fourier transform of infrared (FTIR)
spectroscopic techniques. The optical band gaps (both
direct and indirect) of the samples have been calculated
using Tauc’s equation generated from UV–Visible
absorption data of the samples.
Experimental
The synthesis of Sr2-xLaxSnO4 with composition x = 0,
0.01, 0.02, 0.04, 0.06, 0.10 has been carried out by solid-
state ceramic route using SrCO3, La2O3, and SnO2 (pu-
rity C 99.5%). A stoichiometric amount of these com-
pounds was mixed in a Ball Mill (Retsch PM 200,
Germany) at a constant speed of rotation 200 rpm for 8 h
using acetone as the mixing media. The prepared mixtures
were dried in an oven for 12 h. Thereafter, thermal analysis
(TG and DSC) of the mixtures was carried out using
simultaneous TG-DSC (Mettler Toledo, Germany) thermal
analyzer in the temperature range 30–1000 C at a constant
heating rate of 10 C min-1 in the nitrogen gas atmo-
sphere, to ascertain the calcination temperature. The pre-
pared mixtures were transferred into an alumina crucible
and calcined at 1000 C for 8 h. The X-ray diffraction
(XRD) pattern of the calcined powders was recorded using
X-ray diffractometer (Rigaku Miniflex II Desktop, Japan)
employing CuKa radiation and Ni filter in the angular
range 2h = 20–80 with angular step size D2h = 0.02.
Raman spectroscopic technique (T64000, Jobin-Yvon
Horiba, France) was employed to probe various rotational
and vibrational bands active in the samples. Fourier
transform of infrared (FTIR) spectrum of the calcined
powders in the wave number range of 400–4000 cm-1
were recorded by the spectroscope (Shimadzu, Model DF
803, Japan) using a KBr pellet method. The UV–Visible
Investigation on phase formation of Sr2SnO4 and effect of La-doping...

spectrums of the calcined powders have been recorded in
absorption mode in the range of wavelength 200–800 nm
by a spectrometer (Ocean Optics, HR 4000, USA).
Results and discussions
Thermal analysis (TG/DSC) of raw materials (SnO2
and SrCO3) and their mixture
The thermogravimetric (TG) and differential scanning
calorimetry (DSC) curves of SnO2 and SrCO3 powders
were recorded after grinding for 1 h in an agate mortar with
pestle and are shown in Fig. 1a, b, respectively. No sig-
nificant changes were observed in the TG/DSC curve of
SnO2 in the temperature range 30–1000 C; however, the
TG curve of SrCO3 (as shown in Fig. 1b) shows a single
step mass loss (approximately 27.58%) in the temperature
range 850–1000 C. The observed experimental mass loss
may be due to the evolution of CO2, according to the
reaction given below;
SrCO3 ¼ SrO þ CO2 :
Theoretical mass loss calculated according to Eq. (1) is
29.72% which is slightly higher than the experimental mass
loss (27.58%), which indicates that partial conversion of
SrCO3 into SrO has taken place within investigated tem-
perature range and used rate of heating (10 C min-1). In
the DSC curve of SrCO3, two endothermic reaction peaks
centered at 926 and 977 C were observed, which are in
agreement with results reported by J. Bera et al. The first
peak is assigned to the polymorphic phase transformation
of SrCO3 from orthorhombic (space group Pmcn) to
rhombohedra (space group R-3m), while the second peak
to decomposition of SrCO3 into SrO as indicated by the
reaction (1) [24].
Figure 1c shows TG/DSC curves of the stoichiometric
mixture of 2 mol SrCO3 and 1 mol SnO2 obtained after
ball milling for the formation of Sr2SnO4 (S2L0). The TG
curve shows a mass loss of approximately 19.1% in a
temperature range of 650–950 C. In order to visualize
mass step more clearly, dm/dT versus temperature, i.e.,
derivative thermogravimetric (DTG) plot has been gener-
ated from the TG data and illustrated in Fig. 1d. The DTG
ð1Þ curve depicts two distinct peaks in the temperature range
650–750 and 800–950 C and mass losses corresponding to

(a) 16 (b) 8.5 70

TGA DSC 40 TGA DSC
20 8.0 60
15 0 50
7.5
–20
Heat flow/mW

Heat flow/mW
40
Mass/mg

Mass/mg

–40
14 7.0
–60 30
–80 6.5
20
13
–100
6.0 926 °C 10
–120
977 °C
12 –140 5.5 0
200 400 600 800 1000 200 400 600 800 1000
Temperature/°C Temperature/°C

(c) DSC
(d)
9.5 –0.000
0
TGA
9.0 –0.005
–40
DTG/mg °C–1
Heat flow/mW

760 °C
Mass/mg

8.5 –0.010
–80

8.0 –120 –0.015

897 °C

7.5 –160 937 °C

–0.020
200 400 600 800 1000
200 400 600 800 1000
Temperature/°C Temperature/°C

Fig. 1 Simultaneous TGA/DSC curve of a raw material SnO2 b raw material SrCO3 c mixture of raw material SrCO3 and SnO2 d derivative
thermogravimetric (DTG) curve for mixture of raw materials

123

these peaks were found to be 1.06 and 17.04%. It is
expected that the formation of Sr2SnO4 through a reaction
between raw materials (SrCO3 and SnO2) occurs according
to reaction given by Eq. (2);
2SrCO3 þ SnO2 ¼ Sr2 SnO4 þ 2CO2 :
The mass loss calculated theoretically according to
Eq. (2) is 19.7%, which is approximately equal to the sum
of the experimental mass losses occurred in two different
temperature ranges mentioned above. This result suggests
that the decomposition of the whole amount of SrCO3 into
SrO has taken place below 950 C, which is slightly lower
than the decomposition temperature observed for the
SrCO3 (Fig. 1b). In the DSC curve of the mixture, a weak
endothermic peak around 942 C was observed which may
be attributed to the formation Sr2SnO4. The observed lower
decomposition temperature and absence of a peak in the
DSC curve corresponding to change in the crystal structure
of SrCO3 in the mixture is possible on account of pro-
longed ball milling (8 h). During ball milling, particle size
of the reactants get reduce and due to small particle size
cause change of the crystal structure is also possible.
Considering that major amount of decomposition of SrCO3
into SrO and CO2 in the mixture occurred at temperatures
higher than 800 C (Fig. 1c, d), therefore, the calcination
of the mixture was carried out at three different tempera-
tures 800, 900 and 1000 C for 8 h to understand reaction
steps involved in the formation of Sr2SnO4. In order to
understand the complete reaction mechanism, the help of
the powder X-ray diffraction technique has been used. X-
ray diffraction pattern of the powders obtained after
@SrCO3 # SnO2 ⃰ SrO
COD-1521093
# @
@ @ @ 800 °C
# @@
# @ # # @ #@
Intensity/a.u.
900 °C
* *
*
*
1000 °C
COD-1539931
20 30 40 50 60 70
Angle, 2θ °
Fig. 2 Powder X-ray diffraction pattern of the ball milled mixture
calcined at different temperatures and theoretical X-ray diffraction
pattern of SrSnO3 (COD 1521093) and Sr2SnO4 (COD 1539931)
123
U. Kumar et al.
calcination is illustrated in Fig. 2. These patterns were
compared with standard XRD data available for SrCO3(-
COD-1539128), SrO [25], SnO2(COD-1000062), SrSnO3
(COD-1521093) and Sr2SnO4 (COD-1539931) com-
ð2Þ pounds. X-ray diffraction pattern of the powder obtained
after calcination at 800 C contains peaks mainly of reac-
tant phases SrCO3 and SnO2 along with a small intensity
peak (at 31.44) of SrSnO3 phase. No peak corresponding
to Sr2SnO4 phase was found in the XRD pattern. The
formation of small amounts of SrSnO3 may occur due to
the direct reaction between SrCO3 and SnO2 according to
the following reaction;
SrCO3 þ SnO2 ! SrSnO3 þ CO2 : ð3Þ
This result is in agreement with the DTG result which
also exhibited a small mass loss in the temperature range
below 800 C. However, from the XRD data, it is clear that
a significant amount of reactant SrCO3 has not decomposed
into SrO. As the calcination temperature increased from
800 to 900 C, peaks corresponding to SnO2 and SrCO3
phases disappeared. Furthermore, the intensity of peaks
corresponding to SrSnO3 phase increased and few peaks of
SrO phase appeared in the XRD pattern. The XRD pattern
of the powder calcined at 1000 C contains only peaks of
Sr2SnO4 phase, which confirms that a weak endothermic
peak in the DSC (Fig. 1c) curve is due to the reaction
between SrO and SrSnO3 for the formation of Sr2SnO4
according to the following reaction;
SrO þ SrSnO3 ! Sr2 SnO4 : ð4Þ
On the basis of detailed thermal analysis (Fig. 1a–d)
combined with the XRD results (Fig. 2), the formation
mechanism of Sr2SnO4 from the 2SrCO3–SnO2 mixture is
schematically illustrated by Core–shell model in Fig. 3.
Based on the thermal analysis and X-ray diffraction
results described above, the few compositions of system
Sr2-xLaxSnO4 (x = 0, 0.01, 0.02, 0.04, 0.06, 0.10) have
been synthesized by calcination at 1000 C for 8 h. Cal-
cination temperature and time were kept same for all
compositions, to study the effect of La-doping (at Sr site)
on structural and optical properties of Sr2SnO4. These
compositions have been referred throughout the text and
figures by abbreviated names S2L0, S2L1, S2L2, S2L4,
S2L6, and S2L10. The abbreviated name S2L0 refers
sample Sr2SnO4 and S2L2 to sample Sr1.98La0.02SnO4 etc.
Characterization of La-doped Sr2SnO4
80 Structural analysis using powder X-ray diffraction
technique
The room temperature powder X-ray diffraction pattern of
all the samples has been recorded and shown in Fig. 4. All
Investigation on phase formation of Sr2SnO4 and effect of La-doping...

Fig. 3 Core–shell model for the

formation of Sr2SnO4 phase
using raw materials SrCO3 and SrCO3
SnO2 SrCO3
SrO

≤ 800 °C ≤ 900 °C ≤ 1000 °C

SnO2 SnO2 Sr2SnO4

SrO
SrCO3
SrCO3

Calcination at 1000 °C

S2L10
software suite’ and refined patterns are shown in Fig. 5a.
The refinement was performed by employing crystal
structure as tetragonal and space group (I4/mmm). The
S2L6 pseudo-Voigt function was adopted for the peak shape,
while the background is described by the interpolation
S2L4
Intensity/a.u.

between a set of background points with refinable heights.

S2L2
S2L1
S2L0
COD-1539931
20 30 40 50 60 70
Angle, 2θ °
Fig. 4 Room temperature powder X-ray diffraction pattern of the
samples and theoretical XRD of Sr2SnO4 taken from COD database
the observed peaks in the XRD patterns are indexed using
theoretical crystallographic open database COD-159322
reported in the literature for Sr2SnO4 [16]. The absence of
any extra peaks belonging to starting materials or any
secondary phase confirmed the formation of single-phase
solid solution for all the compositions. The peaks present in
the diffraction pattern of the samples are intense, indicating
good crystallinity of the synthesized powders. Moreover,
the value of the full width at half maxima (FWHM) of the
highest intensity peak is approximately same for all the
samples, suggesting that the solid solutions in the compo-
sitions range of x = 0–0.10 of system Sr2-xLaxSnO4 are
stable.
To get details about structural parameters of the syn-
thesized samples, the Rietveld refinement of the X-ray
diffraction patterns was carried out using ‘FullProf
The scale factor, zero correction, background, half-width
parameters, lattice parameters (a, b, c), angle (a, b, c),
positional coordinate (x, y, z) and the thermal parameters
(B) were varied during the process of refinement, while the
occupancy parameters for all the ions keep fixed. The
structural parameters such as lattice parameter, unit cell
volume, bond lengths, bond angles and other relevant
parameters obtained after refinement are presented in
Table 1. After the repeated refinement, the values of the
80
fitting parameters Rp, Rwp, Rf, and v2 were obtained and are
given in Table 1. The goodness of fit (S = Rwp/Rp) value
lies between 1.02 and 1.22 reasonable for assigning the
structure Sr2SnO4 for the Rietveld refinement of the syn-
thesized samples [26]. The structure obtained using
VESTA software after final refinement of one representa-
tive sample S2L4 is shown in Fig. 5b. The obtained
structure also confirms the stability of the crystal structure
and solubility of La at Sr; no significant change in the bond
length and bond angle is seen. The crystal structure of all
the synthesized samples remains tetragonal, but the
tetragonality, lattice parameters, cell volume is changing
with the concentration of La (x). The variation of degree of
distortion (c/a) and lattice parameters with the concentra-
tion of La (x) are shown in Fig. 6a, b, respectively. A
parameter named as degree of distortion (tetragonality)
(R) for the tetragonal crystal structure is defined as the ratio
of lattice parameter c to lattice parameter a (R = c/a).
Figure 6a shows a decreasing trend in tetragonality up to
x = 0.04 and after that, it becomes almost constant. The

123
 U. Kumar et al.

Fig. 5 a The Rietveld (b)

refinement pattern of calcined (a)

(110)
(013)

(006)

(026)
powders. Here Yobs, Ycal, S2L0

(020)

(123)
(116)
(015)
(011)

(022)

(008)

(130)
(112)

(125)
(220)

(028)
Yobs - Ycal and Braggs
positions represent the
experimental data, calculated
data, the difference between Yobs Ycal Yobs – Ycal Braggs position
both and Braggs position, S2L1
respectively. b Crystal structure
of S2L4 obtained after

Intensity/a.u.
refinement S2L2

S2L4

S2L6

S2L10

20 30 40 50 60 70 80
Angle, 2θ °

reason for the initial decrease in tetragonality is that the
increment in the value of lattice parameter c is smaller than
the increment in the value of lattice parameter a. From
Fig. 6 (b), it is observed that lattice parameters first
increase up to x = 0.04 and thereafter starts decreasing with
further increase in the doping concentration (x). A similar
trend was observed for the variation of cell volume
(Table 1). The change in lattice parameters and cell vol-
ume with increasing La-concentration indicates that La has
successfully substituted the Sr site. In the structure of
Sr2SnO4 (as shown in Fig. 5b), the coordination number of
Sr is 9 and the ionic radii of host ion Sr2? and dopant ion
La3? in coordination number nine is 1.31 and 1.21 Å,
respectively. Based on the value of ionic radii of the host
(Sr) and dopant ion (La), it is expected that lattice
parameters have to decrease with increasing dopant con-
centration, but experimentally it is observed that lattice
parameters increase with increasing dopant concentration.
The observed increase in the lattice parameter is not sur-
prising because similar results have been reported about
La, Sb-doped BaSnO3 systems [27, 28]. In Sr2SnO4
structure, if La is substituted at Sr sites, it can occupy sites
of Sr present in the perovskite SrSnO3 or present in SrO
layers or distribute among both types of Sr sites. The local
environment of Sr site present in the perovskite is different
than present in the layer. The solubility of La at Sr site in
SrSnO3 is limited up to B 2 atom% [27]; the higher solu-
bility of La in layered perovskite Sr2SnO4 as compared to
SrSnO3 may be possible due to occupancy of La at Sr sites
also present in the layer of Sr–O. As the substitution of La
takes place in the layer, there is an attractive force domi-
nates between the Sn and La which results in a decrease in
lattice parameter. Therefore, based on nature of variation of
lattice parameters with dopant concentration and higher
solubility limit, in this case, we propose that up to com-
positions with x = 0.04 La is occupying lattice sites of Sr
present in SrSnO3 and the compositions with x = 0.06 and
0.10, the La is occupying the sites of Sr present in the layer
SrO. In order to understand the effect of La-doping on the
length and angles of different bonds and their numerical
values have been obtained from the refinement and given in
Table 1.
Determination of crystallite size
Debye–Scherrer’s equation The broadening of the
reflection peaks observed in the XRD pattern occurs on
account of small crystallite size. The average crystallite
size (D) of the synthesized powders was calculated from
the X-ray line broadening of (013) peak using Scherer’s
formula [29]:
kk
D¼ ð5Þ
b cos hmax
where k—wavelength of X-rays used (1.54056 Å for CuKa
radiation), b—the full width at half maximum (FWHM) of
the (013) plane in radians, hmax—the corresponding inci-
dent angle, k is Scherer constant equal to 0.94. The width
of the Bragg peak observed in XRD is the combination of
various factors like instrumental broadening, lattice strain

123
Investigation on phase formation of Sr2SnO4 and effect of La-doping...

Table 1 Structural parameters obtained from the Rietveld refinement of XRD pattern of the samples
Sample/Code Sr2SnO4 Sr1.99La0.01SnO4 Sr1.98 Sr1.96 Sr1.94 Sr1.90
(S2L0) (S2L1) La0.02SnO4 La0.04SnO4 La0.06SnO4 La0.10SnO4
(S2L2) (S2L4) (S2L6) (S2L10)

Space group I4/mmm I4/mmm I4/mmm I4/mmm I4/mmm I4/mmm

Lattice parameters 4.05084(6) 4.05225(5) 4.05377(7) 4.05454(5) 4.05430(3) 4.05356(6)
´
(Å) a = bc 12.59040(18) 12.59240(14) 12.5940(14) 12.59570(12) 12.59560(11) 12.59200(11)
Tetragonality 3.1080 3.1075 3.1067 3.1065 3.1068 3.1064
(R = c/a)
´
Cell volume (Å3) 206.60 206.78 206.94 207.06 207.04 206.90
Uiso 0.84 0.82 0.83 0.86 0.89 0.91
La on 4e (0,0,0.3527) 4.05225(4) 4.04977(5) 4.05454(5) 4.0543(3) 4.05356(11)
Uiso – 0.87 0.85 0.81 0.83 0.94
Sn on 2a (0,0,0) 3.412551(18) 3.40992(2) 3.41409(4) 3.41578(3) 3.3976(15) 3.41497(7)
Uiso 0.82 0.84 0.83 0.89 0.87 0.93
O1 on 4c (0.5,0,0) 4.88039(20) 4.88740(6) 4.87607(13) 4.88183(6) 4.8859(3) 4.88032(19)
Uiso 1.18 1.24 1.45 1.34 1.38 1.31
O2 on 4e (0,0,0.1527) 2.74648(8) 2.74270(2) 2.74879(5) 2.74914(3) 2.7266(15) 2.74849(7)
Uiso 1.08 1.04 1.16 1.05 1.09 1.07
´
Selected bond lengths (Å)
Sn–Sr/La (within perovskite) 3.41255(3) 3.41392(6) 3.41409(5) 3.41578(8) 3.39765(4) 3.41297(2)
Sn-O2 (within perovskite) 1.98349(4) 2.03229(7) 2.04795(3) 2.06378(6) 2.05409(9) 2.01978(5)
Sr–O2 (out of perovskite) 2.45677(6) 2.41535(8) 2.34780(7) 2.31462(5) 2.36370(5) 2.34798(3)
Selected bond angles (in degree)
O2–Sr–O2 (within perovskite) 89.884(3) 89.765(6) 89.636(2) 89.545(4) 89.632(5) 89.716(2)
O2–Sn–Sr (within perovskite) lower edge 122.927(7) 122.828(5) 122.790(8) 122.730(7) 122.960(9) 122.930(4)
O2–Sr–O2 (in layer) 174.860(7) 172.660(5) 170.850(8) 168.570(7) 170.610(9) 174.030(4)
v2 4.17 4.07 5.05 5.16 6.42 8.76
Rp 16.7 11.9 13.7 13.9 25.9 23.2
Rwp 20.4 12.6 16.5 14.0 28.1 26.3
RBragg 3.43270 2.53210 3.15420 3.96978 7.26205 6.59891
Goodness of fit (S = Rwp/Rp) 1.22 1.06 1.20 1.01 1.08 1.13

and size of the sample, etc. In order to separate out these
contributions, it is necessary to collect the additional
diffraction pattern from line broadening of the standard
model such as silicon to determine the instrumental
broadening. Now, the b corresponding to the most intense
peak is estimated using the relation:



b2 ¼ b2 measured  b2 instrumental :
After subtracting the instrumental broadening, the
crystallite size for all samples for a most intense peak has
been calculated using Eq. (5) and is listed in Table 2. From
Table 2, it is observed that the crystallite size of doped
samples is lower than the undoped sample. The La3? at the
Sr2? site of the Sr2SnO4 is a donor; it is reported that donor
doping in perovskite oxides inhibits grain growth and
hence the smaller crystallite size of doped samples agrees
with the literature [30].
Size–strain plot method The crystallite size obtained
using Debye–Scherrer’s method is not accurate because
line broadening may have the contribution of microstrain
also. Therefore, it is reported in the literature that in case of
isotropic line broadening, a better evaluation of the particle
size and strain parameters can be obtained using ‘‘Size–
Strain Plot’’ (SSP) [31]. The advantage of this method is
that it gives less weightage to data of reflections arises from
higher angles, where the precision is lower. According to
size strain plot method, Eq. (6) has been used to calculate
the crystallite size and microstrain of the samples:
   2   
dhkl b cos h 2 kk dhkl b cos h e 2
¼ 2
þ ð6Þ
k D k 2
where dhkl is the interplanar spacing corresponding to the
plane (hkl), e is the average strain produced in the lattice
and the description of the parameters k, b, k and D is same
as described above for Eq. (5) and k is the Scherrer

123
 U. Kumar et al.

(a) 3.1083 (b) 4.055

c/a 12.596

Lattice parameter/a = b Å
3.1080 4.054 12.595

Lattice parameter/c Å
Degree of distortion/R
3.1077 12.594
4.053
3.1074 12.593
4.052
3.1071 12.592
4.051 12.591
3.1068
a = b 12.590
4.050
3.1065 c
12.589
4.049
3.1062
0.00 0.02 0.04 0.06 0.08 0.10
0.00 0.02 0.04 0.06 0.08 0.10
Composition/x
Composition/x

Fig. 6 Variation of a degree of distortion (R) and b lattice parameters with a concentration of La (x)

Table 2 Crystallite size and lattice strain obtained from size–strain plot (SSP) and optical band gap from Tauc plot of the samples
S. no. Sample code Crystallite size (nm) obtained from Strain(e) 9 10-3 Optical band gap/eV
Debye–Scherrer method SSP plot method Direct band gap Indirect band gap

1. S2L0 49.3 51.2 3.00 4.74 4.00

2. S2L1 37.6 39.4 5.95 4.78 3.98
3. S2L2 32.4 31.8 5.98 4.81 3.84
4. S2L4 30.8 30.5 6.27 4.87 3.35
5. S2L6 31.6 33.2 5.90 4.73 3.83
6. S2L10 34.2 35.8 5.45 4.78 3.90

constant = 3/4 for spherical particles. The plot of
 2 2 
dhkl b cos h d b cos h
vs. hkl k2 for three representative samples
k
S2L0, S2L2 and S2L4 are shown in Fig. 7a–c, respectively.
Similar plots were obtained for other samples also.
In SSP plot, the value of crystallite size is determined
from the slope of the linear fitting of the data, and the
square root of the intercept on y-axis gives the value of
lattice strain. The value of crystallite size and lattice strain
obtained from SSP of the samples is presented in Table 2.
Slightly higher values of crystallite size obtained from SSP
method than Debye–Scherrer method are because of Debye
Scherer formula contribution of broadening in the XRD
peaks due to lattice strain was excluded, but it was included
in the SSP method. From Table 2, it is observed that the
value of lattice strain for all the La-doped samples is higher
than undoped. The higher value of lattice strain for doped
samples may arise due to the small ionic radius of the La3?
ion (1.21 Å) in comparison with the Sr2? ion (1.31 Å).
Room temperature Raman spectrum analysis
The Raman spectroscopy is a simple and non-destructive
tool to probe structural information at the single unit cell
level. We have used the Raman technique to study the
incorporation of La3? ions in the lattice of Sr2SnO4 and
detect impurity phases even though present in the trace
amount. The Sr2SnO4 synthesized in this work crystallizes
in the tetragonal with space group D17 4h(I4/mmm) having
two formula units per unit cell [32]. The theoretical mode
analysis according to group theory for tetragonal crystal
structure and with symmetry group D17 4h exhibits maximum
14 bands which are given below:
Coptic ¼ 2A1g þ 2Eg þ 4A2u þ 5Eu þ B2u : ð7Þ
Figure 8 illustrates the room temperature Raman spec-
trum of the samples in the wavenumber range from 100 to
1000 cm-1. The Raman spectrum of Sr2SnO4 is not
available in the literature, since the Sr2TiO4 exhibits sim-
ilar symmetry element, structure, and space group as Sr2-
SnO4. Therefore, Raman spectrum of the undoped and
doped samples has been compared with Raman spectrum
of Sr2TiO4 [32, 33], in this it exhibiting an intense and
broadband at 570 cm-1 assigned to A1g mode. However, in
the Raman spectrum of Sr2SnO4, this band has split into
two bands: one at 561 cm-1 and another at 581 cm-1. The
splitting of the A1g band in Sr2SnO4 is attributed to a large
difference in the bond length of Sn–O in the layer and
perpendicular to the layer (perpendicular to c-axis and
parallel to c-axis). The values of these bond length are 2.02
´
and 1.91 Å for Sr2SnO4, whereas for Sr2TiO4 1.94 and
´
1.93 Å [34]. The two characteristics bands observed at

123
Investigation on phase formation of Sr2SnO4 and effect of La-doping...

(a) (b) (c)

3.0 × 10–5 6.0 × 10–5
S2L0 S2L2 3.0 × 10–5 S2L4
(dhkl β cosθ /λ ) 2

2.5 × 10–5 Linear fitting Linear fitting Linear fitting

(dhkl β cosθ /λ ) 2

(dhkl β cosθ /λ ) 2
5.0 × 10 –5
2.0 × 10–5
2.5 × 10–5
1.5 × 10–5 4.0 × 10–5

1.0 × 10–5
3.0 × 10–5 2.0 × 10–5
5.0 × 10–6

0.0 2.0 × 10–5

1.5 × 10–5
0.000 0.002 0.004 0.006 0.008 0.010 0.0050 0.0075 0.0100 0.0125 0.0150 0.004 0.006 0.008 0.010
(dhkl2β cosθ /λ 2) (dhkl2β cosθ /λ 2) (dhkl2β cosθ /λ 2)

Fig. 7 Size–strain plots (SSP) for the determination of crystallite size and lattice strain

A2u(TO) A1g(LO) S2L0 Fourier transform infrared spectroscopy (FTIR) analysis

Eu(TO)

Fourier transform of Infrared (FTIR) technique has been

employed to study the presence of various functional
A2u(LO)

S2L1
A2u(TO)
Eu(TO)
Eu(TO)

Eu(LO)

B2u groups and the changes in vibrational bands due to the

2nd raman band doping of La3? at the Sr2? site of Sr2SnO4. Therefore,
Intensity/a.u.

S2L2 FTIR spectrum of the synthesized powders has been

200 400 600
Position of raman band/cm–1
Fig. 8 Room temperature Raman spectrum of the prepared samples
561 cm-1 and 581 cm-1 are attributed to the mode A2u
(TO—transverse optical phonon mode) and A1g (LO—
longitudinal optical phonon mode), respectively. On initial
substitution of La3? at the site of Sr2?, the position of these
bands moved toward higher wavenumber side due to the
higher atomic mass of La than Sr. Furthermore, it is noticed
that on increasing doping concentration of La, the spacing
between the modes decreases and finally merges into a
single band for S2L4 (x = 0.04) sample which may be due
to almost equal value of Sn–O2 (2.0727) to Sn–O1(2.0637)
bonds. But for higher doping concentration (x = 0.06 and
0.10), i.e., for samples S2L6 and S2L10 Raman spectrum
again split into two bands as it was for the undoped sample
S2L0. The variation in the position and shape of the bands
for doped samples confirms that substitution of La at Sr site
has been taken place successfully in the lattice of Sr2SnO4.
The absence of bands corresponding to starting materials
La2O3 (250, 350, 440 cm-1), SrCO3 (412 and 592 cm-1),
SnO2 (472 and 632 cm-1), or any other secondary phase
such as SrSnO3 confirms the purity of the synthesized
samples at the local level [35–37].
recorded in the range of 400–4000 cm-1 and depicted in
S2L4 Fig. 9a. In the literature, it is reported that the FTIR
spectrum of layered perovskite, Sr2SnO4 contain two
characteristic bands corresponding to Sr–O and SnO6
S2L6
vibrations at 502 and 726 cm-1, respectively. Doping on
S2L10
either Sr or Sn or simultaneously on both Sr and Sn sites
may bring change in the positions, shape as well as the
800 1000 intensity of the characteristic bands of Sr–O and SnO6
[38, 39]. The enlarged view of band observed at 502 and
726 cm-1 is shown in Fig. 9b, and it is noticed that the
position of band corresponding to Sr–O vibration has
moved approximately 10–12 cm-1 toward higher wave-
length side in case of doped samples which may be due
higher atomic mass of La as compared to Sr, while the
other band observed at 702 cm-1 corresponding to the
stretching mode of SnO6 has not shown any significant
shift in the position on increasing the doping concentration
(x). Therefore, the variation in the shape, position, and the
intensity of peak indicates the incorporation of La into the
lattice of Sr2SnO4.
UV–Visible spectroscopy
The ultraviolet–visible (UV) spectroscopy measurement
has been probed to investigate the optical absorbance of the
undoped Sr2SnO4 and La-doped Sr2SnO4. The room tem-
perature absorbance UV spectrum of the samples was
recorded in the wavelength range 200–800 nm and depic-
ted in Fig. 10. The absorbance edge wavelength has been
determined by extrapolation of linear region on the x-axis.
It is observed that the absorbance edge systematically shift
toward the higher wavelength side (approximately 15 nm)
with increasing the dopant concentration (x) of La. On a

123
 U. Kumar et al.

Fig. 9 a Room temperature (a) (b)

Fourier transform infrared 99

Sn–O
(FTIR) spectrum of the sample S2L10

Sr–O
Sn–O6
b enlarged view of the band

Transmittance/%
98
corresponding to stretching
mode of Sr–O and Sn–O6
97 S2L0
S2L6
S2L1
96 S2L2
S2L6
S2L10

Transmittance/%
S2L2 95
690 720 750 780
Wavenumber/cm–1
98
S2L1
Sr–O

Transmittance/%
96
S2L0

94
BaCO3 -OH group

800 1600 2400 3200 4000 480 510 540

Wavenumber/cm–1 Wavenumber/cm–1

careful observation, it is noticed that in the UV spectrum of
doped samples, a shoulder is present in wavelength range
300–350 nm which may be due to the electronic transition
from d to f shell of La3?. With increasing the dopant
concentration, the position of shoulder also moves toward
the visible region (up to 500 nm) for S2L4 which shows
the incorporation of La into the lattice of Sr2SnO4 [40]. To
the best of authors’ knowledge, no report is available in the
literature on UV spectrum of La-doped Sr2SnO4 solid
solutions. The La3? at the Sr2? site in Sr2SnO4 behaves as
a donor, and its energy levels lie just below the conduction
band. The position of donor level moves toward conduction
1.5 1.5
Absorption/α
band on increasing the concentration of La in solid solu-
tion. This donor can act as trapping level for the electrons
which may bring a shift in the position of absorbance edge
toward visible region. In the literature, similar results have
been reported on lanthanide doped ZnO, La-doped per-
ovskite [41, 42]. In order to estimate the optical band gap,
the optical absorbance data can be analyzed through the
following relation which is formerly known as Tauc
equation;


ðah#Þ1=m ¼ B E  Eg ð8Þ
where a is an absorption coefficient related to the optical
absorbance (A0) and thickness of the sample in the sample


S2L0 holder (d) by the equation; að#Þ ¼ 2:303  Ad0 , B is a

S2L1 dimensionless constant, h is Planck’s constant, # is fre-

1.0 quency of incident photon, and Eg is optical band gap of
S2L2
the material, parameter m decides the nature of transition
1.0 0.5 S2L4
based on the numerical value for example m = 1/2 for band
Absorption/α

S2L6
200 240 280 320 to band transition (direct band gap), while m = 2 leads
Wavelength/nm S2L10 transition mediated through the defect levels (indirect band
0.5 gap). In the band to band transition (direct transition), the
Shoulder total energy of the photon and momentum are conserved.
On the other hand, in transitions mediated through defect
0.0
levels (indirect transitions), the total energy of the photon
is conserved through creation of phonon which results in
200 300 400 500 600 700 800 only conservation of energy not momentum. The Tauc plot
Wavelength/nm is generated using Eq. (8) from the absorbance data of the
Fig. 10 Room temperature UV–Visible absorption spectrum of the samples for both the values of index parameter m = 1/2 and
prepared samples 2 and shown in Fig. 11. The optical band gap (both direct

123
Investigation on phase formation of Sr2SnO4 and effect of La-doping...

and indirect) has been determined through the intercept of
linear region in the Tauc plot on x-axis (Energy) where
y = 0. The value of energy for both the band gap obtained
using this method is indexed in Table 2. From Table 2, it is
noticed that the direct band gap for Sr2SnO4 is 4.70 eV and
the indirect band gap is 4.08 eV. The obtained value of
band gaps are consistent with the values reported in the
literature for Sr2SnO4 [23]. From Table 2, it is noticed that
energy value of direct band gap is increasing with an
increase in the dopant concentration (x) up to x = 0.04 and
thereafter decreases on further increase in the dopant
concentration (for x = 0.06 and 0.10). The two possible
explanations for the change in value of the direct band gap
are: (1) the first explanation is based on the charge com-
pensation mechanism. As it is known, La3? at the Sr2? site
is a donor and charge compensation mechanism can be
represented by Eq. (9) [43];
La2 O3 ! Sr2 SnO4 2La:Sr þ 2e0 þ 3Ox0 : ð9Þ
The formation of donor level (LaSr.) lies below the
conduction band compensated by creation of electron as
shown in Eq. (9), which cause a repulsive force between
donor level and conduction band may be responsible for
increase in the band gap up to x = 0.04. With the increase
in the concentration of La (in case of compositions with
x = 0.06 and 0.10), donor level shifts toward the conduc-
tion band and merges together to form a continuous band
causing decrease in the band gap. Similar results have been
reported on other donor doped oxide materials [44, 45].
(2) The second explanation is based on the Quantum
confinement theory. According to this theory, the holes in
the valance band and electrons in the conduction band are
confined within the potential barrier of the surface or/po-
tential well of the quantum box (crystallite size). With

Direct bandgap S2L0 100 3.5

40 2.5 Direct bandgap S2L1
Indirect bandgap Indirect bandgap 3.0
80
2.0
30 2.5
60
(α hν )2

(α hν )2

1.5 2.0

(αhν )½
(αhν )½

20 1.5
1.0 40
1.0
10
0.5 20
0.5
4.00 eV 4.74 eV 3.98 eV 4.78 eV
0 0.0 0 0.0
2 3 4 5 6 2 3 4 5 6
Energy/eV Energy/eV
80 Direct bandgap S2L2 3.0 Direct bandgap S2L4 3.0
Indirect bandgap 80 Indirect bandgap
2.5 2.5
60
2.0 60
(αhν )½

2.0
(α hν )2

(αhν )½
(α hν )2

40 1.5 40 1.5

1.0 1.0
20 20
0.5 0.5
3.35 eV
3.98 eV 4.78 eV 4.87 eV
0 0.0 0 0.0
2 3 4 5 6 2 3 4 5 6
Energy/eV Energy/eV
12 2.0 100 3.5
Direct bandgap S2L6 Direct bandgap S2L10
Indirect bandgap 3.0
10 Indirect bandgap 80
1.6
2.5
8
60 2.0
(α hν )2

(αhν )½
(α hν )2

1.2
(αhν )½

6 1.5
0.8 40
4 1.0
20 0.5
2 0.4
3.90 eV 4.78 eV
3.83 eV 0.0
4.73eV 0
0 0.0 2 3 4 5 6
2 3 4 5 6
Energy/eV
Energy/eV

Fig. 11 Tauc plot (by putting m = 1/2 for direct band gap and m = 2 for indirect band gap) obtained from absorption data of the samples

123

decreases in the particle size, the confinement width of
electron and holes increases and leads to the increase in the
band gap [46]. In the present system, also as concentration
of dopant La (x) changes, particle size and band gap also
change which may be due Quantum confinement phe-
nomenon. The concept of quantum confinement has
already been used to correlate the change in energy band
gap with the particle size/crystallite size [47].
It has inferred from Table 2 that value of indirect band
gap is lower than the value of direct band gap of the same
composition. The lower value of indirect band gap may be
due to the presence of defects such as oxygen vacancies
(Vxo, V•o and V••
o ), lattice defects and distortion in local bond.
Among the various defects mentioned, the most commonly
found defects in oxides materials are oxygen vacancies (Vxo,
V•o and V••o ) which may generate during calcination at high
temperature (1000 C). Furthermore, it is noticed that the
value of the indirect band gap (see Table 2) decreases with
increasing dopant concentration (x) up to x = 0.04 and
slightly increases for the compositions x = 0.06 and 0.10.
Ganguly et al. [48] had investigated the effect of La-doping
at the site of Ba in BaTiO3, and similar results were found.
Conclusions
The reaction mechanism for the evolution of Sr2SnO4 by
solid-state reaction between SrCO3 and SnO2 has been
investigated using thermal (TG and DSC) combined with
X-ray diffraction (XRD) techniques. It has been affirmed
that the formation of single-phase Sr2SnO4 takes place
through a reaction between SrO (from the decomposition
of SrCO3) and SrSnO3 (from the reaction between SrCO3
and SnO2) at a temperature [ 900 C. Single-phase pow-
der of a few compositions of system Sr2-xLaxSnO4
(x = 0.01, 0.02, 0.04, 0.06 and 0.10) has been successfully
synthesized using solid-state reaction method by calcina-
tion at 1000 C for 8 h. Monophasic natures of the syn-
thesized powder have been further investigated by Rietveld
refinement of the XRD data, Raman and Fourier transform
of infrared (FTIR) spectroscopy. These studies indicated
that solubility of La is higher in Sr2SnO4 (10 atom%) than
its perovskite component SrSnO3 (B 2 atom%). The lattice
parameters of the samples initially increase with doping
concentration (x) up to x = 0.04 and thereafter decreases
for x = 0.06, 0.10. The value of crystallite size and lattice
strain obtained from ‘‘Size–Strain plot (SSP)’’ varies from
30 to 50 nm and (3.00–6.27) 9 10-3. The absorption of
the samples studied from UV–Visible spectroscopy indi-
cates that incorporation of La signifies the shift of
absorption edge toward visible region. Moreover, the
absorption data were further used to determine the value of
direct and indirect band gap of the samples. Increase or/
123
U. Kumar et al.
decrease in the value of direct band gap was found which is
attributed to the change in the charge compensation
mechanism or/decreases in the particle size. These mate-
rials can be used for various optical device applications by
manipulating defects levels as a metastable state.
Acknowledgements The authors are grateful to the Head Department
of Physics and Coordinator, Central Instrument Facility Centre
(CIFC), IIT(BHU), Varanasi, for providing the experimental facilities
required for the characterization of the synthesized samples. One of
the authors Mr. Upendra Kumar is thankful to the Ministry of Human
Resource and Development (MHRD), Government of India, for
financial support in terms of Senior Research Fellowship (SRF).
References
1. Fu WT, Visser D, IJdo DJ. High-resolution neutron powder
diffraction study on the structure of Sr2SnO4. J Solid State Chem.
2002;169(2):208–13.
2. Skinner SJ. Characterisation of La2NiO4?d using in situ high-
temperature neutron powder diffraction. Solid State Sci.
2003;5(3):419–26.
3. Skinner SJ, Kilner JA. Oxygen diffusion and surface exchange in
La2-xSrxNiO4?d. Solid State Ion. 2000;135(1–4):709–12.
4. Gu XK, Nikolla E. Design of Ruddlesden–popper oxides with
optimal surface oxygen exchange properties for oxygen reduction
and evolution. ACS Catal. 2017;7(9):5912–20.
5. Sharma RK, Burriel M, Dessemond L, Bassat JM, Djurado E.
Lan?1NinO3n?1 (n = 2 and 3) phases and composites for solid
oxide fuel cell cathodes: facile synthesis and electrochemical
properties. J Power Sources. 2016;1(325):337–45.
6. Aguadero A, Alonso JA, Escudero MJ, Daza L. Evaluation of the
La2Ni1-xCuxO4?d system as SOFC cathode material with 8YSZ
and LSGM as electrolytes. Solid State Ion.
2008;179(11–12):393–400.
7. Khandale AP, Bhoga SS. Effect of Sr doping on structural,
electrical and electrochemical properties of Nd2CuO4 for IT-
SOFC application. Solid State Ion. 2014;1(262):416–20.
8. Chaker H, Roisnel T, Potel M, Hassen RB. Structural and elec-
trical changes in NdSrNiO4-d by substitute nickel with copper.
J Solid State Chem. 2004;177(11):4067–72.
9. Zhang G, Dong X, Liu Z, Zhou W, Shao Z, Jin W. Cobalt-site
cerium doped SmxSr1-xCoO3-d oxides as potential cathode
materials for solid-oxide fuel cells. J Power Sources.
2010;195(11):3386–93.
10. Zhang Z, Greenblatt M, Goodenough JB. Synthesis, structure,
and properties of the layered perovskite La3Ni2O7-d. J Solid State
Chem. 1994;108(2):402–9.
11. Li CX, Liu S, Zhang Y, Li CJ. Characterization of the
microstructure and electrochemical behavior of Sm0.7Sr0.3-
CoO3-d cathode deposited by solution precursor plasma spraying.
Int J Hydrog Energy. 2012;37(17):13097–102.
12. Hou J, Yin X, Fang Y, Huang F, Jiang W. Novel red-emitting
perovskite-type phosphor CaLa1-xMgM0 O6: xEu3?(M0 = Nb,
Ta) for white LED application. Opt Mater. 2012;34(8):1394–7.
13. Sommer C, Hartmann P, Pachler P, Hoschopf H, Wenzl FP.
White light quality of phosphor converted light-emitting diodes: a
phosphor materials perspective of view. J Alloy Compd.
2012;15(520):146–52.
14. Stanulis A, Sakirzanovas S, Van Bael M, Kareiva A. Sol-gel
(combustion) synthesis and characterization of different alkaline
earth metal (Ca, Sr, Ba) stannates. J Sol–Gel Sci Technol.
2012;64(3):643–52.
Investigation on phase formation of Sr2SnO4 and effect of La-doping...
15. Ropp RC. Luminescence and the solid state. New York: Elsevier;
2013.
16. Weiss R, Faivre R. Préparation et structure de plombates et 32.
stannates alcalino-terreux du type A2BO4. C R Hebd Seances
Acad Sci. 1959;248(1):106–8.
17. Lei BF, Yue S, Zhang YZ, Liu YL. Condensed matter: electronic 33.
structure, electrical, magnetic, and optical properties: lumines-
cence properties of Sr2SnO4: Sm3? afterglow phosphor. Chin
Phys Lett. 2010;27(3):1–4. 34.
18. Ueda K, Yamashita T, Nakayashiki K, Goto K, Maeda T, Furui
K, Ozaki K, Nakachi Y, Nakamura S, Fujisawa M, Miyazaki T.
Green, orange, and magenta luminescence in strontium stannates
with perovskite-related structures. Jpn J Appl Phys.
2006;45(9R):6981. 35.
19. Raj AK, Rao PP, Divya S, Ajuthara TR. Terbium doped Sr2MO4
[M = Sn and Zr] yellow pigments with high infrared reflectance
for energy saving applications. Powder Technol. 36.
2017;15(311):52–8.
20. He B, Gong C, Wang Z, Jia L, Zhao L. Novel, cobalt-free, and
highly active Sr2Fe1.5Mo0.5-xSnxO6-d cathode materials for 37.
intermediate temperature solid oxide fuel cells. Int J Hydrog
Energy. 2017;42(15):10308–16.
21. Skaudzius R, Katelnikovas A, Enseling D, Kareiva A, Jüstel T. 38.
Dependence of the 5D0 ? 7F4 transitions of Eu3? on the local
environment in phosphates and garnets. J Lumin.
2014;31(147):290–4.
22. Udawatte CP, Kakihana M, Yoshimura M. Low-temperature 39.
synthesis of pure SrSnO3 and the (BaxSr1-x)SnO3 solid solution
by the polymerized complex method. Solid State Ionics. 40.
2000;128(1):217–26.
23. Kamimura S, Yamada H, Xu CN. Strong reddish-orange light
emission from stress-activated Srn?1SnnO3n?1: Sm3? (n = 1,
2,!) with perovskite-related structures. Appl Phys Lett. 41.
2012;101(9):091113.
24. Bera J, Rout SK. SrTiO3–SrZrO3 solid solution: phase formation
kinetics and mechanism through solid-oxide reaction. Mater Res
Bull. 2005;40(7):1187–93. 42.
25. Chang C, Mao D, Shen J, Feng C. Preparation of long persistent
SrO2Al2O3 ceramics and their luminescent properties. J Alloy
Compd. 2003;348(1):224–30. 43.
26. Kumar U, Ansaree MJ, Verma AK, Upadhyay S, Gupta G.
Oxygen vacancy induced electrical conduction and room tem-
perature ferromagnetism in system BaSn1-xNixO3 (0 O x
0.20). Materials Research Express. 2017;4(11):116304. 44.
27. Hadjarab B, Bouguelia A, Trari M. Synthesis, physical and photo
electrochemical characterization of La-doped SrSnO3. J Phys
Chem Solids. 2007;68(8):1491–9. 45.
28. Mizoguchi H, Chen P, Boolchand P, Ksenofontov V, Felser C,
Barnes PW, Woodward PM. Electrical and optical properties of 46.
Sb-doped BaSnO3. Chem Mater. 2013;25(19):3858–66.
29. Kumar U, Ansaree MJ, Upadhyay S. Structural and optical
characterizations of BaSnO3 nano-powder synthesized by aque-
ous sol–gel method. Process Appl Ceram. 2017;11(3):177–84. 47.
30. Upadhyay S, Parkash O, Kumar D. Synthesis, structure and
electrical behaviour of lanthanum-doped barium stannate. J Phys
D Appl Phys. 2004;37(10):1483.
31. Kumar S, Basu S, Rana B, Barman A, Chatterjee S, Jha SN, 48.
Bhattacharyya D, Sahoo NK, Ghosh AK. Structural, optical and
magnetic properties of sol–gel derived ZnO: Co diluted magnetic
semiconductor nanocrystals: an EXAFS study. J Mater Chem C.
2014;2(3):481–95.
Venkateswaran U, Strössner K, Syassen K, Burns G, Shafer MW.
Pressure dependence of the Raman modes in Sr2TiO4. Solid State
Commun. 1987;64(10):1273–7.
Burns G, Dacol FH, Kliche G, Konig W, Shafer MW. Raman and
infrared studies of Sr2TiO4: a material isomorphic to (La, Sr)2-
CuO4 superconductors. Phys Rev B. 1988;37(7):3381.
Šepelák V, Becker KD, Bergmann I, Suzuki S, Indris S, Feldhoff
A, Heitjans P, Grey CP. A one-step mechanochemical route to
core–shell Ca2SnO4 nanoparticles followed by 119Sn MAS NMR
119
and Sn Mössbauer spectroscopy. Chem Mater.
2009;21(12):2518–24.
Shi J, Li J, Zhu Y, Wei F, Zhang X. Nanosized SrCO3-based
chemiluminescence sensor for ethanol. Anal Chim Acta.
2002;466(1):69–78.
Zuo J, Xu C, Liu X, Wang C, Wang C, Hu Y, Qian Y. Study of
the Raman spectrum of nanometer SnO2. J Appl Phys.
1994;75(3):1835–6.
Lam DJ, Veal BW, Ellis DE. Electronic structure of lanthanum
perovskites with 3 d transition elements. Phys Rev B.
1980;22(12):5730.
Omeiri S, Rekhila G, Trari M, Bessekhouad Y. Physical and
photoelectrochemical characterizations of Ba2SnO4-d elaborated
by chemical route. J Solid State Electrochem.
2015;19(6):1651–8.
Zhou X, Wang X, Wen J. Optical study of Sr2SnO4: Eu3?
phosphor. Opt Int J Light Electron Opt. 2014;125(14):3454–6.
Pandya A, Joshi KV, Sutariya PG, Menon SK. Thioctic acid
modified gold nanoparticles for highly specific and ultrasensitive
detection of lanthanum in soil and water. Anal Methods.
2012;4(10):3102–6.
Surendar T, Kumar S, Shanker V. Influence of La-doping on
phase transformation and photocatalytic properties of ZnTiO3
nanoparticles synthesized via modified sol–gel method. Phys
Chem Chem Phys. 2014;16(2):728–35.
Thi VH, Lee BK. Effective photocatalytic degradation of parac-
etamol using La-doped ZnO photocatalyst under visible light
irradiation. Mater Res Bull. 2017;96:171–82.
Singh P, Parkash O, Kumar D. Scaling of low-temperature con-
ductivity spectra of BaSn1-xNbxO3 (x B 0.100): temperature and
compositional-independent conductivity. Phys Rev B.
2011;84(17):174306.
Ahmed AS, Singla ML, Tabassum S, Naqvi AH, Azam A. Band
gap narrowing and fluorescence properties of nickel doped SnO2
nanoparticles. J Lumin. 2011;131(1):1–6.
Singh M, Goyal M, Devlal K. Size and shape effects on the band
gap of semiconductor. Mater Sci. 2003;48:521.
Anjum S, Saleem H, Rasheed K, Zia R, Riaz S, Usman A. Role of
Ni2? ions in magnetite nano-particles synthesized by Co-pre-
cipitation method. J Supercond Novel Magn.
2017;30(5):1177–86.
Deepa AS, Vidya S, Manu PC, Solomon S, John A, Thomas JK.
Structural and optical characterization of BaSnO3 nanopowder
synthesized through a novel combustion technique. J Alloy
Compd. 2011;509(5):1830–5.
Ganguly M, Rout SK, Sinha TP, Sharma SK, Park HY, Ahn CW,
Kim IW. Characterization and rietveld refinement of A-site
deficient lanthanum doped barium titanate. J Alloy Compd.
2013;5(579):473–84.
123