Materials Letters 227 (2018) 100–103

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Studies on dielectric and electrical properties of Ruddlesden-Popper

oxide Sr2SnO4
Upendra Kumar, Shail Upadhyay ⇑
Department of Physics, Indian Institute of Technology, (Banaras Hindu University), Varanasi 221005, India

a r t i c l e i n f o a b s t r a c t

Article history: Ruddlesden Popper (RP) oxide Sr2SnO4 has been synthesized via a solid state reaction route by calcination
Received 5 April 2018 at 1000 °C for 8 h. The Rietveld refinement of X-ray diffraction (XRD) pattern suggested tetragonal struc-
Received in revised form 7 May 2018 ture; I4/mmm space group and unit cell parameters a = b = 4.05084(5) Å, c = 12.59040(2) Å. Dielectric
Accepted 9 May 2018
properties, electric modulus and ac conductivity have been studied as a function of both frequency
Available online 10 May 2018
(20 Hz–2 MHz) and temperature (70–600 °C) in air atmosphere. Dielectric constant and dissipation factor
remains constant upto 600 °C above 1 KHz. AC conduction mechanism has been explained using
Keywords:
Johnscher’s Power law. The value of the activation energy for conduction, Econd (obtained from DC conduc-
Sr2SnO4
Ruddlesden Popper
tivity) and dielectric relaxation, Erelax (obtained from modulus) is found to be the same indicating similar
Dielectric mechanism for both the processes. Based on the numerical value of activation energy, the conduction and
Conductivity relaxation processes are attributed to transfer of electron from Sn2+ to Sn4+ through the thermally
assisted quantum mechanical tunneling process.
Ó 2018 Elsevier B.V. All rights reserved.

1. Introduction Strontium orthostannate (Sr2SnO4) has an ordered tetragonal

K2NiF4-type structure with space group I4/mmm; lattice parame-
Ruddlesdon Popper (RP) phase having chemical formula; ters of a- and c-axis are 4.052 Å and 12.58 Å [5], respectively. Rare
wherenisan; where n is an integer, for example, n = 1 corresponds earth element (Eu, Sm, Nd, Tb, Dy) doped Sr2SnO4 solid solutions
to A2BO4 etc. [1]. The A2BO4 structure consists stacking of have shown exciting optical emission properties [6]. On the other
perovskite (ABO3) layer and rock salt (AO) layer alternating along hand, terbium (Tb) doped strontium orthostannates system has
c-axis. A2BO4 based mixed ionic-electronic conductors (MIECs) been investigated as yellow pigments with high infrared reflec-
have received interest due to their high thermal stability, high oxy- tance used energy saving applications [7]. To the best of the
gen diffusion coefficient, excellent electronic conductivity and author’s knowledge, no report is available in the literature on
strong electrocatalytic activity towards Oxygen Reduction Reaction dielectric and conduction properties of Sr2SnO4. Therefore, in this
(ORR) [2]. Mixed oxide ion and electron conducting ceramic mate- report dielectric relaxation and electrical conduction mechanism
rials A2BO4+d (where A = La3+, Nd3+ or Pr3+ and B = Cu2+/3+, Ni2+/3+ or have been studied. These studies have importance for exploring
Co2+/3+) have attracted attention for intermediate-temperature new applications of Sr2SnO4 as well as for the basic knowledge of
solid oxide fuel cell (IT-SOFC) cathodes, ceramic membranes for solid state physics.
oxygen separation as well as applications involving partial
oxidation of light hydrocarbons [3]. The oxygen stoichiometry in
La2NiO4+d compounds can be accomplished either by partial substi- 2. Experimental
tution of alkaline earth (Sr, Ba, Ca) at La site or transition metals
(Cu and Co) at Ni site [4]. During the last decade optical properties Powder of Sr2SnO4 has been synthesized by solid state reaction
of alkaline earth orthostannates, M2SnO4 (M: Ca, Sr, Ba) have been route, using raw materials SrCO3 and SnO2 (Alfa, 99.99%) through
extensively investigated and projected as new phosphors materials ball milling (Retsch PM 200) process. In order to ascertain calcina-
because of their stable crystalline structure and high physical and tion temperature, TG/DSC (Mettler Toledo) analysis of the prepared
chemical stability. mixture has been performed. Based on the results of TG, the mix-
ture was calcined at 1000 °C for 8 h. The phase identification of
the sample was studied by employing X-ray diffractometer (Rigaku
⇑ Corresponding author. Miniflex II Desktop, Japan). Calcined powder was pelletized and
E-mail address: [Link]@[Link] (S. Upadhyay). sintered at 1200 °C for 12 h. Initially, the pellets were heated

[Link]
0167-577X/Ó 2018 Elsevier B.V. All rights reserved.
 U. Kumar, S. Upadhyay / Materials Letters 227 (2018) 100–103 101

slowly at a rate of 2 °C/min to 200 °C. They were maintained at this Sn4þ þ 2e0 $ Sn2þ ð3Þ
temperature for 1 h to burn off the binder. After this, the pellets
The presence of these defects was confirmed by the XPS tech-
were heated at a rate of 5 °C/min to the sintering temperature.
nique. XPS spectrum of sample is depicted in Supplementary file.
The pellets were cooled at a rate of 5 °C/min upto 600 °C. The bulk  00
density (db) of the samples was obtained using the Archimedes’s Sn2+ at Sn4+ site is a defect represented by Sn2þ and form
h 00 i Sn4þ
::
principle. The theoretical density (dth) of the pellets was calculated dipoles like Sn2þ
Sn4þ
 V O [8]. These dipoles can change their ori-
from the molecular weight and the lattice parameters. The % poros-
h i entation either by hopping of electrons from Sn2+ to Sn4+ or by
ity was calculated using the formula; % porosity ¼ dthddb  100. jumping of oxygen into the vacant sites [Vo  ].
th

The % of porosity is found to be less than 10%. The micrograph of In order to get a deep understanding about dielectric properties,
the freshly fractured gold-coated surfaces of the sample was electric modulus formalism has been used. The variation of real
recorded using High Resolution Scanning Electron Microscope (M0 ) and imaginary (M00 ) parts of modulus against frequency at var-
(ZEISS EVO-18). Electrical properties of the silver-coated pellets ious temperatures are shown in Fig. 2(c). At lower frequencies the
were measured using a high precision LCR meter (Agilent – 4980A). M0 (f) approaches zero suggest the negligible effect of electrode
polarization [9]. The dispersion in the mid frequency region is
3. Results and discussion related to conductivity relaxation and asymptotic value at higher
frequencies to the mobility of charge carrier. According to the
Fig. 1(a) shows the thermal analysis of the mixture of raw mate- Kohlrauch-Williams-Watts (KWW) model [9], M00 is expressed as
rials. TG curve exhibits a weight loss 19% in the temperature follows;
range 700–970 °C, assigned to decomposition of SrCO3 into SrO. M 00 max:
The derivative of thermogravimetric (DTG) curve was generated M00 ¼     b  ð4Þ
b
from the TG data. The maximum weight loss and presence of an ð1  bÞ þ 1þb b f max
f
þ f f
max
endothermic peak in DSC curve around 937 °C may be due to the
reaction between raw materials to form Sr2SnO4, as given below; where M00max is the maximum value of M00 , f max is the frequency cor-
2SrO þ SnO2 ! Sr 2 SnO4 ð1Þ responding to M00max and b is KWW parameter. The experimental
data points of M00 (f) vs. log f plot (shown in Fig. 2(c)) has been fitted
Based on the TG results, the mixture of raw materials was cal-
to the Eq. (4) to extract value of parameters f max , M00max and b at dif-
cined at 1000 °C. Fig. 1(b) depicts X-ray diffraction (XRD) pattern
ferent temperatures. The variation of KWW parameter (b) with
of calcined powder. All the peaks present in the XRD pattern are
temperature is shown in Fig. 2(d), the value of b remains almost
well matching with peaks present in the crystallographic open
equal to 1; suggests Debye type relaxation process in the sample
database (COD) ID- 1539931 for Sr2SnO4. Rietveld refinement of
which also evident from Nyquist plot, i.e. (M00 ) versus (M0 ) plot
the XRD profile confirmed tetragonal crystal structure, space group
and shown in the inset of Fig. 2(d). In the Nyquist plot, single perfect
I4/mmm and cell parameters a = b = 4.05084(5) Å and c = 12.59040
semicircle (center lying on the real (M0 ) axis is observed confirming
(2) Å consistent with the values reported in the literature [1,5]. The
single relaxation process. The scaling of M00 (f) axis with M max and
crystal structure of refined sample generated from CIF file using
f- axis with f max at various temperatures and shown in Fig. 2(e).
VESTA software and micrograph of the freshly fractured surface
Variation of log f max against 1000/T is shown in Fig. 2(d). The calcu-
of the sintered pellet shown in the inset of Fig. 1(b). Grains of Sr2-
lated value of the activation energy ðErelax Þ from this plot is shown in
SnO4 are spherical in shape with average size 186 nm with dense
inset of Fig. 2(d). The overlapping of curves obtained at different
microstructure.
temperatures on a single master curve suggests that relaxation
Variation of dielectric constant and dissipation factor with tem-
mechanism is same at all the temperatures.
perature is shown in Fig. 2(a) and (b), respectively. The dielectric
Fig. 3(a) depicts the frequency dependence of the real part of ac
constant remains almost constant with increasing temperature
conductivity at various temperatures, which follows universal
while it decreases with increasing frequencies. Similar nature of
Johnscher’s power law [9–11]. The value of dc conductivity (rdc ),
temperature variation is observed for dissipation factor. In this
work Sr2SnO4 has been synthesized at high temperature, therefore power exponent (n) and hopping frequency (f H ) were obtained
defects such as Vo  and Sn2+ may induce during the sintering pro- by fitting Johnscher’s power law to the experimental data points.
cess according to below equations; The variation of dc conductivity with 1000/T is shown in Fig. 3
(b). The activation energy for conduction (Econd ) and relaxation
1 (Erelax ) [Fig. 2(d)] is almost equivalent. Therefore, it seems that
Oo ¼ O2 ðg Þ þ V ::o þ 2e0 ð2Þ
2 the origin of dielectric relaxation and conduction is same i.e. via

Fig. 1. (a) TG (thermogravimetric)/DTG (derivative TG)/DSC (Differential scanning calorimetry) curve of prepared mixture. (b) Rietveld refinement of XRD data (inset shows
crystal structure and microstructure of Sr2SnO4).
102 U. Kumar, S. Upadhyay / Materials Letters 227 (2018) 100–103

Fig. 2. Variation of (a) Dielectric constant (b) Dissipation factor (c) real and imaginary plot of modulus fitted by Eq. (4) (d) KWW parameter (inset shows Arrhenius plot and
Nyquist plot), with temperature (e) Scaled Modulus against scaled frequency at various temperatures of Sr2SnO4.

Fig. 3. (a) Logarithmic conductivity with logarithmic frequency (fitted with power law) (b) Arrhenius plot (c) Power exponent (n) with temperature (d) TTSP plot for Sr2SnO4.

transfer of electrons from Sn2+ to Sn4+. The variation of power Mechanical Tunneling of the electron model is the most suitable
exponent n against temperature is shown in Fig. 3(c) remains model for explaining the AC conduction mechanism. Hence it is
almost constant in the investigated temperature range. In litera- proposed that transfer of electrons from Sn2+ to Sn4+ site is taking
ture various models have been proposed for the AC conduction place via thermal assisted quantum mechanical tunneling process
mechanism [9]. Among the various models, the Quantum [12]. The measured conductivity of the sample has been scaled as
 U. Kumar, S. Upadhyay / Materials Letters 227 (2018) 100–103 103

r=rdc , frequency as ðf =f H Þ and plotted in Fig. 3(d). The overlap of financial support in terms of Senior Research Fellowship (SRF) for
the conductivity data at different temperatures on a single master doctoral programmes.
curve follows time, temperature superposition (TTSP) principle
which indicates the source of conduction at different temperatures Appendix A. Supplementary data
follows similar mechanism.
Supplementary data associated with this article can be found, in
4. Conclusions the online version, at [Link]

RP oxide Sr2SnO4 synthesized in this work has a tetragonal References

structure with space group 14/mmm, lattice parameters
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(2018) 158–161.
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of the activation energy obtained for relaxation ðErelax Þ and conduc- [6] R.C. Ropp, Luminescence Solid State Elsevier, Science (2004).
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[8] Bingcheng Luo, J. Appl. Phys. 122 (19) (2017) 195104.
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Acknowledgments

Mr. Upendra Kumar is thankful to the Ministry of Human

Resource and Development (MHRD), Government of India for