Solid State Communications 219 (2015) 25–27

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Solid State Communications

journal homepage: www.elsevier.com/locate/ssc

Strain effect on the Néel temperature of SrTcO3

from first-principles calculations
Chun-Lan Ma a,b,1, Cheng-Min Dai a,b, Gao-Yuan Chen a, Da Chen a, Tao-Cheng Zang a,
Li-Juan Ge a, Wei Zhou c, Yan Zhu c
a
School of Mathematics and Physics, Suzhou University of Science and Technology, Suzhou 215009, PR China
b
State Key Laboratory of Surface Physics and Department of Physics, Fudan University, Shanghai 200433, PR China
c
Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, PR China

art ic l e i nf o a b s t r a c t

Article history: Generalized gradient approximation with on-site Coulomb corrections (GGAþU) method is used to
Received 7 March 2015 investigate the effect of biaxial strain on the Néel temperature of SrTcO3. A series of hypothetical strains
Received in revised form on SrTcO3 are considered to simulate its being applied in SrTcO3-based devices. It is found that a tensile
8 June 2015
strain will decrease TN, while a compressive strain less than 6.6% will increase TN. At a compressive strain
Accepted 16 June 2015
between 5.5% and 6.7%, a highest TN which is about 26.6% higher than that of the bulk material can be
Communicated by J. Fontcuberta
Available online 25 June 2015 obtained. The higher TN can be experimentally achieved by growing SrTcO3 on the common substrate
STO/LSAT/NGO/LAO. Our work provides a theoretical basis for the application of high-TN SrTcO3 in small
Keywords: devices.
A. Transition metal oxides
& 2015 Elsevier Ltd. All rights reserved.
C. Perovskite
D. Néel temperature
E. Strain effect

1. Introduction ensuring strained SrTcO3 in a device being usable in comparatively

The investigation of 4d transition metal oxides (TMO) lags far
behind 3d TMO, since 4d orbitals are much more extended, which
makes them less special. Following the discovery of unconven-
tional superconductivity in Sr2RuO4 [1], SrTcO3 comes into peo-
ple's sight with an unexpectedly high Néel temperature ðT N Þ of
1023 K [2], which is by far the highest magnetic ordering tem-
perature among all the existent 4d TMOs. The bulk properties of
SrTcO3 have been intensively studied [2–9]. However, SrTcO3 will
inevitably experience strain when it is integrated in a device due
to the mismatch between SrTcO3 and other materials. Can strained
SrTcO3 retain high TN property as bulk material? Up to now, no
experimental or theoretical work is performed to investigate this
issue. We examine the strain effect on TN of SrTcO3 from first-
principles method in this paper. SrTcO3 will experience four
structural phase transitions from Pnma, Imma, I4=mcm, to Pm3m
with temperature increasing [3]. The ground state Pnma phase
cannot exist when the temperature is higher than 390 K and the
orthorhombic Imma will be replaced by tetragonal I4=mcm when
the temperature is higher than 625 K. With the motivation of
E-mail addresses: machunlan@126.com (C.-L. Ma),
zhuyankmust@foxmail.com (Y. Zhu).
1
Tel.: þ86 512 68418463.
high temperature, we consider the tetragonal instead of orthor-
hombic phases [3].
2. Crystal structure and computational details
Fig. 1(a) gives the schematic tetragonal crystal structure
containing 20 atoms, with four Tc atoms, in-plane O1 atom
and out-of-plane O2 atom being indicated. The spin combina-
tions of Tc1, Tc2, Tc3 and Tc4 are þ þ þ þ, þ þ   , þ  þ 
and þ   þ for FM, A-AFM, C-AFM, and G-AFM configura-
tions, respectively. Relative to the experimental lattice constant
a¼ b¼5.59374 Å [3], a series of biaxial strains (from 8.0% to 5.0%)
are employed. For each in-plane lattice constant a (a ¼b), various
out-of-plane lattice constant c values are scanned for the total
energies calculations to determine the ground state. The computa-
tions are carried out by the projector augmented wave (PAW)
method [10,11], as implemented in the Vienna ab initio simulation
package (VASP) [12]. The exchange correlation potential of Per-
dew–Burke–Ernzerhof form [13] is used. The rotationally invariant
on-site Coulomb correlation corrections LSDA þU method accord-
ing to Liechtenstein [14] is employed in GGA þU calculations
(U¼2.3 eV, J¼ 0.3 eV) [5,9]. A k mesh of 8  8 6 is used and
the plane-wave cutoff energy is 500 eV. The magnetic exch-
ange constants are calculated according to Heisenberg model

http://dx.doi.org/10.1016/j.ssc.2015.06.015
0038-1098/& 2015 Elsevier Ltd. All rights reserved.
26 C.-L. Ma et al. / Solid State Communications 219 (2015) 25–27

Fig. 1. (Color online) (a) Magnetic cell of SrTcO3 with four formula units (f.u.). The space group is I4/mcm. The abc coordinate denotes the conventional coordinate system,
based on which the xyz coordinate is obtained by rotating 451 around the z-axis. The x/y direction is along Tc–O–Tc direction. O1 denotes the ab-plane oxygen and O2
denotes the apical oxygen along the c-axis. (b) The total energies as a function of the in-plane lattice constant a for various magnetic phases (shown by the y-axis on the left),
and the calculated structural parameter c as a function of the in-plane lattice constant a (shown by the y-axis on the right).

30
20 Jab 1600 TN
10 Jc
1400
Jab and Jc (meV)

0
-10
*
TN(K)

1200
-20
-30
1000
-40
-50 800
-60
-70 600
5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9
o o
Lattice Constant a (A) Lattice Constant a (A)
Fig. 2. (Color online) (a) The exchange coupling constant Jab/Jc between the neighboring antiferromagnetic Tc atoms as a function of in-plane lattice constant a. (b) The Néel
temperature TN as a function of a.

P , , , , lowest total energies. The lattice parameters a and c for bulk

H ¼  i;j J i;j Si  Sj as follows. The sign of spin–spin interaction Si  Sj
is dependent on the magnetic configurations. The coupling con-
stant J i;j between nearest neighboring (NN) Tc atoms mediated by
O atom is defined as Jc or Jab (Jc is the exchange integral along the
c-axis and Jab is along the x-axis or the y-axis, i.e., in the ab-plane)
[8,9]. Assume that the total energies of FM, A-AFM and G-AFM
SrTcO3 with a unit cell containing 20 atoms shown Fig. 1(a) are
EFM ; EAAFM and EG  GFM , respectively. We would have EFM ¼
   
4  2J ab S2 þJ c S2 ; EAAFM ¼  4  2J ab S2  J c S2 , and EGAFM ¼
 
4  2J ab S2 þ J c S2 , where S ¼ 3=2 due to d3 for Tc4 þ . The exchange
integral can thus be obtained by J c ¼  ð1=8S2 ÞðEFM  EAAFM Þ and
J ab ¼ ð1=16S2 ÞðEAAFM  EGAFM Þ. According to the mean field
P (corresponding to a compressive strain of 6.7%), the absolute value
theory, 3kB T N ¼ SðS þ 1Þ J s [15], where kB is the Boltzmann
constant and Js is the exchange constant of one Tc with its NN
neighbors. For G-AFM SrTcO3, each Tc has ð2J ab þ J c Þ. Therefore,
T N ¼  5  ð2J ab þ J c Þ=4kB .
3. Results and discussion
Fig. 1(b) shows the total energies of the unit cell (shown Fig. 1
(a)) with various magnetic phases and the out-of-plane lattice
constant c as a function of in-plane lattice constant a. It is observed
that for all of the strained epitaxial films, G-AFM phase has the
SrTcO3 are found to be 5.683 Å and 8.041 Å, respectively. The
calculated equilibrium lattice constant a(c) is about 1.6% (1.5%)
larger than the experimental one, which is consistent with
common trend that GGA þU method usually overestimates the
lattice constant within 2% [16–19].
The exchange constant is calculated based on the calculated
total energies for different magnetic configurations (FM, A-AFM
and G-AFM). Fig. 2(a) shows the evolution of J ab ðJ c Þ with the
lattice constant a. For the bulk tetragonal SrTcO3, at the equili-
brium lattice parameter a indicated by vertical pink line, Jab and Jc
are found to be  25.1 meV and 36.5 meV, respectively, which
are very close to the values for orthorhombic SrTcO3 [8,9]. When
the lattice parameter a of the unit cell is larger than 5.3 Å
of Jab decreases with the increase of lattice constant a monoto-
nously. The absolute value of Jc increases with lattice constant a
monotonously when a 4 5.37 Å (corresponding to a compressive
strain of 5.5%). Above the equilibrium lattice parameter a, the
epitaxial films experience tensile strains. The absolute value of Jab
(J c Þ decreases (increases) with a more tensile strain. The phenom-
ena can be explained as follows. When the strain becomes more
tensile, the distance between the neighboring Tc atoms in the ab-
plane largens while the distance between the neighboring Tc
atoms along the c direction shortens (see Fig. 1(b)). In terms of
compressive strain relative to the theoretical equilibrium lattice
parameter, when the strain is less than 6.7%, the absolute value of
 C.-L. Ma et al. / Solid State Communications 219 (2015) 25–27
J ab ðJ c Þ increases (decreases) with a more compressive strain.
When the compressive strain is larger than 6.7%, an abrupt change
of the trend is observed. Fig. 2(b) shows the evolution of Néel
temperature as a function of the in-plane lattice constant a. The
calculated TN for the bulk SrTcO3 at the equilibrium lattice constant
ða ¼ 5:683 Å Þ is 1257 K (indicated by a pink star), which is 23%
larger than the experimental value of 1023 K. The overestimation
of T N is due to the neglect of fluctuations in mean field theory [20].
The error falls in the scope of 33% from quantum fluctuations
[21,22]. For all the tensile strain epitaxial films ða 4 5:683 Å Þ, TN
decreases compared to the bulk material. A compressive strain
smaller than 6.7% can increase TN. When the compressive strain is
between 5.5% and 6.7%, TN approaches a maximum value around
1592 K, which is 26.6% higher than the theoretical TN 1257 K of the
bulk material. When the compressive strain is further increased,
TN dropped rapidly, shown Fig. 2 (b). High-performance epitaxial
oxide films can be grown on [001]-oriented oxides substrates,
such as LaAlO3 (LAO), La0.3Sr0.7Al0.35Ta0.35O9 (LSAT), NdGaO3
(NGO), and SrTiO3 (STO) [19]. Considering the experimental lattice
parameter a is 5.59374 Å for the tetragonal SrTcO3, epitaxial film of
SrTcO3 strained on STO/LSAT/NGO/LAOpwould ffiffiffi experience a com-
pressive strain of 1.3%/2.2%/2.4%/4.1%( 2a0 is compared with a
cubic lattice constant a0 3.905 Å/3.868 Å/3.861 Å/3.793 Å for STO/
LSAT/NGO/LAO). From our theoretical prediction of T N evolution
with strain, one can estimate that the T N of the epitaxial films
strained on the common substrate STO/LSAT/NGO/LAO is 1330 K/
1400 K/1410 K/1530 K, which is 5.8%/11.4%/12.2%/21.7% higher
than that of the bulk tetragonal SrTcO3. Our work suggests that
SrTcO3 epitaxial films strained on the common oxide substrates
have even higher T N than the bulk material.
4. Conclusions
Strain effect on Néel temperature of SrTcO3 is explored from
first-principles calculations. It is found that SrTcO3 epitaxial film
under a compressive strain (less than 6.6%) has an even higher TN.
The maximum TN is 26.6% higher than that of the bulk material.
The TN of SrTcO3 film strained on the common substrate STO/LSAT/
NGO/LAO is 5.8%/11.4%/12.2%/21.7% higher than that of the bulk
27
SrTcO3. Our work provides a theoretical basis for the application of
high-T N SrTcO3 in small devices.
Acknowledgments
This work is supported by National Natural Science Foundation
of China (Grant nos. 11247023, 11304218 and 61405135), the NSF
of Yunnan Province with Grant no. 2011FZ051, the Opening Project
Fund of Fudan University (No. KF2012_03), Jiangsu Qing Lan
Project, and Jiangsu Overseas Research and Training Program.
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