Chemical Physics Letters 402 (2005) 491496

www.elsevier.com/locate/cplett

Theoretical analysis of the structural deformation in Mn-doped

BaTiO3
J.R. Sambrano

a,*

, E. Orhan b,*, M.F.C. Gurgel c, A.B. Campos b, M.S. Goes d,

C.O. Paiva-Santos d, J.A. Varela b, E. Longo c

a
Laboratorio de Simulacao Molecular, Depto. de Matematica, Unesp -Universidade Estadual Paulista, C.P. 473, 17033-360 Bauru, Brazil
Laboratorio Interdisciplinar em Ceramica, Depto de Fsico-Qumica, Instituto de Qumica, Unesp - Universidade Estadual Paulista, C.P. 355,
14800-900, Araraquara, Brazil
c
Laboratorio Interdisciplinar de Eletroqumica e Ceramica, Depto de Qumica, Universidade Federal de Sao Carlos, C.P. 676,
Sao Carlos 13565-905, SP, Brazil
Laboratorio Computacional de Analises Cristalogracas e Cristalinas, Depto Fsico-Qumica, Instituto de Qumica, Unesp - Universidade Estadual
Paulista, C.P. 355, 14800-900, Araraquara, Brazil
b

Received 18 November 2004; in nal form 10 December 2004

Available online 8 January 2005

Abstract
An alternative theoretical method to simulate the structural deformation induced by Mn-doping in BaTiO3 is proposed. The periodic quantum-mechanical method is based on density functional theory at B3LYP level. The structural models were obtained from
Rietveld renement of the undoped and Mn doped BaTiO3 X-ray diraction data. This modelization gives access to the dopant
general eect on the electronic structure. In fact, the inuence of the doping element itself on the electronic conguration is barely
local; therefore, it is not included in the simulation. The simplicity of the model makes it available for working within a wide range of
materials.

2004 Published by Elsevier B.V.

1. Introduction
The ATiO3 titanates perovskites (A = Pb, Ca, Sr and
Ba) have attracted considerable attention in the last
years because are interesting semiconductor materials
[13] with active optical properties such as electroluminescence and photoluminescence (PL) at low temperature and thus may be used as new optoelectronic
devices with superior performance [1,47].
Due to their high technological interest, titanates perovskites are also the focus of numerous theoreticalcomputational studies. Often based on ab initio calculations,

Corresponding authors. Fax: +55 143 103 6096 (J.R. Sambrano).

E-mail addresses: sambrano@fc.unesp.br (J.R. Sambrano), emmanuelle.orhan@liec.ufscar.br (E. Orhan).
0009-2614/$ - see front matter
2004 Published by Elsevier B.V.
doi:10.1016/j.cplett.2004.12.084

they can provide important informations regarding the

electronic and structural properties of solids and the
interpretation of experimental data [810]. Jiang and
co-workers [11] presented the dierent ferroelectric
behaviors of ATiO3 on the basis of theoretical and
experimental techniques. Meyer et al. [12] have performed plane-wave calculations within density functional theory (DFT) using ultrasoft pseudopotentials
for (0 0 1) surfaces of the cubic perovskite ATiO3 compounds. Recently, Zhang et al. [13] have carried out a
theoretical work based on rst principles study of bulk
barium titanate, in the core-level spectra, under scissor
approximation (FLAPW-SAT) and they manage to explain the optical properties.
Ab initio studies of ATiO3 compounds thus can be
performed by dierent methods without many problems and can explain satisfactorily the experimental

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J.R. Sambrano et al. / Chemical Physics Letters 402 (2005) 491496

results. However, if a dopant is introduced in the compound, its properties are dramatically changed and the
ab initio simulations become far more complicated. The
doping of titanate perovskites with several kinds of
transition metals is widely performed because of the
great range of peculiar properties it allows to tune in
elds as diverse as electrical, optical, structural, and
mechanical properties. Recently, Salehi et al. [14] carried out a detailed study of the electronic structure of
Ni-doped BaTiO3 powder using FP-LAPW method.
They used the Large Unit Cell (LUC) approach
[15,16] with 40 atoms in their periodic model. The main
problem of this kind of approach is to achieve a dopant
molar concentration close to the experimental one, for
avoiding a superestimation of its eect. An exaggerated
dopant concentration in the calculation acts as a mask
on the electronic structure and hides the intrinsic properties of the host lattice.
In the present work, an alternative methodology to
characterize the eects of Mn-doping upon structural
and electronic properties of barium titanate (BT) powders is proposed. A periodic quantum-mechanical
method based on DFT theory at B3LYP level has been
used. The models are taken from a Rietveld renement
of the BaTiO3 X-ray diraction data. The structural
deformation induced by the presence of dopant is taken into account in the simulation, giving access to
its general eect on the electronic structure. The inuence of the doping element itself on the electronic conguration is barely local. Therefore, it is not included
in the simulation, avoiding the use of a LUC, which requires a huge computational resources and most of all,
guarantying that the eect of the dopant is not overestimated. In this approach, it is important to control all
the synthesis parameters in order to ensure the continuity and coherence of the Rietveld renement data. In
the following we are thus detailing the synthesis pro-

Table 1
Rietveld agreement indexes at the end of the renements
Agreement indexes

BT

BT:Mn

Rwp
R2F
v2

11.33%
4.10%
1.53

11.48%
3.99%
1.52

cess, the Rietveld renement results and the computational simulation of a pure BT and a Mn-doped BT
powders.

2. Experimental and Rietveld renements

The following discussion concerns two dierent powders, both synthesized by the polymeric precursors method [17,18], one with pure BaTiO3 stoichiometry and the
other one containing 0.01 mol% of manganese oxide.
X-ray diraction data were obtained in a Rigaku
RINT2000 diractometer in the step scan mode
(D2h = 0.02, 20 6 2h 6 120) using copper radiation
monochoromatized by a graphite crystal. The tube power
was 42 kV 120 mA, with divergence slit = 0.5 mm and
receiving slit = 0.30 mm.
The Rietveld renements [19] were carried out with
the program GSAS [20]. The peak prole function was
modeled using the convolution of the Thompson-CoxHastings pseudo-Voigt (pV-TCH) with the asymmetry
function described by Finger et al. [21]. The strain
anisotropy broadening has been corrected by the phenomenological model described by Stephens [22].
Table 1 contains renement indexes for the pure and
Mn-doped BT. The R indexes are dened by Larson and
Von Dreele [20]. The rened cell parameters, tetragonal
distortion c/a and atomic fractional coordinates are presented in Table 2, in the next section. The full width at

Table 2
), tetragonal distortion c/a, volume (A
3) and atomic fractional coordinates obtained by Rietveld renement for pure BT and
Cell parameters (A
Mn-doped BT (exp.) and by theoretical optimization for BT (Theo.)

Model designation
a=b
c
c/a
V
Ba (x,y,z)
Ti (x,y,z)
O1 (x,y,z)
O2 (x,y,z)
a TiO1
b TiO2
c BaO1
d BaO2
e BaO2

BT (exp.)

Mn-doped BT (exp.)

BT (Theo.)

BTExp
4.00099(6)
4.02636(9)
1.006
64.454(2)
(0.0 0.0 0.0)
(0.5 0.5 0.484(1))
(0.5 0.5 0.012(7))
(0.5 0.0 0.508(6))
1.90
2.00
2.83
2.86
2.81

BT:MnExp
4.00021(5)
4.02671(9)
1.007
64.434(2)
(0.0 0.0 0.0)
(0.5 0.5 0.482(2))
(0.5 0.5 0.027(6))
(0.5 0.0 0.473(3))
1.83
2.00
2.83
2.91
2.76

BTTheo
3.98046
4.02646
1.012
63.795
(0.0 0.0 0.0)
(0.5 0.5 0.5)
(0.5 0.5 0.0)
(0.5 0.0 0.5)
2.01
1.99
2.83
2.81
2.81

The ae atomic distances are dened in Fig. 2.

J.R. Sambrano et al. / Chemical Physics Letters 402 (2005) 491496

1.0
BT
Fit BT

0.9
0.8

Mn-doped BT
Fit Mn-doped BT

FWHM

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0

20

40

60

80

100

120

140

2
Fig. 1. FWHM for the pure and doped BT.

half maximum (FWHM) for both materials are plotted

on Fig. 1.

3. Computing method and periodic models

Periodic ab initio quantum-mechanical calculations
performed with the B3LYP hybrid functional [23,24]
have been carried out by means of the CRYSTAL 98 computer code [25]. This functional has already been successfully employed in studies of the electronic and
structural properties of the bulk and surfaces of various
compounds [26], and in particular PbTiO3 [27] and
Ba0.5Sr0.5TiO3 [28] systems. The atomic centers have
been described by all electron basis sets 9763311(d631)G for Ba [29], 86-411(d31)G for Ti and
6-31G* for O atoms [30].
Barium titanate crystallizes in three possible structures, cubic, tetragonal and rhombohedral [11]. In this
work, we focus on the tetragonal structure (space group
P4 mm) following the experimental results. In this structure, the Ba atom is coordinated by 12 oxygen atoms
and the Ti with six oxygen atoms, in an elongated octahedral conguration (see Fig. 2). The cell and atomic

Fig. 2. BT crystalline structure.

493

position parameters used in the calculations are taken

from the results of Rietveld renements, both for the
pure BT and for the Mn-doped experimental structures.
For comparison purpose, an optimization of the cell
parameters has been performed and another model has
been created using those theoretical parameters and
the perfect atomic positions. The Nelder-Mead external algorithm has been used for this purpose [27]. This
third model represents the BT crystal as it should be
at 0 K, i.e., with an ideal structure (Table 2).
They will be designed as BTExp, BT:MnExp and
BTTheo, respectively. This modeling methodology aims
to make out the eect of doping on the crystalline structure and not the direct contribution of the Mn atom on
the electronic properties, therefore the Mn atom was not
inserted in the second periodic model.

4. Discussion
The Rietveld renements show that the presence of
Mn induces slight variations in the cell parameters: a decrease of the a and an increase of c lattice parameter,
thus leading to a small increase of the tetragonal distortion from c/a = 1.006 to c/a = 1.007. The small increase
of the tetragonal distortion leads to a higher deformation of the TiO6 octahedra in Mn-doped BT. The introduction of manganese increases the disorganization of
the crystal.
On Fig. 1 are the FWHM curves for the pure and
Mn-doped BT, and we can see that at low angles the
broadening is the same for both materials, indicating
that the crystallite sizes are the same for them. At high
angles, the broadening is larger for the pure material,
indicating that the microstrains for this material are
bigger.
Fig. 3 represents the band structure for the BTExp,
BT:MnExp and BTTheo models. Table 3 gathers the calculated and experimental optical gaps, Fermi energies and
relative energies.
Our calculation yields an indirect bulk band gap of
3.48 eV for BTExp, in good agreement with the experimental optically measured gap of pure BT powder,
3.06 (this work) and 3.2 eV [31]. The top of valence
(VB), coincident with the origin, is located at A point.
Zhang and co-workers [13] have calculated a small
direct band gap of 1.98 eV in their rst-principles calculations under scissors approximation.
For the BT:MnExp model, the calculated band gap
energy, also indirect between A and C points, is
3.55 eV. This value is in accordance with the optically
measured one, 3.39 eV. Our models, based on experimental data, are consistent with the optical band gap
augmentation linked to the presence of dopant. The
presence of dopant somehow reinforces the chemical
bonds strength. The dierence in total energy between

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J.R. Sambrano et al. / Chemical Physics Letters 402 (2005) 491496

Fig. 3. Band structure for the (a) BTExp, (b) BT:MnExp and (c) BTTheo models.
Table 3
Calculated and experimental optical gaps, Fermi energies and relative
energies (in eV) for the BTExp, BT:MnExp and BTTheo models
BTExp
Fermi energy
CC gap
AC gap
Exp. optical gap
Relative energy

42.86
3.77
3.48
3.06
0.04

BT:MnExp
42.75
3.81
3.55
3.39
0.26

BTTheo
42.88
3.59
3.49

0.00

The experimental optical band gap energy has been extracted from
UVvisible absorption spectra by the Wood and Tauc method [33].

the two structures is 0.22 eV, the BTExp model being the
more stable of the two experimental models.
The top of VB and the bottom of conduction band
(CB) for BTTheo model are located at A and C points,
respectively, as for the two experimental models. The
calculated indirect band gap energy is 3.49 eV. The total
energy of this ideal model is only a little bit lower than
the total energy of BTexp model. The dierence between
the two is 0.04 eV.
An analysis of the density of states (DOS) curves
shown in Fig. 4, indicates that for the three models,
the VB is made of the 2p levels of the oxygen atoms.
The CB is composed of the dierent Ti 3d AOs. Those
contributions will be described in more details in the
next paragraph. The Ba 6p levels are found at 12 eV,
very sharp indicating the strongly ionic character of
the BaO bond. Although the BT:MnExp exhibits one

, distance e in Table 2 and

short BaO distance (2.76 A
Fig. 2), the position and shape of the Ba 6p peak are
not modied at all. The covalent character of the
BaO bond is too weak for having an inuence on the
splitting levels.
Looking at the AO levels plotted on for both models
on Fig. 5, at C point for the CB and at A point for the
VB, the dierences between the three models are more
striking than in the DOS and band curves. The tiny
geometry changes between the models enhance great differences in the crystalline orbitals splitting. The upper O
2p levels of BTC-Theo are degenerated, and the levels of Ti
3d character present the classical t2geg splitting characteristic of an octahedral arrangement of the oxygen
atoms surrounding the Ti. In the BTExp and BT:MnExp
models, the upper O 2p orbitals are not degenerated anymore and the splitting of the Ti 3d levels is strongly perturbed. This degenerescence lift is due to the o-plane
displacement of Ti in those two models. The second order interactions with the network modiers, the Ba
atoms do not have a preponderant role in the splitting
of the orbitals because it was seen on the DOS curves
of Fig. 4 that there are almost no covalent interaction of
those atoms, although the BaO distances are shorter
in the case of the experimental model than in the case
of the theoretical one. However, the radial interaction
mode of Ba contributes to the diminution of the tetragonal distortion that is much more important for the experimental models than for the theoretical model. The most

Fig. 4. Total and projected DOS (arb. unit.) for the (a) BTExp, (b) BT:MnExp and (c) BTTheo models.

J.R. Sambrano et al. / Chemical Physics Letters 402 (2005) 491496

495

Fig. 5. Energy levels main AO contributions taken, respectively, at C point and at A point for the CB and VB for the (a) BTExp, (b) BT:MnExp and (c)
BTTheo models.

important contribution for the disorder in the crystalline

orbitals levels is the o-plane displacement of Ti.
The band gap energy of BT:MnExp model is higher
than the band gap energies of BTC-Theo and BTExp models because a short TiO distance exists in this model,
the bond strength is higher and the Ti 3d and O 2p levels
are pushed away, principally the z axis contributions.
In summary, the dierences between BTTheo, BTExp
and BT:MnExp are well dened. The BTC-Theo model,
the most ordered one is also the more stable one. Its
TiO coordination is almost regular and its only deformation is due to the tetragonal distortion. Such a distortion is due to the nature of the network modier, Ba.
For example, Pb leads to tetragonal perovskites structures because it has a much stronger covalent character
than Ba which is basically ionic. The ionic character of
Ba tends to lead to a cubic structure but the size of its
electronic cloud implies structural deformation, what is
not the case of another ionic network modier, Sr, leading to a cubic perovskite structure. However, the experimental structure of BT, modelized by the BTExp model,
tends towards a cubic structure. The doped BT powder,
represented by the BT:MnExp model, also tends to a
cubic structure. These cubic tendencies are the result
of the TiO6 deformations existing in those structures
and that are compensating the stress caused by the size
of Ba.
The Ti 3d and upper O 2p levels are strongly perturbated by the disorder existing in the experimental structures and their splitting is not typical of an octahedral
coordination like in BTTheo model anymore. In the
BTTheo model, the splitting of the Ti 3d orbitals is due

to the eect of the octahedral crystal eld of the six oxygens surrounding the titanium. In the BTExp model, the
Ti 3d states are perturbated because the TiO bond distances, angles and dihedral angles are not regular anymore. This modication in the splitting of the 3d
orbitals can be associated to the JahnTeller eect, that
not only breaks the local point symmetry but simultaneously also the translational symmetry [32].
In the BT:MnExp model, the orbitals repartition is also
changed by this JahnTeller eect, in a more drastic way.
To close this discussion, it is important to think about
the structural organization that take place along the synthesis process. In solution, the titanium ion is chelated
by the citric acid and almost regular TiO6 clusters without constraints are therefore formed, surrounded by a
random distribution of network modier ions. A certain
kind of organization already exists, a short range organization. When the experimental solution is polymerized, this organization is set in a rigid 3D network.
Then, during the gel calcination, the organic compounds
are eliminated but the local order is conserved. The complete crystallization is achieved when a long range organization appears in addition to the local order. This last
one sometimes deviates from the ideal structure because
of the constrains induced by the long range order. Our
theoretical model permits to compare what would be
an ideal structure with this experimental disordered
structure, allowing determine the orderdisorder existing in the experimental phases. This is a new way of
characterizing our compounds, a ngerprint of the
structural organization. A good understanding of the
orderdisorder rate is very important for a lot of prop-

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J.R. Sambrano et al. / Chemical Physics Letters 402 (2005) 491496

erties like photoluminescence, dielectric constant, remnant polarization, etc. . . It is already well dened that
neither a complete structural order nor a complete structural disorder are favorable for outstanding properties.
The advantage of adding a dopant to the compound is
that it allows to tune this orderdisorder rate, and thus
the properties.

[4]
[5]
[6]
[7]
[8]
[9]
[10]

5. Summary

[11]

Rietveld renements are performed with the X-ray

diraction data of two BaTiO3 powders synthesized by
the polymeric precursors method, one pure and the
other one doped with 0.01% mol of manganese oxide.
The resulting cell parameters and Ba, Ti and O atomic
positions are used in periodic calculations where the
eect of manganese is thus taken into account only indirectly. Both experimental structures are compared with
an ideal structure whose cell parameters have been optimized. The tiny structural dierences lead to perturbations in the crystal orbitals splittings that permit to
characterize the disorder existing in the experimental
compounds. This original study is a new tool for dening structural disorder.

[12]

Acknowledgements
This work is supported by Brazilian Funding Agencies FAPESP, CAPES and CNPq. Computer facilities
of the Laboratorio de Simulacao Molecular,
C.C@Complex, Unesp, Bauru, Brazil, are also acknowledged. The constructive comments of the referees are
gratefully acknowledged.

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