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Appl. Phys.

A (2017)123:563
DOI 10.1007/s00339-017-1173-1

RAPID COMMUNICATION

Observation of room-temperature ferromagnetism in Co-doped


Bi0.5K0.5TiO3 materials
Le Viet Cuong1,2 Nguyen Hoang Tuan1 Dorj Odkhuu3 Duong Van Thiet1

Nguyen Huu Dung4 Luong Huu Bac1 Dang Duc Dung1

Received: 26 June 2017 / Accepted: 26 July 2017


Springer-Verlag GmbH Germany 2017

Abstract We report the band gap modification and strong 1 Introduction


room ferromagnetism by substituting the Co ions for the Ti
site of Bi0.5K0.5TiO3 materials. The predicted band gap of Tailoring the ferromagnetism in ferroelectric materials is
2.11 eV and magnetic moment of 2.7 lB/Co are repro- one of the possible ways to integrate novel function materials
duced precisely in UVVis spectroscopy and supercon- for smart electronic devices. In particular, room-temperature
ducting quantum interference device experiments, ferromagnetism has been discovered in transition metal
respectively. We elucidate the driving mechanisms for (TM)-doped PbTiO3 or epitaxial ferromagnetic/PbTiO3
these results in terms of the spin-exchange splitting multilayers [16]. However, the lead-based ferroelectric
between spin subbands in the presence of substitution ions materials contain more than 60 wt% hazardous Pb materials.
and high-spin crystal field energy spectrum. This method The lead elements cause environmental pollution and are
would provide a promising approach to get single-phase harmful to humans, but the ferroelectric devices using lead-
multiferroics and resolve the problem of the scarcity of based ferroelectric materials are still present in more than
single-phase multiferroics in nature. 94% of the world market in 2014 [7]. The protection envi-
ronmental and health issues have risen for requirement of
non-hazardous materials with properties comparable to that
of Pb-based materials for use in device fabrication [8].
Therefore, considerable efforts have been devoted towards
the development of lead-free ferroelectric materials [9]. In
this regard, Bi0.5K0.5TiO3 and Bi0.5Na0.5TiO3 have been
widely studied because of the competitive properties to
& Dorj Odkhuu
PbTiO3-based materials [10]. Very recently, the room-tem-
odkhuu@inu.ac.kr perature ferromagnetism was reported in Fe- and Ni-doped
& Dang Duc Dung
Bi0.5K0.5TiO3 materials, and similarly in Co- and Fe-doped
dung.dangduc@hust.edu.vn Bi0.5Na0.5TiO3 materials [1114]. Meanwhile, the origin of
observation for room-temperature ferromagnetism in TM-
1
School of Engineering Physics, Ha Noi University of Science doped lead-free ferroelectrics needs to be understood to
and Technology, 1 Dai Co Viet Road, Hanoi, Vietnam
make them more practically.
2
Faculty of Engineering Physics and Nanotechnology, In this work, the room-temperature ferromagnetism is
University of Engineering and Technology, Vietnam
National University, Building E3, 144 Xuan Thuy, Hanoi,
identified in Co-doped Bi0.5K0.5TiO3 materials. Interest-
Vietnam ingly, the saturation magnetization is as large as 2.7 lB/Co
3 at 5 K. Furthermore, the reduction of optical band gap,
Department of Physics, Incheon National University,
Incheon 22012, Korea from 3.28 eV for un-doped to 2.11 eV for 9 mol% doped,
4 is obtained after the substitution of Co ions at the Ti site.
Advanced Institute for Science and Technology, Ha Noi
University of Science and Technology, 1 Dai Co Viet Road, The origin for these results is discussed in terms of the
Hanoi, Vietnam spin-exchange splitting between spin subbands in the

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563 Page 2 of 4 L. V. Cuong et al.

presence of substitution ions and high-spin crystal field location of (110) diffraction peaks in the range of 2835
energy spectrum with density-functional theory (DFT) shows that the peaks position of the samples slightly shifts
calculations. toward a lower 2h values in the case of Co doping, as
shown in Fig. 1b. The distorted structure indicates that Co
ions incorporated with lattice structure and expanded lat-
2 Experiment tice parameter. In the other words, the Co cations were
incorporated into the crystal structure of Bi0.5K0.5TiO3
The Co-doped Bi0.5K0.5TiO3 samples were synthesized by materials.
the solgel technique. Firstly, bismuth nitrate pentahydrate Figure 2a shows the optical absorption spectra of
(Bi(NO3)25H2O), potassium nitrate (KNO3), and cobalt Bi0.5K0.5TiO3 doped with various Co concentrations.
nitrate (Co(NO3)36H2O) were dissolved in acetic acid Clearly, the Co doping into Bi0.5K0.5TiO3 materials makes
(CH3COOH) and deionized water. Then, the acetylacetone its band gap red-shift, indicating the reduced optical band
(CH3COCH2COCH3) was introduced into a prepared gap (Eg). The results were further evident for Co cations
solution after adding the tetraisopropoxytitanium(IV) incorporation into the crystal structure of Bi0.5K0.5TiO3. In
(C12H28O4Ti). The sol was heated at 100C to prepare dry addition, the appearance of absorbance peak at around 581
gels. The dry gels were ground and calcined at 400C for and 768 nm suggested for Co2?/3? local states. The optical
2 h and sintered at 800C for 3 h. Potassium was added to Eg values are estimated 3.28 eV for the pure and 2.11 eV
excess at approximately 10 mol% to prevent potassium for 9 mol% Co-doped Bi0.5K0.5TiO3 by Tauc method, as
loss during the gel and sintering processes. The crystalline shown in Fig. 2b. Inset of Fig. 2b shows Eg values as
structures of the samples were characterized by X-ray function of Co concentration. The reduction of optical band
diffraction (XRD). The optical properties were studied by gap is also observed in recent studies for Fe- and Ni-doped
ultravioletvisible (UVVis) spectroscopy. The magnetic Bi0.5K0.5TiO3 materials [11, 12].
properties were characterized by vibration sample magne- Figure 3a shows the magnetic hysteresis (MH) loops of
tometer (VSM) at room temperature and superconducting the pure and Co-doped Bi0.5K0.5TiO3 samples at room
quantum interference device (SQUID) magnetometer at temperatures. The clear magnetic hysteresis loops were
5 K. observed at room temperature. Moreover, the coercive field
(HC) and remanence magnetization (Mr) were estimated
around 50 Oe and 18 memu/g, respectively, which is the
3 Results and discussion solid evidence for typical ferromagnetism even at room
temperature. The HC value of Co-doped Bi0.5K0.5TiO3
Figure 1a shows the XRD patterns of pure and Co-doped samples was consistent with previously reported values for
Bi0.5K0.5TiO3 samples prepared by solgel method. The TM-doped ferroelectric materials with HC, ranging from 70
observed peak positions and relative intensities were to 135 Oe [13, 1114]. In addition, the magnetization
indexed with standard data of Bi0.5K0.5TiO3 compound, strength increases as the concentration of Co dopants
which confirms the tetragonal perovskite structure of all increases at the same magnetic field strength of 5 kOe, as
prepared samples (JCPDS card no. 33-0152). The impuri- shown in the inset of Fig. 3a. The un-doped Bi0.5K0.5TiO3
ties phase could not be found, even in the logarithmically materials also exhibit weak ferromagnetism at room tem-
scaled h2h XRD pattern. A careful comparison on the perature, which was attributed to the presence of vacancies

Fig. 1 a X-ray diffraction


pattern of Co-doped
Bi0.5K0.5TiO3 samples as a
function of cobalt doping
concentration, b a comparison
of (110) diffraction peak
positions for the patterns

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Observation of room-temperature ferromagnetism in Co-doped Bi0.5K0.5TiO3 materials Page 3 of 4 563

Fig. 2 a UVvis absorption


spectra of the Co-doped
Bi0.5K0.5TiO3 samples as a
function of Co dopant, and b the
(ahm)2 proposal with photon
energy (hm) of the Bi0.5K0.5TiO3
samples as function of Co
dopant. The inset of b shows the
band gap Eg of the
Bi0.5K0.5TiO3 samples as
function of Co dopant
concentrations

Fig. 3 a MH curve of Bi0.5K0.5TiO3 samples with various Co of Co dopant. b The MT curve at 1 kOe magnetic field for
doping concentration at room temperature. The inset of a shows the Bi0.5K0.5Ti0.99Co0.01O3 samples. The inset of b shows MH curve of
maxima spontaneous magnetism of Bi0.5K0.5TiO3 samples as function Bi0.5K0.5Ti0.99Co0.01O3 samples at 5 K

on Ti and/or O sites [4, 11, 12]. Figure 3b shows the entirely degenerate [11]. Such degeneracy does not persist
temperature-dependent magnetization carrying out under anymore after introducing the Co dopants into Bi0.5K0.5-
an applied field of 1 kOe of Bi0.5K0.5Ti0.99Co0.01O3 sam- TiO3 (Fig. 4a). The calculated bandgap is 2.12 eV, which
ples. The inset of Fig. 3b shows the MH curve of Bi0.5- agrees well with the measured value (2.11 eV) in our
K0.5Ti0.99Co0.01O3 samples under magnetic up to 70 kOe at present experiment. Furthermore, the consistency in mag-
5 K. Thus, the saturation magnetization is found to be netization between theory and experiment is also pretty
0.879 emu/g, which corresponds to around 2.7 lB/Co. good; the experimental magnetic moment of Co ions is
Note that the room-temperature ferromagnetism in Co- reproduced precisely in our calculations (2.7 lB). From
doped Bi0.5Na0.5TiO3 was originated from Co cluster while the d-orbital projected DOS (Fig. 4b), the spin-up bands of
the observation of room-temperature ferromagnetism in Co ions are completely filled while some minority-spin
Fe-doped Bi0.5Na0.5TiO3 was resulted from intrinsic bands, having one t2g (dxz/yz) and two eg electrons, are
defects [13, 14]. Recently, the room temperature ferro- above the Fermi level. Thus, according to Hunds rule, the
magnetism in Fe-doped Bi0.5K0.5TiO3 was possible resul- calculated moment (2.7 lB) of Co2? ions can be explained
ted from intrinsic defects which were well explanted by by the electronic configuration of high-spin state in the
both experiment and theoretical [11]. Therefore, we sug- crystal field theory through the unpaired electron spin
gested that the origin of observation room-temperature count (five spin-up and two spin-down electrons with dxy
ferromagnetism in Co-doped Bi0.5K0.5TiO3 materials is and dxz,yz). The reduced band gap in doped Bi0.5K0.5TiO3 is
originated from intrinsic defects. further analyzed in Fig. 4c, d. The spin-up highest orbital
Moreover, the DFT studies, the input parameters states are predominantly contributed by a flat Co-eg band
of which were described in details in Ref. [11], are con- around the RM points. In contrast to the C-point bandgap
ducted to provide insights on the above experimental of the pristine Bi0.5K0.5TiO3, the direct bandgap of 2.12 eV
results. Figure 4a shows the density of states (DOS) of Co- then appears at the R-point. On the other hand, the spin-
doped Bi0.5K0.5TiO3. In pristine Bi0.5K0.5TiO3, the valence down highest occupied (O-2p) and lowest unoccupied (Ti-
and conduction bands are characterized by the O-2p and 3d) bands of the pristine Bi0.5K0.5TiO3 remain unchanged
Ti-3d states, respectively, where the spin subbands are upon the doping effect.

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563 Page 4 of 4 L. V. Cuong et al.

Fig. 4 a Total DOS of Co-


doped Bi0.5K0.5TiO3 and
b the d-orbital-projected DOS
of the dopant Co atom.
c Majority-spin and d minority-
spin band structures of Co-
doped Bi0.5K0.5TiO3, where the
Co dxy, dxz, dyz, d2z , d2x 2-y states
are shown in black, orange,
green, red, and blue,
respectively. The Fermi level is
set to zero in energy

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Acknowledgements This research is funded by Vietnam National
Mater. Sci. Eng. 2014, 365391 (2014)
Foundation for Science and Technology Development (NAFOSTED)
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Program through the National Research Foundation of Korea (NRF-
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