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A (2017)123:563
DOI 10.1007/s00339-017-1173-1
RAPID COMMUNICATION
123
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
123
Observation of room-temperature ferromagnetism in Co-doped Bi0.5K0.5TiO3 materials Page 3 of 4 563
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.
123
563 Page 4 of 4 L. V. Cuong et al.
4 Conclusion 2. L.M. Oanh, D.B. Do, N.D. Phu, N.T.P. Mai, N.V. Minh, IEEE
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3. L.M. Oanh, D.B. Do, N.V. Minh, Mater. Trans. 56, 13581361
The room-temperature ferromagnetism was obtained in (2015)
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6. M. Murakami et al., Appl. Phys. Lett. 87, 112901 (2005)
stitution gave rise to the band gap modification, from 7. W. Jo, R. Dittmer, M. Acosta, J. Zang, C. Groh, E. Sapper, K.
3.28 eV for un-doped Bi0.5K0.5TiO3 materials to 2.11 eV Wang, J. Rodel, J. Electroceram. 29, 71 (2012)
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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)
11. D.D. Dung, D.V. Thiet, D. Odkhuu, L.V. Cuong, N.H. Tuan, S.
under Grant Number 103.02-2015.89 and the Basic Science Research
Cho, Mater. Lett. 156, 129 (2015)
Program through the National Research Foundation of Korea (NRF-
12. D.V. Thiet, D.D. Cuong, L.H. Bac, L.V. Cuong, H.D. Khoa, S.
2017R1C1B5017261).
Cho, N.H. Tuan, D.D. Dung, Mater. Trans. 56, 1339 (2015)
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