ECS Journal of Solid State

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Effect of Defect States on the Upconversion Emission Properties in

KLu2F7 Nanocrystalline
To cite this article: Wenjuan Bian et al 2016 ECS J. Solid State Sci. Technol. 5 R137

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 ECS Journal of Solid State Science and Technology, 5 (9) R137-R141 (2016) R137

Effect of Defect States on the Upconversion Emission Properties

in KLu2 F7 Nanocrystalline
Wenjuan Bian,a Yushuang Qi,a Xuhui Xu,a,b Dacheng Zhou,a,b Yong Yang,a,b Jianbei Qiu,a,b
and Xue Yua,b,z
a Facultyof Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093,
People’s Republic of China
b KeyLaboratory of Advanced Materials of Yunnan Province, Kunming 650093, People’s Republic of China

The influence of the introduction of Li+ ions on the upconversion (UC) properties of KLu2 F7 :Yb3+ , Er3+ nanocrystalline has been
investigated in detail. It is found that the UC emission intensity of 10 mol% Li+ ions doped KLu2 F7 :Yb3+ , Er3+ nanocrystalline is
enhanced about 13 times in comparison with that of Li+ -free sample. Under the excitation of 980 nm laser diode (LD), a significant
improvement of the green to red emission ratio (GRR) in the 10 mol% Li+ -doped sample is observed by increasing pump power
density. Li+ ions could occupy the cationic sites or the interstitial sites in the KLu2 F7 host matrix, which probably eliminate the
defect states via the charge compensation and tailor of the crystal field, leading to the promotion of the UC emission efficiency.
Thus, the introduction of Li+ ions provides new opportunities for enhancing the scope of applications of Yb3+ , Er3+ doped KLu2 F7
nanocrystalline ranging from infrared solar cells to volumetric multiplexed bio-probe.
© The Author(s) 2016. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any
medium, provided the original work is properly cited. [DOI: 10.1149/2.0121609jss] All rights reserved.

Manuscript submitted April 25, 2016; revised manuscript received July 5, 2016. Published July 14, 2016.

The preparation of UC nanoparticles (NPs) that exhibits anti-
Stockes emission is important for applications in fields as diverse as
solar cells, photovoltaics, biological imaging, and photocatalysis.1–4
In particular, lathanide-doped fluorides have some distinct advantages
superior to oxide-based UC materials due to their low phonon energy,
high signal-to-noise ratio and excellent chemical stability. However,
the applications of lanthanide-doped fluorides are still constrained
because of the low UC efficiency and the restricted tunability of the
luminescence color output. Various attempts have been devoted to
improving these aspects, including both internal adjustments and ex-
ternal approaches, such as varying the crystal phase or morphology
of the NPs, adjusting the concentration of the doped rare earth, in-
troducing a co-dopant sensitizer, surface coating or adopting of a
core-shell structure.5–11 The excitation and relaxation dynamics of en-
ergy levels involved in UC process can be manipulated to vary the
relative luminescence intensity in different UC bands of a lanthanide
ion or to realize a combination of UC emission bands from other lan-
thanide ions.12,13 To improve the UC emission efficiency and adjust
the relatively color, a core-shell structure or a combination of activa-
tors is selected, which are aimed at reducing the surface defects.14,15
However, the synthesis of NPs featuring controllable color with high
chromatic purity remains a formidable challenge, as lanthanide ions
generally have more than one metastable excited state and the defects
are unavoidable in NPs. Nowadays, a new class of KLn2 F7 NPs with
orthorhombic crystallographic structure has drawn a widespread in-
terest, in which the lanthanide ions are distributed in arrays of tetrad
clusters. This unique arrangement enables the preservation of excita-
tion energy within the sub-lattice domain and effectively minimizing
the migration of excitation energy to defects. Based on this, the ad-
justment of UC emission color and the unusual four-photon violet UC
process from Er3+ doped KYb2 F7 are observed.16 Nevertheless, the
influence of defects on the photoluminescence properties of KLn2 F7
NPs has not been recognized. With the small cationic radius, Li+
ions can be doped easily into the host lattice substitutionally or in-
terstitially, which will tailor the crystal field around the Ln3+ ions
and have a non-negligible influence on defect states, resulting in the
change of the UC properties.17,18 Although the increase UC emission
intensity has been obtained via Li+ ions doped in NaYF4 :Yb3+ /Tm3+ ,
NaGdF4 :Yb3+ /Er3+ and NaLuF4 :Yb3+ , Tm3+ /Ho3+ NPs,19–21 the in-
vestigation on Li+ doped KLn2 F7 has not been carried out.
In this study, we report a facile and mild hydrothermal process of
the synthesis of water-phased KLu2 F7 NPs. The mechanism of the
z
E-mail: yuyu6593@126.com
enhanced UC emission intensity of the as-synthesized KLu2 F7 :Yb3+ ,
Er3+ NPs with Li+ ions doped under the excitation of 980 nm LD
is investigated. Additionally, the explanation for the power density
dependence of the UC color is given. With Li+ ions doped, the elimi-
nation of the traps in the NPs as well as the tailor of the crystal field
around Er3+ ions play vital roles in the UC properties, which will be
a meaningful research direction.
Experimental
The Li+ doped KLu2 F7 :Yb3+ , Er3+ NPs were prepared by a
hydrothermal method. In a typical experiment, 0.77 mmol Lu2 O3
(99.99%, Aladdin, China), 0.16 mmol Yb2 O3 (99.99%, Aladdin,
China) and 0.02 mmol Er2 O3 (99.99%, Aladdin, China) powder were
dissolved in dilute nitrate solution and the residual nitrate was re-
moved by heating and evaporation, resulting in the formation of clear
solution of Ln(NO3 )3 (Ln = Lu, Yb, Er). Then, 0.05 mmol LiNO3
(99.99%, Aladdin, China) water solution was added into the above
nitrate solution under stirring. 7 mmol KF (99.0%, Aladdin, China)
was dissolved in 10 mL deionized water and dropped into the nitrate
solution. The result solution was transferred into a 100 mL Teflon-
lined autoclave and kept at 180◦ C for 4 h. The NPs were separated
via centrifugation and washed twice with water and once with abso-
lute ethyl alcohol. The products (KLu2 F7 :16%Yb3+ , 2%Er3+ , 5%Li+ )
were obtained as a kind of white powder after drying at 80◦ C in a
baking oven. The other concentration (0%, 10%, 15% and 20%) Li+ -
doped KLu2 F7 :16%Yb3+ , 2%Er3+ samples were synthesized by a
similar procedure except that different moles of LiNO3 involved in the
reaction.
X-Ray powder diffraction (XRD) was performed using a D8 Fo-
cus diffractometer (Bruker) with Cu-Kα radiation (λ = 0.15405 nm)
in the 2θ range from 10◦ to 80◦ . The particle morphology and size
were studied by the Scanning Electronic Microscopy (SEM) with
FEI-Quanta 600. The UC photoluminescence spectra of the sam-
ples under a 980 nm infrared laser excitation were recorded by
HITACHIU-F-7000 spectrophotometer at room temperature. The ther-
moluminescence (TL) curves were measured with a FJ-427 A TL
meter (Beijing Nuclear Instrument Factory). Weight of the mea-
sured samples was constant (0.002 g). Prior to the TL measure,
the samples were first exposed to the radiation from ultraviolet
(UV) light (365 and 254 nm) for about 20 min, then heated from
room temperature to 550 K with a rate of 1 K/s. The photolu-
minescence decay curves were measured by FS980 fluorescence
spectrophotometer.
R138 ECS Journal of Solid State Science and Technology, 5 (9) R137-R141 (2016)

Figure 1. XRD patterns of KLu2 F7 :16%Yb3+ , 2%Er3+ , x%Li+ (x = 0, 5, 10, 15 and 20) and the standard card of KYb2 F7 (a) and the main diffraction peak of
five samples (The insert is the changing of the crystal cell volume with Li+ doped concentration) (b).

Results and Discussion which probably has influence on the UC property. Further increasing
of Li+ concentration to 20 mol%, the particles with a much larger size
Fig. 1a shows the XRD patterns of 0, 5, 10, 15 and 20 mol%
hexagon sheet are formed due to interstitially crystal sites occupied
Li+ ions doped KLu2 F7 :Yb3+ /Er3+ NPs. All samples are orthorhom-
by the Li+ ions, and the crystal size reaches to a micrometer scale. It is
bic structure according to the standard card of KYb2 F7 JCPDF
evident from SEM images that Li+ ions incorporated into the KLu2 F7
27–0459. No impurity peaks are observed, indicating that these
lattice serve as a controller for the morphology.
KLu2 F7 :Yb3+ /Er3+ samples synthesized with different amounts of
UC photoluminescence properties of a series of KLu2 F7 :16%Yb3+ ,
Li+ ions doped are of high purity. The positions of the diffraction
2%Er3+ , x%Li+ (x = 0, 5, 10, 15 and 20) excited by 980 nm LD with
peaks shift slightly when Li+ ions are introduced. Fig. 1b shows the
the power of 50 W/cm2 at room temperature are depicted in Fig. 3. The
main diffraction peak shift toward larger angle gradually from 27.86◦
position of the emission peaks of Er3+ is not affected by introducing
to 28.14◦ as the concentration of Li+ ions increases in the range of
Li+ ions. The dominant green emissions of 525 and 543 nm are
0–15 mol%. It indicates that the lattice shrinks when Li+ ions are
assigned to the transitions of 2 H11/2 →4 I15/2 and 4 S3/2 →4 I15/2 of Er3+
introduced. The peaks shift to smaller angles when Li+ ion concen-
ions, respectively, and the red emission of 668 nm is attributed to the
tration further increase to 20 mol%, implying that the lattice expands. 4
F9/2 →4 I15/2 transition. With an increasing concentration of Li+ ions,
The crystal cell volume is calculated by the cell parameters in a unit
the integrated emission intensities increase firstly and then decrease.
cell with crystal structure of KLu2 F7 . The cell volume of the sam-
The UC luminescence intensity reaches its maximum in 10 mol% Li+
ples decreases linearly when the concentration of Li+ ions changes
ions doped sample, which is 13 times than that of Li+ -free sample. The
from 0 to 10 mol% as shown in Table I and the insert of Fig. 1b,
UC intensity decreases when the concentration of Li+ ions reaches to
which is consistent with Vagard’s law.23–25 Li+ ions are expected to
20 mol%. These phenomena may derive from the contributions that
replace K+ and Lu3+ ions, which leads to lattice shrinking. When the
the introduction of Li+ ions could tailor Er3+ ions’ local environment,
doped concentration increases, the confusion trend of the cell volume
decrease the defect states. A small fraction of Li+ ions substituted
could suggest the occupying of the interstitial sites of host matrix.
in the lattice could induce the asymmetric environment around Er3+
Based on the Shannon theory, the effect ionic radius of K+ is 1.37 Å ions, which promotes the fast energy transfer from Yb3+ to Er3+ ions.
in four-coordination, Lu3+ is 0.861 and 0.977 Å in six- and eight- Furthermore, defects are unavoidably formed during the synthesis
coordination and Li+ is 0.590, 0.760 and 0.920 Å in four-, six- and process, indicating that the introduction of Li+ ions is expected to
eight-coordination, respectively.22 Therefore, Li+ ions are speculated influence the UC properties by changing defect states as well.
to substitute the cationic crystal sites or enter into the interstitial sites Thermoluminescence (TL) spectra are presented to reveal the
of host matrix. It should be noted that both the substitution of cationic change of defect states caused by Li+ ions. As shown in Fig. 4,
sites and the occupation of interstitial sites would tailor the local crys- two TL peaks located around 325 and 387 K can be identified in Li+ -
tal field around Er3+ ions in the host lattice, and then influence their free sample. However, the TL peaks located around 325 and 387 K
anti-Stokes luminescence. are insignificant when Li+ ions are doped, indicating the traps are
The images in Fig. 2 represent the regular hexagonal prism of eliminated. During the synthesis process under high temperature and
the NPs with Li+ ions doped. The introduction of 5 and 10 mol% pressure, the substitution of K+ ions with Yb3+ and Er3+ ions is un-
Li+ ions leads to a larger grain size compared to Li+ free sample, avoidable, though the replacement of Lu3+ ions is dominant. There-
fore, the introduction of the vacancy defects (VK ) cannot be avoided
because of the charge balance principle. Moreover, the surface defects
Table I. Cell parameters and volume of KLu2 F7 :16%Yb3+ , are inevitable in nanoparticles. Both of these defects contribute to the
2%Er3+ , x%Li+ . observation of the traps.26 It could be expected that the introduction
of Li+ ions eliminates the traps efficiently, since the substituting of
sample a/Å b/Å c/Å cell volume/Å3
Lu3+ ions with Li+ ions producing the vacancy of F− (Li Lu 
+2VF• )
accomplishes the charge compensation. Thus, the introduction of Li+
x=0 11.6125 13.4990 7.6572 1200.32 ions could improve the UC emission efficiency significantly.
x=1 11.6130 13.4950 7.6577 1200.10 The photoluminescence decay curves of 4 S3/2 →4 I15/2 (543 nm)
x=3 11.6149 13.4901 7.6570 1199.75 and 4 F9/2 →4 I15/2 (668 nm) of KLu2 F7 :16%Yb3+ , 2%Er3+ , x%Li+ (x
x=5 11.6172 13.4872 7.6561 1199.58 = 0, 5, 10, 15 and 20) NPs are recorded as shown in Fig. 5. All the
x=7 11.6220 13.4754 7.6527 1198.50 decay curves of the samples could be well fitted to a single exponential
x = 10 11.6277 13.4623 7.6442 1196.07 function:
x = 15 11.6614 12.9858 7.4952 1135.02
x = 20 10.9075 13.1652 8.0773 1159.70 I (t) = I0 + A1 ex p (−t/τ1 )
 ECS Journal of Solid State Science and Technology, 5 (9) R137-R141 (2016)
Figure 2. SEM images of the KLu2 F7 :16%Yb3+ , 2%Er3+ , x%Li+ NPs x = 0 (a), x = 5 (b), x = 10 (c) and x = 20 (d). The insets show the histograms of the
average particle size distribution of these samples.
Where I is the photoluminescence intensity of Er3+ ions, A1 is
constant; t is time; and τ1 is the decay time for the exponential com-
ponent. As shown in Fig. 5, the introduction of Li+ ions prolongs
the decay time of 4 S3/2 and 4 F9/2 levels in Er3+ ions indicating that
the local environment around Er3+ ions are tailored with the Li+ ions
doped. With an increasing concentration of Li+ ions, the lifetimes of
4
S3/2 and 4 F9/2 states increase firstly and then decrease, and such trend
is similar to the UC emission intensity change. The decay time of 10
mol% Li+ -doped sample is longer than other samples, indicating that
the UC emission efficiency would be improved with proper concen-
tration of Li+ ions. The large increase in decay time contributes to
Figure 3. UC photoluminescence spectra of KLu2 F7 :16%Yb3+ , 2%Er3+ ,
x%Li+ (x = 0, 5, 10, 15 and 20) NPs under 980 nm (P = 50 W/cm2 ) LD
excitation (The insert shows the energy level diagram of KLu2 F7 :16%Yb3+ ,
2%Er3+ ).
R139
a significant increase of UC photoluminescence intensity, which has
been studied and reported.27
Fig. 6a demonstrates the UC photoluminescence spectra of
KLu2 F7 :16%Yb3+ , 2%Er3+ , 10%Li+ with great enlargement of GRR
under different excitation power density by normalizing the red emis-
sion. The GRR can be tuned by varying the excitation power density.
The emission ratios are calculated by the integrated emission inten-
sities of 525 and 543 nm to 668 nm. The change of GRR can be
attributed to a fast and efficient energy transfer process due to the par-
ticipation of more intensive photons in UC emission process. Since the
electrons could be excited frequently before they decay under higher
power density of 980 nm LD excitation, UC emission favors the tran-
sition from higher energy levels, which would promote the electrons
Figure 4. TL spectra of KLu2 F7 :16%Yb3+ , 2%Er3+ , x%Li+ (x = 0, 5, 10,
15 and 20) after the irradiation 20 min by UV light.
R140 ECS Journal of Solid State Science and Technology, 5 (9) R137-R141 (2016)

Figure 5. Photoluminescence decay curves of KLu2 F7 :16%Yb3+ , 2%Er3+ , x%Li+ (x = 0, 5, 10, 15 and 20) samples monitored by 543 nm (a) and 668 nm (b).

stimulated from 4 S3/2 level. Thus, the emission intensity of the 525 nm
peak increases drastically in comparison with 543 nm and the energy
transition 4 G11/2 →4 I11/2 (380 nm) and 2 H9/2 →4 I11/2 (408 nm) occur as
shown in Fig. 6a1. Therefore, an increasing excitation power density
of 980 nm LD would not only adjust the UC emission color efficiently
but promote the UC photoluminescence intensity in short wavelength.
In addition, with the introduction of Li+ ions, the GRR is enlarged
more greatly as the increasing excitation power density compared with
that of Li+ -free sample (Fig. 6a2) with the assistance of the elimina-
tion of the traps and the tailor of the crystal field around of Er3+ ions.
To visualize the improvement and the tunable color of the UC emis-
sion, the photographs of the UC luminescence of KLu2 F7 : 16%Yb3+ ,
2%Er3+ , 10%Li+ NPs dispersed in the absolute ethyl alcohol (2 wt%)
excited by 980 nm LD are shown in Fig. 6b. With an increasing power
density, a tunable color from yellow to green is clearly observed with
the naked-eye. Fig. 6c shows the photograph model that the cuvette
containing 2%wt sample is keeping away from convex lens gradually,
which indicates a decrease of excitation power density. Evidently, as
further apart from the focus, the GRR decreases, verifying the de-
pendence of GRR on the power density, which are corresponding to
the results of Fig. 6b. Furthermore, based on the spectral data of the
UC photoluminescence, variation of color points of the 10 mol% Li+
ions doped KLu2 F7 : Yb3+ , Er3+ NPs as a function of power density
are obtained, which is illustrated in the Commission International de
I’Eclairage France (CIE) 1931 chromaticity diagram in Fig. 6d. Ob-
viously, the color coordinates of UC emission falls in yellow regions
under the excitation of 980 nm LD with a low power density. It ranges
from yellow to green as the pomp power density increase gradually.
Fig. 7 is the schematic partial energy level diagram and energy
transfer processes involved in the UC process. The energy transfer
from Yb3+ ions to Er3+ ions can promote the electrons from the
ground state to the 4 F7/2 level of Er3+ ions under the excitation of

Figure 6. Pump power density dependence of UC photoluminescence spectra (a), the photographs (b), photograph model (c) and color coordinates (d) of
KLu2 F7 :16%Yb3+ , 2%Er3+ , 10%Li+ excited by 980 nm LD. The inset of (a) shows the amplification of UC spectra in short wavelength (a1) and the power
density dependence of GRR of x = 0 and 10 samples (a2).
 ECS Journal of Solid State Science and Technology, 5 (9) R137-R141 (2016)
Figure 7. Schematic partial energy level diagram and energy transfer pro-
cesses involved in the UC process.
980 nm LD. With the assistance of non-radiative relaxation process,
the electrons can then relax non-radiatively to the 2 H11/2 and 4 S3/2
levels, which contributes to the green emitting as the electrons finally
relax to the 4 I15/2 level. It can be seen that the red emission derives
from relaxation of electrons from 4 F9/2 to 4 I15/2 level. The excited
electrons relax to 4 I13/2 from 4 I11/2 level non-radiatively, and then
populate the red emitting 4 F9/2 state. A high power density excitation
of 980 nm LD would be beneficial to excite the electrons to a higher
energy level of Er3+ ions. It provides much more opportunities for
electrons to be excited at 4 G11/2 level, which would contribute to the
observation of the near-ultraviolet region (380 nm) or depopulate to
purple emitting at 2 H9/2 (408 nm) levels. The elimination of the traps
with the introduction of Li+ ions and the tailor of the crystal field
around Er3+ ions would improve the UC efficiency significantly.
Conclusions
In summary, KLu2 F7 : Yb3+ , Er3+ NPs doping with different con-
centration of Li+ ions are synthesized via the hydrothermal process.
Due to the introduction of Li+ ions, the enhancement of UC emission
intensity and the decrease of TL intensity are observed. The optimized
concentration of Li+ ions for the maximum UC emission intensity in
KLu2 F7 :16%Yb3+ , 2%Er3+ NPs is 10 mol%. Furthermore, the depen-
dence of the adjustment UC color on the excitation power density is
investigated, and the UC photoluminescence color is tuned from yel-
low to green with the increasing power density. The introduction of
Li+ ions could tailor the crystal field around Er3+ ions and eliminate
the traps, which would contribute to the dramatical enhancement of
UC emission intensity and a significant enlargement of the GRR as
R141
the increase of the excitation power density. Thus, the introduction of
Li+ ions will greatly enhance the scope of the applications of KLu2 F7 :
Yb3+ , Er3+ NPs.
Acknowledgments
This work was financially supported by the National Nature Sci-
ence Foundation of China (61308091, 61565009), the Young Talents
Support Program of Faculty of Materials Science and Engineering,
Kunming University of Science and Technology (14078342), and the
Postdoctoral Science Foundation of China (2013M540720).
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