J Mater Sci: Mater Electron (2017) 28:5652–5662
DOI 10.1007/s10854-016-6236-0
Formation of nano-Ag/BiFeO3 composite thin film
with extraordinary high dielectric and effective ferromagnetic
properties
Shulei Cheng1 · Qiankun Xu1 · Xuelin Hao1 · Zongrong Wang1 · Ning Ma1 · Piyi Du1
Received: 8 October 2016 / Accepted: 16 December 2016 / Published online: 28 February 2017
© Springer Science+Business Media New York 2017
Abstract The Ag/BiFeO3 composite thin films were pre-
pared by sol–gel technology on ITO/glass substrate. Most
of the ­Ag+ ions were reduced to form Ag nanoparticles in
the thin film. Some ­Ag+ ions were doped into the ­BiFeO3
lattice to replace Bi, forming Ag doped B ­ iFeO3. The aver-
age size of the Ag nanoparticles is 4–8 nm. The dielectric
constant of the B­ iFeO3 thin film sintered at 550 °C with the
molar ratio of Ag/Fe of 0.2 was enhanced to 139, which
was nearly twice as high as that of pure B ­ iFeO3. The die-
lectric loss kept at a low value of 0.15. The composite thin
film also showed a typical ferromagnetism with the satura-
tion magnetization of 2.2 emu/cm3. The Ag/BiFeO3 com-
posite thin film showed typical ferromagnetism and high
permittivity simultaneously.
1 Introduction
Multiferroic materials have attracted more and more atten-
tion in recent years due to their physical properties and
potential application in multifunctional devices [1–7]. As
a typical single-phasic multiferroic material, B
­ iFeO3 pos-
sesses both ferroelectric and antiferromagnetic orderings
simultaneously at room temperature [8]. Hence, bismuth
ferrites are promising candidates in applications of mem-
ory devices, photovoltaic devices, spintronics and sensors
* Zongrong Wang
zrw@zju.edu.cn
* Piyi Du
dupy@zju.edu.cn
1 conductive nanoparticles are introduced and dispersed uni-
State Key Laboratory of Silicon Materials, School
of Materials Science and Engineering, Zhejiang University,
Hangzhou 310027, China
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Vol:.(1234567890)
[9] etc. And more efforts have been spent on the bismuth
ferrite during the last decades. It is reported that the dop-
ing of Dy to ­BiFeO3 [10] increased the magnetization from
~0.1 to ~0.2 emu/g at 10 kOe with unsaturated magnetiza-
tion loops. Ag doping in B ­ iFeO3 nanometric powder made
the saturation magnetization seven times larger than that of
the undoped one [11]. Moreover, La and Pr co-doping to
­BiFeO3 increased the dielectric constant and decreased die-
lectric loss [12]. Besides, the preparation method [13] and
the domain structure or interfacial structure has also been
discussed [14, 15], which influences importantly the dielec-
tric constant and controls greatly the nonlinear change of
the permittivity.
Thin film is important in promoting miniaturization
of the modern electronic devices. However, ­BiFeO3 thin
films still show relatively weak properties. In this case,
the improvement of ­BiFeO3 thin film properties becomes
highly desirable for better application in devices. As is
known, dielectric nature is one of the properties of multi-
functional materials. It plays an important role in applica-
tion of the multifunctional ­BiFeO3 thin film. The improve-
ment of the permittivity of ­BiFeO3 thin film is therefore one
of important work in its application. In resent work, it is
reported that the permittivity of ­BiFeO3 can be modified by
using different methods as well as doping different ions in
preparation. Such as for the thin film system of ­BiFeO3 pre-
pared by PLD method [13], the dielectric constant is much
higher than those of the thin film by sol gel method. How-
ever, Other than the improvement of the intrinsic permittiv-
ity by changing preparation method, by doping or by other
means, it has been reported that the dielectric constant of
the thin film could be enhanced by several times when the
formly compared with that without conductive nanoparti-
cles [16–19]. It implies that, regardless of the preparation
J Mater Sci: Mater Electron (2017) 28:5652–5662
method, the dielectric properties of the thin film may be
improved expectedly. Hence, if the metal nanoparticles can
be introduced into the ­BiFeO3 thin film matrix, the dielec-
tric property of the ­BiFeO3 thin film is expected to further
increase.
Nevertheless, the preparation of composite thin films is
not as easy as that of bulk composite materials. For bulk
materials, composite can be prepared by directly mixing
different phases. But for thin films, it is easy to generate
conducting path if the conductive phase in micrometer-
scale is introduced into the sub-micrometer-scale thick thin
film and make the composite fail to act as dielectric materi-
als [16]. In order to solve this problem, it is worth studying
how to introduce conductive particles in nano-scale into the
thin film matrix to increase dielectric properties.
Herein, sol–gel technology is proposed to introduce
metal ions in sol and reduce conductive nanoparticles
in situ. In this way, Ag nanoparticles dispersed bismuth fer-
rite composite thin film is obtained and the composite thin
film shows high dielectric constant other than the intrin-
sic magnetic properties. The influence of Ag nanoparti-
cles on both dielectric and magnetic performances of the
­BiFeO3 thin film was investigated. The permittivity of the
Ag/BiFeO3 composite thin film has significantly increased
compared to that of the B ­ iFeO3 thin film without Ag nano
particles dispersed.
2 Experimental methods
The Ag/BiFeO3 thin films were prepared by sol–gel method
with Fe(NO3)3·9H2O, Bi(NO3)3·5H2O and ­AgNO3 as raw
chemicals. Nitric acid and citric acid were used as stabi-
lizing agent and complexing agent respectively. Initially,
Fe(NO3)3·9H2O and Bi(NO3)3·5H2O were dissolved in
ethylene glycol to prepare Fe and Bi solution respec-
tively. Then Fe and Bi solutions were mixed together with
the molar ratio of Bi/Fe of 1.05 and stirred for 10 min to
obtain Fe–Bi solution. After that, citric acid was added
into the Fe–Bi solution with the molar ratio of citric acid/
Fe(NO3)3·9H2O controlled to be 1. Then the mixed solu-
tion was stirred until citric acid was dissolved completely
to obtain the Fe–Bi citric acid solution. In addition, silver
nitrate was dissolved in ethylene glycol in a covered beaker
with nitric acid added. After silver nitrate was dissolved
completely, the Ag solution was added into the Fe–Bi cit-
ric acid solution to obtain Ag–Fe–Bi solution which was
stirred at 60 °C for 2h. The Ag–Fe–Bi solution was con-
trolled to be about 0.1 mol/L of Fe in concentration with
the molar ratio of Ag/Fe (defined as x) of 0, 0.2, 0.4, 0.5,
0.6 and 0.7. After aged for 24 h, the sol precursor was sta-
bly formed and ready for use.
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Thin film was prepared on ITO/glass which was used
as substrate by dip coating method with a withdraw speed
of 3 cm/min. After coating a layer of thin film, we made a
three-step heating process for the thin film. It was heated
to 200 °C initially with a rate of 3 °C/min and remained at
200 °C for 10 min. After that the thin film was heated to
400 °C with a rate of 3 °C/min and then remained at 400 °C
for 10 min during the second step. Finally, in the third step,
the heating temperature was increased to high temperature
of 500 °C (550, 600 °C) with a rate of 5 °C/min and then
kept for 30 min. Then the thin film was cooled down to the
room temperature naturally in muffle furnace and one layer
of the thin film is obtained. In order to obtain a required
thickness of the thin film, the process above is repeated for
proper times.
The phase structure of the thin films was characterized
by the X-ray diffraction (XRD, Empyrean XRD system, Cu
Kα radiation λ = 0.154 nm, 40 kV and 40 mA) with step
width 0.02° and scanning speed 4°/min between 2θ = 10°
and 70°. The morphology of the films was observed by
scanning electron microscopy (SEM, Hitachi S4800 at volt-
age of 5 kV). The size of Ag nanoparticles in the thin films
was measured by absorption spectra of ultraviolet–vis-
ible (UV–Vis) light using a spectrophotometer (UV-3600)
and the high resolution transmission electron microscopy
(HRTEM, Tecnai G2 F20 S-TWIN). The permittivity of
the samples was measured by impedance analyzer (Agilent
4294 A) under frequency over the range within between
40 Hz and 10 MHz at room temperature. Hysteresis loops
were measured by magnetic property measurement system
(MPMS-XL-5).
3 Results and discussion
Figure 1 shows the morphology of the ­BiFeO3 thin films
with the molar ratio of Ag/Fe ranging from 0 to 0.7
observed by SEM. It can be observed that all the thin films
are uniform. The inset in Fig. 1e shows the cross sectional
image of ­BiFeO3 thin film with the molar ratio of Ag/Fe of
0.6. The thickness of the thin film is about 220 nm.
Figure 2 shows the XRD patterns of ­BiFeO3 thin films
with the molar ratio x of Ag/Fe ranging from 0 to 0.7 at dif-
ferent annealing temperatures. All the peaks matched well
with the perovskite phase of ­BiFeO3, which is the same
as general one reported [9] by others for single phased
­BiFeO3, except one at 35.2°, which belongs to ITO. There
is no diffraction peak attributed to Ag and other phases.
The intensity of the peak increases initially with increas-
ing x from 0 to 0.5 and then decreases a little with further
increasing x to 0.7 for thin films sintered at different tem-
peratures. It decreases with the increase in sintering tem-
perature for all the thin films with different addition of Ag.
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5654 J Mater Sci: Mater Electron (2017) 28:5652–5662

Fig. 1  SEM images of ­BiFeO3 thin films annealed at 500 °C with the molar ratio of Ag/Fe of a 0, b 0.2, c 0.4, d 0.5, e 0.6 and f 0.7. The inset of
e is the cross sectional image of Ag/BiFeO3 thin film with the molar ratio of Ag/Fe of 0.6

It is apparent that the ­BiFeO3 thin film with Ag added
can be successfully prepared by sol–gel method, forming
uniform layer with a thickness of about 220 nm through
eliminating the hole sometimes formed and homogenising
the thickness by controlling preparation condition. The per-
ovskite phase of B ­ iFeO3 is formed at annealing tempera-
tures of 500–600 °C regardless of whether the Ag is added
or not. But Ag crystalline phase does not appear in the thin
films.
According to the XRD patterns, unit cell volumes of all
thin films are calculated and rates of volume change are
obtained, as shown in Table 1. The unit cell volume of the
thin films increases with increasing preparation tempera-
ture from 500 to 550 °C and then decreases when the prepa-
ration temperature increases to 600 °C. With Ag added, the
rate of volume change is negative in the thin film annealed
at 500 and 550 °C, but becomes positive in that annealed at
600 °C. Moreover, the unit cell volume changes more in the
thin film annealed at 500 °C than that at 550 °C.
As is known, A ­ g+ may exist in different forms in the
sol–gel derived thin films. One is that ­Ag+ ion replaces the
appropriate ion in the lattice point to form the Ag doped
thin film [17, 20–22]. The other is that A ­ g+ will typically
form Ag nanoparticles in the thin films without being

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J Mater Sci: Mater Electron (2017) 28:5652–5662
Fig. 2  XRD patterns of ­BiFeO3 thin films with the molar ratio x of
Ag/Fe ranging from 0 to 0.7 annealed at a 500 °C, b 550 °C and c
600 °C
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detected by XRD and SEM [16, 17]. In this work, the unit
cell volume of the bismuth ferrite decreases with Ag added
in the thin films prepared at 500 and 550 °C, but increases
in that prepared at 600 °C, although one sample with x = 0.5
shows negative result which may be from the experimental
fluctuation.
Considering the thin film with Ag substituting into the
lattice, the unit cell volume of the thin film may change
compared with that without Ag. In the thin films, Ag is easy
to replace Bi in the lattice structure, according to the size
controlling law considering ion doped into lattice structure.
The defect reaction will probably occur as following.
1
Ag + BiFeO3 → Ag��Bi + FeFe + V∙∙O + O2 + Bi0 + 2OO
2
(1)
As shown in Eq. (1), ­Bi0 would react with some
remaining ions such as ­Ag+ and ­O2− to form Ag-Bi alloy
and bismuth oxide. Meanwhile, the oxygen vacancy
will form as the B ­ i3+ is substituted by the A
­ g+ ion. As
+
is known, the size of A ­ g (1.28 Å) is larger than that
of ­Bi3+ (1.17 Å) when considering their 6 coordination
numbers. There are hence two possible cases appearing
during substituting ­Bi3+ ion by ­Ag+. One is that the cell
volume increases with adding Ag in the lattice because
the size of A ­ g+ ion is larger than that of ­Bi3+ ion. The
other is that cell volume decreases with increasing oxy-
gen vacancies although the large size ­Ag+ ion increases.
It is clear as shown in Table 1, the unit cell volume of the
bismuth ferrite phase decreases when Bi ion is replaced
by Ag ion. It implies that the Ag ions would substitute
for ­Bi3+ ion. The oxygen vacancies control the cell vol-
ume dominantly in this case. Therefore, the more the
Ag doped, the smaller the cell volume of the ferrite sin-
tered at 500 and 550 °C. Moreover, in the ferrite system,
the sintering temperature will control the formation of
the vacancies. Except for the oxygen vacancy discussed
above, the intrinsic Bi vacancies will be formed in the
ferrite sintered at different temperatures. When the tem-
perature is relatively high, such as 600 °C, the intrinsic
bismuth vacancies may be formed significantly due to the
easy evaporation nature of the Bi ion in the ferrite. So
the Ag is easy to fill into the bismuth vacancy instead of
replacing Bi in the lattice structure at high temperature.
In this case, the oxygen vacancies can not form, whereas
the intrinsic Bi vacancies are filled with increasing Ag
in the ferrite. That’s why the cell volume increases with
increasing Ag in the ferrite sintered at high temperature
of 600 °C. But for the sample sintered at low temperature,
oxygen vacancies are more likely to form when substi-
tuting Ag based on Eq. (1). The cell volume decreases
thus with increasing Ag in the ferrite. And, when the fer-
rite is sintered at the medium temperature of 550 °C, the
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5656
Table 1  Unit cell volumes ­Vx x Vx /Å3 − (α)
and rates of volume change
α = (Vx − V0)/V0 of B
­ iFeO3 thin 500 °C
films with the molar ratio x of
Ag/Fe ranging from 0 to 0.7 at 0 368.8699 − (0)
different annealing temperatures 0.2 367.5263 − (−0.00364)
0.4 367.3075 − (−0.00424)
0.5 367.6447 − (−0.00332)
0.6 366.6471 − (−0.00603)
0.7 366.9835 − (−0.00511)
intrinsic Bi vacancies may be partly formed. The small
part of Ag may fill into the Bi vacancy site while the
large part of the Ag may substitute still for Bi in the fer-
rite. The cell volume decreases hence with increasing Ag
but the change rate is smaller than that of the sample sin-
tered at 500 °C as shown in Table 1. As a consequence,
all the experimental results of thin films sintered at differ-
ent temperature revealed that the Ag ions were doped into
the bismuth ferrite phase to substitute for Bi and the Ag
doped ­BiFeO3 was formed.
Furthermore, other than some Ag ions being doped
into the bismuth ferrite, the remaining Ag ions would
form Ag nanoparticles dispersed in the thin film. Figure 3
shows the UV–Vis absorption spectra of the thin films
with different molar ratios of Ag/Fe at different annealing
temperatures. An absorption peak around 403–409 nm
appears in the Ag/BiFeO3 thin film. The peak intensity
and area increase with the increase in Ag content in the
thin film. It is reported that the absorption peak around
410 nm appearing in the UV–Vis absorption spectra of
the thin films is ascribed to the surface plasmon reso-
nance (SPR) of Ag nanoparticles [16, 17, 23]. The size of
Ag nanoparticles can be calculated according to the peak
position and its full width at half maximum as follow [16,
24].
2vf
D= (2)
Δ𝜔1∕2
where νf is the Fermi velocity of an electron, which is
1.39 × 106 m/s for Ag. Δω1/2 is the full width at half maxi-
mum of the absorption peak in angular frequency. D rep-
resents the average diameter of Ag nanoparticles. The
diameter of Ag nanoparticles in this work is 4–8 nm. As
shown in Table 2, the particles do not show dramatic differ-
ence in size among the thin films with different Ag content
from x = 0.2 to x = 0.7 and at different annealing tempera-
ture of 500, 550 and 600 °C. Figure 4 shows the HRTEM
of the Ag doped thin film in which the Ag nanoparticle in
Fig. 4a as well as the fringe image in Fig. 4b can be clearly
seen, confirming that they are Ag nanoparticles in the
­BiFeO3 matrix. The size of the Ag nanoparticle is about
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J Mater Sci: Mater Electron (2017) 28:5652–5662
550 °C 600 °C
371.0962 − (0) 367.6003 − (0)
370.5478 − (−0.00148) 367.7766 − (0.00048)
370.2763 − (−0.00221) 368.1072 − (0.00138)
370.2857 − (−0.00218) 366.7250 − (−0.00238)
370.2682 − (−0.00223) 368.2771 − (0.00184)
369.4757 − (−0.00437) 368.0968 − (0.00135)
10 nm, which is quite close to the size calculated from
the UV–Vis absorption spectra. Obviously, Ag nanoparti-
cles were formed and dispersed in ­BiFeO3 matrix, and Ag/
BiFeO3 composite thin films were obtained.
In fact, the quantity of Ag nanoparticles in the compos-
ite thin film can be estimated from the peak area in UV–Vis
absorption spectra [16–18]. The amount of Ag nanoparti-
cles increases obviously with increasing molar ratio of Ag/
Fe and annealing temperature calculated from Fig. 3.
In order to make it clear how Ag nanoparticles are
formed and what determined the amount, Ag/BiFeO3 thin
film, which is heated at 400 °C for only 5 min instead of
10 min in the second step, was prepared in this work. In
fact, at the beginning of the thin film preparation, Ag par-
ticles had formed in the xerogel precursor as shown in
Fig. 5a. During the heat treatment of the thin film prepa-
ration, Ag particles and Bi started to form Ag-Bi alloys at
262 °C [25]. The higher the temperature, the more rapidly
the Ag particles reacted with Bi. However, Bi would form
­Bi2O3 by oxidization at high temperature above 400 °C
[26] instead of forming the Ag-Bi alloy. In addition, ­Fe2O3
begins to form above 125 °C from the decomposition of
Fe(NO3)3 and starts to react with ­Bi2O3 to form ­BiFeO3
around 480 °C [27]. The formation of alloys would gradu-
ally stop above 400 °C. So the longer the time of the sec-
ond step of heating at 400 °C, the more the Ag-Bi alloy are
formed in the thin film. Meanwhile, as is reported [16, 18],
Ag nanoparticles dispersed in thin film of lead titanate is
synthesized via forming the Ag–Pb alloy as transition phase
during heat treatment and then decomposing to Ag nano-
particles around 400 °C. For the similar perovskite system
of Ag/BiFeO3 in this work, it has almost the same phase
diagram as that of Ag/PbTiO3. The Ag-Bi alloy would most
probably decompose to Ag nanoparticles in the B ­ iFeO3 thin
film above 400 °C instead of being formed dominantly. So
in the second step of heating at 400 °C, 10 min are enough
to make Ag-Bi alloys form completely from large sized Ag
particles. All the Ag-Bi alloys will decompose to Ag nano-
particles at high sintering temperature as shown in Figs. 1
and 3. It is clear when the time for the second step heat is
not long enough, such as 5 min only, some micro-sized Ag
particles are not transformed to be Ag-Bi alloys. They will
J Mater Sci: Mater Electron (2017) 28:5652–5662 5657

Table 2  The size of nano-particles in the thin films with different

molar ratio x of Ag/Bi at the third step of annealing temperature of
500, 550 and 600 °C

Sintering Size of Ag nanoparticles /nm in the thin film

temperature/°C with Ag/Fe molar ratio of
0.2 0.4 0.5 0.6 0.7

500 6.2 4.2 4.4 4.6 4.8

550 5.5 5.2 5.8 4.9 6.3
600 5.1 5.8 4.9 4.6 7.9

Fig. 4  a Morphology of the Ag/BiFeO3 thin film with the molar ratio
of Ag/Fe of 0.4 annealed at 550 °C measured by HRTEM. b Image of
the Ag nanoparticle measured by HRTEM

still remain at high temperature due to its high chemical

Fig. 3  UV–Vis absorption spectra of B ­ iFeO3 thin flms with molar
ratio x of Ag/Fe ranging from 0 to 0.7 annealed at a 500 °C, b 550 °C
and c 600 °C
stability as shown in Fig. 5b, not forming finally nano Ag
particles in the thin film. Obviously in the Ag/BiFeO3 sys-
tem, the Ag-Bi alloys are formed as transition phase prob-
ably during heat treatment and decomposed to Ag nano-
particles in the B
­ iFeO3 matrix eventually. As the annealing
temperature increased, more Ag nano-phase formed and
thus a larger amount of Ag nanoparticles could be obtained
in the thin film matrix. In addition, the Ag nanoparticles

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5658 J Mater Sci: Mater Electron (2017) 28:5652–5662

Fig. 5  SEM image of a Ag–Fe–Bi xerogel coating on the ITO glass

without heat treatment and b Ag/BiFeO3 thin films after treatment
during which it is annealed with the second step of 400 °C for only
5 min

would form dominantly when the content of Ag ions was

higher in the system.
Figure 6 shows the dielectric constant of Ag/BiFeO3 thin
films with the molar ratio x of Ag/Fe ranging from 0 to 0.7
at different annealing temperatures. The dielectric constant
at 40 Hz is about 50 for ­BiFeO3 thin film without Ag and
increases gradually to ~80 with increasing x to 0.5 in the
thin film annealed at 500 °C. After that, the dielectric con-
stant increases sharply to 185 with increasing x to 0.6 and
then decreases slightly to 114 with increasing x to 0.7 as
shown in Fig. 6a. Likewise, as shown in Fig. 6b, c, the die-
lectric constants increase sharply to about 203 annealed at
550 °C and 116 at 600 °C with increasing x to 0.4 and 0.7,
respectively. Clearly, all the samples reveal the standard
dielectric constant-frequency curve, which respond to the Fig. 6  Dielectric constant of B
­ iFeO3 thin films with the molar ratio
x of Ag/Fe ranging from 0 to 0.7 annealed at a 500 °C, b 550 °C and
dipoles with respect to Debye polarization. So the relation- c 600 °C
ship of dielectric constant and frequency of the composite
thin film is intrinsically related with the perovskite phase of

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J Mater Sci: Mater Electron (2017) 28:5652–5662
­BiFeO3. Moreover, there are two important factors which
dominate the permittivity of the composite thin film. One
is the micro-capacitor which will generate significantly in
dielectric composite thin film as the conductive nanopar-
ticles are filled into the thin film matrix [16]. The other is
the inner electric field induced by the conductive filler dis-
persed in the thin film. When the conductive Ag nanopar-
ticles are filled into the thin film matrix, micro-capacitors
can be formed as a series equivalent circuit along external
electric field in which the conductive Ag nanoparticles
are inner electrode and ­ BiFeO3 between two Ag nano-
particles is dielectrics. The more the amount of Ag nano-
particles dispersed in the thin film, the closer the two Ag
electrodes and thus the higher the total capacitance of the
whole micro-capacitor. The apparent dielectric constant of
the composite thin film will increase with the increase in
the amount of Ag nanoparticles. In addition, the conduc-
tive filler of Ag nanoparticles will introduce the electric
field around the nanoparticles as external field is applied
across the thin film. The dipoles in dielectric thin film will
be polarized effectively especially for the area around the
conductive Ag nanoparticles. The dielectric constant will
increase with the increase in the amount of Ag nanoparti-
cles as well. Therefore, The Ag nanoparticles will increase
the permittivity of the composite thin film.
The dielectric constant of the Ag/BiFeO3 composite
thin film is also influenced by intrinsic properties of pure
­BiFeO3 thin film. Thin film sintered at 600 °C would con-
tain considerably oxygen and bismuth vacancies as dis-
cussed above according to the change of lattice constant
as shown in Fig. 2 and Table 1, which results in difficult
oscillation of dipole moment due to interaction between the
dipoles and vacancies. However, for the thin film annealed
at 550 °C, the relatively perfect crystalline phase is formed,
as shown also in Fig. 2 and the number of vacancies would
be hence low according to the variation of lattice constant
shown in Table 1. The dipole moment will oscillate nor-
mally without being restrained. As for the thin film sintered
at 500 °C, vacancies are less than that sintered at 600 °C,
but the crystalline phase is not so perfect compared to that
sintered at higher temperature. So the thin film annealed at
550 °C shows highest dielectric constant and that annealed
at 600 °C shows the lowest. The intrinsic dielectric con-
stant underlies the increase in that of Ag/BiFeO3 compos-
ite thin film. After introduction of the same content of Ag,
the higher dielectric constant will appear in the thin film
annealed at 550 °C but lower one at 600 °C. Obviously,
intrinsic dielectric constant is beneficial to improve the die-
lectric constant of the composite thin film.
Figure 7 shows the dielectric loss of Ag/BiFeO3 thin
films with different Ag contents and different annealing
temperatures, in which the minimum dielectric loss appear-
ing between 1 and 100 kHz is used to consider the influence
5659
of Ag content added in the thin film. The dielectric loss is
0.19, 0.1 and 1.7 in the thin film without Ag annealed at
500, 550 and 600 °C respectively. After introducing Ag, the
dielectric loss becomes a little bit higher in the thin film
sintered at 500 and 550 °C while decreases in the thin film
sintered at 600 °C as shown in Fig. 7d in which dielectric
loss dependence of silver content is revealed.
As mentioned above, the crystalline phase of ­BiFeO3
is formed perfectly relatively at sintering temperature of
550 °C, while lots of Bi and O vacancies will appear in the
thin film sintered at 600 °C. Therefore, the intrinsic dielec-
tric loss is below 0.1 in the thin film without Ag sintered
at 550 °C and up to 1.7 in the thin film sintered at 600 °C.
When Ag is introduced, dielectric loss of the thin film will
change differently at different annealing temperatures. In
the thin film annealed at 500 and 550 °C, Ag ions would
substitute for Bi and oxygen vacancies generated, lead-
ing to the increase in dielectric loss. However, in the thin
film annealed at 600 °C, Ag ions would fill into bismuth
vacancies formed previously due to volatilization of Bi. Bi
vacancies will decrease with increasing Ag in the Bi ferrite,
resulting in the decrease in dielectric loss. Moreover, the
conductive Ag nanoparticles would connect with each other
in the thin film as silver fraction increased to some extent,
leading to the high leakage current. Thus the dielectric loss
typically increased as the molar ratio of Ag/Fe reached to
0.4 and 0.6 respectively for the thin film sintered at 550 and
600 °C as shown in Fig. 7d. In addition, the nanoparticles
will aggregate with other close ones to form large sized
particles in the samples with extremely high content of Ag
such as x = 0.7 sintered at 550 °C. With the similar amount
of Ag added in the thin film, the large sized conductive par-
ticles show little connection in this case and the dielectric
loss thus decrease from high of ~0.7 at x = 0.4–0.6 to low
of 0.1–0.2 at x = 0.7. Apparently, both the intrinsic proper-
ties and conductive filler dominate the dielectric properties
of the Ag/BiFeO3 composite thin film.
Except for the attractable dielectric properties occur-
ring in the Ag/BiFeO3 composite thin film, the Ag/BiFeO3
composite thin film still shows the intrinsic weak ferromag-
netism as revealed by the single phased B ­ iFeO3. Figure 8a,
b show the magnetic hysteresis loops of Ag/BiFeO3 thin
films sintered at 500 and 550 °C respectively, which have
relatively high dielectric constants simultaneously. The
hysteresis loops and the magnetization still appear although
the area of loop and the value of saturation magnetization
decrease a little with increasing Ag content. As is known,
the magnetic moment and the loops result from the canting
of Fe sub-lattices [6] in the ­BiFeO3. The saturation mag-
netization is dependent on the amount of magnetic moment
and its net strength of the moment. On one hand, the mag-
netization of the bismuth ferrite will increase as the dimen-
sion of the ­ BiFeO3 is below the periodicity of cycloid
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5660 J Mater Sci: Mater Electron (2017) 28:5652–5662

Fig. 7  Dielectric loss of ­BiFeO3 thin films with the molar ratio x ▸
of Ag/Fe ranging from 0 to 0.7 annealed at a 500 °C, b 550 °C and
c 600 °C. d Plots of dielectric loss (minimum value) of B
­ iFeO3 thin
films as a function of the molar ratio of Ag/Fe sintered at different
temperatures

modulation of the ordering which is 62 nm. For example, in

the Ag-doped B ­ iFeO3 nanoparticles reported [11], the par-
ticle size is below 62 nm and decreases with increasing Ag
content. The magnetization increases thus with decreasing
the particle size [28]. However, in this work, the decrease in
the size of ­BiFeO3 crystalline phase has not been observed
and more perfect B ­ iFeO3 phase is formed in the thin film. It
implies that the magnetization may decrease with increas-
ing Ag. On the other hand, Ag is a kind of diamagnetic
element, while ­BiFeO3 just exhibits weak ferromagnetism.
Ag nanoparticles formed in the thin film will most prob-
ably make the magnetization weaker. Hence, the saturation
magnetization becomes lower with increasing Ag content.
In addition, the residual magnetization and the coercive
force seem not to change so obviously with Ag added into
the thin film, implying that Ag has almost not affected the
ferromagnetism of the Ag/BiFeO3 composite thin film. The
introduction of Ag would not destroy the ferromagnetic
behavior of the composite thin film other than reducing sat-
uration magnetization.
As a matter of fact, the suitable saturation magnetization
still maintains in the Ag/BiFeO3 thin film with appropriate
Ag content. Such as the thin film with the molar ratio of
Ag/Fe of 0.2 sintered at 550 °C mentioned above, its satura-
tion magnetization of 2.2emu/cm3 is still in the range in the
­BiFeO3 thin film reported [13]. Furthermore, other than the
conventional saturation magnetization and ferromagnetism,
the dielectric constant of 139 and dielectric loss of 0.15
appear in the composite thin film. It is attractive that typical
ferromagnetism and high permittivity appeared in the Ag/
BiFeO3 composite thin film simultaneously.

4 Conclusions

The Ag/BiFeO3 composite thin films were prepared by

sol–gel method with the perovskite phase of ­BiFeO3 as
matrix. Some ­Ag+ ions were doped into the bismuth ferrite
phase to substitute for Bi in the perovskite lattice, forming
the Ag doped B ­ iFeO3 in the composite. Most of the A ­ g+
ions formed Ag nanoparticles dispersed in matrix with the
size of 4–8 nm. Ag nanoparticles introduced both the effec-
tive inner electric field and the equivalent micro-capacitor
in matrix to increase the dielectric constant of the compos-
ite thin film. The dielectric constant increased to 139 for
the thin film with the molar ratio of Ag/Fe of 0.2 sintered
at 550 °C, nearly twice as large as that of pure B ­ iFeO3.

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J Mater Sci: Mater Electron (2017) 28:5652–5662
Fig. 8  Magnetic hysteresis loops of ­BiFeO3 thin films with the molar
ratio x of Ag/Fe ranging from 0 to 0.7 annealed at a 500 °C and b
550 °C
Meanwhile, the dielectric loss kept a low value of 0.15.
Moreover, Ag nanoparticles dispersed ­BiFeO3 weakened
the magnetization but without destroying the ferromagnetic
behavior of the composite thin film. The composite thin
film still kept the general weak ferromagnetism with the
saturation magnetization of 2.2 emu/cm3. Both the ferro-
magnetism and high permittivity are achieved in the com-
posite thin film simultaneously, which make it attractive to
be used as a multifunctional material in electronic devices
for high performance and miniaturization.
Acknowledgements This work was supported by the Zhejiang Pro-
vincial Natural Science Foundation (grant number LY17E020006)
and the Natural Science Foundation of China (grant numbers
51272230 and 50672084). This work was also supported by the Fun-
damental Research Funds for the Central Universities of China (grant
number 2016QNA4009).
5661
Author contributions SC designed and conducted the experiments,
and then finished manuscript. QX analyzed the data and wrote the
manuscript partially. XH participated in measuring the properties of
the samples. ZW has taken care of the proof-reading of the manu-
script and helped to enhance the readability. ZW, NM and PD were
involved in the guidance of the experiments designing, the prepara-
tion and revision of the manuscript.
Compliance with ethical standards
Conflict of interest The authors declare that they have no conflict
of interest.
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