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Reddy, V. V. Bhanu Prasad, S. Bysakh, V. Shanker, N. Y. Hebalkar and S. Roy, J. Mater. Chem. C, 2019, DOI:
10.1039/C9TC00569B.
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Page 1 of 32 Journal of Materials Chemistry C
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DOI: 10.1039/C9TC00569B
Superior energy storage performance, and fatigue resistance in
ferroelectric BCZT thin films grown in oxygen rich atmosphere
Journal of Materials Chemistry C Accepted Manuscript

Seelam Rangaswamy Reddy 1,3, Velidandla Venkata Bhanu Prasad1, Sandip Bysakh2,Vishnu
Shanker3, Neha Hebalkar4 and Subir Kumar Roy1*

Published on 03 May 2019. Downloaded by Idaho State University on 5/3/2019 2:48:30 PM.
Affiliation: 1Ceramics and Composites Group, Defence Metallurgical Research Laboratory, Hyderabad-500058,
India. 2Central Glass and Ceramics Research Institute, Jadavpur, West Bengal, India. 3Department of Chemistry,
National Institute of Technology, Warangal-506004, India, 4International Advanced Research centre for Powder
Metallurgy and new materials (ARCI), Hyderabad-500005, India.
Keywords: Lead free ferroelectric, BCZT, chemical solution deposition, energy storage density,
polarization fatigue.
Abstract: Ferroelectric properties of the chemical solution deposited (Ba0.85Ca0.15Ti0.90Zr0.10O3)
BCZT thin films in the 200 nm thickness range, grown in air and oxygen rich atmosphere were
investigated. Oxygen processed BCZT thin films were found to have very slim hysteresis with
high maximum polarization, lower remanent polarization (Pr), much lower coercivity and much
higher dielectric breakdown strength. Those properties resulted superior energy storage
properties. Oxygen processed BCZT thin films showed energy storage density (ESD) of 64.8
J/cm3 and energy storage efficiency (ESF) of 73% at 2000 kV/cm. Apart from that, the films
showed very low leakage current and improved fatigue properties. Oxygen processed virgin
BCZT film displayed maximum polarization (Pmax) of 106 μC/cm2 and Pr of 12.9 μC/cm2
whereas, the measured Pmax and Pr on the fatigued film after 1010 switching cycles were 105
μC/cm2 and 13.2 μC/cm2 respectively. BCZT thin films with high ESD, ESF at 2000 kV/cm and
with excellent fatigue properties could be considered as the potential candidates for low and
intermediate voltage ferroelectric energy storage applications.

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*Communicating author: Subir K. Roy (e-mail: r_subir@yahoo.com, r_subir@dmrl.drdo.in) Tel.: 040-24586663;
Fax: 040-24340683.

Introduction:
Rapid development of miniature power electronics and pulsed power systems in the recent years
triggered the necessities for the development of low cost high energy storage density (ESD) and
high efficiency dielectric capacitors1-5. Recent advancement in this area has been highlighted
with the reports on polyvinylidene fluoride (PVDF)-based relaxor ferroelectric (RFE) polymer
and Pb-based antiferroelectric (AFE) films. ESD as high as 25 J/cm3 at an electric field > 8
MV/cm and 61 J/cm3 at an electric field of 4.3 MV/cm respectively were reported for these
films6-7. However, high energy densities in these systems were achieved at very high electrical
field where the energy efficiencies were compromised to a higher extent. Recently, worldwide
campaigning for environment friendly functional materials forced the researcher for the
development of the Pb free systems leading to the innovation of some potential Pb free films
with very high ESD. 0.60SrTiO3 −0.40BiFeO3(BFSTO)4 thin films processed by Pulsed laser
deposition(PLD) on Nb-doped single crystal SrTiO3 substrate with ESD 70.3 J/cm3 at an electric
field 3.85 MV/cm, antiferroelectric HfxZr1-xO2(HZO)8 thin films developed by combined DC
sputtering and thermal atomic layer deposition (ALD) on Si/TiN substrate with ESD 46 J/cm3 at
electric field 4.5 MV/cm, multilayered thin film containing barium zirconate titanate (BZT) and
barium calcium titanate (BCT)5 layers processed by magnetron sputtering on Nb-doped single
crystal SrTiO3 substrate with ESD 52.4 J/cm3 at electric field 4.5 MV/cm, PLD processed
epitaxial BNLBTZ9 thin film on single crystal SrTiO3 substrate with ESD as high as 154 J/cm3 at
electric field 3.5 MV/cm, were already reported in the literature. However, implementation of
energy storage at very high electrical field poses critical disadvantages towards practical
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applications of energy storage device. Special insulations are essential to shield the device
components from electrical discharge at high electrical field and for safe charge-discharge cycles

of the electrical capacitor. Moreover, risk of electrical breakdown is higher at high electrical
field10-11. Hence, current research is focused on the achievement of high ESD and energy storage
efficiency (ESF) at lower electrical field10, 12. Additional advantages may be gained by opting
chemical solution deposition (CSD) technique, which is highly suitable for mass production.
Very recently S. Cho et al.13 reported PLD processed BaTiO3-BiFeO3 (BTO-BFO) thin film on
single crystal SrRuO3/SrTiO3 substrate with ESD 52 J/cm3 at electric field of 2.05 MV/cm. Do-
Kyun Kown et al.14 reported CSD processed BaTiO3–Bi(MgTi)O3 (BT-BMT) thin films on Pt-
coated Si wafer with ESD 37 J/cm3 at a low electric field of 1.9 MV/cm. However, there were no
reports on energy storage efficiency and fatigue properties of the films in these two
communications, without which true potential of those systems could not be estimated. CSD
processed ferroelectric films received considerable attention towards practical application in
MEMS industries as films with reproducible properties and larger area can be processed by CSD.
Recently Liu et al.15 reported giant piezoelectric properties (d33=620 pC/N) for a lead free
composition: 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 however, energy storage and fatigue
properties of this composition in the form of thin film remained largely unexplored.
In the present manuscript we report exceptionally high energy density of 64.8 J/cm3 at a
low electric field of 2.0 MV/cm for a CSD processed Pb-free 0.5Ba(Zr0.2Ti0.8)O3-
0.5(Ba0.7Ca0.3)TiO3 (Ba0.85Ca0.15Ti0.90Zr0.10O3) ferroelectric thin film on Pt coated Si wafer with
superior fatigue properties (up to 1010 cycles) and considerable energy storage efficiency (73%).
Reports on such high energy density at that low electric field range along with superior fatigue
properties for a Pb free ferroelectric system are extremely limited in the literature. We have
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observed that the thin films grown and annealed in oxygen rich atmosphere displayed slim
hysteresis loop characteristics with high Pmax (106 µC/cm2) which were suitable for obtaining

high energy density. Effects of oxygen atmosphere during crystallization of the film and
annealing on the oxygen vacancies present in the film were also discussed.
Experimental methods:
BCZT thin films of composition Ba0.85Ca0.15Ti0.90Zr0.10O3 were fabricated on Si/SiO2/TiO2/Pt
(100) substrates following sol-gel spin coating technique. BCZT precursor sol was synthesized
using Barium acetate (Sigma Aldrich, purity 99.5%), Calcium carbonate (Sigma Aldrich, purity
99.95%), Zirconium n-propoxide solution (Sigma Aldrich, 70 wt% in 1-propanol), and Titanium
iso-propoxide (Sigma Aldrich, purity 97%) as the raw materials and 2-Methoxy ethanol (Alfa
Aesar, purity 99%), glacial acetic acid (Merck, purity 99.8%) and distilled water as the solvents.
Acetyl acetone, (Sigma Aldrich, purity 99%) a chelating agent was used as the stabilizer for
Zirconium and Titanium alkoxides. For the synthesis of BCZT precursor sol, Ba-Ca and Ti-Zr
solutions were prepared separately. Ba-Ca solutions were prepared by dissolving Ba (CH3COO)2
and CaCO3 in glacial acetic acid and Ti-Zr solutions were prepared by adding Titanium iso-
propoxide and Zirconium n-propoxide to the mixed solution of 2-Methoxy ethanol and Acetyl
acetone. Then the Ba-Ca and Ti-Zr solutions were mixed on hot plate at 70 oC for 40 minutes to
obtain homogenous precursor sol. The precursor sol concentration was adjusted to 0.25 molarity.
For the synthesis of BCZT thin films the precursor sol was aged for 4-5 days to ensure partial
gelation before it was used for spin coating. BCZT sol was modified for obtaining crack free film
using PVP (Polyvinyl pyrrolidone) binder with an average molecular weight of 10000. PVP was
added to the BCZT sol in the molar ratio of 1:0.5(BCZT : PVP). The weight of one PVP
monomer was taken as the molecular weight of PVP for the calculation of molar ratio.
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BCZT sol-gel chemical reactions

Stage-I
Chemical reactions in Ti and Zr alkoxides stabilized by acetyl acetone

The reactions of Ti and Zr alkoxides [M(OR)4], (M=Ti/Zr) with acetyl acetonate (Acac=C5
H7O2- ) ligands are already reported in the literature16-19. It was revealed that Acac, being a
strong ligand form chelate complex with the transition metals in which OR groups are partially
or fully substituted by Acac. The extent of substitution depends on the amounts (alkoxide-AcacH
molar ratio) of acetylacetone (AcacH) in the solution.
M(OR)4 + AcacH [M(OR)4-x(Acac)x] +xROH
Stage -II: Mixed precursor solution of acetyl acetone stabilized Ti and Zr alkoxide is added to
the mixed solution of Ba and Ca in acetic acid.
The mixed colloidal BCZT sol contains of Ba2+, Ca2+, Ti (O iPr)4-x(Acac)x and Zr(O nPr)4-
x(Acac)x species in organic solvent (Ti-precursor is Ti iso-propoxide and Zr-precursor is Zr n-
propoxide dissolved in n- propanol).
Stage -III:
Drying of the spin coated BCZT sol on the substrate results solvent removal from the sol leading
to BCZT gel. It is well known that chemical reactions in metal alkoxide sol-gel process involve
hydrolysis and condensation reaction of the Ti and Zr- chelate complexes in presence of alcohol
and water resulting 3-dimensional polymeric -M-O-M- network (M= Ti/Zr) in the final mixed
metal alkoxide gel19 (Fig. 1) .

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The role of PVP in chemical sol:

PVP being a strong ligand interacts intimately with the Zr and Ti complex species using its
electron donating sites20. Moreover, steric hindrance of the polymer chains of PVP provides
protective envelope over the Zr and Ti complex species which prevents their agglomeration
(Fig.1) and thus addition of insufficient quantity of hydrolyzing reactant (water) and PVP
ensures controlled hydrolysis avoiding the formation of viscous gel or precipitate. It is to be
mentioned that addition of small amount of water and PVP to the sol before spin coating helps in
obtaining thin films with minimized defects e.g. cracks, micro pores and macro pores etc.
Figure 1. Schematic diagram for the chemical processing of BCZT thin film from chemical
precursor sol
The PVP modified sol was filtered through a 0.2 μm syringe filter and spin coated at 500 rpm for
10 seconds followed by 3000 rpm for 30 seconds on cleaned Pt/Si (100) substrates. The spin
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coated BCZT films were dried on hot plate at ~150 oC. After the spin coating and baking of the
film, the BCZT thin films were processed in two different types of atmosphere. The first set of

films were grown and annealed in ambient air atmosphere and the other set of films were grown
and annealed in oxygen rich atmosphere (oxygen pressure of 3 bars at the entree port of the
tubular furnace) at 700o and 800 oC temperature using conventional tubular furnace. Higher
oxygen pressure was avoided because reported literature indicated that processing of
ferroelectric films in the atmosphere with very high oxygen partial pressure decreased the
crystallinity of the films21. For electrical property characterization Au electrodes were deposited
with 250 µm diameter by sputtering. Phase and crystal structure of the BCZT thin films were
analyzed by grazing incidence X-ray diffraction (GIXRD) using Rigaku smart lab X- ray
diffractometer (Rigaku, Japan). High-resolution transmission electron microscope (HRTEM),
model Tecnai G2 30ST (FEI, Netherland) was used to study the microstructure of the BCZT
films. Capacitance-voltage butterfly loops, dielectric loss, ferroelectric hysteresis loops,
polarization fatigue and leakage current of the films was measured using Keithley semiconductor
characterization system (Model: Keithley 4200 SCS, USA). Surface morphology and roughness
was studied by atomic force microscope. (Dimension icon AFM, Bruker AXS GmbH, Karlsruhe,
Germany). Concentration of Lattice oxygen, oxygen vacancy and chemisorbed oxygen in the
BCZT films were characterized using X-ray photo electron spectroscopy (XPS, Omicron
Nanotechnology, U.K). Crystal structure, microstructure and electrical properties of the BCZT
films were analyzed at room temperature.
Results and discussion:

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Figure 2 (a) GIXRD patterns of the air and oxygen processed BCZT films, (b) cross section
TEM image of the BCZT film, (c) SAED pattern image and (d) HRTEM showing the (100) and

(110) planes of two neighboring BCZT grains.
Grazing incidence X-ray diffraction (GIXRD) patterns of BCZT films processed in air and
oxygen rich atmosphere at 700 and 800 oC temperatures (BCZT700-air, BCZT800-air,
BCZT700-O2 and BCZT800-O2) are presented in Figure 2a. A grazing angle of 0.5o and Cobalt
kα radiation was used in order to avoid Pt and Si peaks from the substrate. X-ray diffraction
patterns of the films demonstrate the occurrence of pure polycrystalline BCZT with perovskite
orthorhombic structure (space group: Amm2). Similar observations were also made earlier by the
researchers working on bulk BCZT polycrystalline ceramics22. Film thickness was measured by
transmission electron microscopy (TEM) and was found to be 200 nm as shown in figure 2b.
Figure 2c shows the selected area electron diffraction (SAED) pattern image of the BCZT film.
The d-spacing values calculated from the SAED patterns are matching with the same calculated
from the GIXRD patterns of the BCZT films. HRTEM image (Figure 2d) of the BCZT film
indicates the presence of neighboring atomic planes (‘100’), (‘110’) and BCZT-Pt interface.
Surface morphology and surface roughness was investigated by atomic force microscope (AFM).
It was observed from the AFM images shown in figure S1 (supplementary information) that the
roughness of the films decreased with oxygen annealing. The measured roughness for BCZT700-
air, BCZT800-air, BCZT700-O2, BCZT800-O2 are 3.15 nm, 2.16 nm, 1.66 nm, 1.64 nm
respectively. Moreover, it was observed from the AFM images that oxygen processing increased
grain size uniformity by suppressing uneven grain growth.

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Figure 3 (a) XPS survey spectrum obtained from the surface of the BCZT700-O2 film, high
resolution O 1s spectrum of (b) BCZT700-O2, (c) BCZT700-air, (d) BCZT800-O2 and (e)
BCZT800-air films.
Since, the BCZT thin film samples were processed in two different atmosphere (ambient air and
oxygen rich atmosphere) it was assumed that some of the oxygen vacancies which usually result
from ambient air processing of the ceramic oxide thin films, would be compensated by
processing the same in oxygen rich atmosphere. To investigate the effect of oxygen processing
on the concentration of oxygen vacancies in the BCZT films, XPS measurements were
performed. The typical XPS survey spectrum obtained from the surface of the oxygen processed
BCZT film is presented in Fig. 3a. As expected the survey spectrum shows the occurrence of
Ba, Ca, Zr, Ti and O peaks. However, the spectrum also indicates the existence of carbon due to
atmosphere contamination. C. Miot et al.23 reported XPS spectrum with high concentration of
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carbon that obtained from the surface of BaTiO3 ceramics. Moreover, in his analyses, the amount
of carbon reflected in the spectrum increased with the time of exposure of the samples in air as

well as in ultrahigh vacuum conditions. In the present analyses on the XPS spectra of BCZT thin
films, carbon 1s peak centered at 284 eV is considered as the reference for calibrating binding
energies of the elements present in BCZT composition. Fig. 3b-e show the O 1s spectra of the
BCZT-air and BCZT-O2 films. The unsymmetrical O 1s peak in each spectrum was
deconvoluted into three different component peaks. The peaks were centered at 528.49, 529.97
and 531.3 eV for the BCZT700-air film. The peak centered at 528.49 eV corresponds to lattice
oxygen ions (O2-) in the perovskite structure, whereas, the peak centered at 529.97 eV is
attributed to the O2-/O- ions caused by oxygen vacancies. And the peak centered at 531.3 eV
originates due to chemisorbed oxygen on the thin film surface as reported earlier by Y. Tu et al.24
and I. Usman et al.25 for the ZnO nano-rods and ZnO thin films respectively. However, the little
shift in binding energy for O 1s spectral components in BCZT thin films is due to different
chemical environment and as well as due to charging during XPS experiments26. Analyses on
the XPS spectra of the air and oxygen processed BCZT thin films revealed that oxygen
processing considerably reduced the area of the peak correlated to the oxygen vacancy in the
BCZT-O2 films and increased the area of the peak correlated to the lattice oxygen. From these
observations it can be concluded that oxygen processing effectively compensated the oxygen
vacancies present in the air- processed BCZT films.

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Figure 4 (a) DC electric field dependant dielectric constant and dielectric loss for BCZT-air
films, (b) DC electric field dependant dielectric constant and dielectric loss for BCZT-O2 films,

(c) Frequency dependant dielectric constant and dielectric loss for the BCZT-O2 films and (d)
Polarization vs. electric field hysteresis loops for the BCZT-air and BCZT-O2 films.
Figure 4a-b present the variation of dielectric constant and dielectric loss with DC
electric field at 10 kHz frequency. BCZT-air films exhibited higher dielectric constant and higher
dielectric loss than that of the BCZT-O2 films. XPS measurements indicated that higher
concentration of oxygen vacancy exists in the thin samples processed in air compared to the
films that were processed in oxygen rich atmosphere. Oxygen vacancies in a ferroelectric film
are believed to create conducting electrons as per the following equation27.
Oo (Oxygen ion at its normal site) Vo2+ (Oxygen vacancy) + 2e- + 1/2O2
The interactions of these electrons with the dipoles result high dielectric constant28. The above
mentioned equation pertaining to creation of the oxygen vacancy shifts to reverse direction in
oxygen rich atmosphere leading to compensation of the oxygen vacancies. The extent of vacancy
compensation will depend on the oxygen partial pressure and processing temperature. The
reduced oxygen vacancies in the oxygen-processed films reduce the formation of conduction
electrons and defect dipoles and thus the dielectric constant is lowered in the BCZT-O2 films.
However, the higher dielectric constant of the BCZT films annealed at 800 oC temperature
compared to the low temperature annealed films is attributed to the dense microstructure of the
films. Dielectric loss of BCZT-O2 films varied between 0.015 and 0.028 in the measured range
of electric field and is comparable to its bulk ceramic counterpart29. Whereas, the same varied
between 0.048 and 0.056 for the BCZT-air films, i.e. the recorded dielectric loss is 2-3 times
higher than that of the BCZT-O2 films. It is known that oxygen annealing reduces both the
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dielectric loss and leakage current in ferroelectric thin films30. Fig. 4c represents the frequency
dependant dielectric constant and dielectric loss for BCZT-O2 films measured at room

temperature with the application of 100 mV AC amplitude and 5V DC amplitude. The figure
indicates that dielectric constant varies minutely with frequency and the dielectric loss increases
slightly as the frequency is increased.
Figure 4d shows the P-E hysteresis behavior of the BCZT-air and BCZT-O2 films
measured at 1000 kV/cm electric field and 10 kHz frequency. In our previous work we observed
the unsaturated P-E loops with higher dielectric loss for the BCZT-air films similar to what given
in the figure31. Previous studies by different research groups revealed that oxygen vacancies are
the major sources of point defects in ferroelectric oxides. These defects usually increase leakage
current which in-turn changes P-E hysteresis behavior as an immediate effect32-33.Air processed
BCZT800 films exhibited fat hysteresis loops with the maximum polarization of 82 μC/cm2 and
remanent polarization of 25 μC/cm2. Whereas the BCZT800 films processed in oxygen rich
atmosphere showed very slim hysteresis loops with the maximum polarization (Pmax) of 73
μC/cm2 and remnant polarization (Pr) of 5 μC/cm2 at an electric field of 1000 kV/cm. Moreover,
coercivity (Ec) decreased by 4-5 times due to processing the films in oxygen rich atmosphere
(Fig. 4d). Similar significant change in polarization and coercivity has also been observed for the
BCZT700-O2 films (Table S1, supplementary information). This decrease in coercivity can be
attributed to the lowering of oxygen vacancies in the oxygen-processed thin films. Oxygen
vacancies are the dominant point defect in oxide ferroelectric materials and have been regarded
as the cause of pinning of domain walls, screening the electric field near the space charge region.
These two factors are strongly considered to increase the coercive field in the ferroelectric oxide
materials particularly in the form of thin films34. Oxygen vacancy also influenced the electrical
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breakdown strength of the BCZT films. It was observed from the electrical measurements that
average electrical breakdown strength of the oxygen-processed BCZT thin films is two times

higher than that of the air-processed BCZT films.
Figure 5. Polarization vs. electric field unipolar loops of (a) BCZT700-O2 and (b) BCZT800-O2
films measured with different electric fields.
Figure 5a-b shows the polarization vs. electric field unipolar loops for BCZT-O2 films recorded
at 10 kHz frequency with different electric fields. Pmax, Pr and coercivity increased with electric
field. BCZT700-O2 film showed maximum polarization of 87 μC/cm2 and remanent polarization
of 11 μC/cm2, while the BCZT800-O2 film showed maximum polarization of 106 μC/cm2 and
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remanent polarization of 12.9 μC/cm2 at an applied electric field of 2000 kV/cm. However,
Pmax-Pr values for BCZT-O2 films were significantly increased with the applied electric filed. A

higher value of Pmax-Pr of the oxygen-processed BCZT films enabled us to obtain high ESD and
ESF. ESD can be mathematically expressed as per the equation (1).

𝑃 𝑚𝑎𝑥
𝑊𝐸𝑆𝐷 =∫𝑃𝑟 𝐸𝑑𝑃 0 ≤ E ≤ Emax …………….. (1)
Where E is the applied electrical field, Pr and Pmax are the remanent and maximum polarization
respectively. The ESD was calculated following the method described in the literature2. The
shaded area as indicated in Figure 6a corresponds to the recoverable energy density. The
maximum ESD values obtained from BCZT700-O2 and BCZT800-O2 at electric field of 2000
kV/cm are 54.5 and 64.8 J/cm3 respectively. Reports of such high values of ESD in Pb based or
Pb free materials of any kind: dielectric/ferroelectric /antiferroelectric at ≤ 2000 kV/cm are very
limited in the literature. For practical energy storage device applications, ESF is as important as
ESD and the former was calculated from the relative ratio of recoverable energy density to the
sum of energy density and loss (calculated from the P-E loops). Energy loss is derived from the
area inside the P-E hysteresis loops (Figure 6a)8. The calculated ESF for the BCZT700-O2 and
BCZT800-O2 thin films at an electric field of 2000 kV/cm are 68% and 73% respectively. Figure
6b shows where the present revelation stands in terms of ESD and ESF compared to the same
published so far in the literature. Reported values for ESD and ESF at ≤ 2000 kV/cm (2 MV/cm)
were considered for comparison because in the recent years research on high energy density
ferroelectric capacitors is emphasized for the achievement of high ESD at lower electrical
field10,12 since there is a greater risk of electrical breakdown at high electrical field10-11. It should
be noted that the ESD calculated from the ferroelectric hysteresis results (Figure 5a-b) of the
oxygen-processed BCZT films are much higher than that of the air processed BCZT films i.e. 17
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J/cm3 as reported in Rangaswamy et al31. The variations of ESD and ESF with electrical field (up
to 2000 kV/cm) is presented in the Figure 6c. The Figure 6c shows that ESD for both the BCZT

700-O2 and BCZT 800-O2 thin films increased steadily with electric field up to 54.5 and 64.8
J/cm3 respectively whereas, ESF for those thin films decreased slowly with electric field from
90% to 68% and from 90% to 73% respectively. The error bars in Fig. 6c indicate the standard
deviations from polarization measurements on different capacitors and associated inaccuracy in
thickness measurements by cross section TEM.
Figure 6d represents the variation of leakage current density with electric field for BCZT-
O2 films. It is observed from the plots that current density increased very slowly with electric
field up to a very high field of 1100 kV/cm followed by a steep increase up to 2000 kV/cm.
Lower current density at higher electric field is very beneficial for ferroelectric energy storage
application as it limits heating of the energy storage device operating under high electric field.
The measured current density for BCZT800-O2 films at 100 kV/cm, 400 kV/cm, 500 kV/cm,
1000 kV/cm and 2000 kV/cm are 7.6 x10-6, 5.5 x10-5, 6.5 x10-5, 1.9 x10-4 and 9.7 x10-3 A/cm2
respectively. It should be noted that the present oxygen-processed BCZT thin films which were
synthesized by chemical solution deposition technique offer much lower leakage current density
than that of the PLD processed PZT based thin films with oxide electrode (0.1 A/cm2 at 400
kV/cm)35 and PLD processed epitaxial BCZT thin film with similar composition grown on
SrTiO3 single crystal substrate (3.0 A/cm2 at 400 kV/cm)36.

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Figure 6 (a) Schematic diagram for energy storage, (b) Comparison of ESD and ESF obtained in
the present work on the oxygen-processed BCZT films with the reported literature so far, (c)
Variation of ESD and ESF with electrical field for BCZT-O2 films and (d) Leakage current
density as a function of electric field for the BCZT-O2 films.
Fatigue resistance of the ferroelectric film is also an important criterion in ferroelectric
energy storage application because any change in Pmax or Pr during cycling will essentially
change both ESD and ESF and hence ferroelectric films with considerably high fatigue
resistance are desirable for this purpose. In the present work, the investigations on fatigue were
performed by applying 5 V amplitude bipolar pulses with repetition at 1 MHz frequency. We
noticed negligible changes in Pmax and Pr for both the BCZT700-O2 and BCZT800-O2 films even
after 1010 switching cycles. The recorded Pmax and Pr for the former after 1010 cycles are 85 and
12.5 μC/cm2 which corresponds to ESD of 50.6 J/cm3 and ESF of 63 % (Figure 7a and Figure
7c). The recorded Pmax and Pr after 1010 switching cycles for the latter are 105 and 13.2 μC/cm2
(Figure 7b and Figure 7c) which corresponds to ESD of 63.6 J/cm3 and ESF of 71 % (Table S2,
supplementary information). The error bars in Fig. 7c indicate the standard deviations from
polarization measurements due to the inaccuracy in thickness measurements by cross section
TEM.
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DOI: 10.1039/C9TC00569B

Figure 7 (a-b) Virgin and fatigued polarization-electric field hysteresis loops recorded at 10 kHz
for the BCZT700-O2 and BCZT800-O2 films, (c) energy density variation with switching cycles
for BCZT-O2 films and (d) Normalized PSW as a function of number of switching cycles
recorded for BCZT-O2 films.
Figure 7d shows the variation of normalized switchable polarization (PSW) with the
number of switching cycles in logarithm scale. A polarization increasing trend was observed up
to 5 x107 switching cycles for the BCZT700-O2 and BCZT800-O2 films. An increasing
polarization trend up to first few switching cycles was also theoretically predicted37 and
experimentally verified by different group of researchers for different ferroelectric
compositions38-39. Park et al.8 attributed this phenomenon to the micro-structural evolution of the
thin film at the film-electrode interface during cycling and/or to the decrease in density of defects
(wake–up effect or polarization- unlocking). However, in the present system the increasing trend
was not limited to the first few cycles but continued up to higher number of cycles before the
system shows some fatigue. Polarization recovery after polarization degradation due to fatigue in
the last few cycles was also observed for both the samples as it has been reported by some other
researchers for different ferroelectric compositions39. It was observed that for both BCZT700-O2
and BCZT800-O2 switchable polarization is well above the base line even after 1010 switching
cycles and this type of polarization switching behavior with negligible fatigue is comparable to
that of the PZT based thin film system with oxide bottom electrodes e.g. RuO2 , IrO2 and
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DOI: 10.1039/C9TC00569B
SrRuO340-42. It is to be noted that reports on fatigue resistance properties of BCZT thin films
particularly of CSD processed BCZT thin films were not reported in the literature. Very recently

Jose P.B. Silva et. al reported ion beam sputtering-processed Pt/BCZT/HfO2:Al2O3/Au
multilayered capacitors with energy density of 99.8 J/cm3 and the capacitors were stable up to
108 switching cycles43. However, the main disadvantage of ion beam sputtering is its low
deposition rate and complexity in obtaining a large area film of uniform thickness.
Conclusion:
Processing of BCZT thin films in oxygen rich atmosphere abruptly modifies the ferroelectric
properties of the films which include much slimmer hysteresis loop, drastic increase in Pmax-Pr,
4-5 fold decrease in coercive field and at least 2 fold increases in electrical breakdown strength.
The film BCZT800-O2 showed highest energy density of 64.8 J/cm3 and Energy storage
efficiency of 73% at 2000 kV/cm and these values are higher than that obtained for the film
BCZT700-O2. Energy density increased steadily with applied electric field whereas Energy
storage efficiency decreased slowly with electric field. Leakage current measured on these
chemical solution deposited BCZT-O2 thin films is much lower than that reported for PLD
processed PZT based thin films or PLD processed BCZT thin films. Both the films showed
excellent fatigue properties. 99 and 97% of polarization recovery was observed for BCZT800-O2
and BCZT700-O2 films respectively even after 1010 switching cycles. Leakage current and
fatigue properties of the BCZT700-O2 is comparable to that of the BCZT800-O2 film, however,
the former showed lower energy storage properties than the latter. Therefore, it can be concluded
that processing of the ferroelectric films in oxygen rich atmosphere is an effective way to
improve the energy storage properties.
Conflicts of interest:
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DOI: 10.1039/C9TC00569B
There are no conflicts to declare.

Supplementary information:
BCZT film AFM images, Table S1: Ferroelectric properties of the air and oxygen processed
BCZT films, Table S2: Polarization and energy storage properties of the oxygen-processed
BCZT films recorded before and after fatigue test.
Acknowledgements:
The authors express sincere gratitude for the financial support from the Defence Research
Development Organization, Ministry of Defence, India, for carrying out the present work and
thank Director, DMRL-Hyderabad for his constant encouragement. Authors are thankful to Dr.
S. V. Kamat former Director, DMRL for his support and encouragement. The help of Dr. P.
Ghosal, and Vajinder Singh, Scientist, DMRL in microstructure analysis are greatly
acknowledged. Authors are thankful to Dr. R. P. Mathur and Dr. Himalay Basumatary, Scientist,
DMRL for the help in GIXRD and AFM measurements. Authors would like to acknowledge the
support from Dr. Abhay Joshi, Application engineer, Tektronix/Keithley for electrical property
measurements.
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Figure captions
Figure 1. Schematic diagram for the chemical processing of BCZT thin film from chemical
precursor sol.
Figure 2 (a) GIXRD patterns of the air and oxygen processed BCZT films, (b) cross section
TEM image of the BCZT film, (c) SAED pattern image and (d) HRTEM showing the (100) and
(110) planes of two neighboring BCZT grains.
Figure 3 (a) XPS survey spectrum obtained from the surface of the BCZT700-O2 film, high
resolution O 1s spectrum of (b) BCZT700-O2, (c) BCZT700-air, (d) BCZT800-O2 and (e)
BCZT800-air films.
Figure 4 (a) DC electric field dependant dielectric constant and dielectric loss for BCZT-air
films, (b) DC electric field dependant dielectric constant and dielectric loss for BCZT-O2 films,
(c) Frequency dependant dielectric constant and dielectric loss for the BCZT-O2 films and (d)
Polarization vs. electric field hysteresis loops for the BCZT-air and BCZT-O2 films.
Figure 5. Polarization vs. electric field unipolar loops of (a) BCZT700-O2 and (b) BCZT800-O2
films measured with different electric fields.
Figure 6 (a) Schematic diagram for energy storage, (b) Comparison of ESD and ESF obtained in
the present work on the oxygen-processed BCZT films with the reported literature so far, (c)
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DOI: 10.1039/C9TC00569B
Variation of ESD and ESF with electrical field for BCZT-O2 films and (d) Leakage current
density as a function of electric field for the BCZT-O2 films.

Figure 7 (a-b) Virgin and fatigued polarization-electric field hysteresis loops recorded at 10 kHz
for the BCZT700-O2 and BCZT800-O2 films, (c) energy density variation with switching cycles
for BCZT-O2 films and (d) Normalized PSW as a function of number of switching cycles
recorded for BCZT-O2 films.

DOI: 10.1039/C9TC00569B
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Table of contents entry:

Processing in oxygen rich atmosphere induced superior energy properties in lead free
ferroelectric BCZT thin films.

Swamy JPC-C

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acceptance, before technical editing, formatting and proof reading.

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Superior energy storage performance, and fatigue resistance in

ferroelectric BCZT thin films grown in oxygen rich atmosphere

Journal of Materials Chemistry C Accepted Manuscript

Shanker3, Neha Hebalkar4 and Subir Kumar Roy1*

Metallurgy and new materials (ARCI), Hyderabad-500005, India.

Abstract: Ferroelectric properties of the chemical solution deposited (Ba0.85Ca0.15Ti0.90Zr0.10O3)

intermediate voltage ferroelectric energy storage applications.

*Communicating author: Subir K. Roy (e-mail: r_subir@yahoo.com, r_subir@dmrl.drdo.in) Tel.: 040-24586663;

Journal of Materials Chemistry C Accepted Manuscript

field 3.85 MV/cm, antiferroelectric HfxZr1-xO2(HZO)8 thin films developed by combined DC

Journal of Materials Chemistry C Accepted Manuscript

processed ferroelectric films received considerable attention towards practical application in

composition: 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 however, energy storage and fatigue

0.5(Ba0.7Ca0.3)TiO3 (Ba0.85Ca0.15Ti0.90Zr0.10O3) ferroelectric thin film on Pt coated Si wafer with

Journal of Materials Chemistry C Accepted Manuscript

BCZT thin films of composition Ba0.85Ca0.15Ti0.90Zr0.10O3 were fabricated on Si/SiO2/TiO2/Pt

BCZT sol-gel chemical reactions

Journal of Materials Chemistry C Accepted Manuscript

Chemical reactions in Ti and Zr alkoxides stabilized by acetyl acetone

molar ratio) of acetylacetone (AcacH) in the solution.

M(OR)4 + AcacH [M(OR)4-x(Acac)x] +xROH

the mixed solution of Ba and Ca in acetic acid.

x(Acac)x species in organic solvent (Ti-precursor is Ti iso-propoxide and Zr-precursor is Zr n-

propoxide dissolved in n- propanol).

metal alkoxide gel19 (Fig. 1) .

The role of PVP in chemical sol:

Journal of Materials Chemistry C Accepted Manuscript

ensures controlled hydrolysis avoiding the formation of viscous gel or precipitate. It is to be

Journal of Materials Chemistry C Accepted Manuscript

diffractometer (Rigaku, Japan). High-resolution transmission electron microscope (HRTEM),

films. Capacitance-voltage butterfly loops, dielectric loss, ferroelectric hysteresis loops,

films were analyzed at room temperature.

Results and discussion:

Journal of Materials Chemistry C Accepted Manuscript

Journal of Materials Chemistry C Accepted Manuscript

oxygen rich atmosphere at 700 and 800 oC temperatures (BCZT700-air, BCZT800-air,

grain size uniformity by suppressing uneven grain growth.

Journal of Materials Chemistry C Accepted Manuscript

Journal of Materials Chemistry C Accepted Manuscript

Journal of Materials Chemistry C Accepted Manuscript

vacancies present in the air- processed BCZT films.

Journal of Materials Chemistry C Accepted Manuscript

Journal of Materials Chemistry C Accepted Manuscript

are believed to create conducting electrons as per the following equation27.

Journal of Materials Chemistry C Accepted Manuscript

slightly as the frequency is increased.

Journal of Materials Chemistry C Accepted Manuscript

films measured with different electric fields.

Journal of Materials Chemistry C Accepted Manuscript

ESF. ESD can be mathematically expressed as per the equation (1).

Journal of Materials Chemistry C Accepted Manuscript

deviations from polarization measurements on different capacitors and associated inaccuracy in

thickness measurements by cross section TEM.

SrTiO3 single crystal substrate (3.0 A/cm2 at 400 kV/cm)36.

Journal of Materials Chemistry C Accepted Manuscript

Journal of Materials Chemistry C Accepted Manuscript

density as a function of electric field for the BCZT-O2 films.

Fatigue resistance of the ferroelectric film is also an important criterion in ferroelectric