DR SUBIR KUMAR ROY (Orcid ID : 0000-0002-4771-4276)

Accepted Article
Article type : Article

Ferroelectric and piezoelectric properties of

Ba0.85Ca0.15Ti0.90Zr0.10O3 films in 200 nm thickness range

Seelam Rangaswamy Reddy1, 2, V. V. Bhanu Prasad1, Sandip Bysakh3, Vishnu

Shanker2, Joydip Joardar4 and Subir Roy1*

Affiliation: 1Ceramics and Composites Group, Defence Metallurgical Research Laboratory, Hyderabad-

500058, India. 2Department of Chemistry, National Institute of Technology, Warangal-506004, India. 3Central

Glass and Ceramics Research Institute, Jadavpur, West Bengal, India. 4International Advanced Research centre

for Powder Metallurgy and new materials (ARCI), Hyderabad-500005, India. *Address of the communicating

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

24340683.

Abstract: Lead free piezoelectric Ba0.85Ca0.15Ti0.90Zr0.10O3 (BCZT) thin films were fabricated on

Si/SiO2/TiO2/Pt (100) substrates following chemical solution deposition technique. Microstructure of

the nano-sized BCZT particles crystallized in the thin film was thoroughly characterized.

Ferroelectric, dielectric and piezoelectric properties of the films were investigated in detail. The

BCZT films annealed at 800 oC temperature exhibited high remanent polarization of 25±1 μC/cm2,

energy density of 17 J/cm3, dielectric constant of 1550±50 and dielectric tunability of 50%. Converse

piezoelectric coefficients (d33) obtained from piezo- response force microscopy (PFM) measurements

on BCZT grains of different grain size (20 nm -100 nm) distributed on the BCZT 700 film varied
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 widely from 90 pm/V to 230 pm/V. The same for BCZT 800 measured on different grain size (30 nm

-130 nm) varied from 120 pm/V to 295pm/V. These BCZT thin films with high dielectric,
Accepted Article
ferroelectric and piezoelectric properties might be good alternative to the PZT films for thin film

piezoelectric device applications.

Key words: Chemical solution deposition; Lead free piezoelectric; BCZT; Remanent

polarization; Piezoelectric coefficient

1. Introduction:

Microelectromechanical systems (MEMS) based on piezoelectric thin films have been

commercially extremely attractive due to their availability in wide ranges, high energy

density, accuracy and low power requirements. In the recent years, lead based piezoelectric

thin films exploited extensively for MEMS applications due to their high piezoelectric and

electromechanical coupling coefficients, and were widely used in sensing and actuating

applications.1-2 However, growing environmental concerns over poisonous Pb (Lead) in

present global scenario restricted the extensive use of PZT (PbZr1-xTixO3) based piezoelectric

materials. Therefore, the researchers in this area all over the world started finding the

alternatives. In the recent years a composition 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 (BZT-

0.5BCT) that exist within the morphotropic phase boundary separating ferroelectric R (BZT

side) and T (BCT side) revealed surprisingly high piezoelectricity (d33=620 pC/N).3 Since

this remarkable discovery in the area of lead free piezoelectric some further research works

have been performed in the form of bulk materials as well as in the form of thin films.

Although there are some reports on BZT-BCT thin films up to now, reports revealing the

excellent dielectric, ferroelectric and piezoelectric properties of BZT-BCT films are limited.

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 W. L. Li et al.4 reported giant piezoelectric properties (d33=258 pm/V) of BZT-0.5BCT thin

films synthesized by magnetron sputtering, however ferroelectric properties of the films were
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not reported. Zeng-mei Wang et al.5 reported high remanent polarization (Pr= 22.15 µC/cm2)

for sol-gel developed thicker (800 nm) BZT-0.5BCT film without any report on the

piezoelectric properties. Wei Li et al.6 reported piezoelectric coefficient (d33) of 50 pm/V and

dielectric tunability of 64% for sol-gel processed BZT-BCT (Ba0.92Ca0.08Ti0.95Zr0.05O3 ) films,

but ferroelectric properties were not reported for these films.

Integration of piezoelectric films of higher thickness (≥ 500 nm) in the low voltage

MEMS induces issues that may be shorted out by scaling down the thickness of the films.

Usually physical deposition methods such as metal organic chemical vapor deposition

(MOCVD), pulsed laser deposition (PLD) had been used to develop piezoelectric films.

However, these methods are extremely expensive and become practically ineffective when

larger areas are required to be deposited. Sol-gel spin coating technique offers the fine control

on stoichiometry, composition and homogeneity. Lowering of crystallization temperature,

larger surface covering and cost effectiveness are the additional advantages over the physical

deposition methods2.

In this communication, we report considerably high dielectric, ferroelectric and piezoelectric

properties of ~200 nm thick 0.5BZT-0.5BCT (BCZT) films with the composition

Ba0.85Ca0.15Ti0.90Zr0.10O3. The piezoelectric films were developed by simple sol-gel

methodology without any seed layer. From the literature it is observed that except W. L. Li et

al.4, almost all the communications made so far on BCZT thin films having thickness range ≥

400 nm. The present report reveals that a 200 nm BCZT film developed by sol-gel technique

is able to show excellent ferroelectric properties. Moreover, the dielectric constant and

dielectric tunability of these films are comparable to the best reports available so far in the

literature. Piezoelectric properties of these thin films are also discussed in this manuscript.

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 2. Experimental methods:

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

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(100) substrates using sol-gel spin coating technique. Thickness of Platinum, TiO2 and SiO2

layers are 200 nm, 40 nm and 500 nm respectively. 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 chemical

precursors, 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 in the calculation of molar ratio. 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

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 on cleaned Pt/Si (100) substrates. The spin coated BCZT films were dried on hot plate at

~150 oC for solvent evaporation followed by calcination at 500 oC in a tubular furnace for
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decomposition of organic moieties present in the films. The spin coating, drying and

calcination cycles were performed three times to obtain the desired thickness of around 200

nm. Then the films were annealed using conventional tubular furnace at 700 oC and 800 oC

temperatures for an hour with heating rate of 2o C/min in air. Finally the films were heat

treated in Rapid thermal annealing (RTA) furnace in oxygen atmosphere at those

temperatures with the heating rate of 50 oC/sec for 4 minutes. RTA annealing with the

volumetric flow of 1-5 cubic feet per minute (1-5 CFM) oxygen was performed with the aim

to reduce oxygen vacancies and leakage current density. It was reported earlier that RTA for

even a very short duration (30 sec) in presence of oxygen gas decreased the leakage current

density in metal oxide thin film7. Phase and crystal structure of the annealed BCZT films

were analyzed by Grazing-incidence X-ray diffraction (GI-XRD) using Rigaku Rapid II

D/Max (Rigaku, Japan) rotating anode system. A grazing angle of 0.5o and Chromium kα

radiation was used in order to avoid Pt and Si peaks from the underlying substrate and to

obtain appropriate separation of the phase peaks. XRD peak decomposition was performed

by XRFIT software (as incorporated in Full proof Rietveld Suite) using Marquardt type least

square fitting technique. High-resolution transmission electron microscope (HRTEM), model

Tecnai G2 30ST (FEI, Netherland) was used to study the microstructure of the BCZT films.

Capacitance-Electric field butterfly loops, dielectric loss, and ferroelectric hysteresis loops of

the films were measured with the application of DC voltage sweep using Keithley

semiconductor characterization system (Model: Keithley 4200 SCS, USA). Leakage current

behavior of the films was also studied using the same system. Surface topography, local

polarization switching and piezoelectric response of the BCZT films was studied using Piezo-

response force microscopy (Dimension icon AFM, Bruker AXS GmbH, Karlsruhe,

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 Germany). Phase images of the BCZT films were obtained with piezo-response force

microscopy (PFM) using a Pt coated silicon tip with an AC driving voltage of 5 Vrms at a
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driving frequency of 345 kHz between the tip and the grounded electrode. Local polarization

switching and piezoelectric responses (phase and amplitude responses) were studied with DC

bias voltage sweep from -12 V to 12 V. Crystal structure, microstructure and electrical

properties of the annealed films were analyzed at room temperature. For measurements of

electrical properties gold dots (diameter : 230 µm) were sputtered on the annealed films as

top electrodes and on ~2 cm x 2 cm film coated on Si/Pt (100) substrate there were hundreds

of sputtered gold dots. Each gold dot along with Pt bottom electrode and BCZT thin film in-

between, worked as a ferroelectric capacitor during dielectric and ferroelectric measurements.

We observed some variations, when the properties were measured on different capacitors.

The graphs in the figures, included in ‘Results and discussion’ portion, represent the results

obtained from the best ferroelectric capacitor; however, errors bar applied on each quoted

data reflect the variations in properties measured on different capacitors.

3. Results and discussion:

3.1. Structure and microstructure characterizations

GI-XRD patterns of BCZT films annealed at 700 oC and 800 oC temperatures (abbreviated as

BCZT 700 and BCZT 800) are presented in Fig.1a. Since Chromium kα radiation wavelength

is higher when compared to that of Copper kα radiation, peak spacing increases slightly,

making it possible to separate the tetragonal and rhombohedral peaks. X-ray diffraction

patterns of the films demonstrate that the occurrence of pure polycrystalline BCZT with

tetragonal (P4mm) structure as the major fraction while rhombohedral (R3m) BCZT is also

present in minor fraction. On relative terms higher fraction of rhombohedral phase is evident

in the high temperature annealed film (Fig.1b-c). Intensity ratio of I002-T/I202-R are 1.16 and

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 0.74 for BCZT 700 and BCZT 800 respectively. Since the BCZT film thickness was only

about few tens of nm, underlying Pt peaks are also evident in Fig. 1a-c. These results indicate
Accepted Article
that Ca+2 and Zr+4 ions diffused into the BaTiO3 lattices to form a homogeneous solid

solution. W. Liu and X. Ren3 have earlier reported that the rhombohedral and tetragonal

phases coexist in the BCZT composition at room temperature as their bulk counterparts and it

is usually indicated by the splitting of (200) peak.

TEM image of the film cross section shows the thickness of film is ~ 200 nm (Fig.2a).

The d-values calculated from the electron diffraction pattern (Fig.2b) for the (100), (110),

(111), (200) and (211) planes are matching the same calculated from the GI-XRD patterns.

HRTEM image (Fig.2c) of three neighboring grains shows lattice spacing of the (110) (111)

and (200) planes. A common problem which is usually encountered in the development of

ferroelectric films is the diffusion of the constituent elements through the interface during

annealing of the film at high temperatures.8 The Fig.2d represents the TEM-EDS mapping

images for the elements Ca and Zr of the cross-sectioned BCZT 800 film. The film area

shows the presence of Ca and Zr. TEM-EDS mapping analyses showed (although only Ca

and Zr are shown in the figure) that neither Pt nor Si could be found within the BCZT film

thickness and none of the BCZT elements were found within the Pt electrode or SiO2 layer.

Thus, none of the constituent elements of BCZT or, Pt from bottom electrode showed any

sign of diffusion across the film-electrode interface.

3.2. Dielectric and ferroelectric property characterizations

Fig.3a-b represents the variation of capacitance and dielectric loss with DC electric field at 10

kHz and 100 kHz frequency. Capacitance decreased and dielectric loss increased with

increasing the frequency. The maximum capacitance values at 10 kHz frequency for BCZT

700 and BCZT 800 films are 2.1±0.15 nF and 2.9±0.15 nF respectively and the same at 100

kHz frequency for BCZT 700 and BCZT 800 films are 1.8±0.15 nF and 2.4 ±0.15 nF

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 respectively (Fig.3 a and b). The error bars indicate standard deviations from measurements

on different capacitors. Dielectric loss of the BCZT 700 film at 10 kHz frequency varied from
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0.055 to 0.061 and the same for BCZT 700 film at 100 kHz frequency varied from 0.067 to

0.077 (Fig.3a). Magnitude and variation of dielectric loss with electric field at 10 kHz and

100 kHz frequency for BCZT 800 film were similar to that of the BCZT 700 film (Fig.3b).

The measured dielectric loss on BCZT 700 and BCZT 800 films are comparable with the

dielectric loss reported for the sol-gel derived BCZT films.9 The higher capacitance of the

BCZT films annealed at 800 oC temperatures is due to the dense microstructure of the films.

Butterfly-shaped (C-E) loops of the BCZT films are caused by switching of the ferroelectric

domains and indicate that the films are ferroelectric in nature.10 However, butterfly curves

for BCZT 700 are minutely shifted from the zero bias. This could be attributed to the

generation of oxygen non-stoichiometry in the film during annealing which led to the shift of

C-E loop on the electric field axis.11 BCZT 800 film is expected to have lower oxygen

vacancy than BCZT 700 film. It was reported earlier that in metal oxide thin film oxygen

vacancy decreased with increasing annealing temperature.12 However, some researchers

attributed the same to the presence of internal space charge field due to charge trapping at the

electrode-film interface which can be enhanced by oxygen vacancy associated defect

dipole.13 It is to be noted that the C-E butterfly curves are associated with very low hysteresis.

The values of dielectric constant were calculated from the corresponding capacitance values.

Dielectric constants (εr) of 1120±50 and 1550±50 were obtained at 10 kHz frequency for the

BCZT 700 and BCZT 800 films. The error bars indicate standard deviations from capacitance

measurements on different capacitors and associated inaccuracy in thickness measurements

by cross section TEM. The reports on the dielectric tunability of BCZT thin films are limited.

In the present work, the dielectric tunability percentage is derived from the equation (1),

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 where ε(E0) and ε(E) represent the dielectric constant at zero electric field and at maximum

electric field, respectively.14

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o
The dielectric tunability of the BCZT films annealed at 700 and 800 oC temperatures are

40% and 50% respectively. These values are comparable to the reported high-end dielectric

tunability values of BCZT films6, 15

and multilayered BST films known for their high

dielectric tunability.16

The ferroelectric nature of the BCZT thin films annealed at 700o and 800 oC

temperatures is confirmed by the hysteresis loops of polarization (P) as a function of applied

electric field (E) (Fig.3c and d). Polarization versus electric field measurements were carried

out at 10 kHz frequency. The hysteresis loops reveal that both the maximum polarization

(Pmax) and remanent polarization (Pr) increased as the electric field is increased. Maximum

polarization (Pmax) and remanent polarization (Pr) for BCZT 800 film measured at 1000

kV/cm electric field are 82 µC/cm2 and 25 µC/cm2 respectively, and for the BCZT 700 film

maximum polarization and remanent polarization measured at 985 kV/cm electric field are 70

µC/cm2 and 22 µC/cm2 respectively. The error bar for Pmax is ±2 and the same for Pr is ±1.

The error bars indicate standard deviations from measurements on different capacitors. The

BCZT 800 films showed higher maximum polarization (Pmax) and higher remanent

polarization (Pr) than that of the BCZT 700 films. The measured remanent polarization of

BCZT films is comparable with the reported high-end values of remanent polarization for

BCZT film with similar composition.5 The higher polarization of BCZT 800 films is

attributed to the dense microstructure of the films. Porosity present in the low temperature

annealed films can change the bottom electrode-film interface properties including alignment

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 of the domains at the film bottom electrode interface. Thin films with higher porosity having

slower polarization reversal and thus shows comparatively lower polarization than the dense
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film.17 Coercive field of a ferroelectric thin film largely depends on the thickness of the film

and grain size. Coercive field of 186 kV/cm is obtained for BCZT 800 film from the P-E loop

measured at 1000 kV/cm electric filed, while for the BCZT 700 film 222 kV/cm coercive

filed is obtained from the P-E loop measured at 985 kV/cm electric field. The error bar for the

measurements of coercive field is ±5. The coercive fields of the BCZT films are much higher

than that of the bulk BCZT ceramics3 (1.68 kV/cm) with similar composition because of

clamping effect of the substrate, which is very pronounced on the thin film with very low

thickness (~200 nm). BCZT thin film of lower coercive field (68.06 kV/cm) was also

reported; however, the BCZT film thickness involved in that measurement was 800 nm and

was expected to experience much lower clamping effect 5. The coercive field decreases with

increasing grain size 5,18 and the lower coercive fields of BCZT 800 film can be attributed to

its higher grain size. The average grain size in BCZT 800 thin film material is relatively

higher than that in BCZT 700 as the annealing temperature of the former is higher.

Potential of a dielectric material is usually characterized by its energy storage.

Recoverable energy density19 of dielectrics can be calculated by the following equation:

= 0 ≤ E ≤ Emax …………….. (2)

Where E is the applied electrical field, Pr and Pmax are the remanent and maximum

polarization respectively. The shaded area in Fig.3c corresponds to the recoverable energy

density for BCZT 700 film. Earlier reports suggest that recoverable energy density of

antiferroelectric ceramics20-21 (≤ 2.75 J/cm3) and ferroelectric ceramics22 (0.59 J/cm3) are

very low. However, with the advent of modern thin film technology it was confirmed that

very high energy density could be achieved from ferroelectric thin films. For example, high

energy density of ~18 J/cm3 was reported for doped PbZrO3 thin films.23-24 Integration of the

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 discharge portions of the P-E hysteresis loops following the equation (2) yielded energy

densities of the BCZT 700 and BCZT 800 films. The calculated WED value from the P-E loop
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measured at 985 kV/cm electric field for BCZT 700 is 15 J/cm3 and the same calculated from

the P-E loop measured at 1000 kV/cm electric field for BCZT 800 is 17 J/cm3. These values

are comparable to the energy density of doped PbZrO3 thin films which are known for

offering high energy density.23-24 It is to be mentioned that the obtained values of WED for

BCZT thin films are much higher than that of the BCZT bulk ceramics (0.59 J/cm3).22

It has been observed that the measured P-E hysteresis loops for the BCZT thin

samples are not saturated and hence it is essential to understand the behavior of the leakage

current with the bias field since leakage current of a ferroelectric thin film is a major concern

for most of the thin film device applications. The leakage current can be correlated to the

various defects including oxygen vacancies, trap states (acceptors and donors) present in the

thin film.25 Leakage current and leakage current density of the BCZT 800 film were found to

be 2.5 x 10-10 A and 0.6 μA/cm2 respectively (Fig.3e). This level of leakage current density is

comparable to the reported leakage current density of the BCZT thin film with similar

composition grown on SrTiO3 substrate and on Pt-Si substrate with (Pb0.8Ca0.2)TiO3 seed

layer.26-27

3.3. Characterizations by piezo-response force microscopy (PFM)

PFM phase images of the BCZT films are shown in Fig.4a-b. The phase images revealed that

the size range of BCZT 700 and BCZT 800 thin films surface grains are: 20-100 nm and 30-

130 nm respectively. Piezo-response force microscopy (PFM) was employed to study the

local piezoelectric response of the BCZT films. The experiments were performed with the

application of DC bias voltage +12 V to -12 V on the BCZT grains of different size, located

at different portion of the thin film. A conductive tip (Tip diameter~ 20 nm) was applied for

this purpose. The grains having different grain size and neighborhood (Packing environment:

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 closely packed or surrounded by fewer neighbors) were selected randomly on the BCZT

films for PFM measurements. It can be assumed that during the application of DC bias
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voltage by the PFM tip to the film, the tip is taping only one grain on the surface at a time as

the diameter of the tip is only 20nm. The applied voltage stimulates the deformation in the

grain due the converse piezoelectric effect. Deformation of the grain was measured as vertical

deflection of the cantilever in terms of amplitude and phase as a function of bias voltage

using standard lock-in amplifier technique.28 Phase versus DC bias voltage hysteresis loops

demonstrate the local domains switching behavior (Fig 5a and 5b).29 The amplitude versus

bias voltage (V) exhibited butterfly loops corresponding to displacement which contains

information about piezoelectric deformation under applied bias voltage. It was observed that

the PFM response varied widely with varying grain size. The deformation increased with

increasing grain size with the application of same electrical input. The PFM responses of the

similar sized grains also varied with the packing density of the neighborhood grains

associating the BCZT grain of interest. Moreover, the amplitude versus DC bias voltage

butterfly curves obtained from the results of PFM measurements on both BCZT 700 and

BCZT 800 thin films were unsymmetrical and slightly shifted from zero bias voltage. From

the amplitude versus bias voltage butterfly curves, the converse piezoelectric coefficient

(d33)-voltage loops (Fig. 5c and d) can be determined through the following equation (3)

(converse piezoelectric effect).30

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 In equation (3), D is the measured value of piezoelectric deformation, V is the applied

voltage at each point on the D–V curve, DI is the piezoelectric deformation and VI is the
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applied voltage of the intersection.

The d33 values calculated from the results of the PFM measurements when measured

randomly on different BCZT grains of different size (20 nm -100 nm) distributed on the

BCZT 700 film varied widely from 90 pm/V to 230 pm/V. The d33 values obtained for BCZT

800 of different grain size (30 nm -130 nm) varied from 120 pm/V to 295 pm/V. The value of

d33 increased with increasing grain size (The wide variation of d33 may be verified further

with the communicated ‘Supplemental material’). It should be noted that different localized

piezoelectric responses from piezoelectric grains having different grain size were also

reported earlier31. Since the D-V butterfly curves were unsymmetrical, obtaining a constant

d33 on either side of the voltage axis (+ve or –ve) was not possible, although the PFM

experiments were performed using a properly calibrated PFM measurement set up. Due to

space limitation, only the most symmetric amplitude versus DC bias curves derived from

PFM responses of larger sized BCZT grains (100-130 nm) distributed on BCZT 700 and

BCZT 800 films and the corresponding d33 curves have been incorporated in the manuscript

(Fig. 5c and d). Fig. 5c and d showed that the converse piezoelectric coefficients (d33) of the

BCZT 700 and BCZT 800 films are 210 pm/V and 250 pm/V as indicated by the maxima of

the d33-voltage loops. Deformation of a clamped piezoelectric thin film under applied electric

field is confined by the substrate and hence the resultant piezoelectric response is smaller

than that of the corresponding bulk ceramics3 (~1140 pm/V). It is observed that the

polarization, dielectric constant and piezoelectric coefficients are increased as the annealing

temperature is raised from 700 o to 800 oC. The electrical properties of the BCZT films were

compared with the reported literature (table I).

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 4. Conclusion:

In summary, BCZT thin films of thickness ~200 nm were grown on Si/SiO2/TiO2/Pt (100)
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substrates using sol-gel spin coating technique. BCZT films exhibited pure polycrystalline

perovskite structure with dense microstructure. GI-XRD analyses of the thin films concluded

pure polycrystalline BCZT phase with tetragonal (P4mm) structure as the major fraction and

rhombohedral (R3m) as the minor fraction. The polarization versus electric field loops

indicated the ferroelectric nature of the films. The BCZT films annealed at 800 oC showed the

higher remanent polarization (Pr) of 25±1 µC/cm2, higher dielectric constant( r) of 1550±50

and dielectric tunability of 50%, while the BCZT films annealed at 700oC showed remanent

polarization of 22±1µC/cm2, dielectric constant of 1120±50 and dielectric tunability of 40%.

Moreover, the energy densities estimated from the P-E loops of the BCZT films are

comparable with that of the PbZrO3 thin films which are known for offering high energy

density. The large converse piezoelectric coefficients (d33) of ~ 250 pm/V were obtained from

the larger sized BCZT grains of grain size ~130nm distributed over the annealed BCZT thin

films. These results indicate that the BCZT films might be used as alternative to lead based

thin films for ferroelectric and piezoelectric MEMS applications.

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. The Authors would like to acknowledge the support from Dr. Abhay Joshi,

Application engineer, Tektronix and Keithley for electrical property measurements.

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Figure captions

Fig.1.(a) GI-XRD patterns of BCZT films (at GI angles of 0.5o) annealed at 700 oC and 800
o
C temperatures, (b) Decomposed tetragonal and rhombohedral BCZT peaks in the films

annealed at 700 oC and (c) 800 oC temperatures.

Fig.2.(a) TEM image of the film cross section, (b) Electron diffraction pattern image, (c)

HRTEM image showing the (110) (111) and (200) planes of three neighboring BCZT grains

and (d) TEM-EDS elements mapping for Zr, Ca and Pt at BCZT film-substrate interface.

Fig.3. (a) Capacitance and dielectric loss loops of BCZT 700 film as a function of electric

field, (b) Capacitance and dielectric loss loops of BCZT 800 film as a function of electric

field, (c) Polarization vs. electric field hysteresis loops of BCZT 700 film, (d) Polarization vs.

electric field hysteresis loops of BCZT 800 film and (e) leakage current density variation with

electric field for BCZT 800 film.

Fig.4. PFM phase images of (a) BCZT 700 and (b) BCZT 800 films.

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 Fig.5. PFM loops (a) Phase vs. bias voltage hysteresis loop of BCZT 700 film (b) Phase vs.

bias voltage hysteresis loop of BCZT 800 film, (c) Amplitude and d33 vs. bias voltage loops
Accepted Article
of BCZT 700 film, (d) Amplitude and d33 vs. bias voltage loops of BCZT 800 film.

Tables

Table1: Comparison of electrical properties of the synthesized BCZT films with reported

data in literature.

Annealing Thickness Dielectric Dielectric Remanent Converse Energy

temp. constant tunability polarizatio piezoelectric storage
(nm)
percentage n (μC/cm2) coefficient density
(εr)
(pm/V) (J/cm3)

BCZT (Sol-gel 700 oC 200 1120 40 22 210 15

technique,
±50 ±1
Manuscript data)

BCZT (Sol-gel 800 oC 200 1550 50 25 250 17

technique,
±50 ±1
Manuscript data)

BCZT (dual 750 oC 200 - - - 258 -

magnetron
sputtering(ref.4))

BCZT (Sol-gel 850 oC 800 - - 22.15 - -

technique(ref.5))

BCZT(Sol-gel 700 oC 450 - - 6.1 104 -

technique(ref.27))

BCZT(Pulsed 750 oC 600 1010 - - 80 -

laser
deposition(ref.11))

Pb(Zr,Ti)O3 900 800 - - 100 -

(ref.32)

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Accepted Article

This article is protected by copyright. All rights reserved.

Accepted Article

This article is protected by copyright. All rights reserved.

Accepted Article

This article is protected by copyright. All rights reserved.