Alternate Current Conduction and

Impedance Spectroscopy of Laser

Ablated BaZro3 Thin Films
V. Rajasekarakumar, P. Victor, R. Ranjith, S. Saha1, S. B. Krupanidhi,
S. Rajagopalan2 and A. K. Tyagi2.
Materials Research Center, Indian Institute of Science, Bangalore- 560 012,
India.
1 Materials Science Division, Argonne Laboratory, Argonne, IL, USA.

2 Materials Science Division, IGCAR, Kalpakkam.

MRS fall meeting, Boston, USA, dec 2, 2002.
INTRODUCTION:

Presently there had been demand for monolithic microwave integrated circuit
technologies (MMIC) for its essential use in the microwave communication
applications, such as mobile phones, satellite communications and global positioning
systems.

Paraelectric materials used as resonators and filters in microwave circuits require
high dielectric constants, low dielectric losses (tanδ), and low temperature coefficient of
resonance frequency (τf).

Since 1970’s, in bulk several materials including BaZrO3 have been developed for
the microwave applications. BaZrO3 also finds its potential use in the protonic
conductors and recently there had been extensive research performed on this material.

Polycrystalline Barium zirconate (BZ) thin films were grown using a KrF excimer
laser ablation technique. A dense target with single phase of BZ ceramic was used as a
target. The films were deposited on platinum coated silicon substrates.

Barium Zirconate thin films were deposited at an operating pressure between 20 to
100 mTorr in the ultra high pure oxygen gas ambience.

The structural and stoichiometry was confirmed by x-ray diffraction technique
(XRD) and energy-dispersive x- ray analysis (EDAX) respectively.

The interface has been analysed by Secondary ion mass spectrometry (SIMS).

The Metal – Insulator – Metal (MIM) capacitor has been formed to perform to
electrical characterization on the BZ thin films.
 Structure and Stoichiometry
Effect of substrate temperature in the
crystallinity

BZ Films were grown at different substrate

temperature at a constant partial pressure of 50
*
mTorr.
(110)

(211)
(111)

(220)
* PtK β (200)

The perovskite phase evolves at 5500C and at

Intensity (arb. unit)

PtKα

* 0
650 C 6000C the enhancement of (110), (111) and (211)
planes are observed.

All the single phase BZ thin films exhibited
* 0
600 C polycrystalline nature for the thin films deposited
*
0
550 C upto 6000C.

Further increment of substrate temperature to
6500C, there is a tendency for the orientation along
pow (110) direction with the disappearance of other
20 30 40 50 60 prominent perovskite peaks.
2θ
This is accordance with the Thorton’s model
which suggests that at higher substrate temperatures
the thin films tend to exhibit columnar structure and
higher orientation along a favourable plane.
 Effect of ex-situ annealing temperature
in crystallinity

The BZ thin films

90 min_ 20 mTorr

(200)
(110) deposited at the substrate
PtKβ

(211)

(220)
PtKβ
PtKα
Intensity(arb.unit)

0
800 C temperature of 4000C in the
pressure of 20 mTorr and
0
775 C
subsequently annealed at
different temperatures for 90
0
minutes.
750 C

20 30 40 50 60

The perovskite peak
2θ enhanced with increasing of
temperatures upto 7750C.
 Depth profile of in-situ annealed
BZ thin film using SIMS.
5
10

2
1 -> 138Ba
2 -> 16O

The interface is sharp and almost no
1
*
3 -> 90Zr
4 -> 195Pt diffusion of Ba and Zr in to platinum
4
10
layer when compared to the thickness
* of the platinum thickness.
2
3
10 *
The peaks (*) observed in all elements
3 (Ba, Zr, O) reveals that there is a fixed
[C/s]

proportion of the constituent species of

2
10 4
4 the expected phase. So the film growth
at the interface is good. Moreover, the
1 3
10
1
stoichiometry and sputtering rate are
Tp different at the interface which has lead
0
10 to humps in the region.
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Thickness (µm)

Oxygen concentration increases after
platinum layer because we have an
Type of deposition : In-situ inter-face of (Pt/ TiO2/ SiO2/ Si) in our
Oxygen partial pressure: 50 mTorr substrate.
Annealing temperature : 650 0 C
Tp shows the thickness of the platinum
layer (0.18 µm).
 Depth profile of Ex-situ annealed
BZ thin film using SIMS.
5
10
1 -> 138Ba
2 -> 16O
# 3 -> 90Zr
4 -> 195Pt
The interface is not sharp and all the
1
4
10
* 2 elements are interdiffused.
4
In the (*) region both Zr and Oxygen
3
10
2 have a uniform rise, whereas Ba falls
3 * down suddenly ( Zirconium oxide have
[C/s]

formed or segregated).
2
10 4

Hump in the * region due to interface
effects.
1
1
10
Flat nature was observed in the region
(//). It has given the conclusion of
0
10
compound formation (ZrO2) at the
0.0 0.2 0.4 0.6 0.8 1.0
interface, a flat nature reveals that we
Thickness (µm)
have constituents species of definite
Deposition pressure : 50 mTorr proportion.
Substrate temperature : 400 0 C
In # area there is a hump in oxygen,
Annealing time : 90 min. that due to TiO2 interface.
Annealing temperature: 600 0 C
The diffusion length is around 0.16
µm.
 Dielectric Properties

Dielectric constant and loss factor dispersion

With frequency at room temperature

100 10
-1

tanδ

At 100 kHz frequency in room

75 Temperature

tanδ
⇓
ε'

50

Dielectric constant ⇒ 24.4

Loss factor ⇒0.03
25
-2
10
2 3 4 5
10 10 10 10
frequency (Hz)
 AC electrical properties

Ac conductivity plot as a function of

frequency for different sample
temperatures

T= 100

The plot at low temperature
T=150
T= 175 respond to the power law.
T= 200
10
-7
T= 225
T= 250

The power law dependency
T= 275
T= 300 corresponds to the short range
hopping of charge carriers through
10
-8
trap sites separated by energy
-1
σ ac (Ω.cm)

barriers of varied heights.

The plot for the different
10
-9 temperature at high frequency
region converges with one another,
since the electronic conduction
10
-10 which is dominant in that region is
2 3 4 5
10 10 10 10

Frequency(Hz)
independent of frequency.
 Arrhenius plot of ac conductivity Vs
(1000/T) in BZ thin film.

The plot contain two different regions corresponds

to two different activation energies.

At lower temperature the obtained σac is independent
-7
of temperature upto 1270C. It’s probably due to the
10

100kHz
saturation in the number of liberated electrons from the
donor states.

Beyond 1270C, the shape of the curve becomes more
10
-8 10kHz steeper and linear with the calculated activation energy
LnσT(ω) (S.cm-1)

of 1.5 eV. This might be attributed either to the oxygen

vacancy motion or due to the deep trap space charge
10
-9
1kHz conduction mechanism.

The activation energy was considerably lower than
0.1kHz
the band gap energy, which implies that the conduction
-10
in this range of temperatures were dominated by the
10
1.5 2.0 2.5 3.0 3.5
charge carriers other than electrons, possibly by ionic
-1
1000/T (K ) charge carriers such as oxygen vacancies.

The non linear shape of the Arrhenius plot indicated
that, at different temperatures different mechanisms
involved in the ac conduction process.
 Impedance Analysis
Imaginary part of the impedance Imaginary part of the modulus
Vs frequency Vs frequency
7
2.0x10 -5
1.5x10
0
T= 125 C
T= 125 0
T= 150 C
T= 150 0
T= 175 C
7 T= 175 0
T= 200 C
1.5x10 T= 200 0
T= 225 C
0
T= 225 -5
1.0x10 T= 250 C
0
T= 250 T= 275 C
0
T= 275 T= 300 C

1.0x10
7 T= 300
Z (Ω)

M''
-6
5.0x10
''

6
5.0x10

0.0
0.0

2 3 4 5 2 3 4 5
10 10 10 10 10 10 10 10

Frequency (Hz) Frequency (Hz)

No coincidence of peak frequency
Peak found to shift with increase of

of Z″ and M″ ⇒ Non Debye type temperature towards high frequency
relaxation phenomenon. ⇒ Single RC combination

This type of asymmetric behavior in real materials largely

determined by the Johnscher’s power law
Conclusions:

Single phase polycrystalline Barium Zirconate thin films were
deposited on the Pt coated Si substrates by pulsed excimer laser
ablation technique.

The SIMS analysis exhibit a sharp transition existing at the substrate
– film interface indicating that here was no interdiffusion in the case of
in-situ annealed thin films.

In the case of ex-situ films the interdiffusion and segregation of ZrO2
at the interface was observed.

The calculated activation energy from the ac analysis was 1.5 eV
and the activation energy is attributed to the oxygen vacancy
migration.

The impedance spectroscopy reveals that the relaxation behavior
was more like Johnscher’s model.