ARTICLE IN PRESS

Physica B 399 (2007) 21–26

www.elsevier.com/locate/physb

Electrical and structural properties of zirconia thin films

prepared by reactive magnetron sputtering
K.P.S.S. Hembrama, Gargi Duttab, Umesh V. Waghmareb, G. Mohan Raoa,
a
Department of Instrumentation, Indian Institute of Science, Bangalore 560 012, India
b
Theoretical Sciences Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore 560 064, India
Received 10 September 2006; received in revised form 5 May 2007; accepted 11 May 2007

Abstract

Thin films of ZrO2 were prepared by reactive magnetron sputtering. Annealing of the films exhibited a drastic change in the properties
due to improved crystallinity and packing density. The root mean square roughness of the sample observed from atomic force
microscope is about 5.75 nm which is comparable to the average grain size of the thin film which is about 6 nm obtained from X-ray
diffraction. The film annealed at 873 K exhibits an optical band gap of around 4.83 eV and shows +4 oxidation state of zirconium
indicating fully oxidized zirconium, whereas higher annealing temperatures lead to oxygen deficiency in the films and this is reflected in
their properties. A discontinuity in the imaginary part of the AC conductivity was observed in the frequency range of tens of thousands
of Hz, where as, the real part does not show such behavior.
r 2007 Elsevier B.V. All rights reserved.

Keywords: Zirconia; Magnetron sputtering; AC conductivity

1. Introduction studied on the basis of structural characteristics of the

interface.
The race for miniaturization of electronic devices has led Apart from the dielectric applications, ZrO2 can be used
to search for high dielectric constant (k) materials such as in optical coatings [7], oxygen sensors [8], ion conductors
TiO2, Ta2O5, barium strontium titanate (BST) and some [9], heat resistant coatings [10], buffer layers for growing
dopant hosted in BST [1,2]. These materials need to be superconductors [11], etc. In most cases the above
compatible with the existing technology of microelectronic applications require the ZrO2 layer on silicon surface and
fabrication for commercial implementation. Higher di- hence require more studies on the structural, optical,
electric constant oxide materials with suitable desired morphological and electrical characteristics of ZrO2 coat-
properties are required to replace SiO2 (k3.9) for device ings on silicon.
performance, with ease in fabrication. Conventionally ZrO2 films are prepared by sol gel
Although TiO2, Ta2O5, BST are some of the high k [12,13], spray pyrolysis [14], atomic layer deposition [15],
materials, they are thermodynamically unstable on silicon plasma enhanced atomic layer deposition [16], electron
at higher temperatures, where as, zirconia (ZrO2) on silicon beam evaporation [17], and metal organic CVD [18,19].
is more stable [3]. Thermal stability of ZrO2 deposited on However, the advantage of reactive magnetron sputtering
silicon with respect to silicide formation at higher for this purpose is mainly due to the high deposition rate
temperature, is one of the main factors to be considered by sputtering from metallic target [20], which also enables
for various applications [4]. Factors like interface engineer- control of the stoichiometry of the deposited films.
ing [5], reaction steps for silicide formation [6], are well The high sputter rates also reduces the target poisoning
effects which normally affect the reactive sputtering
process. Hence in this study we have chosen reactive
Corresponding author. Tel.: +91 80 22932349; fax: +91 80 23604533. magnetron sputtering process for the deposition of zirconia
E-mail address: gmrao@isu.iisc.ernet.in (G. Mohan Rao). thin films.

0921-4526/$ - see front matter r 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2007.05.022
 ARTICLE IN PRESS
22 K.P.S.S. Hembram et al. / Physica B 399 (2007) 21–26

The present study deals with the growth of ZrO2 on 400

silicon substrates at ambient and post deposition annealing
up to 1073 K. The effect of annealing on the structural, 360
optical, morphological and electrical properties of zirconia

Voltage (Volt)
films has been studied. 320

280
2. Experimental
50 mA
240 100 mA
Thin films of zirconia were deposited on polished p-type 200 mA
300 mA
silicon /1 0 0S substrates using reactive magnetron sput- 200 400 mA
tering. The substrates were subjected to standard cleaning 500 mA

procedures before introducing into the deposition cham- 0 2 4 6 8 10

ber. A circular zirconium disk of 99.99% pure and 100 mm X 10-4 mbar Oxygen Partial Pressure
diameter was made the target. Argon and oxygen gas flow
was controlled independently and a total pressure of Fig. 1. Variation of target voltage as a function of oxygen partial
pressure.
6  103 mbar was maintained during deposition. The
details of deposition conditions are listed in Table 1. After
deposition, the samples were annealed in the same chamber the present study, all the oxide films have been deposited
under vacuum for 30 min at a temperature ranging from with a discharge current of 450 mA and an oxygen partial
773 K to 1073 K. In order to study the AC electrical pressure of 8  104 mbar.
conductivity, the electrodes were made by silver contact.
The thickness of the films used in this study was measured 3.2. X-ray diffraction (XRD)
to be 110 nm by stylus profilometer.
The structure of the samples was characterized by XRD
with CuKa radiation and the diffraction pattern is shown
3. Results and discussion in Fig. 2. There was no crystallinity in the samples grown at
ambient temperature, but with annealing at 873 K the
3.1. Glow discharge characteristics monoclinic phase appears as seen from the diffraction
pattern. This is the normally observed phase of bulk
The glow discharge characteristics during reactive zirconia at room temperature (RT) and pressure. With
sputtering were studied under different oxygen partial annealing at higher temperatures, tetragonal phase is seen
pressures, in order to optimize the region where the ZrO2 from the hump appearing in the samples annealed at
films can be prepared. Fig. 1 shows the variation of target around 1073 K and simultaneously the intensity of mono-
voltage as a function of oxygen partial pressure. When the clinic phase reduces. The average grain size D for the
target current is maintained constant, the characteristics deposited film was determined to be around 6 nm using
show that the voltage increases initially, reaches a Scherrer’s formula
maximum at a particular oxygen partial pressure and later
it decreases and after certain pressure, almost remains D ¼ ð0:9 l=b cos yÞ,
constant. This behavior has been explained earlier by where y is the Bragg angle, b is the full width at half
Mohan Rao and Mohan [21] and attributed to the target maximum of the peak, and l is the wavelength of X-ray
poisoning effects. The ideal region for the deposition of [22].
oxide films with reasonable deposition rates is the region
where the cathode voltage starts decreasing. However, 3.3. UV–visible transmittance spectroscopy
when the target current is low, due to low deposition rate
of the metal, the target gets poisoned even with low partial Fig. 3(a) shows UV–visible transmittance spectra of
pressure of the reactive gas. Based on these results, during zirconia thin films. Annealed samples show higher trans-
mittance indicating the improved crystalline nature of the
thin film. The transmittance showed a slight decrease in
case of films annealed at 1073 K. This could be due to the
Table 1 removal of oxygen due to high temperatures. Fig. 3(b)
Deposition conditions for zirconia films
shows the plot of (ahg)1/2 as a function of energy (hg)of the
Base pressure 2.5  105 mbar incident light. The band gap can be calculated by
Oxygen partial pressure 8  104 mbar extrapolating the linear portion of the curve to the abscissa
Total pressure (argon+oxygen) 6  103 mbar intercept. The calculated results are listed in Table 2. The
Substrate to target distance 110 mm band gap value shows the insulating nature of the thin film
Discharge current 450 mA
Deposition time 15 min at all the conditions. While the amorphous nature of the
films deposited at RT exhibits lower band gap value, the
 ARTICLE IN PRESS
K.P.S.S. Hembram et al. / Physica B 399 (2007) 21–26 23

annealed films exhibited higher band gap and a maximum band gap with annealing could be a combined effect of
(4.83 eV) was seen in the films annealed at 873 K. Further improved packing density and improved crystallinity.
increase in annealing temperature did not show much Approximations have been taken in the computation of
variation in the band gap. It is well known that the n and k as the oscillations of the amplitude of transmit-
sputtered films have lower packing density and annealing tance is not observed due to small thickness of the films [23,
improves the packing density. Thus the increase in the 24]. The variation of the refractive index and extinction

t(002)
1073K m(022) m(310)
Intensity (a.u.)

973K
m(221)

m(112)
873K t(111)

773K

RT

10 20 30 40 50 60
2 Theta (Degree)

Fig. 2. X-ray diffraction of the ZrO2 thin films grown at different conditions.

100 1200
1073K
90 973K
1000 873K
80
RT
70
Transmittance (%)

800
60
(α hν)1/2

50 600

40
400
30
1073K
20 973K
200
873K
10
RT
0 0
100 200 300 400 500 600 700 800 900 0 1 2 3 4 5 6 7
Wave Length (nm) hν (eV)

2.5
1073 K
0.20
973 K 1073 K
2.4 873 K 973 K
RT 873 K

2.3 RT
Extinction coefficient (k)

0.15
Refractive Index (n)

2.2

0.10
2.1

2.0
0.05
1.9

1.8 0.00
100 200 300 400 500 600 700 800 900 100 200 300 400 500 600 700 800 900
Wave Length (nm) Wave Length (nm)

Fig. 3. (a) Transmittance spectra of ZrO2 thin film with and without annealing; (b) (ahg)1/2 as a function of energy (hg); (c) Refractive index as a function
wavelength; (d) extinction coefficient as a function of wavelength.
 ARTICLE IN PRESS
24 K.P.S.S. Hembram et al. / Physica B 399 (2007) 21–26

Table 2 coefficient as a function of wavelength at different sample

Band gap at different conditions preparation conditions is shown in Fig. 3(c) and (d). From
Samples prepared Band gap (eV)
this it can be seen that k is nearly 0.05 and hence the films
are fully transparent in the visible range. The refractive
RT 4.37 index of the films is nearly the same (about 1.95) for all the
873 K 4.83 films in the visible range. Higher value of the refractive
973 K 4.70
index is observed at the lower wave length regime.
1073 K 4.78
Our values compare well with the results obtained by
Venkataraj et al. [25].

3.4. Atomic force microscopy (AFM)

Fig. 4(a) shows the two dimensional surface morphology

of the zirconia film with scan size 5  5 mm2. The
corresponding three dimensional image is shown in
Fig. 4(b). The columnar growth with dense structure is
observed from the top and lateral view. The mean height of
the surface morphology is 188.92 nm obtained from the
linear fit of the scan height taken over 256 points with
standard deviation of 0.00532 and correction coefficient
0.08169. The mean of root mean square (RMS) rough-
ness of the film is found to be 5.75 nm as shown in Fig. 4(c).
The image clearly shows a dense microstructure and is
reflected in the improved properties of the annealed films as
discussed above.

3.5. X-ray photoelectron spectroscopy (XPS)

The as deposited and annealed (873 K) films were studied

using XPS. The wide range survey scan spectra of the
annealed film is shown in Fig. 5(a). The more specific
scanning of Zr 3d spectra, which splits into its two
spin–orbit components 3d5/2 at 183.3 eV and 3d3/2 at
185.7 eV separated by 2.4 eV and at the intensity ratio of
10:7 as shown in Fig. 5(b). This can be explained by
considering complete oxidation of zirconium to zirconia in
its +4 oxidation state [4,26,27]. The specific scanning O1s
spectra, which is at 531.2 eV is primarily due to Zr–O
bonding which is shown in Fig. 5(c). The shift in peak
position for zirconium and oxygen for the as deposited
sample may be due to partial bonding of zirconium atoms
with the oxygen. The XPS data thus show that the
annealed films are completely stoichiometric resulting in
better optical characteristics.

3.6. AC conductivity

Fig. 6(a) shows the real part of the AC conductivity of

the as prepared and annealed samples measured at
different temperatures. The low frequency conductivity of
the as deposited samples differs from that of annealed
samples. At higher frequencies all the samples show similar
behavior for the real part. But the imaginary part gives
discontinuity in the range of tens of thousands of Hz. This
Fig. 4. (a) 2D surface morphology of ZrO2 thin film annealed at 873 K; may be due to the reason that the thermal fluctuations of
(b) 3D surface morphology of ZrO2 thin film annealed at 873 K; (c) RMS the conducting species are suppressed at low temperature,
surface morphology of ZrO2 thin film annealed at 873 K. reducing the scattering probability. (At the RT the data
 ARTICLE IN PRESS
K.P.S.S. Hembram et al. / Physica B 399 (2007) 21–26 25

873K
RT
O 1S
O KLL

Intensity (a.u.)
Zr 2P 3/2
Intensity (a.u)

Zr 3d Zr 2P 1/2
Zr 2S

C 1S

Zr 4P

0 200 400 600 800 1000 180 182 184 186 188 190
Binding Energy (eV) Binding energy (eV)

873K
RT
Intensity (a.u.)

525 530 535 540 545

Binding Energy (eV)

Fig. 5. (a) Wide scan XPS spectrum of ZrO2 thin film annealed at 873 K; (b) XPS spectrum of Zr 3d 5/2 and Zr 3d 3/2 of ZrO2; (c) XPS spectrum of O1s of
ZrO2.

points are not consistent and we are not able to get clear correlated barrier hopping (CBH) model [28,30] can be
data). The same explains the behavior in the imaginary part used to describe sAC (o) of these oxides and is described
of the AC conductivity, shown in Fig. 6(b). elsewhere [31–34].
The measured conductivity can be related by the
equation sAC ¼ sDC(0) +sAC (o) [28,29], where sDC(0) 4. Conclusions
is a zero-frequency (DC) conductivity. sAC(o) is a
frequency-dependent component of the conductivity, Zirconia thin films were prepared by reactive magnetron
expressed as a power law sAC (o) ¼ Aos, (where A is sputtering. The electrical and optical properties of the films
the proportionality constant that depends on the tempera- were found to show improvement after annealing. Anneal-
ture and s is the frequency exponent) which describes the ing at 873 K resulted in a higher band gap of 4.83 eV for the
conduction by hopping of charge carriers [28,29]. The films and further annealing showed no significant change in
 ARTICLE IN PRESS
26 K.P.S.S. Hembram et al. / Physica B 399 (2007) 21–26

Acknowledgement
103
d
c The authors are grateful to Prakash of Department of
b
a Physics, Indian Institute of Science, for assistance in
electrical characterization of samples.
102
Real σ(ac) (S/cm)

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