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Procedia Technology 23 (2016) 336 343

3rd International Conference on Innovations in Automation and Mechatronics Engineering,

ICIAME 2016

Investigation of various properties for zirconium oxide

films synthesized by sputtering
a

Uttkarsh S. Patel , Kartik H. Patel , Kamlesh V. Chauhan , Amit Kumar Chawla ,

Sushant K. Rawal
a

a*

CHAMOS Matrusanstha Department of Mechanical Engineering, Chandubhai S. Patel Institute of Technology (CSPIT),
Charotar University of Science and Technology (CHARUSAT), Changa- 388421, Gujarat, India
b

Institute of Nanoscience and Nanotechnology, University of Petroleum and Energy

Studies, Energy Acres, Dehradun-248 007, Uttarakhand, India
*Corresponding Author: Sushant K. Rawal E-mail address: sushantrawal@outlook.com Tel.: +912697 265060

Abstract
The aim of this paper is to deposit zirconium oxide films by magnetron sputtering process at different argon partial pressure values
of 45%, 55%, 62% and 67%. The effect of argon partial pressure on structural, optical and wettability properties of zirconium oxide
films is investigated in this research work. The increase in argon partial pressure leads to increase in intensity of (111) peak for
zirconium oxide thin films as observed by X-ray Diffraction. The average crystallite size of zirconium oxide films increases from
19nm to 25nm with increase in argon partial pressure. Wettability properties of zirconium oxide films such as contact angle and
surface energy were determined by contact angle measuring system. The minimum transmission values above 63% were observed
for all zirconium oxide thin films deposited at different argon partial pressure. Band gap and refractive index of zirconium oxide thin
films varies as a function of argon partial pressure.
2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
2016 The Authors. Published by Elsevier Ltd.

(http://creativecommons.org/licenses/by-nc-nd/4.0/).

Selection and/or peer-review under responsibility of the Organizing Committee of ICIAME 2016.

Peer-review under responsibility of the organizing committee of ICIAME 2016

Keywords: Zirconium oxide; Sputtering; Optical; Wettability; Band Gap

1. Introduction
Zirconium oxide (ZrO2) is an innovatively essential material characterized by a high melting point (2680C), vast
resistance against oxidation, high refractive index, broad region of low absorption from the near-UV (above 240nm) to
the mid-IR range(below 8mm) [1], [2]. This combination of properties is attractive for an extensive variety of
applications which include laser mirrors, broadband interference filters and ionic conductors. In addition, thin ZrO 2

2212-0173 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Peer-review under responsibility of the organizing

committee of ICIAME 2016
doi:10.1016/j.protcy.2016.03.035

Uttkarsh S. Patel et al. / Procedia Technology 23 (2016) 336 343

337

film is considered as a potential contender to supplant SiO 2 as high k gate dielectric in complementary metal-oxidesemiconductor technology, due to its high bulk dielectric constant (15-30), wide energy band gap and offsets alonf with
good thermal stability with silicon surface [3], [4]. However, in practice the suitability of ZrO 2 for these applications is
questionable because it is known to experience several structure transformations (cubic phase, tetragonal phase,
monoclinic phase, and amorphous structure) as a function of temperature [5]. As a thin-film, ZrO 2 generally condense
in a partially crystalline form, yet an amorphous ZrO 2 film is always preferred to a polycrystalline for its applications
in optical and microelectronic devices. Scattering from such crystallites and/or grain boundaries in ZrO 2 films may
cause optical component degradation if such coatings are exposed to elevated temperatures or high laser intensities. In
addition, grain boundaries in crystalline ZrO 2 thin films may induce undesired effects on their leakage current
characteristics and different anisotropic crystalline phases existing in the films will lead to non-uniformities in k value
and in film thickness.
These intriguing applications have prompted various endeavors to synthesize amorphous or polycrystalline ZrO 2 films
by various techniques, including electron-beam evaporation [6], ion-beam assisted deposition [7], [8], reactive
sputtering [9], [10], chemical vapour deposition [11], [12], pulsed laser abrasion [13], chemical solution deposition
[14], anodization [15], sol-gel method [16], atomic layer deposition (ALD) [17]. In general, it has been noted that
structures and properties of the films show a pronounced dependence upon the deposition process and the precise
deposition parameters chosen. Reactive magnetron sputtering offers good control over the deposition rate, film
composition and minimizes target poisoning. However, this technique has not yet been well studied to produce ZrO 2
thin films with the purpose of the referred applications. The aim of this research work is to prepare ZrO 2 thin films by
magnetron sputtering method at different argon partial pressures and to systematically investigate on how argon partial
pressures affect various properties of deposited films.
2. Experimental details
Zirconium Oxide films were deposited using metal target of zirconium (99.99% purity) by magnetron sputtering
-4
process in a vacuum chamber (Excel Instruments, India). The chamber was initially evacuated to about 410 Pa by a
turbo pump backed by a rotary pump, than oxygen and argon gases of high purity (99.999%) were supplied into the
chamber. The ratio of the gas mixtures was controlled using mass flow controllers (Alicat, USA). The argon partial
pressure was varied at 45%, 55%, 62% and 67% using mass flow controllers, the corresponding sample names are
represented by A45, A55, A62 and A67 respectively. The sputtering pressure was kept at 1.25Pa for above mentioned
depositions. Sputtering was carried out for a time of 60 minutes at a fixed radio-frequency (RF) power of 150W,
deposition temperature of 500C and at fixed substrate to target distance of 50mm. Structural characterization of the
deposited samples was done by X-ray diffractometer (XRD) using Bruker D2 Phaser Advance diffractometer. The
wettability studies of films were done by contact angle measurement system (rame-hart Model 290) to find the contact
angle and surface energy of films. Optical transmission and absorption of the films were measured by UV-Vis-NIR
spectrophotometer (Shimadzu, Model UV-3600 Plus).
3. Results and discussions
X-Ray Diffraction (XRD) graphs of zirconium oxide films deposited at different argon partial pressure is shown in Fig.
1. When partial pressure of argon is 45%, it depicts weak (111) peak of ZrO 2 phase. When the argon partial pressure is
increased to 55%, a slight increment in (111) peak for ZrO 2 phase is observed. At 62% argon partial increase in
intensity of (111) peak for ZrO 2 phase is observed. Thereafter a further increase of argon partial pressure to 67%, a
drastic increase in the intensity of (111) peak for ZrO 2 phase is observed imparting maximum intensity at this
deposition condition for zirconium oxide films. The variation of argon partial pressure from 45% to 67% performed
during this experiment resulted in development of single (111) peak of monoclinic ZrO 2 phase. It is a consequence of
precisely controlled process parameters of reactive magnetron sputtering process that has led to formation of
crystalline zirconium oxide films.

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Scherrer formula [18] was utilized to calculate the average crystallite size of deposited zirconium oxide films. The
average crystallite size of zirconium oxide films deposited at different argon partial pressure varies from 19nm to
25nm respectively as shown in Table 1.

Fig. 1. XRD patterns of zirconium oxide films deposited at different argon partial pressure.

Gas pressure in the chamber during sputtering is inversely proportional to mean free path of the gas atoms as reported
in literatures [19][21]. The quantity of gas atoms present in the chamber will increase with increase in argon partial
pressure from 45% to 67%. As a result, mean free path will decline, the gas atoms will collide with each other and
agglomeration of grains will take place causing formation of larger crystallite size zirconium oxide films with increase
in argon partial pressure.
Table 1: Calculated parameters of zirconium oxide thin films.
Avg
Band Gap
Refractive
Thickness (nm)
d(xrd)(nm)
(eV)
index (n)
by %T data
19
4.28
1.53
433
20
4.34
1.53
408

Sample
Name
A45
A55

Argon partial
pressure
45%
55%

Surface
Roughness (nm)
1.75
1.42

A62

62%

23

4.40

1.52

391

1.24

A67

67%

25

4.46

1.52

385

1.07

The AFM images of zirconium oxide films deposited at 45% and 67% argon partial
pressure are shown in Fig. 2. (a) & (b) respectively. It is evident from AFM images that
average crystallite size of zirconium oxide films increases with increase in argon partial
pressure. Contact angle for zirconium oxide films was measured for two liquids water and
aniline. The effect of surface roughness on contact angle of zirconium oxide films for
water and aniline is shown in Fig. 3. (a) & (b) respectively. The deposited zirconium oxide
films are hydrophobic for water having contact angle values of more than 90 at various
argon partial pressures. Zirconium oxide films show hydrophilic behaviour for aniline. The
variation of surface energy and contact angle for zirconium oxide films as a function of
argon partial pressure for water and aniline is shown in Fig. 4. (a) & (b) respectively. The
surface energy is inversely proportional to the contact angle values [22]. The maximum
contact angle values of 101 for water were observed at 45% argon partial pressure
whereas contact angle of 49 for aniline was observed having surface roughness of
1.75nm at 45% argon partial pressure for deposited zirconium oxide films.

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339

Fig. 2. AFM images of the zirconium oxide films deposited at (a) 45% argon partial pressure and (b) 67% argon partial pressure.

Fig. 3. Variation of contact angle and surface roughness of zirconium oxide films as a function of argon partial pressure for (a) water and (b)
aniline

The contact angle of 97 is observed for water and 50 for aniline with surface roughness of 1.42nm at 55% argon
partial pressure. A further increase in argon partial pressure to 62% leads to decrease in contact angle value of 95 for
water and insignificant change in contact angle of 50 for aniline having surface roughness of 1.24nm. Increasing

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argon partial pressure to 67% gives contact angle of 90 for water which is higher than that of 87 for water as reported
in literatures [23], [24]. The contact angle for aniline is 52 and surface roughness of 1.07nm at 67% argon partial
pressure. The lowest surface energy value is observed for zirconium oxide films deposited at the 45% argon partial
pressure due to higher surface roughness of 1.75nm and contact angle value of 101 for water and 52 for aniline. The
surface energy is having maximum values for zirconium oxide films deposited at 67% argon partial pressure as evident
from Fig. 4. The maximum contact angle observed for water is 101 at 45% argon partial pressure and 52 for aniline at
67% argon partial pressure. So developed zirconium oxide films is hydrophobic for water and hydrophilic for aniline.

Fig. 4. Variation of contact angle and surface energy of zirconium oxide films as a function of argon partial pressure for (a) water and (b)

aniline

Transmittance spectra for all samples of zirconium oxide films deposited on the glass substrates at different argon
partial pressure measured by UV-vis-NIR spectrophotometer is shown in Fig. 5. With increase in argon partial pressure
the transmittance of zirconium oxide films increases as evident from Fig. 5.

Fig. 5. Optical transmission curve of zirconium oxide films deposited at different argon partial pressure.

A model suggested by Manifacier et al. [25], [26] was used to determine refractive index of

zirconium oxide films from transmission data. The refractive index of zirconium oxide
films as given in Table 1 shows minimal variation

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with increase in argon partial pressure. Transmission date was also utilized to decide the thickness of deposited
zirconium oxide films by the method reported in literatures [27], [28]. The thickness of zirconium oxide films is given
in Table 1. When argon partial pressure is increased from 45% to 67%, the thickness of zirconium oxide films
decreases from 433nm to 385nm.
Westwood, (1978) [29] was able to establish a relation between deposition rate and proportion of scattered sputtered
atoms. He observed that as partial pressure of gases used in sputtering process increases, it leads to more collisions
within atoms and decline in deposition rates. When argon partial pressure is elevated from 45% to 67% for deposited
zirconium oxide films, the number of gas atoms within chamber increases, thereby increasing collisions among them
resulting reduction in deposition rate and thinner films.

Fig. 6. Optical absorption curve of zirconium oxide films deposited at different argon partial pressure.

Absorption coefficient () obtained from the absorption spectra was used to find the band gap of zirconium oxide films
using Tauc relation [30][32]. The band gap of zirconium oxide films deposited at various argon partial
pressures are shown in Fig. 6. The literatures has widely stated that ZrO 2 is an indirect band gap semiconductor having
r = 2 [33]. The band gap of zirconium oxide films increases from 4.28eV to 4.46eV as argon partial pressure is
increased from 45% to 67%.
4. Conclusion
The zirconium oxide films shows the formation of crystalline films with (111) m-ZrO 2 phase by increasing argon
partial pressure. When argon partial pressure is increased, thickness of zirconium oxide films decreases from 433nm to
385nm. The decrease in film thickness leads to higher transmission values of zirconium oxide films whereas an
increase in band gap from 4.28eV to 4.46eV is observed. The zirconium oxide films are hydrophobic for water having
maximum contact angle of 101 at 45% argon partial pressure. Zirconium oxide films are hydrophilic for aniline
having maximum contact angle values of 52 at 67% argon partial pressure.
5. Acknowledgements
This work has been supported by AICTE grant number 20/AICTE/RIFD/RPS (POLICY-III) 24/2012-13 sanctioned
under Research Promotion Scheme (RPS). We are thankful to President and Provost of CHARUSAT for supporting
this research work. We are thankful to Dr. T. K. Chaudhuri, Professor and Head, Dr. K. C. Patel Research and

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Development Centre (KRADLE) affiliated to Charotar University of Science and Technology (CHARUSAT), India for
granting permission to use various equipments available in their characterization laboratory.
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