Materials Science and Technology

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Effects of anodisation parameters on thin film

properties: a review

Y. H. Wong, M. G. Affendy, S. K. Lau, P. C. Teh, H. J. Lee, C. Y. Tan & S. Ramesh

To cite this article: Y. H. Wong, M. G. Affendy, S. K. Lau, P. C. Teh, H. J. Lee, C. Y. Tan & S. Ramesh
(2016): Effects of anodisation parameters on thin film properties: a review, Materials Science
and Technology, DOI: 10.1080/02670836.2016.1193654

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 Effects of anodisation parameters on thin film
properties: a review
Y. H. Wong∗ 1 , M. G. Affendy1,2, S. K. Lau1, P. C. Teh1, H. J. Lee3, C. Y. Tan1 and
S. Ramesh1
Electrochemical anodisation is a well-received method in the complementary metal-oxide-
semiconductor field as it is advantageous; best performed at room temperature which translates
into being more affordable and a simple alternative to form nano-structured oxide films for
different metals. The quintessential parameters involved allow numerous formations of metal
oxide films according to desired morphology and thickness. Therefore, this paper aims to review
the effects of anodising parameters such as applied voltage, concentration, temperature, time,
current density and post-anodisation annealing among them.
Downloaded by [New York University] at 15:54 28 June 2016

Keywords: Anodisation, Thin films, Applied voltage, Temperature, Thickness

Introduction fabrication process.22 Thus, it is crucial then to search

For the past few decades, complementary metal-oxide-
semiconductor (CMOS) has received huge attention due
to their potential use in advanced areas of sensors, photovol-
taic cells, biomedical and photocatalytic engineering.1–3 In
addition to that, these metal oxides of controlled micro/
nano-morphologies have found significant applications
such as nanomaterial synthesis, super capacitors, water puri-
fication systems, and self-cleaning and self-sterilising
materials.4–6
Generally, the application performance of metal oxides
is determined by their structure and surface features.7
Thin oxide films are widely favoured compared to bulk
materials because of cost considerations, processing flexi-
bility, and suitability for various substrates, types and
shapes. Since SiO2 has been well explored in past litera-
tures, several oxides with higher dielectric constant have
been proposed as alternatives to it. Among them are
ZrO2,8 TiO2,9 Al2O3,10 CeO11 12
2 and HfO2 to name a
few. Taking ZrO2 as an example, it is deemed to be one
of the highest potential candidates due to its wide band
gap, high conductivity barrier and high dielectric
constant.13
There are different methods, both chemically and phys-
ically, which are available to prepare these metal oxides on
Si substrate for instance chemical vapour deposition
(CVD),14 spray pyrolysis,15,16 sol-gel,17 thermal oxi-
dation,18–20 and reactive sputtering.21 However, these
methods require high thermal budget and huge amount
of time. In addition to that, these properties may result
in a damaging effect on further sub-micrometer
1
Department of Mechanical Engineering, Faculty of Engineering, University
of Malaya, Kuala Lumpur 50603, Malaysia
2
School of Metallurgy and Materials, University of Birmingham, Edgbaston,
Birmingham, West Midlands, B15 2TT, United Kingdom
3
Center for Photonic Technologies, Universiti Tenaga Nasional, Bandar
Baru Bangi, Selangor 43650, Malaysia
∗
Corresponding author, email yhwong@um.edu.my
for and implement a method which is relatively low in
thermal budget as well as consuming less time.
With that taken into account, electrochemical anodisa-
tion of metals can be widely considered as the suitable
method to allow the formation of metal oxide films. By
definition, anodisation is a simple process of converting
metal into its oxide in a liquid bath under applied voltage
or current. Anodisation is preferred as this particular pro-
cess can be performed at room temperature; thus, it offers
a cheaper and easier alternative for producing nano-struc-
tured metal oxide films on a range of metals and alloys.23
As a result, the morphology and the thickness of metal
oxide formed depend on the parameter applied. Accord-
ing to Lewandowska,24 anodic oxidation of alloy in an
acidic electrolyte is deemed beneficial in the biomedical
field as this method may produce an effective barrier
between alloy and the surrounding environment without
affecting the bio-compatibility of the material.
Apart from the importance for a practical application
in industry, clarification of the factors controlling the
dielectric properties of anodic oxide film has essential sig-
nificance for an understanding of the fundamental anodi-
sation mechanism.25 It is therefore vital for researchers to
investigate the effects of anodising conditions which
include applied voltage, current density, concentration,
temperature and type of electrolyte. For example, the
type of electrolyte used and electric conditions applied
can affect the surface morphology, chemical composition
and crystalline structure of the oxide films formed.26,27
Furthermore, geometrical features of the nanopores, like
the pore diameter, interpore distance, thickness of the por-
ous oxide layer etc. are in a strong relation with anodising
conditions as mentioned earlier.28–30
Thick and porous oxide films can be fabricated via a
high voltage to facilitate dielectric breakdown. These
films increase the surface roughness of titanium and pro-
vide high bond strength between the oxide film and the
titanium substrate. Moreover, the hardness of titanium

© 2016 Institute of Materials, Minerals and Mining

Published by Taylor & Francis on behalf of the Institute
Received 23 December 2015; accepted 20 May 2016
DOI 10.1080/02670836.2016.1193654 Materials Science and Technology 2016 1
 Wong et al. Effects of anodisation parameters on thin film properties
substrate metal close to the oxide layer could be improved
by anodic oxidation due to incorporation of oxygen into
titanium metal.31
Kuromoto et al.32 has stated that the colouration of
TiO2 oxide produced through anodisation can be indica-
tive to the thickness of the oxide film. Furthermore, this
relation between colour and thickness of oxide film
depends strongly on the process and the nature of the elec-
trolyte.33 Any change in these parameters can modify the
colouration of the oxide surface. Sul et al.33 have indicated
that the electrochemical growth behaviour of the oxide
film is strongly dependent on anodic parameters such as
electrolyte concentration, applied current density, anodic
forming voltage, the given temperature, agitation speed
and the surface area ratios of cathode to anode.
Therefore, with all of the parameters mentioned above,
it has become an imperative issue on what are the opti-
mum conditions for preparing the anodic metal oxide
films in order to provide the best properties. Important
and frequently applied parameters which are applied vol-
tage, temperature, time and post-anodisation annealing
will be discussed from past literatures to determine their
impacts on the properties of produced metal oxide film.
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Anodisation of thin film and growth
modes
Anodisation is a relatively simple and easy method to
form a gate dielectric. Yet, only limited effort has been
done so far to investigate properties of anodised ZrO2
thin film. One of the reasons is because this technique is
not a single flow process. High purity of metal thin film
is first deposited with the assistance of physical vapour
deposition (PVD) technique, such as sputtering followed
by anodisation to grow the metal oxide dielectric.
Anodisation is a highly versatile technique as it can be
conducted under room temperature. In addition, the
apparatus setup is comparatively easier and cheaper
than other advanced thin film deposition technologies.22
Prior to the execution of anodisation process, some prep-
aration on the sputtered Si has to be done. First, Zr depos-
ited Si has to be attached to the conductive metal
(commonly Cu or Al) using silver paste. The conductive
1 Apparatus setup for the anodisation of Zr thin film
2 Materials Science and Technology 2016
metal has then to be connected to the positive potential
of electrochemical cell, where the negative bias has to be
connected to platinum electrode as illustrated in
Fig. 1.34 Acidic solution such as hydrochloric acid
(HCl), nitric acid (HNO3) and sulphuric acid (H2SO4)
or alkaline solution such as sodium hydroxide (NaOH)
and potassium hydroxide (KOH) can be used as electro-
lyte. However, alkaline solution is better fit for anodisa-
tion process in comparison to acidic solution. This is
because large quantity of hydroxide is produced in the
alkaline solution and it serves as the source of oxygen to
grow the oxide gate layer.35–37 This is sometimes known
as wet oxidation process. On the other hand, if the dielec-
tric layer is grown by direct heating inside a furnace in an
oxidation-contained ambient, it is then called the dry oxi-
dation process.
The growth rate of oxide in wet oxidation is much faster
than dry oxidation because oxygen molecules are bulkier
than hydroxide ions so they take longer time to diffuse.
The rapid growth rate of ZrO2 is undesired as sometimes
it may degrade the quality of thin film; this is because it
might be difficult to control the oxide formation mechan-
ism as well as inducing contamination.
This rapid growth of oxide through anodisation process
is well compensated by the unique crystal structure for-
mation under room temperature as compared to other
synthesis techniques. In general, ZrO2 can exist in three
different structures with respect to the processing and
post treatment temperature.38 Via anodisation method,
it is able to generate high thermal stability phase at low
temperature. This is an achievement offered by anodisa-
tion as compared to other deposition techniques. For-
mation of different crystal structures correspond to
various voltages applied was reported by Lockman
et al.22 Only native amorphous ZrO2 was produced
when there was no voltage supplied to the electrochemical
cell. Then high temperature phase of cubic or tetragonal
ZrO2 was formed at low anodisation voltage of 5 V. By
subsequent addition of anodisation voltage, monoclinic
phase of ZrO2 (m-ZrO2) was found present in the thin
film. After that, grain size continues to grow with anodi-
sation voltage and at the same time crack was identified
on the thin film. The crack phenomenon was observed
at about 25 V of voltage supply. Such defect is highly
undesirable as it significantly affects the performance of
electrical properties especially the dielectric constant. It
was suggested that the amount of defects can be con-
trolled by varying the anodisation voltage and the purity
of anodised ZrO2 thin film can be maintained owing to
low diffusivity of impurities in the thin film.
There are three possible growth modes during the depo-
sition process namely Frank-van der Merwe, Volmer-
Weber and Stranski-Krastanov as illustrated in Fig. 2a–
c, respectively.39 Basically, there is no restriction in the
growth mode for every deposition process. The growth
mode is highly dependent on the deposition temperature
and surface energy of film and substrate.
In the Frank-van der Merwe growth mode, adatoms
form a complete monolayer on the surface of substrate
followed by a second layer. This is because adatoms are
able to bond intensively with substrate. This layer-by-
layer growth usually results in a single crystalline struc-
ture.40 Volmer-Weber is another growing mechanism in
which adatoms are prone to attach to each other rather
than to the substrate. Therefore, the adatoms form a

2 The possible growth modes of the thin film during deposition a Farank-van der Merwe, b Volmer-Weber and c Stranski-Kras-
tanov (retrieved from Oura et al.39)
three-dimensional island instead of a complete layer. Fur-
thermore, the substrate surface may not be wholly covered
until a large deposition has been made. Next, Stranski-
Downloaded by [New York University] at 15:54 28 June 2016
Krastanov is characterised by the formation of one or
more monolayers followed by the island growth.
Effects of applied voltage on thin film
morphology
Basically, the metal oxide films produced from electroche-
mical anodisation attain distinct morphology and phases
present which were characterised thoroughly. In that mat-
ter, both issues can be investigated with respect to the
applied voltage in order to understand the effects of vol-
tage in the mechanism of growth of oxide film during
anodisation.
First, morphology evaluation of oxide films is normally
performed by scanning electron microscope (SEM).
According to Kuromoto et al.,32 TiO2 films were pro-
duced on Ti samples by anodic oxidation at different vol-
tages. Figure 3 shows two types of surface morphologies;
a non-porous structure on natural Ti [Fig. 3a] and a por-
ous structure where the pore size increases with increasing
applied voltage [Fig. 3b–f ].
From the AFM evaluation, the pores began to develop
and become more uniform with increasing applied vol-
tage. The process occurred with the oxide film breaking
down locally attributed by the dielectric breakdown.41
As a result, the porosity and pore size increased. This
morphology resembled the results obtained by Kawashita
et al.42 on the surface of Ti anodically oxidised at 180 V in
2 M H3PO4 electrolyte. Larger pore size observed is due
to the interconnections of some pores with each other.43
Moreover, the uniformity of oxide film can be observed
as well in the works of Xing et al.44 At low potential
(200 mV), the film surface is relatively flat, with only a
few grains can be seen. However, with increasing potential
values, multiple individual grains of with an average
diameter of approximately 100 nm emerged on sample
surface. Lastly, at the highest potential (2000 mV), grain
shapes appeared to be clearer, and uniform throughout
the film surface. According to past literatures, these
nanoscale grains formed on Ti anodised film surfaces
are anatase nanocrystals.45 Thus, it is deemed
Wong et al. Effects of anodisation parameters on thin film properties
advantageous for the production of crystalline Ti oxides
by implementing high applied voltages.
Besides that, Fig. 4 depicts the FESEM images of the
ZrO2 thin film surface after anodisation process in 1 M
NaOH for 15 min at a 10 V, b 20 V, c 30 V, d 40 V and e
60 V. Similar to previous observations, the surface of the
film anodised at low voltages such as at 10 V [Fig. 4a]
and 20 V [Fig. 4b] are relatively smooth.
The grains appeared spherical in shape with diameters
measured in the nanoscale. The grains are spherical with
diameters in the nanoscale. Following a parallel pattern,
the diameter of the grains increased when anodisation vol-
tages were increased. At 40 V, blistering and cracks are
very obvious on the sample’s surface. Anodisation at
even higher voltage of 60 V leads to more blistering and
severe delamination of the oxide from the substrate
[Fig. 4e].
Effects of applied voltage on thin film
formation mechanisms
Normally, film formation via anodic oxidation begins
with the following steps; first, the natural TiO2 particles
grow, coalesce together and form a smooth region.
After a while, some areas begin to develop cracks and
become porous. As the applied voltage increases, the
film breaks down locally, hence regions of original and
altered film develop simultaneously. The resulting film is
a combination of flat and porous regions.
When the anodic voltage is at a high value, TiO2 film
formation occurs as a result of the migration of O2−
ions into the metal/film interface and migration of the
Ti4+ ions from metallic Ti to the film/electrolyte inter-
face.32 There are many reactions occurring during the
process and the most relevant reactions that participate
in the film growth are those that give rise to O2 and
TiO2. The O2 formation in the film can create a pressure
that can destroy the film. Dielectric breakdown was
detected when voltage is increased. High electric field
between the inner and outer interfaces of the film
cause it to break down and give rise to pore formation.
At this stage, the TiO2 growth rate becomes smaller
than during the initial stage. The pores in the surface
Materials Science and Technology 2016 3
 Wong et al. Effects of anodisation parameters on thin film properties
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3 AFM images of anodic titanium oxide films on Ti surface: a Ti; b 50 V; c 100 V; d 150 V; e 200 V; f 250 V (retrieved from Kur-
omoto et al.32)
of the film are filled with the electrolyte favouring the
passage of the current.
In the case of ZrO2, it is accepted that the inward
migration of the O2− is the controlling process for the
oxide growth.46 O2− is produced by water dissociation.47
Figure 5 is a model explaining the growth of ZrO2 as a
function of anodisation voltages. This proposed mechan-
ism is adapted from those established by Azuma et al.,48
Abdel Rahim et al.,49 and Mamun et al.50 for anodised
Zr foils.
Assuming that the anodisation of thin Zr film follows
the same route as the Zr foils, therefore, once the initial
oxide layer formed, which is normally amorphous as
depicted in Fig. 5a, a growth can be possible when O2−
is moving inwards through this initial layer to the metal/
oxide interface. If O2− is not transported inwards, the
growth would stop and the underlying metal layer
maybe protected. The Zr metal layer is shown as the dar-
ker shaded region in the figure.
As shown in Fig. 5b, anodisation at 5 V may lead to the
formation of crystalline ZrO2 nanocrystals, represented
4 Materials Science and Technology 2016
by shaded circles, embedded in and amorphous or non-
stoichiometric ZrO2 matrix. The size of the crystallite is
in the nanoscale and this contributes to the broadness of
the X-ray diffraction (XRD) peaks (Fig. 6). If there is a
concentration gradient of O2− across the film with less
O2− near the metal/oxide interface then higher concen-
tration of oxygen vacancies is expected in this region.
Consequently, this would promote the nucleation and
stabilisation of tetragonal or cubic ZrO2.
With an increase of the anodisation voltage to 10 V,
more O2− ions are transported across the oxide layer
[Fig. 5c]. When more O2− enters the oxide, nanocrystals
will grow presumably by the migrations of both cations
and anions to the boundary wall of each crystal increasing
its size. The shaper and more intense XRD peaks reflect
the increase of the crystallite size of the tetragonal or
cubic ZrO2. While the inner layer near the substrate is
crystalline with either tetragonal or cubic ZrO2, the
outer layer of the oxide is predominantly amorphous.
Regardless of its crystallinity, as a whole, the oxide is
demonstrating an insulating property with the preferred

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4 FESEM images of ZrO2 surface for sample anodised in 1 M NaOH for 15 min at different formation voltages: a 10 V, b 20 V, c
30 V, d 40 V and e 60 V (retrieved from Lockman et al.22)
orientated ZrO2, acting as a leakage path when a trans-
verse voltage is applied.
As the anodisation voltage is increased to 20 V, mono-
clinic ZrO2 can start to be detected by the XRD. The
peaks of tetragonal or cubic phases still retain but the
intensity is slightly reduced. Two possibilities can be con-
cluded: (1) the transformation of high temperature phase
to monoclinic phase or (2) transformation of the amor-
phous oxide to monoclinic ZrO2. At a high enough vol-
tage, according to Mamun et al.50 oxygen evolution is
possible on the hydrated oxide. This occurs by the
removal of water from the amorphous film and crystalli-
sation starts. Since there is excess oxygen in the region,
monoclinic ZrO2 is thought to nucleate and grow at the
surface of the film.
Growth of oxide at 20 V is shown schematically in Fig.
5d. As the oxide is consisted of ZrO2, with different
phases and orientations the insulating property of the
oxide is much enhanced, in which current passing through
the oxide is minimised when a transverse voltage is
applied.
Often, crystallisation of the outer layer is followed by
the formation of cracks within the film. Cracks lead to
the physical breakdown on the film as seen for the sample
anodised greater than 30 V where obvious blistering has
Wong et al. Effects of anodisation parameters on thin film properties
occurred. This can be illustrated in Fig. 5e for sample
anodised at 30 V. At even higher voltages, oxide delami-
nates from the substrate; with the degree of delamination
more severe as the anodisation voltages are increased to
60 V.
In Fig. 5f, oxide delamination is shown. As the films
have cracks, oxygen penetrates through the layer via
these cracks towards the oxide/substrate interface. As
this region is consisted of tetragonal or cubic ZrO2, with
the excess amount of oxygen existing in the vicinity of
the crystals, transformation to monoclinic will occur in
this region. In addition to that, the transformation
would lead to volume changes within the oxide, inducing
oxide to crack. Oxygen penetrates through the oxide layer
inwards via the cracks may also oxidised the underlying
Si.
Effects of temperature on thin film
In the works of Lin et al.,13 on the effects of annealing
temperature on the photocatalytic activity of TiO2 thin
films, the surface morphology was examined as shown
in Fig. 7. The surface roughness appeared to increase
with annealing temperature although AFM results have
stated that little growth was evident on TiO2 grain sizes.
Materials Science and Technology 2016 5
 Wong et al. Effects of anodisation parameters on thin film properties
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5 Proposed mechanisms of formation of ZrO2 by anodisation as a function of increasing anodisation voltages (a–f : 0–40 V) in
NaOH (re-drawn from Lockman et al. 22)
This can be attributed to minimal densification with the
grains becoming more faceted with the increase in anneal-
ing temperature. It is worth noting that the film thickness
remained the same at ∼255 nm for all TiO2 films at differ-
ent annealing temperatures.
Temperature also affects the anodising behaviour of
thin films, as investigated by Ono et al.25 of anodic
oxide films formed on niobium. From the voltage–time
curves presented, the slopes, dV/dt derived from them
can be seen in Fig. 8. As the temperature increases, the
thickness of the film increases too with consideration
that the film property is similar and the oxide dissolution
during film growth is perceived negligible. Increase in
electricity consumption was the factor for thickness issue.
6 XRD of anodised ZrO2 at various potentials (5–60 V)
(retrieved from Lockman et al.22)
6 Materials Science and Technology 2016
Effects of time on thin film
Jeon and Hwang51 studied on the effect of anodising time
towards the electrical characteristics of zirconium oxide
by anodisation employing ammonium tartrate electrolyte
(pH = 6.7) as the electrolyte. It is found that the surface
roughness is dependent to the anodising time, in which
increasing the anodising time will improves the surface
smoothness. Also, as anodising time increases, thickness
of anodic oxide ZrO2 films will also increase. However,
the thickness increases slowly at longer anodising time,
as the saturated oxide thin films are achieved. This
shows that anodisation is a self-limiting growth process,
offering a better control over the oxide thickness. The
7 AFM surface morphologies of TiO2 thin films annealed at
different temperatures (retrieved from Lin et al.13)

8 Slope of voltage–time curves for various pHs and temp-
eratures (retrieved from Ono et al.25)
electrical characteristics at 400 s are proposed to be the
most acceptable anodising time, with relatively low leak-
Downloaded by [New York University] at 15:54 28 June 2016
age currents of 1.5 × 10−3 A cm−2 at −1 V, high break-
down voltage of 27 MV cm−1, acceptable effective oxide
thickness (EOT) of 11.5, and comparable interface state
density of (5.5–6.5) × 1011 cm−2 eV−1. The ZrO2 pro-
duced by anodisation at 400 s are calculated to have the
high k value of 13.9. At the anodising time lower than
400 s, it was found to be in the under-anodised condition,
in which Zr metal layer are present in the interface of
ZrO2/Si. The leakage current is also found to be relatively
high with anomalous high capacitance. In other hands, at
longer anodising time of 1200 s, it was found to have rela-
tively low amount of fixed charge density, which then can
induced the lower mobility characteristics of the device.51
Therefore, it is important in obtaining the optimising time
of anodisation in order to have the most optimum features
for MOS technology.
Allah et al.52 have studied on the kinetic of anodic
oxide films on Zr elecrode in 1 M NaOH. The oxide
build are observed for the first 30 min, longer than anodi-
sation time of 30 min, dissolution takes place. The rate of
dissolution on the other hands also depends on the defects
that presents in the oxide films.
Effect of post-anodisation annealing on
thin film
Post-anodisation annealing is conducted to reduce the
damage during the processing steps after the formation
of gate dielectric. This step is a way to improve mechan-
ical and electrical properties of dielectric thin film through
modification of crystallography structure and grain mor-
phologies. In other words, post-anodisation annealing is
Table 1 Capacitance and insulator properties of three
different ZrO2 polymorphs
Crystal structure Dielectric constant Band gap energy (eV)
Monoclinic 19.7 5.42
Tetragonal 46.6 6.40
Cubic 36.8 5.55
Wong et al. Effects of anodisation parameters on thin film properties
indispensable to acquire high quality and good perform-
ance of gate dielectric. In addition, the effects of post
treatment are often manifesting for ZrO2.
Relationship of annealing temperature and
crystal structure
Typically, ZrO2 is a polymorph which exists in three
different (monoclinic, tetragonal and cubic) structures
correspond to the surrounding temperature. Orthorhom-
bic structure is another possible state of ZrO2 which nor-
mally occurs at relative high pressure as compared to the
other three polymorphs.53 Figure 9 is a phase diagram of
ZrO2 which explains the transformation of these crystal-
lography structures.
α-ZrO2, β-ZrO2 and γ-ZrO2 in the phase diagram cor-
respond to the monoclinic, tetragonal and cubic struc-
tures, respectively. It shows that monoclinic phase is
stable up to 1205°C, whereas tetragonal phase exists
between 1205 and 2377°C. Cubic phase of ZrO2 with-
stand the highest temperature (2377°C) until the melting
point of ZrO2 is reached.
High-κ thin films usually have poor diffusion barrier
towards the oxygen source.54 This implies that they can
grow easily into oxide state with little external effort.
This fact holds true for Zr thin film because Zr has a
high affinity of oxygen at standard condition (273 K
and 1 atm) with Gibbs free energy of ΔG = −1037 kJ
mol−1.55 The absorptivity and diffusivity of oxygen in
Zr are enhanced at higher temperature. On the contrary,
ZrO2 produced during the deposition process displays a
high oxygen exchange rate especially at elevated tempera-
ture. Thus, SiO2 is formed at the interface when high
temperature process is involved during the growth of
dielectric film and post-heat treatment. This will therefore
increase the EOT of gate dielectric layer and is unnecess-
ary in most circumstances.
Combination of PVD and anodisation can possibly
generate tetragonal and cubic structures at low tempera-
ture.22 On the contrary, monoclinic phase is the predomi-
nant structure that existed in the as-deposited ZrO2 with
reactive sputtering,56 atomic layer deposition (ALD)57
and metal-organic CVD (MOCVD).58 Among the three
crystallography structures mentioned, t-ZrO2 would be
the most suitable candidate to act as gate oxide due to
its good dielectric and insulating properties. The theoreti-
cal values of dielectric constant59 and band gap energy60
of monoclinic, tetragonal and cubic crystal structures are
given in Table 1 and Fig. 10.
Unfortunately, fabrication of solely t-ZrO2 is impracti-
cal due to temperature stability. Therefore, a mixture of
these three phases is often observed for all deposition
techniques. This explains the fact where κ of ZrO2 usually
falls around 25. The only exception is that anodisation
can produce large quantity of tetragonal structure; further
annealing is required to yield a reasonable amount of
monoclinic structure to stabilise the metastable tetragonal
phase. Annealing is carried out for reactive sputtering,
ALD and MOCVD to produce tetragonal phase in the
predominant monoclinic structure and hence oppose to
the course of anodisation. Aside from that, annealing
temperature that is applied in anodisation is much lower
than the other methods because monoclinic phase is
able to crystallise at relative low temperature as compared
Materials Science and Technology 2016 7
 Wong et al. Effects of anodisation parameters on thin film properties
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9 Phase diagram of ZrO2 (retrieved from Patil53)

to the tetragonal and cubic structures. In brief, the phase
transformation is tabulated in Fig. 11.
The ultimate goal of current ongoing research is to
determine the optimum mechanical and electrical proper-
ties that can be achieved by ZrO2 through the alternation
in crystal structure. Currently, the best conformation of
ZrO2 gate dielectric is to compose both monoclinic and
tetragonal structures in thin film. Sometimes, cubic
phase is incorporated into the thin film to acquire high
thermal stability.
Relationship of annealing temperature and
grain morphologies
The effect of annealing on the ZrO2 grain morphologies is
similar to the basic zone model as proposed by Movchan

10 Band gap energy and dielectric constant values of three different ZrO2 polymorphs

8 Materials Science and Technology 2016


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11 Phase transformation of ZrO2 for a anodisation with annealing and b reactive sputtering/ALD/MOCVD with calcination
and Demchishin,61 namely MD diagram. The MD dia-
gram is suggested primarily for temperature used during
deposition, it may also be used for the grain growth mech-
anism during normal annealing process.
The effect of annealing temperature on grain mor-
phologies is rather straight forward. For instance, the
void density is drastically reduced at high annealing temp-
erature because atoms have high mobility in restructuring
12 XRD of annealed ZrO2 dielectric thin film (retrieved from
Chinchamalatpure et al.63)
Wong et al. Effects of anodisation parameters on thin film properties
themselves into a more closed pack structure which is
accompanied by the grain growth. As a result, this
reduces the accumulation of residue stress in the system
therefore improves the performance of gate dielectric.
On the contrary, high mobility of atoms creates a rough
surface and it is undesirable for the precision of CMOS
fabrication. Thus, there is a limitation for the annealing
temperature therefore the optimum temperature is still
under investigation.62
XRD analysis on the annealed zirconia
dielectric
Chinchamalatpure et al.63 studied the effect of post-
annealing on ZrO2 thin film where suspension of ZrO2
is first synthesised via the sol-gel method followed by
spin coating on Si surface. Afterwards, two of the ZrO2
deposited substrates are calcinated at 400 and 700°C for
2 h. Sol-gel technique is suggested because of its high
compatibility in the generation of ceramic and dielectric
film in the micrometer thickness range.
Figure 12 shows XRD result where only t-ZrO2 is
observed when it is annealed at 400°C. Then, monoclinic
phase started to crystallise and appear at 700°C of calci-
nation temperature. This is because tetragonal phase of
ZrO2 is stable at 1205–2377°C. Hence, if sufficient heat
energy is supplied to ZrO2 at temperature below 1205°
C, recrystallisation of ZrO2 will take place to yield the
monoclinic phase. However, information regarding trans-
formation of crystallography structure is limited as only
two calcination temperatures were involved in this pro-
ject. More parameters should have been tested to provide
a better overview on the change in phase. The tetragonal
Materials Science and Technology 2016 9
 Wong et al. Effects of anodisation parameters on thin film properties
diffraction peaks are identified at 29.50° and 33.15° while
monoclinic diffraction peaks are found at 28° and 51°.
Capacitance–voltage (C–V ) characteristic of
the annealed zirconia thin film
Chinchamalatpure et al.63 discussed on the relationship
between capacitance and voltage behaviour of annealed
ZrO2. Figure 13 shows that the flat band voltage of p-
type silicon substrate happened at −0.5 V. The capaci-
tance of ZrO2 dielectric layer decreases drastically when
negative bias is applied to the gate voltage. This phenom-
enon is due to accumulation of charge carriers on the
MOSFET structure. However, when gate voltage
exceeded −0.5 V, the capacitance is reduced and this gra-
dient reduction portion is commonly identified as the
depletion region. Lastly, the curve becomes relatively
flat with no further reduction for capacitance above 0.5 V.
Obviously, the capability of ZrO2 dielectric to store
charge increased tremendously if annealing is conducted
during fabrication. The charge accumulation of as-ZrO2
is about 225 F. Capacitances of ZrO2 calcinated at 400
and 700°C are roughly 410 F and 820 F. The increment
Downloaded by [New York University] at 15:54 28 June 2016
in capacitance happens because of the co-existence of
monoclinic and tetragonal phases which act as a good dif-
fusion barrier towards charge carriers. On top of that,
integration of ZrO2 and Si at the contact interface is
improved which in turn enhanced the capacitance
property.64
Current–voltage (I–V ) characteristic of
annealed zirconia thin film
Another interesting result reported by Chinchamalatpure
et al.63 is the current to voltage properties of ZrO2 dielec-
tric which measured the leakage current of thin film when
electric field present in the thin film. The bias applies at
the gate contact is highly dependent on type of substrates.
For instance, positive potential is used as a p-type sub-
strate to prevent flow of electrons from source to drain
which will then possibly affect the intended current
measurement. Besides, good insulation is a result of low
13 C–V characteristic of annealed zirconia thin film
(retrieved from Chinchamalatpure et al.63)
10 Materials Science and Technology 2016
leakage current across the thin film. The I–V character-
istic of the ZrO2 is indicated in Fig. 14.
Saturation leakage current of ZrO2 thin film is low with
respect to annealing process at high temperature. The
average saturation leakage current density of as-deposited
ZrO2 thin film is about 10 A cm−2, whereas (400–700°C)
annealed ZrO2 has leakage current density of 10−1
and10−2 A cm−2, respectively. The leakage density is
reduced at the order of 10 for these three samples. One
explanation is that thickness of film continues to grow
at higher annealing temperature which will further
impede the charge flow. At high temperature, defects
found on the interface are eliminated hence allow for-
mation of smooth ZrO2 at the interface. This is significant
as defects are always served as the transportation path for
charge carriers such as electrons and holes.
Effect of annealing condition on the EOT of
zirconia
The environment in which the annealing process is carried
out has a big impact on the thickness of ZrO2. This
relationship is defined by Yao and Tay54 First, a layer of
ZrO2 is deposited on Si substrate through CVD at 500°
C. After that, rapid thermal annealing (RTP) is conducted
to the samples at three types of modes: 800°C for 60 s,
800°C for 2 s and 1000°C for 2 s. The rapid annealing
for 2 s is referred as spike condition. Five different anneal-
ing environments are involved which include nitrogen gas,
dry hydrogen, wet hydrogen (15% of water), dry oxygen
and wet oxygen (15% of water) as shown in Fig. 15.
ZrO2 is found to be thicker if it is annealed under ambi-
ent environment with abundant oxygen molecules. In
addition, it is also clear that nitrogen gas provides the
slowest growth rate for ZrO2 thin film as compared to
the other four conditions. This phenomenon is because
Zr and ZrO2 has a poor diffusion barrier towards oxygen.
As a result, oxygen can readily diffuse into the atomic
structure and oxidise Zr into dielectric film. On the
other hand, thickness of ZrO2 dielectric continues to
grow when longer annealing time is allowed. As an
example, thicknesses of ZrO2 annealed at 800°C under
ambient environment are recorded to be 18.1 and
31.4 Å for 2 and 60 s, respectively.
14 I–V characteristic of annealed ZrO2 thin film (retrieved
from Chinchamalatpure et al.63)

15 Annealing environment and EOT of zirconia (retrieved
from Yao and Tay54)
Leakage current as a function of EOT
Research by Yao et al.54 also provides a good explanation
on the leakage current of ZrO2 with respect to EOT.
Samples annealed at various RTP conditions undergone
the current test by applying −1.0 V to the gate voltage.
Downloaded by [New York University] at 15:54 28 June 2016
Figure 16 illustrates the leakage current density is
decreased as the EOT of ZrO2 is increased. For example,
the leakage current densities of 18.1, 31.4 and 32.0 Å
ZrO2 grew on ambient environment are about
8 × 10−6 A cm−2, 3 × 10−8 A cm−2 and 7 × 10−9 A cm−2,
respectively. This implies that ZrO2 is a good insulator
against electric current, since the leakage current density
with magnitude lower than 10−5 A cm−2 is able to achieve
for −0.1 V of gate potential applied. Furthermore, the
leakage current curve of SiO2 generated under dry oxygen
source is plotted in the same graph to ease the compari-
son. For 18.1 Å, the leakage current of ZrO2 is about
10−5 A cm−2, whereas SiO2 records 1 A cm−2 with the
similar thickness. As a result, it is clear that the capability
to hinder leakage current is enhanced by replacing SiO2
with ZrO2. The leakage current of ZrO2 produced in
nitrogen gas is also higher as compared to oxygen because
of the thin dielectric film.
Surface morphologies of annealed zirconia
thin film
The surface morphologies of ZrO2 thin film are inspected
by Khojier et al.65 Zr thin film were deposited on a glass
16 Relationship of leakage current density and EOT of zirco-
nia (retrieved from Yao and Tay54)
Wong et al. Effects of anodisation parameters on thin film properties
17 AFM image of ZrO2 thin film annealed at temperature of a
100°C, b 300°C and c 500°C in a tube furnace (retrieved
from Wong and Cheong19)
substrate via direct current magnetron sputtering method
followed by the annealing in tube furnace at temperature
100–500°C. Aside from that, atomic force microscopy
(AFM) is the characterisation instrument used to study
the surface morphologies such as surface roughness and
grain size of samples. Figure 17 presents the AFM result.
It is observed that the surface of ZrO2 annealed at high
temperature is rough. In addition, granular structure is
also formed in ZrO2 thin film and the grain size increases
with the annealing temperature. Rough surface and big-
ger grain size of ZrO2 thin film are attributed to high
mobility of atoms at high annealing temperature where
ZrO2 atoms have sufficient kinetic energy to transport
to the nearby grain and then coalescence into a bigger
size grain. Non-uniform surface with deep valleys are
highly undesirable as this creates a variation in the applied
voltage and increases the threshold voltage.
Conclusion and future challenges
Clarification of factors regarding the electrochemical ano-
disation method is important to ensure that the formation
of metal oxide thin film is well defined and received
according to demands. Parameters such as applied voltage
and temperature play a significant role in moulding the
outcomes, both morphologically and characteristics.
Increase in applied voltage will result in the breakdown
of the uniformed thin film, causing blisters and large
pore sizes. This can be said as well for the increase in
temperature during anodisation in terms of grain sizes.
There is more room for improvement in the formation
of gate oxide through anodisation so that it would have
the most optimum feature for CMOS technology. For
example, the oxide must be smooth, crack free and
adhered to the substrate.
Acknowledgements
The authors would like to acknowledge the financial sup-
port from Universiti Malaya Research Grant [RP024A-
13AET] and Ministry of Science, Technology and Inno-
vation through ScienceFund [03-01-03-SF1083].
Materials Science and Technology 2016 11
 Wong et al. Effects of anodisation parameters on thin film properties
ORCID
Y. H. Wong http://orcid.org/0000-0003-3254-9420
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