JURNAL TEKNIK MATERIAL DAN METALURGI ITS 1

General Review of Atomic Layer Deposition Method for

Zirconium Oxide (ZrO2) as Diaelectrics in Transistors
Adella Fahdarina Piliang
Institut Teknologi Sepuluh Nopember
e-mail: fahdarinaadella@gmail.com

Abstract— Atomic layer deposition (ALD) is a thin film operates within the temperature window, the point where the
deposition technique where chemical precursors are temperature and concentration of the precursor per pulse, and
sequentially introduced to the surface of a substrate where they the purge times are balanced and the growth per cycle (GPC)
chemically react directly with the surface to form sub- is stable.
monolayers of film. One of its example is synthesis of ZrO2 thin As the technology grows, the needs of nanometer-size is
films by ALD. As a dielectric metaloxide, ZrO2 has been of
increasing to produce smaller size of electronics. Zirconium
interest at first as a potential candidate for gate dielectrics in
transistors. ZrO2 has found, in nanoelectronics, with application oxide (ZrO2) has been studied as possible high-k oxide
as a memory capacitor dielectric, and is investigated also as a material for future microelectronic circuits owing to its high
potential dielectric for resistive random-access memories. In permittivity. ZrO2 has different crystal structures, from which
addition, ZrO2 has been considered as a host ion conductor the monoclinic phase has permittivity value of 23, while
material for solid oxide fuel cells or encapsulation material layer tetragonal and cubic phases show nearly twice as high values
for organic electronic devices. In relation to different of 42 and 40. ZrO2 is a good oxide ion conductor which has
applications, energetically enhanced growth mechanisms of been utilized, for example, in fuel cells as a solid electrolyte.
metal oxides, incl. ZrO2 as well as structural development of In relation to different applications, energetically enhanced
ZrO2 layers have been research directions of interest. This
growth mechanisms of metal oxides, including ZrO2 as well
review will explain about the effect of temperature, morphology,
electrical properties, and application of ZrO2. as structural development of ZrO2 layers have been research
directions of interest.
Keywords— Atomic Layer Deposition, Zirconium Oxide Atomic layer deposited zirconium oxides, and the closely
related hafnium oxides, have been doped with cations to
stabilize their high permittivity cubic and tetragonal phases.
I. INTRODUCTION With ALD, the doping level can be straight forwardly
Thin film can be defined as a layer of material that its controlled by introducing the doping oxide cycles in between
thickness ranges from nanometre to several micrometres. the matrix oxide cycling. In ALD, the most widely studied
Thin film can be produced using varieties of techniques precursor system for ZrO2 is ZrCl4 and water. Besides
which are based on either physical or chemical processes. The chloride, zirconium tetraiodide (ZrI4) has been utilized as
thin film coating finds applications in many fields such as another metal halide precursor for ZrO2 ALD. With ZrI4,
semiconductors, which enables the design of smaller hydrogen peroxide (H2O2) was also applied as the oxygen
semiconductor for a smaller device while performing better source. Zirconium alkoxides, aminoalkoxides, alkylamides,
with higher energy efficiency. and cyclopentadienyl (Cp) complexes as well as complexes of
Atomic layer deposition (ALD) is gaining attention as one their combinations have been utilized as metal sources. In
of thin film deposition method. Atomic layer deposition addition to water and hydrogen peroxide, ozone has been used
(ALD), is a relatively new and sophisticated technique as a source for oxygen. In this review, we will analyze the
derived from CVD. It is a surface-controlled process allowing properties and application of ZrO2 using ZrCl4 and H2O as
one to produce dense films of less than 1 mm by building the presecusors.
them up monoatomic by monoatomic layer. The structure and
growth of the material are controlled in one reaction sequence
II. EXPERIMENTAL METHODS
involving separated introduction of the precursors and regular
purging. Thus, parasitic reactions of the precursors in the To analyze the growth kinetics as a function of temperature
vapor phase are avoided. so we can optimize the deposition process of ZrO2 on a
In the industry, the PVD and CVD have been the popular substrate, different techniques were used to analyzed the
deposition methods, however, ALD has been recognized as deposited layers. In this experiment, ultra thin films of ZrO2
the leading emerging technology as nanometre-size layer were synthesized on soda lime glass and SnO2-coated glass,
thickness or pinhole free layers are becoming more important. using ZrCl4 and H2O precursors by atomic layer deposition
In comparison to CVD which relies on high temperatures to (ALD). Formation of ZrO2 at high temperature proceeds from
decompose the precursor at the substrate surface, ALD the following global reaction of the precursor with water :
processes are performed at lower temperatures. The growth ZrCl4 + 2H2O -> ZrO2 + 4HCl
rate of ALD is related to the precursor’s flux at the substrate. Pulsing lengths varied between 0.5 and 2 s. The standard
It is complicated to determine the growth rate and it often pulsing sequence is the following:
JURNAL TEKNIK MATERIAL DAN METALURGI ITS 2

(i) pulse 1: ZrCl4 for 1.5 s; temperatures superior to 400 oC (part V), the growth rate
(ii) pulse 2: N2 purge for 2 s; decreases with the temperature. Beyond 430 oC, the curve
(iii) pulse 3: H2O for 0.5 s; slope decreases, which can be due to the desorption of
(iv) pulse 4: N2 for 2 s. reactants.
In the standard operating mode, both sequences are repeated Based on Fig 3 that shows XRD patterns of ZrO2 films
during 2000 cycles. The temperature of the deposition deposited on soda lime glass by ALD at different
chamber varied from 250 to 450 oC. The ZrCl4 precursor was temperatures we can see that the deposit crystallinity
evaporated at a temperature between 165 and 170 oC. increases with the temperature; therefore, it could be that the
Substrates were square samples 5 x 5 x 0.5 cm3 and lack of diffraction signals is due to the fact that the deposit is
constituted either of soda lime glass or SnO2-coated (500) not crystallized. The most intense peak for a powder diagram
glass. The result is analyzed by several methods: of monoclinic ZrO2 phase corresponds to the (1 1 1) peak at
(i) XRD with a CGR type Theta 60 diffractometer using a Cu 28.38. In our case, this peak is not observed, which shows
Ka radiation (1.5418 A˚ ), with y varying from 10o to 40o that the deposit is strongly oriented according to (1 1 0) peak
(ii) SEM S440, from Leica. Deposit thickness was determined at 24.58.
from cross-sectional SEM micrographs.
(iii) Mercury porosimetry, commercialized y CE Instrument.
(iv) The impedance measurements were carried out with an
Autolab spectrometer (ECO Chemie BV) with a 50 mV AC
signal amplitude and no DC bias for frequencies from 106 to
103 Hz. Thin layers of ZrO2 deposited on SnO2-coated glass
were measured in 0.01 M KNO3 electrolyte. The counter
electrode was a platinum wire and the reference was a
saturated sulfate electrode (SSE)

III. RESULT AND DISCUSSION

III.1 Effect of Temperature

Figure 3 XRD patterns of ZrO2 films deposited on soda lime

glass by ALD at different temperatures; t and m refer to
tetragonal and monoclinic structures, respectively.

III.2 Morphological Characterization of ZrO2

Figure 2 Growth rate and thickness for 2000 cycles of

ZrO2 deposited on soda lime glass by ALD as a function of
temperature.
The rate function can be divided into five parts. Between
250 and 280 oC (part I), growth rate increases with the
temperature and is under kinetic control. Between 280 and
350 oC (part II), a first plateau depicts a stationary deposition
rate of about 1 A˚ /cycle. This so-called ALD window
indicates surface-controlled reaction. Between 350 and 380
o
C (part III), the growth rate increases with the temperature
and the deposition is again under kinetic control. This
tendency is followed by a second maximum between 380 and
400 oC (part IV). In this domain, the growth rate is five times
higher (5 A˚ /cycle) than for the ALD window, which
corresponds, as we will show later, to
approximately one monolayer/cycle. In the case of
JURNAL TEKNIK MATERIAL DAN METALURGI ITS 3

III.3. Electrical Properties of ZrO2

Figure 4 SEM micrographs of ZrO2 films deposited on

soda lime glass by ALD (2000 cycles) at different
temperatures: (a) 250 oC; (b) and (c) 300 oC; (d) and (e) 450
o
C; (f) and (g) 400 oC.
The evolution of the tetragonal/monoclinic ratio in the
experiment is due to the fact that at the temperatures involved
in the deposition process, the stable phase is the monoclinic
one. At the lowest temperatures, the tetragonal phase with a
lower surface energy is favored. On the contrary, at higher
temperatures under thermodynamic equilibrium conditions, Figure 5 Impedance diagrams obtained for ZrO2 (deposited
the monoclinic phase is favored. Another explanation might on SnO2-coated glass) in KNO3 0.01 mol l-1: (a) Nyquist plot;
be that the phase change occurs through a martensitic (b) Bode plot
transformation that can be activated thermally or by a Typical impedance diagrams obtained at 25 oC on ZrO2
mechanical constraint. In fact, during the quenching process, thin layers (deposited on a SnO2-coated glass at 400 oC) in an
a constraint appears due to the difference between the thermal aqueous 0.01 mol l-1 KNO3 electrolyte are represented in Fig.
expansion coefficient between glass (about 33 x 10-7 K-1) and 5. The Nyquist plot (Fig. 5a) exhibits only one semi-circle,
zirconia (63 x 10-7 K). The resulting tension constraint on the corresponding to the electrical behavior of ZrO2 layer. An
film favors the formation of the monoclinic phase, because important fact is that no additional semi-circle associated
the transformation of tetragonal to monoclinic structure is with porosity is observed. The Bode plot (Fig. 5b) confirms
accompanied by a volume increase of 2–7%. This constraint this observation
increases with the synthesis temperature. Based on the experiment, The associated resistance is 2.5 x
The morphology evolution seems to indicate that the film 109 ohm (for a surface of 1.13 cm2 and a thickness of 475 nm)
growth follows two modes. At low temperature, rapid and the resistivity 6.25 x 1015 ohm cm. The resistivity value is
nucleation occurs on a limited number of surface sites, i.e. in agreement with the value given for pure ZrO2 in the
surface defects. At higher temperature, the nuclei formed literature, about 1015 ohm cm at room temperature. The
grow tri-dimensionally, according to a Volmer–Weber growth conductivity is 1.6 x 10-14 S cm-1 is also relatively close to the
mode. But the film formation between the granules shows literature, about 10-12 S cm-1. The capacity is 5.65 x 10-8 F,
that the rest of the surface is also reactive even though which means a capacitance of 3.7 x 10-8 F cm-2. These results
nucleation is less rapid. Nevertheless, nucleation becomes correspond to the behavior of a dielectric material. In effect,
more homogeneous (more nucleation sites per surface unit) the capacity value allows one to deduce a film dielectric
which shows that zirconia grows in a film form rather than in constant of 27, which is very close to the values given in the
a granular form. The growth of ZrO2 on the zirconia already literature: between 20 and 31.
deposited on soda lime glass also seems to follow a nucleation
process; nevertheless, the nucleation sites are smaller and III.4 Application of ZrO2
more numerous on the zirconia layer (previously deposited on A comprehensive study on growth kinetics and
glass) than on glass. These smaller nuclei can be observed on dielectricproperties of the ALD-ZrO2 which conducted from
the granules. So, it is clear that we cannot obtain a monolayer TDMAZr precursor shows that it is suitable for low-voltage
per cycle. inkjet printed transistors. Inkjet printing itself is a popular
technology for printed electronics that have many advantages,
such as low material wastage, the ability of large area
JURNAL TEKNIK MATERIAL DAN METALURGI ITS 4

fabrication, a limited number of process steps, low cost, and

compatibility with many substrates.

IV. CONCLUSIONS
To simplify the review, Atomic Layer Deposition (ALD) is
one of thin film deposition method that can deposited uniform
and conformal films. One of its application is in Zirconium
Oxides. ZrO2 can be used for microelectronic circuits. The
analysis of its properties are shown below:
1. The higher the ALD temperature, the thicker the film
and the purer the resulting material, the more likely the
resulting film will be crystalline.
2. The morphological study of the first deposition steps and
of the thin layers, allowed one to determine two growth
modes, depending on the deposition temperature: one in
a granular form at the level of surface defects, and the
other in the form of a homogeneous film. SEM analysis
also showed that the films are dense and non-porous,
which was confirmed by impedance spectroscopy and
porosity measurements.
3. The analysis on electrical properties of ZrO2 shows that
it is suitable for diaelectrics in transistor. One of the
example is inkjet prnting transistors.

ACKNOWLEDGEMENT
This journal review was created to fulfill the task of coating
technology courses. Author would like to thank Mr. Agung
Purniawan for providing and explaining knowledge about
coating technology and a variety of its methods that assist
author in understanding the latest technology and its
development.

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deposition: growth kinetics, structural and electrical properties. France:
Elsevier Science

[3] Moh Uddin Jewel et al. 2019. Low temperature atomic layer deposition of
zirconium oxide for inkjet printed transistor applications. Journal of Royal
Society of Chemistry.

[4] Peter Ozaveshe Oviroh. 2019. New development of atomic layer

deposition: processes, methods and applications. Journal of Science And
Technology Of Advanced Materials 2019, Vol. 20, No. 1

[5] Ville Miikkulainen. 2013. Crystallinity of inorganic films grown by atomic

layer deposition: Overview and general trends. Journal of AppliedPhysics