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Synthesis of Alumina Thin Films Using Reactive Magnetron Sputtering Method

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2017 J. Phys.: Conf. Ser. 850 012022

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5th Colombian Conference of Engineering Physics (V CNIF) IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1234567890
850 (2017) 012022 doi:10.1088/1742-6596/850/1/012022

SYNTHESIS OF ALUMINA THIN FILMS USING

REACTIVE MAGNETRON SPUTTERING METHOD

G Angarita, C Palacio, M Trujillo, M Arroyave

Universidad EAFIT, Applied Electromagnetism Research Group, Cr49, No.7 sur 50,
Medellin, Colombia

Email: [email protected]

Abstract. Alumina (Al2O3) thin films were deposited on Si (100) by Magnetron Sputtering in
reactive conditions between an aluminium target and oxygen 99.99% pure. The plasma was
formed employing Argon with an R.F power of 100 W, the dwelling time was 3 hours. 4 samples
were produced with temperatures between 350 and 400 ºC in the substrate by using an oxygen
flow of 2 and 8 sccm, the remaining parameters of the process were fixed. The coatings and
substrates were characterized using Atomic Force Microscopy (AFM), Scanning Electron
Microscopy (SEM), X-ray diffraction (XRD) and Energy Dispersive Spectroscopy (EDS) in
order to compare their properties before and after deposition. The films thicknesses were
between 47 and 70 nm. The results show that at high oxygen flow the alumina structure prevails
in the coatings while at lower oxygen flow only aluminum is deposited in the coatings. It was
shown that the temperature increases grain size and roughness while decreasing the thicknesses
of the coatings.

1. Introduction

Aluminum oxide or Alumina (Al2O3) is an outstanding ceramic material which, due to its several
excellent physical and chemical properties like high electric resistivity, low thermal conductivity, high
melting temperature, high hardness, refractive index of 1.7 [1], high abrasion and oxidation resistance,
finds application in cutting tools, optoelectronics devices, diffusion and thermal barriers [2]. Al2O3 has
several metastable phases structures where the most reported are: cubic γ and η phases, the monoclinic
θ phase, the hexagonal χ phase, the orthorhombic κ phase and the δ phase that can be tetragonal or
orthorhombic [3]. Al2O3 only has one stable phase (α-Al2O3) with a trigonal hR30 structure, melting
point of 2043 ºC, and a relatively high hardness (21 GPa) [4]. The metastable phases appear when
alumina is being heated in thermal processes like annealing; the ranges in which the metastable phases
are formed depend upon the composition and structure of the initial material, where the stable α-Al2O3
is formed at about 650 ºC [4]. A large number of techniques have been reported for the deposition of
amorphous and crystalline alumina in the literature, such as magnetron sputtering, ion assisted
deposition, pulsed laser deposition, electron beam evaporation, chemical vapor deposition and sol-gel
deposition [5]. This work focuses in the deposition of crystalline alumina from reactive magnetron
sputtering technique by controlling the substrate temperature and oxygen flow.

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Published under licence by IOP Publishing Ltd 1
5th Colombian Conference of Engineering Physics (V CNIF) IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1234567890
850 (2017) 012022 doi:10.1088/1742-6596/850/1/012022

2. Materials and Methods

Al2O3 films were deposited by reactive magnetron sputtering on p-type silicon (100) substrates (15 x 15
mm2) with a native oxide layer on top of around 10 nm thick. The substrates were ultrasonically cleaned
in isopropanol for 10 minutes and dried with nitrogen gas. A 99.9995_% pure Aluminum target with
50.80 mm in diameter and 6.35 mm thick was used. Prior to the deposition, the chamber was evacuated
with a turbomolecular pump to a background pressure of 4.2 x 10-6 Torr. Ultra high purity (99.9999%)
argon and oxygen gasses (Oxygen/Argon ratio of 1/5) were then introduced into the chamber using a
mass flow regulator system. The desired working pressure of 6 x 10-3 Torr was obtained by regulating
the pumping speed, which is controlled by a throttle valve in the path of high vacuum line connecting
the chamber to the turbomolecular pump. Before deposition, a pre-sputtering was performed at 100 W
RF power for 10 minutes in order to clean the surface of the Al target. The deposition time for all
coatings was fixed at 3 hours and the influence of the substrate temperature and oxygen flow was
evaluated by employing a factorial design using these two parameters at two different levels chosen
according to the ranges found in the literature (22 factorial design) [6]. Oxygen flow varied from 2 to 8
sccm and the temperature levels were chosen at 350 and 400ºC.
The morphological properties and deposition rate of the films were evaluated using Atomic Force
Microscopy (AFM) with a NANOSURF EasyScan 2 device using a CT170 tip in noncontact mode. The
deposition rate of the coatings was measured by marking a line on the substrates with an alcohol soluble
marker in order to create step heights that were then measured by AFM. The roughness measurements
were made over an area of 50 x 50 µm2 and the grain size measurements were made over 5 x 5 µm2.
Meanwhile, Scanning Electron Microscopy (SEM) was used to evaluate the morphology of the coatings,
and Energy Disperse Spectroscopy X-Ray (EDS) was used to qualitatively observe the different
elements in the deposited coatings, these two techniques were accomplished by using a JEOL JSM-
6701F Field Emission Scanning Electron Microscope (FESEM). X-Ray Diffraction (XRD) was used to
study the crystalline phases of the coatings with a PANalytical Diffractometer Empyrean device using
a copper anode (K = 1.5405 Å and Kβ = 1.5444 Å).

3. Results and discussion

3.1. Scanning Electron microscopy

Figure 1. shows a micrograph taken by FE-SEM at 270,000 magnifications of the deposited films, where
a granular structure can be seen, this structure is typical of coatings deposited by sputtering.

Si

Figure 1. FE-SEM micrograph of a coating Figure 2. EDS analysis of a coating deposited at

deposited at 350ºC and 8sccm. 350ºC and 8sccm.

EDS graph (Figure 2) shows the presence of aluminum, oxygen, silicon and carbon in the samples,
which proves that aluminum in presence of oxygen was deposited; the silicon is attributed to the
substrate and carbon to the impurities of the environment.

2
5th Colombian Conference of Engineering Physics (V CNIF) IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1234567890
850 (2017) 012022 doi:10.1088/1742-6596/850/1/012022

3.2. Atomic force microscopy

The measured thickness and calculated deposition rate of the films can be observed in Figure 3, which
reveals that the higher the temperature, the more material is deposited, this can be attributed to a greater
affinity of the aluminum and oxygen adatoms [7] to the substrate surface at high temperatures.
100 50
350ºC

Deposition rate
Solid line (nm)

Dashed line
400ºC 40
Thickness

(nm/hr)
50 30
20
0 10
2 Oxigen Flow (sccm) 8
Figure 3. Oxygen and temperature influence in the thicknesses (solid lines) and sputtering rates
(dashed lines) of the coatings.

Figure 4 shows the morphology of the coating, were a granular structure with some cluster type grain
agglomerations can be seen, this structure is typical of coatings deposited by sputtering where the films
growth is of columnar nature.

Figure 4. AFM micrographs of deposited coatings at: (a) 350ºC and 2 sccm, (b) 350ºC and 8 sccm,
(c) 400ºC and 2 sccm and (d) 400ºC and 8 sccm.

Figure 5 shows the grain sizes and roughness of the coatings. It can be seen that the grain size and
roughness decreases when the temperature increases, this behaviour can be explained by the increase of
the nucleation sites due to a larger travel time of the adatoms in the substrate surface which in turn
produces higher quantity of grains with small grain sizes in the film [7].
120 18
350ºC
Solid line (nm)

15
Dashed line
Roughness

110
Grain Size

400ºC
12
(nm)

100
9
90 6
80 3
2 Oxigen Flow (sccm) 8
Figure 5. Oxygen flow and substrate temperature influence in the grain size (solid line) and roughness
(dashed line) of the deposited films.

3.3. X-Ray diffraction

The normalized XRD spectra of the films is shown in Figure 6. The patterns used for the identification
of the XRD peaks belong to the ICCD and COD databases and have the following reference codes: 00-
026-0031 (Al2O3) [8], 96-901-2003 (Al) [9] and 96-901-2602 (SiO2) [10].

3
5th Colombian Conference of Engineering Physics (V CNIF) IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1234567890
850 (2017) 012022 doi:10.1088/1742-6596/850/1/012022

8 sccm - 350 ºC 1
3 1 1
Counts (A.U)

8 sccm - 400 ºC
3
2 2
2 sccm - 350 ºC
2 sccm - 400 ºC

20 25 30 35 40 45 50 55 60
2 Angle
Figure 6. XRD spectra of the synthetized coatings, 1) -Al2O3 [8], 2) Al [9], 3) SiO2 [10].
Figure 6 shows that under high oxygen flow (8 sccm) orthorhombic alumina (κ-Al2O3) was formed
in the films. At low oxygen flow (2 sccm) only aluminum and a greater noise in the XRD can be
observed, this is attributed to the low content of oxygen in the chamber, which is not enough to form a
stoichiometric alumina structure in the entire film. The high noise can be attributed to a film rich in
aluminum with a somewhat amorphous structure from the little reaction between aluminum and oxygen.
In the other hand, the temperature at which the experiments were carried out was not enough to make
an important change in the XRD spectra of the coatings.

4. Conclusions
Orthorhombic alumina (-Al2O3) films were produced by reactive RF magnetron sputtering with grain
sizes ranging from 100 and 115 nm. The oxygen flow plays a crucial role in synthesizing alumina; it
was found that at 2 sccm only Aluminium was deposited whereas at 8 sccm the quantity of oxygen was
enough to form Al2O3. In addition, it was found that at higher oxygen flow rates, the coatings had an
increase in their grain size and roughness.
It was found that the substrate temperature was not sufficient to cause changes in the crystalline
structure of the material; however, there were found significant decreases in the thickness of the coatings
at higher temperatures as well as increases in their roughness and grain size.

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