Hindawi Publishing Corporation

Advances in Mechanical Engineering

Volume 2014, Article ID 373847, 6 pages
http://dx.doi.org/10.1155/2014/373847

Research Article
Effects of Annealing on TiN Thin Film Growth by
DC Magnetron Sputtering

Azadeh Jafari,1 Z. Ghoranneviss,2 A. Salar Elahi,1 M. Ghoranneviss,1

N. Fasihi Yazdi,1 and A. Rezaei1
1
Plasma Physics Research Center, Science and Research Branch, Islamic Azad University, Tehran, Iran
2
Department of Physics, College of Basic Sciences, Islamic Azad University, Karaj Branch, Alborz, Iran

Correspondence should be addressed to A. Salar Elahi; salari phy@yahoo.com

Received 23 June 2014; Accepted 29 June 2014; Published 24 July 2014

Academic Editor: Hamid Rouhparvar

Copyright © 2014 Azadeh Jafari et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

We have reviewed the deposition of titanium nitride (TiN) thin films on stainless steel substrates by a DC magnetron sputtering
method and annealing at different annealing temperatures of 500, 600, and 700∘ C for 120 min in nitrogen/argon atmospheres.
Effects of annealing temperatures on the structural and the optical properties of TiN films were investigated using X-ray diffraction
(XRD), atomic force microscope (AFM), field emission scanning electron microscopy (FESEM), and UV-VIS spectrophotometer.
Our experimental studies reveal that the annealing temperature appreciably affected the structures, crystallite sizes, and reflection
of the films. By increasing the annealing temperature to 700∘ C crystallinity and reflection of the film increase. These results suggest
that annealed TiN films can be good candidate for tokamak first wall due to their structural and optical properties.

1. Introduction
Titanium nitride (TiN) thin films were used for diffusion bar-
riers, gate electrodes in field-effect transistors (FET), contact
layers in solar cells, and replacement of polycrystalline Si in
large-scale integrated circuits due to their excellent hardness,
wear resistance, and metallurgical and chemical stability
[1–4]. In nuclear fusion power research, the plasma-facing
material is any material used to construct the plasma-facing
components, those components exposed to the plasma within
which nuclear fusion occurs, and particularly the material
used for the lining or first wall of the reactor vessel [5–9].
Selection of the plasma facing mirrors material and research
on the behavior of these mirrors under plasma irradiation are
currently underway all over the world [10, 11]. Understanding
of the plasma-wall interactions provides the basis for
developing new materials or choosing among existing
ones. Compatibility between the fusion plasma and the
surrounding materials is one of the main challenges for the
construction of a fusion reactor. For the most exposed areas
in a tokamak, the aim is to develop materials that are heat
resistant, thermally conductive, and resistant to physical and
chemical erosion and show low fuel retention. The sputtering
performance of plasma facing components (PFCs) surface
materials is critical to future fusion devices. The critical issues
are (1) net erosion rates and lifetime, (2) tritium code position
in redeposited materials, and (3) core plasma contamination.
As recently reviewed in [12], erosion/redeposition codes have
been extensively used to assess PFC sputtering performance,
with most of the focus, however, being on b or limiter
surfaces. There has been much less work done on wall erosion
and on mixed material surfaces. Plasma energy containment
in tokamak fusion devices is considerably dependent on
impurity radiation from the plasma. The amount of impurity
radiation is almost proportional to 𝑍3 , where 𝑍 is the atomic
number of impurity ions. Low 𝑍 materials (such as graphite),
high melting point and high thermal conductivity (such
as carbon and tungsten), low nuclear activation, and low
propensity to absorb tritium (favouring tungsten most of all,
steel and beryllium less, and all but ruling out carbon-based
material) are therefore considered to be candidate materials
for the limiter and the wall which are the source of plasma
impurities. Because of the high radiation of neutron and
gamma rays in tokamak, all of the optical components that

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2 Advances in Mechanical Engineering
DC H.V.
Gas valve
Target
Substrate
Plasma
Pump valve
(a)
Figure 1: Schematic view of (a) sputtering system and (b) oven used in this experiment.
are close to plasma center must be metallic mirrors because,
in contrast to the characteristics of the refractive optical
components, the optical properties of metal mirrors are
not significantly affected by any of these radiations [13].
It is well known that the TiN coated on S.S.316L has a
good capability of maintaining a smooth surface for a long
time due to its unique optical and mechanical properties
[14, 15]. Currently there is a great interest in designing
and engineering thin films with morphologies tailored to
specific requirements for various application fields. The
connection between the surface morphology of the films and
functionality is especially important for optical applications,
as surface microstructure generates scattering and stray
light in optical components [6–8]. Physical vapor deposition
(PVD) techniques such as direct-current (DC) magnetron
sputtering, ion plating, and plasma-based ion implantation
are employed to deposit TiN thin films [16–18]. Process
conditions in PVD techniques affect microstructural features
and different physical properties of TiN thin films. In
this study, TiN thin films are prepared by DC magnetron
sputtering method on stainless steel 316L (S.S.316L) substrate.
The effect of annealing temperature on the microstructure,
preferred layers orientation, surface morphology, and optical
properties of the TiN thin films is investigated.
2. Experimental Method
Titanium nitride thin films were deposited with a DC planer
magnetron sputtering system, which is shown in Figure 1(a),
using a circular 50 mm diameter and 2 mm thick Ti target
of 99.998% purity. The target-to-substrate distance was at
3 cm. A continually variable DC power supply of 700 V and
15 mA was used as power source for sputtering. The substrates
were 10 × 10 mm2 stainless steel 316L (S.S.316L) and were
ultrasonically cleaned in acetone and ethanol. The substrate
temperature was 300∘ C. The base pressure was lower than
2 × 10−5 Torr. Pure argon gas and nitrogen gas were used
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Quartz tube
Ar/N
Gas
outlet
Sample
Quartz
Oven
boat
(b)
Table 1: The RMS roughness for different annealing temperatures.
Annealing temperature RMS roughness
500∘ C 3.5 nm
600∘ C 5.2 nm
700∘ C 8.9 nm
as sputter and reactive gases, respectively. A reactive gas
mixture of 95% argon and 5% nitrogen in volume was
used at 2 × 10−2 Torr. With Ar+ bombardment on titanium
target and reaction of titanium with nitrogen in plasma
the titanium nitride was deposited on stainless steel 316L
(S.S.316L) substrate fixed on the sample holder. The growth
time for all three samples was 120 min. The deposited samples
were furnace-annealed under nitrogen/argon for 120 min at
temperatures of 500, 600, and 700∘ C (Figure 1(b) and Table 1).
The crystal structures of the deposited films were evaluated
by X-ray diffraction (XRD) with Cu K𝛼 radiation (1.5405 Å);
the surface roughness of the films was studied with an atomic
force microscope (AFM) and optical property was studied
with UV-VIS spectrophotometer.
3. Results and Discussion
XRD patterns of all TiN on S.S. thin film samples (as-deposit-
ed and annealed) prepared in this work are shown in Figure 2.
The XRD pattern of the deposited film in addition to the
substrate peak shows a weak peak at 35.33∘ that can be related
to the (111) crystallographic orientations of TiN with a face-
centered cubic (FCC) structure (with reference to JCPDS
card number 02-1159; 2𝜃 = 35.317∘ ). It is known that FCC
structure of TiN may form when nitrogen atoms occupy
all the octahedral sites of titanium with hexagonal close-
packed (HCP) or body centered cubic (BCC) structures.
This transformation in titanium structure from HCP and
BCC to FCC structure occurs due to accommodation of
Advances in Mechanical Engineering 3

TiN(111) Steel
Steel

Intensity (a.u.)

20 30 40 50 60 70
2𝜃 (deg)
(d) (b)
(c) (a)

Figure 2: X-ray diffraction patterns of prepared TiN thin films (a) as-deposited and annealed at different annealing temperatures (b) 500∘ C,
(c) 600∘ C, and (d) 700∘ C.

(a) (b)

(a) (b)

(c) (d)

(c) (d)

Figure 3: FESEM images of TiN thin films as-deposited and annealed at different annealing temperatures.

nitrogen atoms with small size in the interstitial sites of Ti
with larger size. The absence of a titanium peak in the XRD
pattern demonstrates the absence of Ti atoms in the structure
of the films and completes nitride formation process. The
competition between the surface energy, the strain energy,
and the stopping energy of different lattice planes of a film
affects the preferred orientation and lowest total energy of the
film [17, 19]. In case of TiN film, the direction of lowest energy
is ⟨111⟩ direction. Annealing the film did not influence the
preferred orientation but increased the intensity of the peak.

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4 Advances in Mechanical Engineering

500 ∘ C
As-deposited

0.020

(𝜇m/div)
0.031
(𝜇m/div)

0 0
div)

v)
0.50

/di
0.50
(𝜇m/

(𝜇m
0.50 0.50
v) v)
/di /di
(𝜇 m (𝜇m

(a) (b)

600 ∘ C 700 ∘ C

0.040
(𝜇m/div)

0.020
(𝜇m/div)

0
0
div)
div)

0.50 0.50
(𝜇m/
(𝜇m/

0.50 0.50
v) v)
/di /di
(𝜇m (𝜇m

(c) (d)

Figure 4: AFM images of TiN films with different annealing temperature, as-deposited and annealed at different annealing temperatures.

By increasing the annealing temperatures to 700∘ C, TiN
(111) peak intensity is increased. Thermal energy produced
by annealing leads to enhancement of mobility of active
sites. The increase of mobility can be attributed to grain
growth and the reduction of defects during the annealing
treatment [20, 21]. In the sample with a higher value of
annealing temperatures, this process is repeated so that the
TiN (111) diffraction line can be introduced as a preferred
orientation. Figures 3(a), 3(b), 3(c), and 3(d) show the surface
morphologies of the TiN films before and after annealing
at 500∘ C, 600∘ C, and 700∘ C, respectively. The morphology
of TiN grains is found to be continuous and dense. It can
be observed that the crystal lite sizes increase on elevating
the annealing temperature from 500 to 700∘ C, which agrees
with the XRD results. This could be explained by considering
the annealing induced coalescence of small grains by grain
boundary diffusion which resulted in major grain growth
[22]. The grain growth mechanism includes the transfer of
atoms at grain boundaries from one grain to another and
the final grain size depends upon the specific annealing
conditions. As it was mentioned earlier in this study AFM is
used to study the morphology of thin films. Figure 4 shows
AFM images and the roughness (rms) values of TiN films.
The root mean square (RMS) roughness and thickness of
the thin films were investigated using AFM images. Root
mean square roughness is defined as the standard deviation
of the surface height profile from the average height and
is the most commonly reported measurement of surface
roughness [23]. Figures 4(c) and 4(d) display fine grains
that exhibit greatly improved vertical alignment (nanotips-
like morphology) compared to the unannealed films. The
grain size increased as the annealing temperature increased.
This can be explained by the thermal energy being supplied
by annealing used for filling the microvoids or defects
among columnar structures by active species. So the grain
size increased by annealing and this caused the increase of
roughness. This phenomenon is in good agreement with the
previous study about the relationship between roughness

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Advances in Mechanical Engineering
100
80
60
R (%)
40
20
0 more diffuse activation energy and then to migrate into the
400 600 800 1000 1200 1400
Wavelength
(b) (d)
(c) (a)
Figure 5: Reflection spectra of prepared TiN thin films (a) as-
deposited and annealed at different annealing temperatures (b)
500∘ C, (c) 600∘ C, and (d) 700∘ C.
and grain growth [24]. The increase in surface roughness
may enhance scattering and reduce the channel mobility. It
is known that the surface roughness has a great effect on
the optical measurements, mainly at wavelengths (energies)
close to electronic transitions [25]. In Figure 5 the reflection
spectra, in the wavelength range of TiN fundamental edge
(250–1500 nm) for TiN thin film deposited and annealed
film, are presented. From Figure 4, it can be seen that, for
annealed TiN thin film, the reflection increases. This can
be attributed to structural transformation, increasing grain
size and roughness. It was previously reported that surface
roughness strongly affects the transparency of thin films
[26]. So it could be inferred that the major reason for the
increase in reflection with higher annealing temperature
may be due to the rough surface scattered and reflected
light, as surface roughness increases upon annealing. It can
also be thought that scattering due to irregular grains or
aggregates influenced the reflection of the films. Such an
explanation can be understood by the surface microstruc-
ture shown in Figure 3 where the degree of irregularity in
the grain size distribution was severe compared to other
films. As shown, reflection edge for TiN thin films shifts
to lower wavelength, indicating that the bandgap for TiN
thin films declines with increasing annealing temperature.
Nevertheless, all annealed samples exhibit more than 70%
of reflection in the visible light region. The ripples as shown
in the reflection spectra may result from the interference of
light, since they show wave forms that are characteristic of
the interference light. The rms roughness and mean grain
size are key factors influencing the photocatalytic activity.
It is generally accepted that the high specific surface area
and improved crystallinity degree may be responsible for the
increase of photocatalytic activity [23, 24]. As demonstrated
by XRD and AFM, the rms roughness and mean grains size
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5
of the TiN thin films increase with increasing annealing
temperature. So, we can conclude that photocatalytic activity
of the thin films is enhanced with the increase of annealing
temperature.
4. Conclusions
TiN thin films were prepared by DC magnetron sputtering
method, and it was thermally annealed at different tem-
peratures. The structural and optical properties of the TiN
thin films were characterized using XRD, AFM, and UV-
Vis spectrophotometer. The grain size of the films increases
with the increase of annealing temperatures. The increase
in the annealing temperatures causes the atoms to receive a
energetically favorable site in the crystal lattice. The XRD
diffractogram revealed that the thermal annealed film at
700∘ C possesses good crystalline face-centered cubic (FCC)
structure, with a preferred plane orientation along (111). The
diffraction peaks of the film become more intense when
the annealing temperature increases, which in turn leads
to increase in the grain size as well as the enhancement of
crystallinity. The TiN films show an increase of reflection with
the increase of annealing temperature.
These results show that TiN on stainless steel substrates
has a good capability for tokamak first wall due to its fine
grain structure, high reflectivity, and hardness property.
Conflict of Interests
The authors declare that there is no conflict of interests
regarding the publication of this paper.
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