Applied Surface Science 256 (2010) 3077–3080

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Reactive Pulsed Laser Deposition of titanium nitride thin film: Optimization of

process parameters using Secondary Ion Mass Spectrometry
R. Krishnan a,*, Tom Mathews a, A.K. Balamurugan a, S. Dash a, A.K. Tyagi a, Baldev Raj a, Vikram Jayaram b
a
Surface and Nanoscience Division, Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu, India
b
Department of Materials Engineering, Indian Institute of Science, Bangalore 560012, India

A R T I C L E I N F O A B S T R A C T

Article history: Reactive Pulsed Laser Deposition is a single step process wherein the ablated elemental metal reacts with
Received 18 May 2009 a low pressure ambient gas to form a compound. We report here a Secondary Ion Mass Spectrometry
Received in revised form 17 September 2009 based analytical methodology to conduct minimum number of experiments to arrive at optimal process
Accepted 25 November 2009
parameters to obtain high quality TiN thin film. Quality of these films was confirmed by electron
Available online 2 December 2009
microscopic analysis. This methodology can be extended for optimization of other process parameters
and materials.
Keywords:
ß 2009 Elsevier B.V. All rights reserved.
TiN
SIMS
Thin films
Reactive Pulsed Laser Deposition
Multilayer

1. Introduction
Pulsed Laser Deposition (PLD) is a simple yet versatile
technique suitable for the synthesis of thin film of materials
ranging from metals and ceramics to polymers [1,2]. Since it has a
definite edge over other deposition techniques, it is being pursued
vigorously in various research and development laboratories for
several potential technical applications and successfully march-
ing towards full commercial exploitation. In recent years,
significant attention has been given to the synthesis of oxide,
nitride and carbide thin films from elemental targets using
Reactive PLD [3,4] (RPLD). As the physical processes in RPLD are
highly complex and interrelated, many of the process parameters
such as laser energy, deposition pressure and substrate tempera-
ture need to be optimized to obtain high quality film. Until now,
either no attempt has been made to optimize the process
parameters for getting stoichiometric nitride films [5] or any
one of the process parameters such as pressure or temperature is
optimized in circuitous manner [6,7]. Even in few of such
systematic investigations reported so far, by Mihailescu et al.
[6] and Gu et al. [8], the authors have conducted several different
experiments to optimize these parameters. Designing an experi-
ment for optimizing the process parameters with minimum
number of experiments is of paramount importance not only for
* Corresponding author. Tel.: +91 44 27480081; fax: +91 44 27480081.
E-mail address: krish@igcar.gov.in (R. Krishnan).
the efficient use of available resources but also to minimize the
gestation period. Present investigations based on Secondary Ion
Mass Spectrometry (SIMS) methodology attempts to achieve
optimized synthesis criteria for TiN films and it is the subject of
this letter.
2. Experimental
2.1. Coating deposition
Complete description of the experimental facility is given
elsewhere [9]. A Q-switched Nd:YAG laser beam having a
wavelength of 1064 nm was introduced into an ultra-high vacuum
(UHV) compatible reaction chamber through a quartz window and
was focused to approximately 2 mm diameter circular spot at the
target surface at an oblique incidence of 458. The laser pulse
duration was 5 ns. A high purity (99.9%) titanium disc of 24.5 mm
diameter and 10 mm thickness was used as a target. The target was
rotated at 3 rpm to prevent crater formation and to expose fresh
material for laser ablation. Prior to deposition, the silicon
substrates were de-greased, cleaned and vacuum dried. Part of
the ablating plume was made to deposit on the substrates
positioned on a substrate heater, located just in front of the
target. A target–substrate distance of 40 mm was maintained
during the deposition. The chamber was evacuated to a base
pressure of 5.0  107 mbar using a turbomolecular pumping
system backed by a rotary pump. Ultra-high pure N2 gas was bled
into the chamber using a mass flow controller.

0169-4332/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2009.11.076
3078 R. Krishnan et al. / Applied Surface Science 256 (2010) 3077–3080
2.2. Characterization of coatings using SIMS
SIMS is a versatile analytical technique for compositional
characterization of surfaces and interfaces of a solid. In this
technique, the information about spatial as well as depth
dependent composition is obtained from mass spectroscopic
measurement of sputtered secondary ions arising due to progres-
sive and controlled erosion of specimen surface by ion bombard-
ment [10]. The secondary ion current, Is, of the species in the
charged state q registered with the SIMS machine is expressed as
I s ¼ q  Ip  Y  a  C  T
where a is the ionization probability, Ip is the primary ion current
(mA), Y is the total sputter yield, C is the atomic concentration and
T is the instrument transmission. The Is is typically in the range of
pico-ampere to nano-ampere. Though large variation in a poses
some difficulty in quantification, better quantitative information in
concentration variation can be achieved by monitoring CsX+ (X:
sputtered elemental species) clusters under Cs primary ion
bombardment [11,12]. We used a SIMS instrument (Cameca-
ims4f, France) with 1.75 keV Cs+ primary ions. The primary beam
was rastered over an area of 150 mm  150 mm. The sputtered ions
were collected from a central circular area having a diameter of
65 mm.
In this study, we made multilayers of TiNx by varying one key
processing parameter viz., deposition pressure or substrate temper-
ature or pulse energy, keeping all other parameters a constant. In
order to facilitate clear distinction on the composition brought
about by change in the key processing parameter, an niobium
interlayer was deposited between successive TiNx layers. Niobium
was chosen because of its lower diffusion mobility due to its
relatively larger atomic radius. Also, in a recent study, by Barshilia
et al. [13], TiN/NbN multilayers were shown to have very high
stability even at 700 8C, indicating that niobium will be a good
interlayer with minimum nitrogen diffusion. Hence niobium was
chosen as an interlayer material and deposition temperatures were
well below 700 8C, in our studies. Resultant multilayer films were
characterized for chemical composition using SIMS depth profiling
mode. Due to its ability to resolve these multilayer with high depth
resolution, we monitored the change in composition brought
about by the change in one of the processing parameters. By
comparing the titanium to nitrogen ratio in these layers, one can
easily arrive at the optimal process parameter to get high quality
TiN. In this way, by analyzing one multilayer we can get the
optimal value of the particular parameter that was iterated.
Fig. 1. SIMS depth profile of TiNx–Nb multilayer for varying deposition pressures at constant substrate temperature (100 8C) and pulse energy (400 mJ).
3. Results and discussion
3.1. Optimization of deposition pressure
Fig. 1 shows the depth profile of TiNx/Nb multilayer deposited
by varying the deposition pressure by bleeding a controlled quantity
of ultra-high pure N2 gas. The substrate temperature was kept
constant at 100 8C. This specimen consists of (TiNx/Nb)6 layers. The
Nb layers were deposited at chamber pressures lower than
1.0  106 mbar. The first titanium layer close to the substrate
was deposited by ablating titanium target for 20,000 laser pulses
(1) having energy of 200 mJ under UHV conditions (vacuum better
than 1.0  106 mbar). The corresponding SIMS analysis shows
titanium films with very low oxygen and nitrogen intensity. It also
serves as a reference. The second titanium layer was deposited
after feeding in controlled quantity of nitrogen (6 sccm) through
mass flow controller and adjusting the chamber pressure to
7.0  103 mbar. Since the relative sensitivity factor of NCs2+
complex is more than that of NCs+ for nitrogen analysis, we present
the profile of NCs2+complex. The marked upward change in
nitrogen signal by one order of magnitude clearly indicates the
incorporation of nitrogen in the titanium layer. The successive
titanium layers show a systematic change in N to Ti ratio reaching a
maximum value at 3.0  102 mbar and decreasing thereafter. It is
also at this deposition pressure that the oxygen levels are lowest
indicating high purity of the deposited TiN film. The titanium layer
deposited at 7.0  102 mbar shows not only a reversal in nitrogen
pickup but also a higher intake of oxygen into the film. Mihailescu
et al. [14] reported the formation of nano-structured f.c.c.
polycrystalline TiN in the pressure range of 7.0  103 to
7.0  102 mbar. As a further improvement in the process
parameter optimization, in the present study we have systemati-
cally carried out the synthesis at various intermediate pressures
and found that a maximum N to Ti ratio is achieved at
3.0  102 mbar. The resemblance of SiCs+ depth profile in the
TiN films can be attributed to the N2Cs+ which has the same
nominal mass as that of SiCs+. Successive experiments for
optimization of substrate temperature and laser pulse energy
were carried out using this deposition pressure (3.0  102 mbar)
for which the Ncounts/Ticounts is maximum.
3.2. Optimization of substrate temperature
In order to optimize substrate temperature, TiNx/Nb multilayer
was deposited by varying the substrate temperature at constant
chamber pressure and pulse energy. Corresponding SIMS depth
 R. Krishnan et al. / Applied Surface Science 256 (2010) 3077–3080 3079

Fig. 2. SIMS depth profile of TiNx–Nb multilayer for varying substrate temperatures at constant chamber pressure (3.0  102 mbar) and pulse energy (400 mJ).

profile of is shown in Fig. 2. First Ti layer (adjacent to the substrate)
and the top most layer were deposited at chamber pressure lower
than 1.0  106 mbar. Rest of the TiNx layers were deposited at
3.0  102 mbar with constant pulse energy of 400 mJ. Starting from
room temperature successive titanium layers were deposited at
substrate temperatures of 100, 200 and 400 8C, respectively. Though,
the Ncounts/Ticounts, as seen from the SIMS profile, is largely unaffected
by the substrate temperatures from 25 to 400 8C, 100 8C was chosen
as optimal temperature in view of the lower oxygen content as
compared with the TiN film deposited at room temperature.
3.3. Optimization of pulse energy
Laser pulse energy is an important engineering factor determining
the stoichiometry of the film. Energy per pulse will have a direct
impact on the expanding plasma plume, ion and electron densities
thereby influencing N2 dissociation pattern which makes availabili-
ty of N+ and N radicals for TiN synthesis. Fig. 3 shows the depth
profile of TiNx/Nb multilayer deposited by varying the pulse energy
at an optimal chamber pressure of 3.0  102 mbar and substrate
temperature 100 8C, derived from earlier experiments. Excluding
the bottom most layer (close to the silicon substrate marked Layer-I),
this profile depicts five layers of TiNx. These layers were deposited at
five different energies of 100, 200, 300, 400 and 500 mJ/pulse,
respectively. The layers were separated with a vertical line and
marked Layer II–VI, accordingly. It is observed that the thickness of
the individual TiNx layer increases with the increase in pulse energy
which can be attributed to enhanced flux. The Ncounts/Ticounts ratio
shows a steady increase when the pulse energy increased from 100
to 500 mJ with simultaneous decrease in Ocounts. Enhanced plasma

Fig. 3. SIMS depth profile of TiNx–Nb multilayer for varying pulse energies at constant chamber pressure (3.0  102 mbar) and substrate temperature (100 8C).
3080 R. Krishnan et al. / Applied Surface Science 256 (2010) 3077–3080

3.4. TEM analysis of the TiN thin film

In order to validate the above findings, TiN films were grown on

NaCl substrates at optimized process parameters viz., using a pulse
energy of 500 mJ; chamber pressure of 3.0  102 mbar and
substrate temperature of 100 8C. The resultant films were
characterized using a High Resolution Transmission Electron
Microscopy. The corresponding high resolution micrograph is
shown in Fig. 4(a). The measured d-spacing (shown in the
magnified image) is consistent with, the d-spacing corresponding
to TiN(2 0 0), reported in standard JCPDS No: 38-1420 (Table 1).
Further analysis of HRTEM image in larger area indicate that there
are oriented TiN(2 0 0) domains (5–10 nm size) surrounded by
regions of high defect density leading to smearing and disappear-
ance of regular arrays. The orientation of these domains is found to
vary from lower left to upper right corner of the image to the extent
of 10–158 and the angles are marked. This subtle change in
orientation of the domains corresponds to the angular streaking
seen in SAED pattern and this misorientation is possibly due to the
large lattice mismatch between film (TiN) and the substrate (NaCl).

3.5. Conclusions

In summary, we present here a novel way of using SIMS analysis

for the optimization of three important process parameters used in
growth of TiN films using RPLD technique with minimal number of
experimental runs. The resultant films were characterized using
TEM and the lattice parameters obtained match well with the
values reported in literature. The same methodology has the
potential to be extended not only to optimize any other parameter
like target–substrate distance, laser wavelength and repetition rate
but also other oxides, nitrides and carbides. Efforts are on to
quantify the SIMS data that will enable us not only to improve the
phase purity and stoichiometry of the films but also synthesize
intermediate phases like Ti2N. Similar optimization procedure for
the synthesis of nanocrystalline NbN thin films and nano-
structured TiN/NbN multilayers is in progress.

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