SCIENCE-48

Nanostructured Thin Films Of TiAlN And TiN prepared by

Magnetron Sputtering
n EXECUTIVE SUMMARY
Nanocrystalline thin films of titanium nitride and titanium aluminium nitride were deposited on (111) Si substrates by
reactive d.c. magnetron sputtering under various nitrogen flow rates and at constant substrate temperature. The effect of
nitrogen flow rate on the structural and electrical properties of TiNx and Ti1-xAlxN thin films deposited at substrate
temperatures of 973 K and 773 K, respectively is investigated. While the resistivity of TiNx films showed a minimum at a
nitrogen flow rate of 5 sccm, the resistivity of Ti1-xAlxN films increased with increasing nitrogen flow rate.

n OUTLINE
Titanium nitride (TiN) thin films exhibit remarkable physical and (a)
chemical properties. Due to their high thermal stability, low electrical

Si (111)

(200)
resistivity and good diffusion barrier characteristics, TiN thin films find

(220)

(311)
(111)
Intensity (arb. units)
numerous applications in microelectronics industry. But TiN coatings
oxidize at temperatures ≥873 K and lose their hardness and hence are 2 sccm
not very suitable for dry cutting and high speed cutting tools. Instead of
adding further metalloids to the titanium-nitrogen composition, 5 sccm
addition of aluminium as a substitute of titanium has produced good
results concerning wear and oxidation resistance. Al atoms can 20 sccm
substitute some of the Ti atoms in TiN lattice in various proportions
30 sccm
and thus form Ti1-xAlxN structure. The latter material not only greatly
enhances the wear, thermal, and mechanical properties of the coating, 20 30 40 50 60 70 80 90
but also improves its oxidation resistance. TiNx and Ti1-xAlxN thin films Two theta (degrees)
were deposited on (111)-oriented silicon wafers at different N2 flow rates
by reactive d.c. magnetron sputtering. The TiNx films were prepared by
sputtering a 99.99% pure Ti disc of 3 inch diameter and 2 mm (b) Ti(Al)N Al(Ti)N Si

units)

(111)
thickness in a mixture of high purity argon (99.99%) and nitrogen

(100)

(200)

(220)
(110)
(111)
(99.99%) plasma. The Ti1-xAlxN thin films were prepared by sputtering a
composite target comprised of discs of 99.99% pure Ti and Al having 2 sccm
surface area in the ratio 2:1 in a mixture of high purity argon (99.99%)
and nitrogen (99.99%) gas. In both the cases, the sputtering was Intensity (arb. 5 sccm
carried out in a stainless steel chamber of 45 cm diameter and 20 cm 10 sccm
height using a Mighty MAK, US sputtering gun of 3 inch diameter. 15 sccm
20 sccm
The deposition rates and the grain size of both types of films decreases
with increasing nitrogen flow rates. The decrease in the deposition rate 25 sccm
is attributed to differential target poisoning. The TiNx films are 20 30 40 50 60 70 80
polycrystalline at all N2 flow rates and exhibit only δ-TiN phase. The Two theta (degrees)
Ti1-xAlxN films are polycrystalline only at lower nitrogen flow rates (≤ 5
sccm). At nitrogen flow rate of 2 sccm, the Ti1-xAlxN films are composed Fig. 1 : XRD patterns of (a) TiN thin films and (b) TiAlN
of Ti(Al)N (B1 NaCl) phase as well as Al(Ti)N (Hexagonal close packed) thin films deposited under different N2 flow rates
phase ( Fig.1). At higher flow rates of nitrogen (≥10 sccm), only Ti(Al)N
phase is observed because of the decreased sputtering rates of the 40
TiN Ti Al x N
poisoned composite target. The lattice parameter of TiNx films initially 35 x 1-x
G r a in s iz e (n m )

increases with increasing nitrogen flow rates due to possible 30

transformation from substoichiometric to stoichiometric and slightly 25
hyperstoichiometric TiN and remains almost constant beyond 5 sccm. 20
But the lattice parameter of Ti1-xAlxN films initially remains almost 15
constant with increasing nitrogen flow rates and starts decreasing at 10
flow rates >10 sccm. The latter could be related to the incorporation of 5
more nitrogen atoms through the generation of metal vacancies. 0
The grain size of both types of films decreases with increasing N2 flow 0 5 10 15 20 25 30
rates (Fig. 2). The grain size of TiNx films decreases from 36 nm to 10 N 2 Flow rate (sccm)
nm and the grain size of Ti1-xAlxN films decreases from ~14 nm to 5 nm Fig. 2: Variation of grain size of TiNx and Ti1-xAlxN films
as the N2 flow rate is increased from 2 sccm to 30 sccm. HREM images with N2 flow rate.
of TiAlN and TiN showed mostly nanocrystalline containing a high
concentration of defects in the films. For instance the TiN films
prepared at 673 K show dislocations and bending of lattices because
of the fact that these films are formed by a non-equilibrium process
(Fig. 3). Nanoindentation technique showed a hardness exceeding
20 GPa for TiN (Fig. 4) and TiAlN films prepared under optimized
processing conditions. Photoacoustic measurement of the thermal
properties of the films revealed that the thermal diffusivity and thermal
conductivity of the TiAlN and TiN thin films is very much less than the
bulk values. Results demonstrated that the thermal conductivity is
drastically reduced due to increased phonon scattering for fine grained
materials, particularly when the grain size is of nanometer dimensions. Fig. 3 : HREM of TiN film formed at 673 K showing
a high concentration of dislocations

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 SCIENCE-48

n MAGNETRON SPUTTERING PROCESS

The sputtering deposition process is performed 80

H ard ness (G Pa)

in a vacuum chamber where argon atoms are
ionized and accelerated to strike a target 60
material, for example, aluminium. Coating
material enters the vapor phase through a
physical process (momentum exchange) rather 40
than by a chemical or thermal process. The
argon atom dislodges aluminum atoms when it 20
strikes the target, then these ejected aluminum
atoms strike the steel part to be coated, and this 0
continuous process eventually applies a dense
aluminum coating to the steel part. Figure 5 0 50 100 150
depicts the basic sputter technology. By simply
Displacement Into Surface (nm)
adding a magnetic field to the target material,
the sputter rate can be greatly increased. The Fig. 4 : Nanohardness as a function of penetration depth for TiN films
magnetic field causes more of the ionized argon
atoms to strike the target and this increases the
amount of aluminum atoms being ejected. This
process is called magnetron sputtering.
Thin films prepared by sputtering exhibit
different structure and properties depending on
the growth conditions and process parameters.
Due to their several potential applications, an
understanding of the structure and properties of
the TiN and Ti1-xAlxN thin films as a function of
deposition parameters is very important. Hence
a comparative study on the influence of nitrogen
flow rate on the structural and mechanical
properties of TiNx and Ti1-xAlxN thin films
prepared by DC magnetron sputtering has been
carried out. Fig. 5 : Schematic of sputtering process

n ACHIEVEMENT
It has been demonstrated that hard coatings of TiAlN and TiN could be prepared under optimum processing conditions
using magnetron sputtering. The preferred orientation of these films could be altered by the appropriate flow rates of
nitrogen. The study also suggested that these films contain nanocrystals and a high density of defects especially when
they re formed at low deposition temperatures. The thermal conductivity of these films decreased considerably compared
to those of bulk materials due to a reduction in grain size. The lower thermal conductivity of these films are technologically
important and are best suited for heat resistance coating and thus these films might enhance tool life, and optimum
machine performance.

n PUBLICATIONS ARISING OUT OF THIS STUDY AND RELATED WORK

1 A. Albert Irudayaraj, P. Kuppusami, R. Thirumurugesan, E. Mohandas, S. Kalainathan, and V.S. Raghunathan,
Surface Engineering, 23 (2006) 7.
2. A. Albert Irudayaraj, R. Srinivasan, P. Kuppusami, E. Mohandas, S.Kalainathan, and K. Ramachandran, Intnl J
Mod. Phys B. 21 (2007) 3889.
3. A. Albert Irudayaraj, P. Kuppusami, R. Thirumurugesan, R. Srinivasan, E. Mohandas, K. Ramachandran, and
S. Kalainathan, Intl. Symposium of Research Students on Materials Science and Engineering, Dec 18-20, (2006)
IITM, Chennai.

Further inquiries:
Dr. P. Kuppusami and Shri E. Mohandas, Physical Metallurgy Division
Metallurgy and Materials Group, IGCAR, e-mail: pk@igcar.gov.in ; mohandas@igcar.gov.in

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