Vol.2, No.1, 26-31 (2011)
Copyright © 2011 SciRes. Openly accessible at http://www. scirp.org/journal/JBPC/
Journal of Biophysical Chemist ry
Features of the formation and nanostructure of the film
with the basic hexagonal pha se TiN0.3 by arc evaporation
Anna L. Kameneva1, Lybov N. Gu selnikova2, Tatyana O. Soshina2
1State educational institution of the higher vocational education Perm state technical university, PSTU, Perm, Russia;
*Corresponding author: annkam789@mail.ru
2Branch of PSTU, Lys’va, Russia
Received 27 September 2010; revised 21 October 2010; accept 3 November 2010.
Forming and nanostructuring processes of TiN
film by electric arc evaporation under the condi-
tions of the reactive nitrogen gas deficit in the
gas mixture (30%) have been investigated. The
results of a technological experiment, electron
microscopic examination, X-ray diffraction phase
analysis and mechanical testing of the film re-
vealed that a significant increase in ion density
and mobility leads to deterioration of the
formation temperature condit ions, structural and
phase changes in TiN film and change of the main
cubic phase (111)TiN on a hexagonal (101)TiN0.3.
In the end repeated decrease of the the film mi-
crohardness with (101)TiN0.3 was caused not
only by erosion of the film, but also because of
change in the processes of its formation and
nanostructuring in comparison with similar
processes of the film with (111)TiN.
Keyw ords: TiN Film; Arc Spraying; Forming and
Nanostructuring Processes; Structure and Phase
It is known [1-27] that films’ exploitation conditions
depend on raw materials, methods and technological
parameters of the application, providing the necessary
energy mass transfer of precipitable atoms, ions, mole-
cules, nano and ionized particles. The main technologi-
cal parameters are: the pressure of the gas mixture, the
bias voltage on the substrate, the contents of the reaction
gas in the gas mixture, the cathode-substrate distance,
arc current (for electric arc evaporation), the temperature
of the substrate and film, the maximum rate of deposition.
The aim of this paper is to study the effect of the ni-
trogen minimum concentration in the gas mixture at the
temperature conditions, the direction of preferential crys-
tallographic orientation, phase composition, mechanical
conditions, formation and nanostructuring of TiN film
during electric-arc evaporation.
2.1. Methods of the Preparation of
Substrates and Formation of TiN Film
TiN film was formed on an industrial installation
NNV-6.6-I4 with a single arc evaporation with a tita-
nium cathode (s BT1-00) with 30% nitrogen content in
the gas mixture. To increase the adhesive strength of TiN
film on the surface of the test samples from Article 2 [2],
Ti underlayer was applied after its ion cleaning- heating.
2.2. The Method of Substrate and TiN Film
Temperature Control
Temperature of test pieces surface as well as the film
temperature after each 10 minutes of the film deposition
have been measured by infrared contactless pyrometer
after both ionic cleaning and sublayer applying, a whole
duration of the precipitation process was 30 minutes.
2.3. Methods of Studying the Structure,
Phase Composition and Conditions
of TiN Film
Morphological traits of the formed films have been
investigated by bitmapped electron microscope BS 300
with prefix for microanalysis EDAX Genesis 2000.
X-ray diffraction phase analysis of TiN film was carried
out using X-ray diffractometer DRON-4 in Cu Kα radia-
tion. Microhardness of the composition has been meas-
ured by microhardness tester PМТ-3 with indenter load
A. L. Kameneva et al. / Journal of Biophysical Chemistry 2 (2010) 26-31
Copyright © 2010 SciRes. Openly accessible at http://www.scirp.org/journal/JBPC/
of 0.5 N after the film precipitation process.
Technological parameters of processes for preparing
the substrate surface before precipitation process of the
film: ion cleaning- heating and deposition of Ti under-
layer are shown in Table 1, the technological parameters
of electric arc evaporation process and microhardness of
the composition: the TiN film - substrate (hereinafter the
microhardness of the composition) are listed in Table 2.
The results of X-ray diffraction phase analysis of
TiN film plots, formed by arc evaporation at a nitrogen
content in the gas mixture of 30% do not correspond
with the previous similar studies of TiN film, formed at
different contents of bias potential on the substrate
(Figure 1, Tables 3,4). It was found previously [2] that
regardless of the bias voltage at a maximum tempera-
ture of the film > 700 K and the rate of heating on the
substrate > 14.2 K/min, the film is formed, consisting
of the main cubic phase of TiN with the direction of
preferred crystallographic orientation (111) and more -
hexagonal phase TiN0.3.
It was established for the first time that the nitrogen
content decrease in the gas mixture to 30%, a significant
increase in ion density and its mobility, as well as dete-
rioration of the formation temperature conditions (the
original film temperature was 613 K, the rate of its heat-
ing - 12.0 K/min) lead to a change in the basic cubic
phase 111(TiN) to the hexagonal (101)TiN0.3 phase, the
emergence of new additional phases with volume frac-
tions: tetragonal Ti2N - 3.7% and hexagonal Ti - 2.1%
and more than twofold decrease of the composition mi-
crohardness. It ought to be noted that minimal deviation
of the interplanar distance from the table value, a maxi-
mum width of the peaks of the hexagonal phase
(101)TiN0.3 and homogeneous internal stresses in the
film happened due to unidirectional displacement of the
peaks (111)Ti2N and (101)TiN0.3, (111)Ti.
To determine the cause of changes in the mechanical
conditions of TiN film, based on the structural charac-
teristics and phase composition, which differs from all
previously received TiN film, the morphological features
of its surface were studied.
Through a small increase it was possible to find out
only the rough surface of TiN film (Figure 2).
Based on the results of electron microscopic studies of
the film surface at higher magnification it was revealed
that the formation and nanostructure processes of the
film with the basic hexagonal TiN0.3, or cubic TiN phase
are different. In constructed thermal conditions two
processes consistently occur: the formation of coarse-
grained film and when the temperature of the film gets
close to 700 K (650 K) - nanostructuring polycrystalline
part of the film.
When the initial temperature conditions of formation
is 613 K and heating rate is 12.0 K/min coarse-grain film
of laminose structure is formed (Figure 3). Erosion of
the film surface and its maximum surface roughness, as
a result of intense bombardment and sputtering lead to
Table 1. Process conditions of ion cleaning- heating and deposition of Ti underlayer.
Process U, V
Substrate - plazma source
distance, mm T, minP, PaIfocusing coil, AIstabilizing coil,
rpm GasFinal temperature,
Ionic cleaning high 600 270 5 0.01 1.50 2.50 80 2.5 Ar 651
Sublayer applying bias 200 270 3 1.0 1.50 2.50 80 2.5 Ar 613
Table 2. Process conditions of the TiN film applying.
Table 3. Structural characteristics of the TiN-based films produced by arc spraying. V is phase inclusion volume fraction,
dTi2N/dTi2Ntable is cleavage spacing, ITi2N/ITiN0,3 is intensity ratio of all reflexes of tetragonal Ti2N phase and hexagonal TiN0,3 the one,
maxI111Ti2N/IΣ and maxI101TiN0.3/IΣ are ratios of maximum reflex intensities (111) or (101) to total intensity of all TiN phase reflexes,
and β0 is breadth of X-ray diffraction line.
V, %
Ti Ti2N TiN0,3
dTitable, nm
dTiN0,3table, nm
IΣ max
max I
max ITi
max ITiN0,3
2.1 3.7 94.2 0.2353
0.03 0.08 119.50.03 0.07 0.90 0.07 0.67
N2, % L, mm P, Pa Iarc, A Ubias, V Tfilm, K Vfilm heat, Hμ, GPa
tprocess = 10 mintprocess = 20
tprocess = 30
min K/min
30 270 1.0 80 200 625 635 660 12.0 10.0
A. L. Kameneva et al. / Journal of Biophysical Chemistry 2 (2010) 26-31
Copyright © 2011 SciRes. Openly accessible at http://www. scirp.org/journal/JBPC/
Table 4. Positions of the diffraction peaks.
Film Phase Lattice type Grain orientation 2θтабл, grad 2θ, grad
Ti Hexagonal <002> 38,3911 38,25
Ti 2N Tetragonal <111> 39,3267 39,20
Ti N0,3 Hexagonal <101> 39,7086 39,649
Figure 1. Comparative band of diffractogram fragments for TiN-based film pieces produced by arc spraying with 30% nitrogen
content in the gas mixture.
defects in the form of discontinuity at the interface of
grains (Figure 4(a)), cracking (Figure 4(b)), grain pit-
ting (Figure 4(c)), and grain boundary fracture of the
film Figur e 4( d)).
It was discovered for the first time that film tempera-
ture increase up to 650 K leads to change of processe
from coarse-grain film formation to nanostructuring of
the polycrystalline film constituent, connected with the
following indispensable stage consequence.
z Forming of the globules (Figure 5(a)).
z Integration of the globules (Figure 5(b)) followed
by surface texturing at the end (Figure 5(c)).
z Forming of 3D- formations with grain substructure
(Figure 5(d)).
z Surface coarsening of the 3D- formations with
grain substructure (Figure 5(e)).
z Nucleation of polycrystalline constituent of the film
(Figure 5(f)).
z Nanostructuring of the film polycrystalline con-
stituent (Figure 5(g)) followed by seed integration to
microsystems with incoherent boundaries (Figure 5(h)).
z Forming of cone textures <111> on the surface of
the 3D-formations with laminose structure (Figure 5(i)).
The whole process of nanostructuring polycrystalline
constituent of the film is shown in Figure 6.
Phase-structural state of TiN film, formed by electric
arc evaporation with a minimum content of nitrogen in
the gas mixture (30%) was investigated by X-ray dif-
Figure 2. Photomicrographs of TiN films formed
by arc spraying at 30% nitrogen concentration in
mixed gas.
A. L. Kameneva et al. / Journal of Biophysical Chemistry 2 (2010) 26-31
Copyright © 2010 SciRes. Openly accessible at http://www.scirp.org/journal/JBPC/
(а) (b)
Figure 3. Photomicrograhs of continuous coarse-grained film (a) having laminar grains (b).
(а) (b)
(c) (d) (e)
Figure 4. Photomicrographs of TiN film formed at minimum nitrogen concentration (30%) in mixed gas. The film has surface
defects: (a) Discontinuity on grain interface; grain (b) Cracking and (c) Roughening; (d) Grain-boundary film destruction, max
grain dimensions are 4.5 × 29.0 μm; (e) Discontinuity (“lack”) of the film material.
fraction phase analysis method. For the first time ever
was established that the maximum possible content of
argon in the gas mixture leads to a change in the main
phase of the film from a cubic (111)TiN to the hexagonal
Results of electron-microscopic studies of the films
surface morphology revealed that at the film temperature
less than 650 K coarse-grained film with various defects
is formed on the substrate surface. Nanostructuring
process of polycrystalline constituent of the film with
the main hexagonal TiN0.3 phase differs from the same
film process with the main cubic (111)TiN phase.
Based on previous experimental studies of the struc-
ture and conditions of films formed by nitrogen content
in the gas mixture of 90% and a variable bias to the sub-
strate 80 ... 250 V was found that the nucleation of a
polycrystalline film with the main component of the
cubic phase (111)TiN occurs only at temperatures of
films > 700 K and the rate of heating > 14.2 K/min [2].
The obtained results allow to suggest that the main
reason for changing the phase ratio in the film, the orig-
inal course of the process of coarse-grained film forma-
tion, and then the process of nanostructuring of poly
crystalline constituent of the film with the main compo-
nent of the hexagonal phase (101)TiN0.3, under conditions
of low nitrogen content and intensity ion bombardment
of the surface forming a film by argon is in sufficient
temperature conditions, characterized by the temperature
A. L. Kameneva et al. / Journal of Biophysical Chemistry 2 (2010) 26-31
Copyright © 2011 SciRes. Openly accessible at http://www. scirp.org/journal/JBPC/
(а) (b) (c)
(d) (e) (f) (g)
(h) (i)
Figure 5. Photomicrograhs of the film having main hexagonal TiN0.3 phase on various stages: (a) globular with
globule dimension up to Ø9.0 μm; (b) integration of the globules with maximum dimensions of Ø7.5 μm and Ø6.5
μm into structures with length L = 14.0 μm and/or (c) integration of the globules into islands dimensioned up to
Ø17.0 μm having globular structure; forming of 3D formations with grain substructure (d) and further their sur-
face coarsening (e) (respectively Ø12.0 μm and Ø9.0 μm); (f) forming of seeds of polycrystalline constituent of
the film having form of frustums with upper base dimension of 120x250 μm; (g) forming of laminar 3D forma-
tions (Ø4.0 μm) sustaining border coherence, (h) their integration into laminar microsystems (Ø9.0 μm) having
non-coherent borders and discontinuity, (i) forming of conic surface structures <111>.
Figure 6. Stages of nanostructuring of TiN films with main hexagonal TiN0.3 phase by arc spraying method (~ 660
K, 30% N2,Vfilm heating = 12.0 K / min).
of the film and its rate of heating, nucleation,formation
and nanostructure of the film with the main cubic phase
We can assume that one of the main reasons for dou-
ble reduction in the microhardness composition is dif-
ferent structural states of formed continuous film-grain
lamellar structure and formed on its surface as a result of
nanostructuring 3D structures with a lamellar substruc-
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