Dependence of surface nano-structural modications of Ti implanted

by N
+
ions on temperature
Masoumeh Firouzi-Arani
a
, Hadi Savaloni
b,
*, Mahmood Ghoranneviss
a
a
Plasma Physics Research Center, Science and Research Branch, Islamic Azad University, P. O. Box 14665-678, Tehran, Iran
b
Department of Physics, University of Tehran, North-Kargar Street, Tehran, Iran
1. Introduction
With increasing interest in high performance mechanical parts,
advancement has been made in improving the surface properties
of materials [1]. Surface modication technologies which are
efcient methods to enhance specic properties of the surface can
be classied as: (a) ion implantation or ion irradiation method, the
ion particles accelerated by electric eld are inserted into the
surface of sample to change the structure and composition of the
surface layer [2], (b) thin lm or thick lm coating, another
complementary material is spread on the sample [1,3,4].
The ion implantation has been applied to manufacturing
processes of semiconductors, and has been used for improvement
of engineering materials [1]. In particular, it has been reported that
the ion implantation of nitrogen enhances the expected life span of
machining tools [4,5].
Titanium nitrides, carbides, carbonitrides and titanium alloys
have found a large number of applications in modern technology
owing to their unique physical, chemical and mechanical char-
acteristics suchas goodcorrosionresistance and biocompatibilityas
well as structural properties, such as high elastic modulus, yield
strength and fracture toughness [611]. Since TiNis a nonpoisonous
compound, it is also widely used in the medical applications [12].
Adherence strengthof TiNcoating withsubstrate is not as good
as expected. However, when implanted with ions, its adherence is
improved to a great deal. Taking the advantage of ion implanta-
tion, TiN coatings have been modied with high dose and ion
uence [13].
Nitrogen ion implantation in titanium is used to enhance its
surface mechanical properties and its corrosion resistant in
different environments, using Ringers solution [9,14], NaCl [15
24], HCl [17,19], H
2
SO
4
[25] of different concentrations.
In recent years, there has been an increasing interest in
elucidating the mechanisms which lead to thin lm property
modication caused by the so-called substoichiometric condition
[2629]. Vaz et al. [30] studied structural, physical and mechanical
properties of substoichiometric TiN
x
thin lms. However, although
there exists a great amount of literature on TiN, but to the best of
our knowledge, there has been no study on the stoichiometric
changes made during the N
+
ion implantation of titanium massive
Applied Surface Science 256 (2010) 45024511
A R T I C L E I N F O
Article history:
Received 25 October 2009
Received in revised form 23 December 2009
Accepted 22 January 2010
Available online 2 February 2010
PACS:
68.55.Ln
68.49.Sf
82.80.Ms
68.37.Ps
Keywords:
SEM
AFM
XRD
SIMS
Ion implantation
Depth prole
Ion implantation
A B S T R A C T
The surface modication of titanium thin foil/sheet samples (0.5 mm) implanted by nitrogen ions of 30
keV energy and a uence of 1 10
18
N
+
cm
2
at different temperatures is studied using XRD, AFM, SEM,
and SIMS. XRD patterns showed the development of titanium nitride with different compositions in the
implanted samples, while the presence of different titanium compositions such as titanium oxides was
also observed. AFM images at 654 K showed the formation of grains, that after initial sputtering of the
grain boundary at 728 K temperature, the morphology of the surface changed from small grains to a
bimodal distribution of grains at 793 K which consisted of larger grains with bright hillocks within them.
This was considered to be due to phase transformation/compositional changes, explained by correlating
XRD and SIMS results. The SIMS results showed a maximum at about 730 K and a minimum at about
790 K for both N
+
density and depth of N
+
penetration in the Ti sample. The variation of these results with
temperature was explained on the basis of the residual gas, substrate temperature, dissociation of water
in the chamber and the gettering property of titanium.
2010 Elsevier B.V. All rights reserved.
* Corresponding author. Tel.: +98 21 88635776; fax: +98 21 88004781.
E-mail address: savaloni@khayam.ut.ac.ir (H. Savaloni).
Contents lists available at ScienceDirect
Applied Surface Science
j our nal homepage: www. el sevi er . com/ l ocat e/ apsusc
0169-4332/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2010.01.083
(sheet/foil) sample. Since the design and manufacture of materials
with improved surfaces are needed in different applications, the
detailed information about the processes involved in ion implan-
tation is of fundamental importance. In particular, when a highly
reactive material, such as titanium is of interest, one should also
consider the gettering property of titanium and the presence of
titanium oxide in the unimplanted sample and the formation of
different titaniumoxide phases during the ionimplantation caused
by the residual gas in the vacuum system and in particular around
the sample.
The aim of this article is to investigate the nature of
substoichiometric nitride formation in titanium (TiN
x
) during
nitrogen ion implantation, as a function of substrate temperature,
using X-ray Diffraction (XRD), Atomic Force Microscopy (AFM),
Scanning Electron Microscopy (SEM) and Secondary Ion Mass
Spectroscopy (SIMS).
2. Experimental details
The samples used were cut in two different sizes of 3 3 mm
(for SIMS analysis), 10 5 mm (for XRD, SEM and AFM analysis)
from 0.5 mm thick polycrystalline Ti foil (Goodfellow Metals,
99.6+% purity). Neither mechanical nor chemical polishing
treatments were applied to the samples surfaces.
The nitrogen ion implantation of the samples was carried out at
30 keV and a uence of 1 10
18
N
+
cm
2
for 1600 seconds. The ion
current density during implantation was 100 mA cm
2
. The base
pressure of the chamber was 2 10
5
mbar, which during the
implantation process increased to 5 10
5
mbar.
A substrate holder system with controlled heating system was
designed and constructed. Detailed description of this is given in
our earlier work [31]. On the copper disk substrate holder, two of
each size of the substrates can be xed by a stainless steel mask.
The substrate temperatures were controlled by programmed
thermostats and thermocouples xed inside a hole on the surface
of copper disk substrate holder.
Just before use, all Ti samples were ultrasonically cleaned in
heated acetone then ethanol. The microstructure of the samples
was obtained using a Philips, Xpert MPD Diffractometer (CuK
a
radiation) with a step size of 0.028 and a count time of 2 s per step,
while the surface physical morphology and surface roughness
(root mean square R
q
and average R
a
) was obtained by means of
AFM (Auto probe PC, Park Scientic Instrument, USA; in contact
mode, with low stress silicon nitride tip of less than 200 A

radius
and tip opening of 188) analysis. The density of implanted N
+
ions
in Ti samples as well as depth proling was carried out, using SIMS
(Cameca, IMS 6F) analysis. Cs
+
ions were used as primary ions with
+5 keV impact energy on the surface of the sample and positive
secondary ions (N
+
, Ti
+
, O
+
and C
+
) were detected. The spot size for
SIMS measurements was 5 mm. Prior to each real sample analysis,
the stability of the ion source was checked and during the process
of SIMS analysis of each sample, in addition to the depth prole
analysis of N
+
, the Cs
+
Ti
+
and Ti
+
were also analyzed and no
instability in the ion source was observed.
The details of Ti samples produced for investigation in this work
are given in Table 1.
3. Results
3.1. X-ray diffraction (XRD)
X-ray diffraction patterns obtained from untreated titanium,
and those of N
+
implanted Ti at four different temperatures and
N
+
energy of 30 keV are given in Fig. 1. It should be mentioned
that the initial temperature (T
si
) which is given in column 2 of
Table 1, was set before implantation and it changed during
implantation process owing to heat transfer from ion beam to
the samples. The nal temperature of the samples (T
sf
) at the
end of implantation process is given in column 3 of Table 1. The
progress of temperature during implantation of 30 keV N
+
ions
with time for four different initial temperatures is given in
Fig. 2. The data were analyzed according to this nal
temperature, as in fact this temperature effectively acts on
the activated processes in the sample, until the sample cools
down to room temperature in vacuum (which took 3 to 5 hours
depending on nal temperature), although the change of
temperature during implantation can play a role in the
nucleation and post nucleation stages of the surface modica-
tion. This, we could not take into account, and on the other hand
in most cases did not change dramatically. In Fig. 2, it can be
observed that the time required to reach almost the nal
temperature for all initial temperatures is about 800 s (i.e., one
half of the implantation time).
The comparison of the XRD patterns obtained for unimplanted
and implanted titanium foils at different temperatures in Fig. 1,
shows the formation of the following Ti-nitride diffraction lines
after implantation of N
+
in the samples:
TiN(111) (cubic) (with respect to JCPDS card No: 02-1159);
TiN(200), TiN(220), TiN(400) (cubic) (with respect to JCPDS card
No: 38-1420);
Ti
2
N(101), Ti
2
N(103), Ti
2
N(111), Ti
2
N(002), Ti
2
N(212) (tetrago-
nal) (with respect to JCPDS card No: 17-0386);
TiN
0.26
(102), TiN
0.26
(10-3) (hexagonal) (with respect to JCPDS
card No: 44-1095);
h-Ti
3
N
2-x
(2014), h-Ti
3
N
2-x
(1022) (rhombohedral) (with respect
to JCPDS card No: 40-0958);
and intensity changes in the following Ti-oxide diffraction
lines;
Ti
2
O
3
(131), Ti
2
O
3
(404), (rhombohedral) (with respect to JCPDS
card No: 43-1033);
A(105), A(400), A(411), A(228) (with respect to JCPDS card No:
21-1272);
B(160), B(332), B(024), B(125) (with respect to JCPDS card No:
29-1360).
It must be emphasized on the variation of these diffraction lines
with the temperature and the fact that some of themare very week
and also on the presence of titanium oxide diffraction lines of
different nature (i.e., Ti
2
O
3
and anatase and brookite phases in the
unimplanted sample due to the high reactivity of titanium with
oxygen (e.g., gettering property of titanium). The above exhausting
list shows the cumbersome task involved in the analysis of the
data. This also forced us to divide the diffraction patterns into three
ranges, namely 30 to 60, 60 to 90 and 90 to 120 degrees for
presentation in Fig. 1.
The d-spacing of the titanium nitride lines obtained from the
XRD patterns are listed in Table 2a. The variation of all the data in
Table 2a with temperature is almost negligible.
Crystallite size, D (coherently diffracting domains) was
obtained by applying the Scherrer formula [32] to measurements
of the full width at half maximum (FWHM) of the dominant peaks
of different titanium composites (i.e., TiN(111), Ti
2
N(111),
Table 1
Details of titanium samples implanted by N
+
ions of 30keV and uence of
110
18
N
+
cm
2
.
Sample no. Initial temperature T
si
(K) Final temperature T
sf
(K)
Ti RT RT
Ti2 300 654
Ti5 400 728
Ti9 530 793
Ti13 673 824
M. Firouzi-Arani et al. / Applied Surface Science 256 (2010) 45024511 4503
TiN
0.26
(103) and hTi
3
N
2-x
(1022)), with a correction for instru-
mental broadening. The results are given in Table 2b. The results
show that the crystallite size for all of these composites decreases
with increasing the temperature, which is consistent with the
observation and the discussion made on the AFM results (see
Section 3.2) and the correlation and conclusions deduced from the
analyses carried on this work on XRD, AFM and SIMS (see Section
3.3) results.
Some of these lines are very close to each other and in order to
resolve these peaks, it was necessary to t Voigts functions plus a
level background to the experimental peaks [33]. Typical examples
of this are given in Fig. 3(a and b).
Fig. 1. XRD patterns obtained from N
+
ion implanted titanium samples at different temperatures. (a) 2Q= 30608; (b) 2Q= 60908; (c) 2Q= 901208.
M. Firouzi-Arani et al. / Applied Surface Science 256 (2010) 45024511 4504
The variation of the intensity of different compositions of
titanium(area under the peak which was resolved using the tting
procedure mentioned above) as a functionof temperature is shown
in Fig. 4 according to the following list:
titanium peaks Ti(002) and Ti(101) (Fig. 4-a);
titanium nitride peaks Ti
2
N(111), TiN(111), TiN(200),
Ti
2
N(002), TiN(220) (Fig. 4-b), and Ti
2
N(103), Ti
3
N
2-x
(2014),
Ti
3
N
2-x
(1022) TiN
0.26
(102), TiN
0.26
(103), TiN(400) (Fig. 4-c);
the brokite phase of titanium oxide B(125), B(332), B(160)
(Fig. 4-d);
the anatase phase of titanium oxide A(411), A(400), A(105) and
A(228) (Fig. 4-e);
and Ti
2
O
3
(131) and Ti
2
O
3
(404) (Fig. 4-f).
It can be observed that all of these diffraction lines show a
maximum between 700 and 800 K temperature. However, a more
careful examination of these maxima for the different composi-
tions of titanium shows that the maximum occurs at different
temperature for different compositions of titanium. This is given in
more detail in Table 3.
This information will be used in Section 3.4, where the SIMS
data is givenand a correlationbetween the results will be obtained.
In obtaining the preferred orientation of thin lmsamples, it is
a usual practice to determine the ratio of the intensity of two
associated peaks (i.e., in cubic structures the ratio of (111)/(200)
[34,35] and in hexagonal samples the ratio of (002)/(101) [36]).
Fig. 5 shows the variation of the intensity ratio of the XRD lines
(the associated crystallographic lines, depending on the presence
of these lines on the obtained XRD patterns) for the following
composites by considering their structure as cubic, hexagonal,
and etc.
Ratio of I(111)/I(103) for Ti
2
N with cubic structure, Ratio of
I(002)/I(101) for Ti with hexagonal structure, Ratio of I(111)/I(200)
for TiN with cubic structure, Ratio of I(125)/I(332) for brokite TiO
2
,
Ratio of I(400)/I(411) for anatase TiO
2
, Ratio of I(1022)/I(2014) for
Ti
3
N
2x
.
Ratio of I(404)/I(131) for Ti
2
O
3
, A minimumis obtained for all of
these ratios, though it may be claimed that some of them are not
associated crystallographic orientations. However, the analyses
are carried out according to the availability of the diffraction lines
in the obtained diffraction patterns. It can also be observed that the
temperature at which these minima occur correspond almost to
the temperature of the maxima points in Fig. 4.
In the previously reported thin lm data [34,35] and in our
earlier works on the implantation of nitrogen ions in tungsten and
molybdenum sheets [3739], a minimum was also reported for
these kind of ratios at reduced temperature T
s
/T
m
of about the
boundary between zone I and zone II of the thin lms structure
zone model (SZM) [40,41], which was explained on the bases of
the residual gas, substrate temperature, dissociation of water in
the chamber and the ion energy. Considering that a shift in the
zone I/zone II boundary is reported by Grovenor et al. [42] for
oxide lms, the minimum obtained for different titanium
composites in this work can also be considered to occur at the
same region (taken into account their different melting points).
Although, in case of titanium, one should also consider that Ti is
a strong getter for oxygen and hydrogen, that can be responsible
for activation of additional processes and the formation of different
phases of titanium oxide and other composites, which makes the
analysis of the results more complex as is experienced in this work.
As mentioned before, this will be further discussed in Section 3.4,
where the results for SIMS analysis are given. In fact, to the best of
our knowledge, the occurrence of the minimum in the X-ray
intensity ratio of diffracted lines, as described above, is not being
explained neither in case of thin lms, using Waltons model [43]
(based on the stability of the critical nuclei, the structure of which
determines the orientation of the lm) to explain the increased
intensity ratio at lower temperature than the minimum, and Lees
model [44] (in which planes with higher surface energy are favored
at higher temperature because they have more ledges) for higher
temperatures than this minimum, nor in case of N
+
ion implanted
W and Mo samples [3739].
However, the formation of different Ti composites in this work,
as mentioned above, could be due to the strong reactivity
Fig. 2. The progress of Ti foil temperature during N
+
ion implantation of 30 keV
energy and uence of 1 10
18
N
+
cm
2
for different initial temperatures.
Table 2a
The d spacing of different titanium nitride lines in A

.
Sample TiN (111) TiN (220) TiN (400) Ti
2
N (111) Ti
2
N (002) Ti
2
N (103) Ti
2
N (212) TiN
0.26
(102) TiN
0.26
(103) Ti
3
N
2-x
(20 14) Ti
3
N
2-x
(10 22)
Ti2 2.5467 1.5063 1.0664 2.2911 1.5161 2.3593 1.2510 1.7381 1.3377 0.9898 0.9182
Ti5 2.5439 1.5014 1.0648 2.2956 1.5120 2.3534 1.2510 1.7326 1.3344 0.9896 0.9174
Ti9 2.5453 1.5054 1.0658 2.2889 1.5174 2.3548 1.2521 1.7375 1.3348 0.9898 0.9184
Ti13 2.5509 1.5129 1.0701 2.2900 1.5210 2.3593 1.2521 1.7381 1.3397 0.9913 0.9194
Table 2b
The crystallite size, D for different titanium composites.
Sample no. Initial temperature T
si
(K) Final temperature T
sf
(K) D
TiN111
A

D
Ti
2
N111
A

D
TiN
0:26
103
A

D
hTi
3
N
2x
1022
A

Ti RT RT - - - -
Ti2 300 654 1600 1630 470 850
Ti5 400 728 730 820 450 450
Ti9 530 793 720 800 400 360
Ti13 673 824 570 520 260 300
M. Firouzi-Arani et al. / Applied Surface Science 256 (2010) 45024511 4505
(gettering effect) of Ti with different gases (residual gases) in the
experimental chamber. Titanium oxide exists on the sample
surface in its different composite forms and can form during
implantation more vigorously as can be recognized from the XRD
results in Fig. 1. These on themselves can perturb the surface
crystallography of the sample while implantation of nitrogen ion in
the sample (again as can be seen in the XRD results) causes the
formation of different titanium nitride composites with different
crystallographic structures/orientations. Hence, in this case, there
exists a complex and amalgamated situation involving different
structures/morphologies (substoichiometric condition), while as
reported in our earlier works [3739], in case of N
+
implanted W
and Mo, we only observed one diffraction line for tungsten nitride
or molybdenum nitride. While the observed minimum in previous
work remained unexplained by the available theories, we believe
that the minima in this work are of the same nature and could be
explained on the same bases, if a theory can be developed for it.
3.2. Surface morphologies obtained by AFM
Surface morphologies of untreated and N
+
ion implanted Ti
samples were observed by AFM and the inuence of substrate
temperature on them has been studied. The 3D surface morpholo-
gy image of untreated Ti, which shows a granular morphology is
given in Fig. 6(a). The 3Dsurface morphology images of Ti samples
implanted with 30 keVN
+
ions at different temperatures are shown
in Fig. 6(be).
In the AFMimages (Fig. 6(be)), the lowest temperature sample
(T
sf
= 654 K) (Fig. 6(b)), distinct grains of columnar structure are
formed on the surface of Ti. At higher temperature of 728 K
(Fig. 6(c)), a sudden change in the structure occurs. The clear
granular structure observed at lowest temperature (T
sf
= 654 K)
disappears and much smaller grains are observed. This might be
due to the preferential sputtering of the original structure (grain
boundaries) which has modied the surface to a nearly homoge-
neous structure (a few large grains that have not been totally
affected by this process can also be seen). In Fig. 4 and Table 3, it
can be seen that the intensities of diffracted lines of Ti
2
N, TiN
0.26
,
and Ti
2
O
3
have increased to a maximumat about this temperature.
Therefore, it may suggest that this temperature is quantitatively
favored for the formation of these composites. Hence, these
reactions could be the other cause of the above-mentioned change
in the lmsurface morphology, producing smaller grains with high
population. By increasing the substrate temperature to T
sf
= 793 K
(Fig. 6(d)), again larger grains are formed, though they are very
different from those in Fig. 6(b). This is due to enhanced surface
diffusion effect at higher temperatures. From the data in Table 3
and Fig. 4, it can be deduced that just before reaching this
temperature, the afore mentioned maximum is shifted to higher
temperature (770 K) which is peculiar to the formation of TiN,
Ti
3
N
2-x
, brookite and anatase phases of Ti-oxide. Hence, it shows
the crystallographic structural changes of the sample by increasing
the temperature. Finally, at highest temperature of 824 K, the
sample surface is covered with homogenous smaller grains. Here,
surface diffusion and the implantation process as well as the
gettering effect have inuenced the formation of different
composites of titanium (Figs. 1 and 4).
The root mean square and the average roughness values R
q
and
R
a
, respectively, obtained from AFM measurements are shown in
Fig. 7. Both R
q
and R
a
follow similar trend and are consistent with
microscopic observations. Typically, at lowest sample tempera-
ture, the roughness has the highest value. When the temperature
increased, due to the diffusion processes, roughness is sharply
decreased and a minimumroughness can be distinguished at about
750 K. However, again at slightly higher temperature of 824 K,
because of activation of more processes in the sample the structure
is changed as described above and the roughness increases to the
same level as that observed for the lowest sample temperature.
3.3. SEM electron micrographs
The comparison of SEM micrographs of untreated and N
+
implanted Ti samples, showed the inadequacy of the SEM in
resolving the structural changes to the degree obtained by AFM.
Therefore, there is no point in further discussing SEM results.
3.4. SIMS depth prole analysis
Fig. 8(ad) showthe SIMS proles for N
+
, Ti
+
and O
+
and C
+
from
untreated and implanted Ti foil for four different nal tempera-
tures of 654, 728, 793 and 824 K. The proles obtained are
Fig. 3. (a) XRD peaks of Ti(002) and Ti
2
N(103) obtained for 30 keV N
+
ions with a
uence of 1 10
18
N
+
cm
2
implanted in Ti sample, tted to two Voigt functions
and a level background. (b) XRD peaks of Ti(110) and B(160) obtained for 30 keV N
+
ions with a uence of 1 10
18
N
+
cm
2
implanted in Ti sample, tted to two Voigts
functions and a level background.
M. Firouzi-Arani et al. / Applied Surface Science 256 (2010) 45024511 4506
analyzed in two ways, shown in Fig. 9(a and b). The area under
each curve, peculiar to each temperature was obtained, as a
measure of the amount (density) of the implanted nitrogen ions
and O
+
, C
+
and Ti
+
sputtered fromthe Ti samples (Fig. 9(a)). Ideally,
in order to investigate the penetration depth quantitatively, the
sputtering time should be converted to depth. This requires some
means of measurement of the depth of the crater formed, such as
large scan AFM or a suitable prolometer. Unfortunately, we did
not have access to such instruments, hence the results presented
here can be considered as qualitative information. The results
show that, there exists a maximum for both N
+
and O
+
curves at
about 730 K, while C
+
density decreases with temperature and
shows a minimumat 790 K. A similar behavior to that of N
+
and O
+
density variation is observed for the penetration depth of N
+
in Ti
samples (Fig. 9(b)). One may correlate the maximum obtained for
the area (density) and the penetration depth at about 730 K in
Fig. 9(a) and 9(b) to the maximumintensity of the diffraction lines
obtained for Ti
2
N, TiN
0.26
and Ti
2
O
3
in the XRD results summarized
in Table 3 fromFig. 4 (see Figure 4(b), 4(c) and 4(f)). InFig. 4, it can
be observed that the intensity of all of the diffraction lines
belonging to Ti
2
N, TiN
0.26
and Ti
2
O
3
decreased to one half of their
maximum at 790 K. Hence, it may be concluded that these three
composites are almost in their lowest density at this temperature
region and the minima obtained for both N
+
and O
+
densities and
the N
+
penetration depth in Fig. 9 (a and b) are due to this
phenomenon, while one should also consider the fact that the
Fig. 4. (a) The intensity of X-ray diffraction fromdifferent lines of Ti, titaniumnitride and titaniumoxide. (a) Ti, (b and c) Titaniumnitride, (d) Brookite, (e) Anatase, (f) Ti
2
O
3
, as
a function of nal temperatures.
Table 3
Position/temperature of the maximum intensity of diffraction lines for different
titanium composites.
Titanium composition Maximum intensity temperature
Ti
2
N 730K
TiN
0.26
730K
Ti
2
O
3
730K
TiN 770780K
Ti
3
N
2-x
770780K
Anatase (TiO
2
) 760K
Brookite (TiO
2
) 770780K
M. Firouzi-Arani et al. / Applied Surface Science 256 (2010) 45024511 4507
density of other titanium nitride composites (see Fig. 4b and 4c)
which have their maximum values at 770 to 780 K, is much less
than the sum of Ti
2
N and TiN
0.26
(the intensity for TiN
0.26
(103) is
dominant on all other intensities (Fig. 6c)). However, one may
relate these changes (loss of N
+
, O
+
and Ti
+
) at 790 K and their
maxima about 730 K to the variation of carbon inclusion
(contamination). As it can be seen in Fig. 10, the C
+
/Ti
+
ratio
shows a broad minimumat 730 K (corresponding to the N
+
, O
+
and
Ti
+
maxima in Fig. 9) and a maximum at 790 K (corresponding to
the N
+
, O
+
and Ti
+
minima in Fig. 9). Therefore, it may be concluded
that there exist a correlation between the results of SIMS and XRD
in this work. The re-increase of both N
+
and O
+
densities and N
+
penetration depth at higher temperatures is due to summation of
the intensities of all of the diffraction lines of titanium-oxide and/
or titanium-nitride and their phases. In addition, careful examina-
tion of the AFM results in Fig. 6 shows that after initial sputtering
of the grain boundary at 728 K temperature, the morphology of the
surface consists of small bright hillocks with a wavy background
that changes to more prominent grains with valleys/grooves (grain
boundaries) between them and bright hillocks within them. This
Fig. 6. AFM images of untreated and N
+
ion (30 keV, with a uence of 1 10
18
.N
+
cm
2
) implanted titanium at different nal temperatures. (a) untreated; (b) T
sf
= 654 K; (c)
T
sf
= 728 K; (d) T
sf
= 793 K; (e) T
sf
= 824 K.
Fig. 5. (a) The intensity ratio of different titanium-niride and titanium-oxide
compositions as a function of nal temperature.
Fig. 7. Root mean square roughness and average roughness of Ti samples produced
at different nal temperature.
M. Firouzi-Arani et al. / Applied Surface Science 256 (2010) 45024511 4508
may be accepted as the phase transformation (compositional
changes) conrming the above discussion.
The above-mentioned analyses of XRD and SIMS showed the
formation of titanium nitride by N
+
ions implantation into Ti foils
while Ti-oxide is also formed due to strong gettering property of
titanium. The process of titanium nitride formation and occurrence
of a maximum in the plot of titanium nitride intensity versus
temperature may be explained by considering both the residual gas
behavior in the chamber and the role of substrate temperature on
the residual gas reaction with Ti surface as well as the gettering
property of Ti, as follows: the residual gas in the chamber contains
oxygen via CO, CO
2
and decomposition of water at higher
temperatures explained in the following paragraph. This oxygen
can react easily with the fresh Ti surface. This reaction enhances by
increasing the substrate temperature, as it is well known that the
oxide becomes thermodynamically more stable at higher tempera-
tures [45,46]. If one plots the ratio of N
+
/Ti
+
and O
+
/Ti
+
from the
results of SIMS presentedinFig. 9(a) versus temperature (T
sf
), which
is shown in Fig. 10, it can be observed that there exists a maximum
for both of these ions at a substrate temperature between 790 and
800 K and that O
+
content in the sample is less than N
+
.
Hence, by increasing the substrate temperature, the oxide and
nitride build up together on the Ti surface. This can be
quantitatively concluded from the results presented in Fig. 4
(discussed in Section 3.1) and the N
+
/Ti
+
and O
+
/Ti
+
ratios resulted
fromthe SIMS analysis (Fig. 10). In Fig. 10, it can be seen that both
N
+
/Ti
+
and O
+
/Ti
+
ratios increase almost with the same rate up to
730 K substrate temperature, then N
+
/Ti
+
ratio becomes dominant.
The formation energy of Ti-oxides [47] is the highest among the
Ti-compounds, and although the oxygen content in the vacuum
system is very low compared to the nitrogen, Ti-oxides and Ti-
nitrides form together near the surface layer, while nitrogen ions
due to their energetic as well as their higher uence
(1 10
18
N
+
cm
2
) relative to the oxygen not only can penetrate
in deeper layers but also cause higher density as can be seen in
Fig. 9(a).
Hence, when titanium oxide is in near surface layers, the
formation of titanium nitride is thermodynamically unfavorable.
This process is usually the cause of decreasing metal (e.g., Wor Mo)
nitride intensity and the presence of a minimum [3739,48]
(though in the titaniumcase we have observed a maximum, which
will be explained further in the following text). However, this
thermodynamically unfavorable reaction becomes possible when
the oxide becomes a reactive suboxide Ti
2
O
3x
that results from
preferential oxygen sputtering, which perhaps becomes enhanced
by increasing the substrate temperature that transfers higher
Fig. 8. SIMS proles of implanted titanium with N
+
ions of 30 keV energy and a uence of 1 10
18
N
+
cm
2
at different temperatures. (a) N
+
proles; (b) Ti
+
proles; (c) O
+
proles; (d) C
+
prole.
M. Firouzi-Arani et al. / Applied Surface Science 256 (2010) 45024511 4509
energy to oxygen atoms, so that their binding to Ti atoms can break
more easily. The dissociated oxygen reacts with the bombarding
nitrogen ions at the surface to form Ti
x
(N,O). With further ion
implantation, Ti
x
(N,O) gradually transforms into Ti
2
N and TiN
0.26
and other Ti-nitride composites. Here, one should emphasize on
the role of gettering property of titanium, since this can violate
many usual expected reactions between metal and oxygen and the
fact that there exist many different phases of titanium oxide and
nitride, each of which may favor a different condition for formation
(e.g., different temperature as discussed in detail in Section 3.1 and
the SIMS results for N
+
/Ti
+
and O
+
/Ti
+
ratios) and occurrence of a
maximum mentioned above instead of a minimum.
The existence of oxygen in the vacuum chamber and
particularly around the heated substrate holder is reported by
Savaloni et al. [36], who used a quadrupole mass spectrometer and
analyzed the partial pressure of the residual gas inside their UHV
chamber (base pressure of 10
10
mbar; evaporation pressure of
10
8
to 10
7
mbar) before and after deposition of erbium as a
function of substrate temperature. They reported that the
substrate holder assembly is an important site for out gassing
and for reactions, including those between deposited erbium and
residual gases. In particular, they found that water decomposes at
about 600 K (see Fig. 4 in reference [16]). They suggested that the
water and its products arise from out gassing and reactions at the
substrate and substrate holder. They also related the low partial
pressure of oxygen to its rapid reaction with deposited erbium.
Therefore, as mentioned above, there should be oxygen of different
concentration (depending on the substrate temperature) around
the heated sample, which can react with Ti surface to form Ti-
oxides, that initially forms on the titanium surface.
It is also worthto mention that the pressure in our chamber (i.e.,
10
5
mbar) is much higher than Savaloni et al.s work (10
10
mbar) [36]. Therefore, there should be much higher partial
pressure for residual gases, in particular for water. Hence at high
temperatures (e.g., > 500 K), there should be a large amount of
oxygen and hydrogen as a result of decomposition of water and out
gassing from substrate holder assembly in the vacuum chamber.
The distribution of N
+
ions of 30 keV implanted in Ti foil was
also simulated using SRIM2000 code. The nominal N
+
ion average
projected range (R
p
= 53.5 nm), straggling (DR
p
= 23.3 nm), maxi-
mum/peak nitrogen concentration (C
p
= 1.5 10
23
atoms/cm
3
)
and the expected sputtering rate (R
S
= 0.4804 atoms/ion) at the end
of implantation process (i.e., after 99000 ions implanted), were
obtained. With respect to the results of the sputtering rate, it
should be noted that since the binding energy of the surface atoms
for titaniumis not available, the heat of sublimation is used instead
in the SRIM2000 calculation, which apparently does not predict the
realistic values and should be considered as a rough estimate. It
should also be noted that the role of temperature, ion uence and
some other parameters, such as surface roughening, hence change
of surface binding energy are not included in SRIM2000 computer
simulation code.
4. Conclusions
The surface nano-structural modications of titaniumfoil/sheet
samples (0.5 mm) made by nitrogen ions at different temperatures
are studied by means of XRD, AFM, SEM and SIMS. XRD patterns
clearly showed the formation of different Ti-nitride and Ti-oxide
composites. AFM images, at lowest temperature, showed the
formation of grains that after initial sputtering of the grain
boundary at 728 K temperature by implanted N
+
ions the
morphology of the surface changed from small and wave-like
grains to more prominent grains with bright hillocks within them
(bimodal grain distribution indicative of phase transformation/
compositional changes).
The SIMS results showed a maximum at about 730 K and a
minimum at about 790 K for both N
+
density and depth of N
+
penetration. A correlation between the XRD and SIMS results as
well as those obtained from AFM analysis was achieved. The
variation of these results with temperature was explained on the
basis of the residual gas, substrate temperature, dissociation of
water in the chamber, carbon contamination and the gettering
property of titanium.
Acknowledgements
This work was carried out with the support of the university of
Tehran and the I. A. university. H. S. is grateful to the Institute for
Research and Planning in Higher Education for the partial support
of this work.
Fig. 9. (a) N
+
, O
+
, C
+
and Ti
+
ions densities and (b) penetration depth of N
+
ions in Ti
versus nal temperature for 30keV N
+
ion with a uence of 1 10
18
N
+
cm
2
implanted in titanium sample.
Fig. 10. Density ratios of N
+
/Ti
+
, O
+
/Ti
+
and C
+
/Ti
+
, from data presented in Fig. 9.
M. Firouzi-Arani et al. / Applied Surface Science 256 (2010) 45024511 4510
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