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Comparison of WTi and WTi(N) as diffusion barriers for Al and Cu

metallization on Si with respect to thermal stability and diffusion
behavior of Ti
M. Fugger a,b,⇑,1, M. Plappert c,d,1, C. Schäffer c, O. Humbel c, H. Hutter b, H. Danninger b, M. Nowottnick d
a
KAI – Center of Expertise in Automotive and Industrial Electronics GmbH, Europastraße 8, 9524 Villach, Austria
b
Vienna University of Technology, Institute of Chemical Technology and Analytics, Getreidemarkt 9, 1060 Wien, Austria
c
Infineon Technologies Austria AG, Siemensstraße 2, 9500 Villach, Austria
d
University of Rostock, Institute of Electronic Applications and Circuits, 18059 Rostock, Germany

articleinfo
abstract
Article history:
Received 26 August 2013 The thermal stability of WTi and WTi(N) as diffusion barriers for Al and Cu metallization on Si (10 0)
Received in revised form 10 March 2014 was investigated by time of flight secondary ion mass spectrometry (ToF-SIMS) depth profiling, X-ray
Accepted 30 April 2014 diffrac- tion (XRD), electron microscopy (SEM and TEM) and X-ray photoelectron spectroscopy (XPS).
Available online xxxx For both, Al and Cu, Ti diffusion out of WTi into the metal was proved to occur at elevated temperatures
(400 °C for Al and 600 °C for Cu) which further results in barrier film failure. Nitrogen incorporation
Keywords: into WTi leads to an elimination of the Ti diffusion and consequently to a better thermal stability of the
Diffusion barrier film. It is shown that besides crystal structure, Ti diffusion into the metallization is an essential
Diffusion barrier factor of the barrier failure mechanism. The failure temperature for Al is lower than for Cu.
Thin films © 2014 Elsevier Ltd. All rights reserved.
ToF-SIMS
WTi
WTiN

+43 4242 34890 99.

E-mail address: Michael.fugger@k-ai.at (M. Fugger).
1. Introduction 1
Authors with equal contribution.

Aluminum and copper are widely used as metallization in semi-

conductor devices but they cannot be applied in direct contact to
silicon without a diffusion barrier. Si reacts with Al because of a
Si solubility in Al up to 0.5% at standard semiconductor assembly
and process temperatures (up to 450 °C) which leads to Al spiking
[1–2]. Copper on the other hand reacts with silicon at the Cu/Si
interface region to Cu3Si already at low temperatures (150 °C) [3–
5]. The formation of Cu3Si on the one hand causes stress due to
the different thermal expansion coefficient of the Cu film, the
silicide film and Si [6] and on the other hand catalyzes the oxida-
tion of the Si substrate [7]. Due to these facts diffusion barriers
are introduced between the metallization (Al, Cu) and Si to prevent
device failure. Diffusion barriers consisting of WTi were investi-
gated for both metals in former studies with respect to failure tem-
perature and barrier stability depending on the crystal structure of
the barrier film [8–12]. It is shown that the crystal lattice switches

⇑ Corresponding author at: KAI- Center of Expertise in Automotive and Industrial

Electronics GmbH, Europastraße 8, 9524 Villach, Austria. Tel.: +43 4242 34890; fax:
Please cite this article in press as: Fugger M et al. Comparison of WTi and WTi(N) as diffusion barriers for Al and Cu metallization on Si with respect to
thermal stability and diffusion behavior of Ti. Microelectron Reliab (2014), http://dx.doi.org/10.1016/j.microrel.2014.04.016
 failure model of Ti diffusion and why nitrogen incorporation leads
from bcc to fcc when N 2 is incorporated and smaller grains were to a higher temperature stability for Al and Cu metallization.
build which leads to a superior barrier performance. The present Furthermore it will be outlined for which of the two metals the
investigation focuses on the thermal stability of the barrier and barrier perfor- mance is better.
the diffusion behavior of its components. In contrast to previous
researchers also the influence of different annealing times at a
2. Experimental
con- stant temperature on barrier performance was investigated.
In a previous investigation the diffusion of Ti out of WTi into Al
Float zone silicon wafers with 200 mm in diameter, (100) ori-
which leads to a barrier breakdown was proved [1]. In addition,
entation and a phosphorus (P) adjusted resistivity of 65 X cm were
this work describes the Ti diffusion for Cu metallization and
used for the investigations. Removal of native silicon oxide and
explains why WTi(N) is an option to prevent Ti diffusion for Al as
organic and inorganic particles was done in HF (1 wt.%) for 7 min
well for Cu metallization. ToF-SIMS depth profiling certified the
and in standard clean-1 (SC-1) and standard clean-2 (SC-2) in a

http://dx.doi.org/10.1016/j.microrel.2014.04.016
0026-2714/© 2014 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Fugger M et al. Comparison of WTi and WTi(N) as diffusion barriers for Al and Cu metallization on Si with respect to
thermal stability and diffusion behavior of Ti. Microelectron Reliab (2014), http://dx.doi.org/10.1016/j.microrel.2014.04.016
2 M. Fugger et al. / Microelectronics Reliability xxx (2014) xxx–xxx

chemistry bench [13]. The deposition of the metallization stack WTi thin films specified in Section 2 were analyzed on micro-
was done immediately after etching and cleaning in an industrial structural properties after deposition. Fig. 1 shows the X-ray
scale magnetron sputtering equipment with a multi chamber
alignment. This configuration allows deposition of the metalliza-
tion stack in situ without a vacuum break to prevent the
formation of native oxides at the interface of the metal (Al and
Cu) and WTi. Deposition of the barrier layer (50 nm) and the
metal layer was done in separate chambers. The barrier layer
was deposited analo- gous to [1] to compare the WTi barrier
layer produced with equal process parameters. A WTi (30 at.%
Ti) target was used. The process pressure during sputtering was
adjusted by a constant argon (Ar) and nitrogen (N2) gas flow. Ar
was used as discharge gas and N2 as the reactive component in a
partial ratio of 0.33 for the WTi(N) barrier thin film. A 50 nm
thick WTi layer was deposited with a constant deposition rate of
a few nm/s. The stoichiometry of WTi is depending on the N 2
flow and derived between 24 and 27 at.%. Deposition of the
1000 nm Al was done in situ with 9.6 kW target power and Ar as
a discharge gas at a base pressure of 1.0 m 10—7 mbar. During
deposition the platen was heated up to 300 °C. The deposition
rate was 18 nm/s. Deposition of the 1000 nm Cu layer was done
in situ in another sputtering chamber. The target power was set
to 4 kW. Ar was used as discharge gas at a base pressure of
1.0 m 10—7 mbar. The samples were annealed in N2 atmosphere to
avoid oxidation, especially for the Cu film. The Al/barrier/Si sam-
ples were annealed at 400 °C for 8 h and 16 h. For the Cu/barrier/
Si samples other temperature conditions were necessary to com-
pare the results due to Ti diffusion with Al metallization. The
annealing conditions for Cu metallization were 400 °C for 8 h,
600 °C for 4 h, 16 h and 48 h and 650 °C, 700 °C, 750 °C and
800 °C for 4 h each.
For film characterization a X-ray fluorescence measuring sys-
tem and a capacitive wafer bow measurement tool were used.
The mechanical film stress was determined by using the Stoney
equation [18]. X-ray diffraction (XRD) was carried out using a
PAN- alytical X0 Pert PRO Bragg–Brentano diffraction tool. For
analysis
the Cu Ka (k1 = 1.5406 Å and k2 = 1.5444 Å) line was used. To detect
the contact resistance we used a MOS structure with highly p and n
doped areas. For Al spiking analysis the Al metallization was wet
chemically removed with phosphoric acid (H 3PO4) and nitric acid
(HNO3) after annealing to analyze the WTi layer. For imaging the
surface and the cross section of the metal/barrier/Si stack we used
a scanning electron microscope (SEM) and a STEM and HRSTEM.
By using a dual beam-FIB and in situ lift out technique in a FEI DB
Strata400 a lamella was prepared out of the sample for TEM.
A TOF.SIMS5 by ION-TOF GmbH was used to investigate diffu-
sion processes and elemental distribution of the layer films. Depth
profiles were taken using static SIMS. A bismuth liquid metal ion
gun (LMIG) was used to generate elemental information and layer
by layer removal was carried out with a dual source column (DSC).
The LMIG was operated using Bi3+ clusters in a high mass resolu-
tion mode. The analysis area was 100 lm × 100 lm. Sputtering
of the sample surface was executed using O 2+ in the DSC. It has to
be considered that the sputter rate of O2+ is different for every
material. This results in different sputter times for the Al and the
Cu layer.
The XPS analysis of WTi was done in a Kratos AXIS Nova with
an Al Ka X-ray source on the WTi surface and after sputtering
removal of 15 nm.

3. Results

3.1. Barrier film characterization

Please cite this article in press as: Fugger M et al. Comparison of WTi and WTi(N) as diffusion barriers for Al and Cu metallization on Si with respect to
thermal stability and diffusion behavior of Ti. Microelectron Reliab (2014), http://dx.doi.org/10.1016/j.microrel.2014.04.016
Fig. 1. XRD patterns of 50 nm WTi and 50 nm WTi(N) deposited on Si (10 0)
substrate.

diffraction (XRD) pattern for the WTi and the WTi(N) films.
The XRD measurement for WTi indicates the W (110) peak
slightly shifted to lower angles indicating a larger unit cell. The
shift is a result of the presence of Ti besides W building a mixed
crystal. Similar conclusions are found by Qingxiang et al. [10].
There is only a single peak that refers to the WTi layer. The
structure of the WTi film is body-centered cubic (bcc). This
result is in good agreement with previous research found in
literature [9,12,14,15].
The XRD result for the WTi(N) film shows also a single peak.
The H value can be referred to WN (100) or TiN (200). The
two phases cannot be separated clearly which indicates a mixed
phase of the two nitrides. The structure of the WTi(N) film is
face-centered cubic (fcc). The absence of the W (110) peak
suggests a full reaction of the layer components with N 2.
Raaijmakers et al. [9] pronounce a change in the structure of
the WTi(N) film from bcc to fcc if the N2 content in the gas
flow is increased to more than 10% [9]. This is in good
agreement with other researchers [15] and the WTi(N)
barrier film established in this work.

Fig. 2. HRSTEM micrograph of WTi(N) indicating a polycrystalline structure.

Please cite this article in press as: Fugger M et al. Comparison of WTi and WTi(N) as diffusion barriers for Al and Cu metallization on Si with respect to
thermal stability and diffusion behavior of Ti. Microelectron Reliab (2014), http://dx.doi.org/10.1016/j.microrel.2014.04.016
 M. Fugger et al. / Microelectronics Reliability xxx (2014) xxx–xxx 3
WTi 15 n/a n/a 6.1 66.6

Fig. 2 shows a HRSTEM micrograph of the WTi(N) thin film. A

polycrystalline structure is visible and even the grain size of 5–
10 nm can be seen. The visibility of all grains is strongly dependent
on the lamella thickness and the grain orientation. EELS and EDX
spectra on this layer did not show single Ti/TiN crystal or a segre-
gation of Ti/TiN to grain boundaries. Therefore it can be assumed
that Ti/TiN and W/WN form a mixed phase W–Ti–N. To confirm
nitrogen incorporation and generation of WN or TiN an XPS analy-
sis on the WTi(N) layer was performed (Table 1).
The devices for XPS analysis were prepared without an
encap- sulating Al layer. Therefore the XPS analysis was done
after in situ sputtering removal of 15 nm barrier film to avoid
measuring surface oxidation. A nitridation is significantly
detected in N1s detailed spectra calculated to a total amount
of nitrogen of
10.2 at.%. A classification to TiN and WN is not possible because
of peak super positions. Spectra of Ti2p show an increased signal
detected at 455.8 eV representing TiN. WN x is not significantly ver-
ified at 31.4 eV in W4f spectra because of a superposition to a W
peak. Because of the proportion of the increased N2s spectra com-
pared to nitride content in Ti2p detailed spectra it can be supposed
that a WNx quantity is hidden in super positioned W peak at
31.4 eV. The TiO2 level falls below the detection limit after sputter-
ing up to 15 nm depth. The oxygen content shown originates from
oxidized sample surface and organic adsorbates. These organics are
visible in C1s detail spectra and carbon ratio (not listed). The differ-
ence in Ti content compared to XRF measurements could be a
sequence of a sputter yield difference of W and Ti described in
[1] because Ar is used as sputtering gas.
Concluding film properties are shown in Table 2. It is clearly vis-
ible that the Ti content is increasing in case of WTi(N). It has to be
considered that all films have been sputtered without an additive
bias and because of that the Ti content is higher in case of WTi
without N2 addition [1]. A higher Ti content in case of WTi(N) could
be a consequence of reduced re-sputtering of Ti because of built
TiN in the barrier film. The film stress is significantly increasing
due to N2 incorporation. The specific sheet resistance is increasing
by a factor of about 4 due to incorporation of nitrogen. It has been
seen that the N incorporation also leads to a higher contact resis-
tance by a factor of 2 in case of highly doped p and n areas com-
pared to WTi.
Comparison of WTi and WTi(N) clearly shows that the grain size
is decreasing from 13–15 nm to 5–10 nm, if N 2 is added reactively
[1,8]. The grain size of WTi(N) is consistent with previous investi-
gations [9].

3.2. Results for aluminum metallization

In our previous investigation it has been shown that the main

failure mechanism for WTi with Al(Cu) metallization is Ti
diffusion out of the barrier into the Al layer. A time and
temperature depen- dency with calculated activation energy of
2.28 eV was shown [1]. Up to 16 h and 400 °C a leading Ti
diffusion into the Al layer was measured which leads to defects
in the barrier film and conse- quently enhance the diffusion
paths for Al through the WTi film. In addition, the present
publication focuses on a reactively sput- tered WTi(N) barrier
under the same temperature conditions and

Table 1
XPS results for 50 nm WTi and 50 nm WTi(N) on Si (10 0).

Sputtered (nm) N (at.%) O (at.%) Ti (at.%) W (at.%)

WTi(N) 0 9.2 42.1 8.7 21.5
WTi(N) 15 10.2 n/a 9.4 61.0
WTi 0 n/a 46.5 8.0 24

Please cite this article in press as: Fugger M et al. Comparison of WTi and WTi(N) as diffusion barriers for Al and Cu metallization on Si with respect to
thermal stability and diffusion behavior of Ti. Microelectron Reliab (2014), http://dx.doi.org/10.1016/j.microrel.2014.04.016
 Table 2
Barrier film properties for 50 nm WTi and 50 nm WTi(N).

WTi WTi(N) (0, 33)

Ti content (at.%) 24 28
Mechanical film stress (GPa) —1.27 —4.48
Specific sheet resistance (X m) 0.58—6
2.06—6

Structure bcc fcc

Grain size (nm) 21, 13–15 [8], 78 [1] 5–10, =10 [1]
Deposition rate (nm/s) 2.29 1.81

compares the diffusion behavior of Ti. The pronounced failure

mechanism could be confirmed and was compared with WTi(N)
which is an estimated more dense barrier. In Fig. 3 the SEM
results of these experiments are shown. A 50 nm WTi (a) to a 50
nm WTi(N) (b) was compared after a 400 °C temperature storage
for 16 h with 1000 nm Al as metallization. According to [1] the
identi- cal temperature and time dependency were used, where a
high Ti diffusion and a barrier breakdown are expected. Although
the Ti content in [1] is lower (due to RF bias supply) the diffusion
profile remains the same. After removing the Al and the barrier
layer the diffusion of Si and Al, respectively the barrier breakdown
can be detected on the basis of Al spiking. This is clearly seen
in Fig. 3(a) with a sputtered WTi barrier without nitrogen
incorpora-
tion. Al spiking up 5 lm in width is detected. In contrast to this
the
reactively sputtered, N containing barrier shows a higher barrier
density because of absence of Al/ Si diffusion and therefore no Al
spiking is observed (Fig. 3(b)). Even after 24 h at 400 °C (not
shown) no barrier breakdown is visible. Fig. 4 shows the ToF-
SIMS depth profiles from an identical sample as shown in Fig. 3
but before removing the metal layers. In Fig. 4(a) the Ti profiles of
annealed samples are shown and in Fig. 4(b) the Si signals,
respec- tively. In both profiles sputter times <1200 s represent the
Al layer and >1200 s the WTi and WTi(N) layer. A higher Si
content in the Al layer of the WTi sample in Fig. 4(b) proves the
barrier breakdown and agrees with to the optical spiking results
shown in Fig. 3(a). The Ti signal shown in Fig. 4(a) shows the
effect of reactive sputter- ing. The sample with the WTi(N) barrier
showed a distinctly reduced Ti diffusion after this temperature
treatment. According to optical spiking results shown in Fig. 3
we can conclude that the superior barrier density is a result of
the reduced Ti diffusion following from reactive sputtering. There
is no phase reaction between Al and Si or Ti. Above 250 °C Si is
solvable in Al but pre- cipitates again at lower temperatures. No
phase between Ti and Al is formed at these low temperatures.
As concluded from XRD and XPS analysis nitrogen is bound to Ti
building TiN which pre- vents a Ti loss in WTi(N) because of a
more inert behavior of TiN compared to Ti. Therefore the crystal
structure of WTi(N) is con- served and the barrier performance as
well. It has to be noted that the superior barrier density could also
be an interaction with a more dense structure followed by smaller
grains [16]. To get an idea of the influence of the nitrogen content
in the WTi(N) barrier the results were compared to a WTi(N) film
with half of the nitro- gen content. The results were slightly better
than for pure WTi but worse than the described WTi(N) barrier.
This indicates that a cer- tain amount of nitrogen is necessary to
get a proper improvement of the barrier density.

3.3. Results for copper metallization

To compare the results for Cu metallization with those of Al the

Cu/WTi/Si samples were annealed at 400 °C for 8 h. As shown in
Fig. 5(a) the Ti signal in the ToF-SIMS depth profile does not indi-
cate any Ti diffusion into the Cu layer at these conditions. The
WTi film also remains stable against Cu diffusion and Cu 3Si
forma- tion. The annealing temperature was therefore increased
up to
Please cite this article in press as: Fugger M et al. Comparison of WTi and WTi(N) as diffusion barriers for Al and Cu metallization on Si with respect to
thermal stability and diffusion behavior of Ti. Microelectron Reliab (2014), http://dx.doi.org/10.1016/j.microrel.2014.04.016
4 M. Fugger et al. / Microelectronics Reliability xxx (2014) xxx–xxx

Fig. 3. SEM images of (a) 50 nm WTi and (b) 50 nm WTi(N) after 400 °C for 16 h and removal of Al and the barrier film.

Fig. 4. ToF-SIMS depth profiles of (a) Titanium and (b) Silicon into aluminum after 400 °C for 16 h.

600 °C for 4 h. In this case, Ti diffusion out of the WTi film into temperature.
the Cu layer occurred which is outlined in Fig. 5(a). However,
the bar- rier still remained stable against Cu diffusion and Cu3Si
formation. A further increase of the temperature up to 650 °C
for 4 h results in formation of a Cu3Si layer proved by XRD in
Fig. 6(a). The growing silicide phase forced W and Ti to the
sample surface (Fig. 5(a)). During annealing up to 600 °C grain
growth occurred in the Cu layer (Fig. 7). The phenomenon of Cu
grain growth with increasing temperature has been described in
detail by Kwon et al. [17]. Grain growth also increases the
surface roughness which leads to a broader Ti signal in the ToF-
SIMS depth profiles after annealing (Fig. 5). This important fact
has to be considered when interpreting the depth profiles
otherwise the signal broadening could be misin- terpreted as
barrier degradation. The Cu/WTi/Si system has also been
investigated by other researchers. Wang et al. [8] propose a
barrier failure at 700 °C after 1 h annealing for 100 nm WTi
(10 wt.% Ti). No results for 650 °C are given. Ramarotafika et al.
[11] also present a failure temperature for Cu/WTi/Si of 700 °C.
A
100 nm thick WTi (30 at.% Ti) film was used and rapid thermal
annealing (RTA) for 30 s was carried out. Ti diffusion into the Cu
layer at 600 °C is also mentioned [11] but not described in detail.
However, Chiou et al. [15] pronounce a barrier failure after
775 °C for 200 nm Cu/60 nm WTi/Si. The samples were annealed
for 30 s with rapid thermal annealing. Most of these results are
in good agreement with the experiments done in the present work.
However, some discrepancies may occur due to a different sample
setup and heat treatment procedure. The present results compared
to other researchers show that the film thickness, the annealing
time and the barrier composition have an influence on the failure
Please cite this article in press as: Fugger M et al. Comparison of WTi and WTi(N) as diffusion barriers for Al and Cu metallization on Si with respect to
thermal stability and diffusion behavior of Ti. Microelectron Reliab (2014), http://dx.doi.org/10.1016/j.microrel.2014.04.016
 To investigate the factor of annealing time on the diffusion
behavior of Ti into the Cu layer the temperature was kept
constant at 600 °C and the annealing time was varied. Thermal
treatment was carried out for 4 h, 16 h, and 48 h. An overlay of
the Ti signals measured by ToF-SIMS analysis is shown in Fig.
5(b). Ti diffusion increases up to 16 h of annealing at 600 °C.
The depth profile shows
that the Ti content rises to the Cu surface, indicating Ti
diffusion there. After 48 h at 600 °C Cu3Si spots (5–15 lm)
occur all over the sample surface. The result is outlined in
the SEM image in Fig. 7(a). The presence of Cu3Si on the
sample surface explains
the stagnating Ti signal for the 48 h anneal in Fig. 5(b). As men-
tioned in chapter 2 the total analysis area in ToF-SIMS was
100 lm 100 lm for all samples. The presence of Cu 3Si in the ×
analysis region after 48 h annealing reduces the area of the
Cu
layer and therefore also the Ti intensity.
The results show that annealing time plays an important role
on the stability of WTi as diffusion barrier for Cu. Increasing
diffusion of Ti out of WTi into Cu as a factor of heat treatment
duration is proved up to 16 h at 600 °C. After 48 h at 600 °C no
reliable predic- tion of increasing Ti diffusion can be made due
to the presence of Cu3Si in the analysis area. But it can be
assumed that the diffusion of Ti has further increased and
enhanced the formation of defects in the barrier film and
consequently the barrier failure.
The investigation of the Cu/WTi(N)/Si layer stack was done
analogous to the experiments for WTi. Compared to the WTi
barrier, the WTi(N) film remained stable for 4 h at 650 °C. The
ToF-SIMS depth profile in Fig. 5(c) does not show any sign of Ti
dif- fusion into the Cu layer nor any formation of Cu 3Si which
indicates that the WTi(N) film remained stable against Cu
diffusion. Increas- ing the temperature in 50 °C steps (4 h each)
provides a failure

Please cite this article in press as: Fugger M et al. Comparison of WTi and WTi(N) as diffusion barriers for Al and Cu metallization on Si with respect to
thermal stability and diffusion behavior of Ti. Microelectron Reliab (2014), http://dx.doi.org/10.1016/j.microrel.2014.04.016
 M. Fugger et al. / Microelectronics Reliability xxx (2014) xxx–xxx 5

Fig. 5. Ti signals in ToF-SIMS depth profiles of (a) Cu/WTi/Si annealed up to 650 °C for 4 h, (b) Cu/WTi/Si annealed at 600 °C up to 48 h, (c) Cu/WTi(N)/Si annealed up to 800 °C
for 4 h and (d) Cu/WTi(N)/Si annealed at 600 °C up to 48 h.

Fig. 6. XRD patterns of (a) Cu/WTi/Si after 650 °C for 4 h and (b) Cu/WTi(N)/Si after 800 °C for 4 h.

temperature for the WTi(N) system of 800 °C for 4 h isothermal

degradation is documented in Figs. 5(c) and 6(b). The results thus
soaking time. Up to 750 °C no Ti diffusion occurred which is figured
show a notable improvement of the barrier properties after incor-
out in Fig. 5(c). At 800 °C for 4 h Cu3Si formation and barrier
porating the WTi system with nitrogen. A remarkable difference to
Please cite this article in press as: Fugger M et al. Comparison of WTi and WTi(N) as diffusion barriers for Al and Cu metallization on Si with respect to
thermal stability and diffusion behavior of Ti. Microelectron Reliab (2014), http://dx.doi.org/10.1016/j.microrel.2014.04.016
6 M. Fugger et al. / Microelectronics Reliability xxx (2014) xxx–xxx

Fig. 7. SEM image of (a) surface of Cu/WTi/Si (Cu 3Si spot indicates barrier failure) and (b) surface of Cu/WTi(N)/Si after 600 °C for 48 h.

the plain WTi barrier film is the absence of Ti diffusion into the Cu failure mechanism for both metallization variants. It could be
layer during the whole temperature range. As concluded from XRD
and XPS analysis Ti is bound to nitrogen which prevents the emi-
gration of Ti into the Cu layer and consequently the formation of
defects in the barrier film.
The incorporation of nitrogen into WTi to improve barrier per-
formance is already outlined in literature. Chiou et al. [15] investi-
gated a 60 nm WTi(N) barrier for 180 nm Cu which was sputtered
in an Ar:N2 = 1:5 ambient pressure. The WTi(N) remained stable up
to 1000 °C for 30 s rapid thermal annealing [15]. Qingxiang et al.
[10] used an amorphous 50 nm WTi(N) barrier for a 200 nm Cu
layer. WTi (10 wt.% Ti) was deposited in an Ar:N 2 = 5:1 ambient
pressure. First signs of Cu3Si spots were observed after
annealing at 700 °C for 1 h [10]. A barrier composition of
WTi(N) produced in an Ar:N2 = 4:1 ambient pressure was
investigated by Ramarotaf- ika et al. [11] for a 300 nm Cu layer.
The system endured a heat treatment at 800 °C for 30 s rapid
thermal annealing. No failure temperature is referred [11]. The
failure temperatures for a Cu/WTi(N)/Si setup mentioned in the
literature differ from each other and are also different to the
results in the present work. But it has to be recognized that the
Ar:N2 ratio used for reactive sputtering of WTi varies between
the researches. This fact presumes that the Ar:N2 ratio plays an
important role on barrier performance. Also the thickness of the
layer system is not the same and different annealing procedures
were used.
The WTi(N) barrier was also compared to a WTi(N) film with
half of the nitrogen content. The result was similar to Al. The bar-
rier performance was better than for pure WTi but worse than the
described WTi(N) film.
The barrier stability for different annealing times at a constant
temperature (600 °C) for Cu/WTi(N)/Si was also studied analogous
to the experiments for Cu/WTi/Si. The SEM results are shown in
Fig. 7(b). The image does not show any formation of Cu 3Si spots
over the whole annealing time range. ToF-SIMS depth profiles in
Fig. 5(d) do not indicate any Ti diffusion into the Cu layer at any
time. Apparently the formation of TiN in the WTi(N) film decreases
the mobility of Ti and keeps it in the barrier layer. This fact and the
more compact structure result in a remarkable improvement of
barrier stability, not only to higher temperatures but also for
longer annealing time periods.

4. Conclusion

The barrier stability of WTi and WTi(N) was compared with

respect to thermal and chemical stability for Al and Cu metalliza-
tion. Ti diffusion out of WTi into the metallization layer is the main
Please cite this article in press as: Fugger M et al. Comparison of WTi and WTi(N) as diffusion barriers for Al and Cu metallization on Si with respect to
thermal stability and diffusion behavior of Ti. Microelectron Reliab (2014), http://dx.doi.org/10.1016/j.microrel.2014.04.016
shown for the first time that nitrogen incorporation to WTi
eliminates Ti diffusion and therefore improves the barrier
stability significantly. Furthermore it could be shown that next
to blocking the diffusion the nitrogen incorporation decreases
the grain size of the diffusion barrier and changes the crystal
structure from bcc to fcc, which also lead to a superior barrier
density. Furthermore it is striking that the thermal stability of
WTi and WTi(N) as a diffusion barrier for Cu is superior to Al.
The threshold temperature for Ti diffusion out of WTi into Al is
reached at 350 °C [1] whereas this phenomenon appears in Cu
not before 600 °C. This occurrence is also present for WTi(N) in
the case of Al but much lower and completely vanishes in the
case of Cu which proves that nitrogen incorporation is
strengthen the barrier density for Al as well for Cu.

Acknowledgments

The authors gratefully thank Elisabeth Eitenberger for the

SEM measurements and Prof. Erich Halwax for the XRD
measurements. They would also like to express their
appreciation to Stefan Krivec, Michael Ehmann, Ravi Joshi and
Mark Harrison for assistance with the experiments. Beneficial
discussions with Werner Robl and Michael Nelhiebel facilitated
a deepened knowledge in the exper- iment results.

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Please cite this article in press as: Fugger M et al. Comparison of WTi and WTi(N) as diffusion barriers for Al and Cu metallization on Si with respect to
thermal stability and diffusion behavior of Ti. Microelectron Reliab (2014), http://dx.doi.org/10.1016/j.microrel.2014.04.016