Applied Surface Science 257 (2010) 1211–1215

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsus c

An investigation of structural phase transformation and electrical

resistivity in Ta films
A. Javed a,∗ , Ji-Bing Sun b

a
Department of Engineering Materials, University of Sheffield, Mappin Street, Sheffield, S1 3JD, UK
b
School of Material Science and Engineering, Hebei University of Technology, Tianjin 300130, China

a r t i c l e i n f o a b s t r a c t

Article history: In this work, we report the effect of substrate, film thickness and sputter pressure on the phase transfor-
Received 20 June 2010 mation and electrical resistivity in tantalum (Ta) films. The films were grown on Si(1 0 0) substrates with
Received in revised form 17 July 2010 native oxides in place and glass substrates by varying the film thickness (t) and pressure of the work-
Accepted 4 August 2010 ing gas (pAr ). X-ray diffraction (XRD) analysis showed that the formation of and phases in Ta films
Available online 11 August 2010 strongly depend on the choice of substrate, film thickness t and sputter pressure pAr . A stable -phase
was observed on Si(1 0 0) substrates for t ≤ 200 nm. Both and phases were found to grow on glass sub-
Keywords:
strates at all thicknesses except t = 100 nm. All the films grown on Si(1 0 0) substrates for pAr ≤ 6.5 mTorr
Metallic films

Growth parameters had -phase with strong (1 1 0) texture normal to the film plane. The glass substrates promoted the
Phase transformation formation of -phase in all pAr except pAr = 5.5 mTorr. The resistivity was observed to decrease with
Surface roughness t, whereas was increased with pAr on Si(1 0 0) substrates. In all films, the measured resistivity was
Electrical resistivity greater than the bulk resistivity. The resistivity was influenced by the effects of surface roughness and
grain size.
Crown Copyright © 2010 Published by Elsevier B.V. All rights reserved.

1. Introduction phases strongly depend on the deposition conditions; for example,

Tantalum (Ta) thin films are of interest for technological appli-
cations in microelectronics industry such as diffusion barriers,
decorative and protective coatings due to their excellent corrosion,
wear resistance, high melting point (≈3000 ◦ C) and high hard-
ness [1,2]. Ta thin films generally grow in two crystal structures;
a body-centered-cubic (bcc) structure known as -phase and a
metastable tetragonal structure known as -phase [3]. Each phase
has different microstructural, electrical and mechanical proper-
ties [4]. For example, stable bcc -phase Ta films which have low
resistivity (15–70 cm) are commonly used in thin film capac-
itors. A metastable tetragonal -phase which has high resistivity
(140–210 cm) is used in thin film resistors [5] and heaters [1].
The coexistence of and phases in thin films limited their use in
microelectronics industry. Thin Ta films are also used (by the mag-
netic community) as seed layer (or as protective layer) during the
growth of magnetic thin films and multilayer systems to improve
the magnetic properties [6,7]. The presence of two phases may not
be useful to improve the properties of magnetic thin films. Due to
high melting point of Ta, the Ta films are usually grown using sput-
tering technique rather than evaporation. The formation of these
∗ Corresponding author.
E-mail address: a.javed@sheffield.ac.uk (A. Javed).
sputter pressure, substrate temperature and film thickness [8].
For the growth of single phase ( or ) Ta films, several
approaches have been adopted by various groups [9–13]. For exam-
ple, Zhang et al. [3] fabricated low resistivity -Ta films on Si(1 0 0)
substrates by varying the Cr under layer thickness. They found that
-Ta films with low resistivity (∼20 cm) can be obtained with
Cr under layer thickness 20 Å. Liu et al. [8,10] studied the annealing
effect on the structure of 550 nm thick Ta films grown on Si(1 0 0)
and SiO2 /Si substrates. They observed phase transformation from
to at annealing temperature of 500 ◦ C in the films grown on Si
substrates. They concluded that there was no phase transformation
at annealing temperature of 500 ◦ C in the films grown on SiO2 sub-
strates. In the films grown on Si(1 0 0) substrates, they observed 80%
-Ta phase transformation into -Ta at 600 ◦ C, whereas 20% of -
Ta transformation into -Ta occurs at this temperature in the films
grown on SiO2 substrates. They suggested that the oxygen diffusion
into Ta/SiO2 interface could be the possible reason to limit the phase
transformation from to . Ren and Sosnowski [9] fabricated Ta
films on Si(1 0 0) and Al substrates using RF magnetron sputtering.
They studied phase transformation in Ta films by varying the sub-
strate bias voltage (0–300 V) and found that both and phases
co-existed on both substrates for substrate bias voltage of 0 V and -
phase disappeared with increase in substrate bias. They found that
the grain size decreased linearly with the increase in bias voltage.
Recently, Zhou et al. [4] investigated the effect of deposition param-

0169-4332/$ – see front matter. Crown Copyright © 2010 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2010.08.023
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eters (sputter power and substrate temperature) on the structure

and transport properties of Ta films. They fabricated 540 nm thick
Ta films on the glass substrates by varying the sputter power from
25 to 100 W. They observed a metastable tetragonal -phase in
all films grown on glass substrates. They investigated the effect of
substrate temperature (300–650 ◦ C) on the film sputtered at 100 W
and observed that a (2 0 0) reflection corresponding to -phase
appeared at substrate temperature of 650 ◦ C. They found that the
resistivity significantly reduced (320–50 cm) with increase in
substrate temperature (300–650 ◦ C). Recently, Grosser and Schmid
[2] reported the effect of sputter conditions on microstructure and
resistivity of Ta films fabricated on glass substrates. They observed
-phase in all films of thickness up to 940 nm. They found that a
stable -phase occurred in the film of thickness 1300 nm. From SEM
studies they observed that the microstructure change from dense
to voided structure with increase in back pressure. They also found
that the resistivity of the films increased with the increase in back
pressure. One drawback in their work was that the influence of the
variation in film thickness was not systematically studied, see Ref.
[2]. The phase transformation and the resistivity in Ta films of thick-
ness down to few nanometer needs to be studied for applications,
where as-deposited films are required without complex processing
[14,15] of the films to achieve single phase ( or ).
The purpose of this work was to study the effects of substrate,
film thickness and sputter pressure on the structural phase trans-
formation and electrical resistivity in Ta films by extending the
work reported by Grosser and Schmid [2].

2. Experimental detail

Four sets of Ta films were grown using a DC magnetron sput-

tering technique. Two sets were grown on Si(1 0 0) substrates with
native oxides in place and the other two sets were grown on glass
substrates. High purity Ta (99.99%) target of thickness 2 mm and
diameter 50.8 mm was DC sputtered with sputter power P = 100 W
for the growth of all four film sets. The deposition conditions for all
four film sets were as follows: set-1 (on Si substrates) was grown
at fixed P = 100 W and sputter pressure pAr = 5.5 mTorr, but varying
the film thickness t from 20 to 500 nm. Set-2 was grown on glass
substrates under similar conditions as set-1. Set-3 of film thick-
ness 50 ± 2 nm were grown (on Si substrates) at fixed P = 100 W
but varying pAr from 5.5 to 7.0 mTorr. Set-4 was grown on glass
substrates under similar conditions as set-3. The substrate-target
distance d = 7.5 cm was kept constant during the growth of all film
sets. Before growing Ta films, the chamber was first calibrated for
thickness so that the film thickness could be controlled by control-
ling the deposition time.
All film sets were grown at room temperature. A piece
(1 cm × 1 cm) of Si substrate was cut from a 3 in. diameter Si(1 0 0)
wafer and a 1 cm × 1 cm glass pieces were cut from 2 cm × 5 cm
glass slide. Prior to film deposition, the substrates were cleaned
in ultrasonic bath with acetone and industrial methylated spirits
(IMS) to ensure that the substrate is free from contamination. After
cleaning, the substrate was immediately placed in the deposition
chamber. Before deposition, the base pressure inside the chamber
was achieved better than 4.0 × 10−6 Torr.
The phase transformation and crystal structure of all the film
sets were studied using X-ray diffraction (XRD) technique. A
Siemens D5000 X-ray diffractometer (in standard –2 geome-
try) operating at 30 kV and 40 mA with Co radiation ( = 1.78896 Å)
was used. Surface morphology, grain size and surface roughness
of all the films were studied using an atomic force microscope
(AFM; IIIa Veeco Digital Nanoscope). Scanning electron microscope
(SEM) was used to study the preferred grain growth in the films.
The square resistance (R) of all film sets was measured using a
Fig. 1. XRD spectra of Ta films grown on (a) Si(1 0 0) substrates and (b) glass sub-
strates. (i) t = 50 nm, (ii) t = 100 nm, (iii) t = 200 nm, (iv) t = 300 nm, (v) t = 400 nm and
(vi) t = 500 nm.
standard four-point-probe method. Finally, the electrical resistiv-
ity, was measured using the relation, = R(w × t)/l, where w
and l represents the width and the length of a thin film sample,
t is film thickness and R is resistance of a square (l = w = 1 cm)
sample.
3. Results and discussion
Fig. 1(a) shows the XRD spectra of Ta films of different thick-
nesses grown on Si(1 0 0) substrates. The XRD spectra showed
that the films with t ≤ 200 nm grew with body-centred-cubic (bcc)
structure ( -phase). For t ≤ 200 nm, all films had (1 1 0) texture nor-
mal to the film plane and no peak other than the (1 1 0) reflection
was observed. For t ≥ 300 nm, the phase transformation ( to )
occurs. A strong peaks corresponding to -phase were observed in
400 nm thick film. Reflections corresponding to both and phase
were found to be co-existed in 300 and 500 nm thick films [Fig. 1(a)].
Fig. 1(b) shows XRD spectra of Ta films of different thicknesses
grown on glass substrates. On glass substrates (Fig. 1(b)], it was
observed 50 nm thick film crystallized into -phase as a dominant
phase, but a small trace of -phase at 2 ≈ 51.4◦ was also observed
at this film thickness [Fig. 1(b)]. A pure -phase was observed in
the film of t = 100 nm. With the increase in film thickness, the phase
transformations ( to ) were found in the film of t = 200 nm. At
this film thickness, it was found that the -phase dominated with a
small trace of -phase (2 2 0) at 2 ≈ 99.9◦ . For 200 nm ≤ t ≤ 400 nm,
it was found that Ta films grew with a dominant -phase. Both
1213 A. Javed,
A. Javed,
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Sun Sun
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Surface
Surface
Fig. 2. XRD spectra of Ta films grown at different pAr on (a) Si(1 0 0) substrates and
(b) glass substrates.
and phases were observed to be existed in 500 nm thick Ta film
on glass substrates with a strong -(1 1 0) peak [Fig. 1(b)].
Our results in Fig. 1(b) differ with the work of Grosser and
Schmid [2]. Grosser and Schmid observed a pure -phase in
the films of 210 nm ≤ t ≤ 940 nm on glass substrates. Their work
showed that the phase transformation was independent of t in this
thickness regime. The minimum thickness of the film studied by
Grosser and Schmid [2] was 210 nm. They reported that the -phase
appeared for t ≥ 1300 nm; whereas our results indicated that the
film thickness had a significant effect on the phase transformation.
It can be seen that a pure -phase was formed in the film of thick-
ness t = 100 nm, while mixed phases were observed for all other
thicknesses studied [see Fig. 1(b)]. This could be due to the differ-
ence in (i) substrate–target distance (ii) size of the target used or
(iii) deposition conditions. It should be noted that the phase forma-
tion in Ta films is also sensitive to growth rate [16]. It is known that
the higher growth rate promoted the formation of -phase [2,16].
According to Ref. [2], the growth rate associated with the -phase
was 0.2 nm s−1 , which was less than that we achieved (∼0.5 nm s−1 )
according to our sputter conditions.
Fig. 2 shows the XRD spectra of 50 ± 2 nm thick Ta films grown
on Si and glass substrates by varying pAr . In all the films grown
on Si(1 0 0) substrates, -phase was observed for pAr ≤ 6.5 mTorr.
A small satellite peak (3 1 1) at 2 ≈ 37.8◦ corresponding to -
phase was found to be appeared at pAr = 7.0 mTorr. On glass
substrates, a completely different phase formation was observed.
For pAr ≥ 6.0 mTorr, at best only a low intensity (330) reflection cor-
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responding to -phase was observed above the noise [Fig. 2(b)].
Other peaks may be present but it was difficult to observe their
presence due to background noise signal in the XRD spectra. At
pAr = 5.5 mTorr, both and phases were found to be co-existed.
From Fig. 1(a), it can be seen that the (1 1 0) peak shifted towards
higher 2 value with increase in t from t = 20 nm up to t = 100 nm.
For t = 200 nm film, the peak shifted towards lower 2 value. For
the films which were grown on Si(1 0 0) substrates by varying pAr
(set-3), the (1 1 0) peak shifted towards lower 2 value [Fig. 2(a)]
with the increase in pAr . The shift in (1 1 0) peak position attributed
the presence of homogeneous strain in these films. For the films,
which grew with pure bcc -phase (set-1 with t ≤ 200 nm and set-
3), the lattice constant, ‘a’ normal to the film plane was determined
from the (110) peak position. It was found that the thin film lat-
tice constant (a) decreased from 3.388 ± 0.006 Å to 3.355 ± 0.001 Å
with an increase in t from 20 to 200 nm. Further, it was found that
the thin film lattice constant, a was greater than the bulk lattice
constant, ao = 3.306 Å . The homogeneous strain ε = (a − ao )/ao was
determined from the lattice constant data and it was found that
the films (t ≤ 200 nm) were in the state of tensile strain. The lattice
constant was also determined for set-3 films (see Table 1), and it
was found that the lattice constant increased from 3.365 ± 0.003 Å
to 3.443 ± 0.005 Å linearly with the increase in pAr from 5.5 to
7.5 mTorr. The estimated homogeneous strain was positive for all
the films and increased with pAr which meant that the tensile strain
increased with an increase in pAr (Table 1). It is known that the
stress (i.e. strain) in sputtered metallic thin films changes from
compressive to tensile depending on the product of the pressure
pAr and the substrate-target distance d [17]. In our deposition set-
up, for d = 7.5 cm, the chosen range of pAr gave tensile stress in our
films over the range of pAr studied. For set-3 films ( -phase), the
stress can be estimated using, = (ε/2 )Y, where Y is the Young’s
modulus and is the Poisson ratio of Ta. For stress evaluation, the
constants Y = 1.962 × 1011 Pa and = 0.35 were taken from Ref. [9].
The estimated stress in set-3 films was increased from 5 to 11.5 GPa
with the increase in strain from 1.8 to 4.1%, respectively. The (1 1 0)
peak broadened due to both grain size and inhomogeneous strain
effects. The grain size was also calculated using Scherrer equation
[18], which was less than the grain size calculated from AFM mea-
surements. The extra breadth of the (1 1 0) peak was due to the
inhomogeneous strain. This point is discussed later in this paper
after presenting the AFM data.
Fig. 3 shows the cross-sectional SEM images of 400 nm and the
500 nm thick films grown on Si substrates. A clear columnar grain
growth was observed in these films. For t ≤ 200 nm, the columnar
grain growth was not clearly resolved using SEM. Fig. 4 shows the
AFM 3D topographic images of Ta films of different t, grown on Si
substrates. From the analysis of the AFM images, both the average
grain size (D) and the root-mean-square (RMS) surface roughness
were found to increase with t. For the films grown on Si sub-
strates, the RMS surface roughness was found to be increased from
1.1 ± 0.3 to 4.0 ± 0.8 nm with the increase in t from 20 to 500 nm.
On glass substrates, the surface roughness was found to be var-
ied from 1.0 ± 0.1 to 2.5 ± 1.2 nm over the thickness range studied.
On Si(1 0 0) substrates, the grain size increased from 25 ± 3 nm to
60 ± 5 nm with the increase in t. On glass substrates, the grain size,
D varied over a narrow range (66 ± 2 to 70 ± 4 nm) with the increase
in t, and was effectively constant.
Using the AFM grain size data (for films set-1 and set-3), the
FWHM was estimated using Scherrer equation and was compared
with the FWHM determined from the XRD (1 1 0) peak. It was found
that the FWHM estimated from the AFM grain size data was less
than the FWHM measured from XRD (1 1 0) peak (Table 1). As men-
tioned above, in thin films, the peak broadened due to the effect of
both grain size and the inhomogeneous strain. The difference in
FWHM showed that the extra breadth of the (1 1 0) peak was a sig-
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Table 1
Summary of some structural parameters for set-3 films derived from XRD and AFM data.

pAr (mTorr) Phase Lattice constant, a (Å) Strain (%) FWHM XRD (◦ ) Grain size, DAFM (nm) Surface roughness (nm)

5.5 3.365 ± 0.003 1.8 5.8 ± 0.2 32.3 ± 1.2 1.2 ± 1

6.0 3.412 ± 0.004 3.2 6.3 ± 0.2 35.5 ± 1.5 2.3 ± 1
6.5 3.409 ± 0.006 3.1 5.7 ± 0.5 33.2 ± 1.7 3.6 ± 1
7.0 3.443 ± 0.005 4.1 6.0 ± 0.4 36.0 ± 1.2 3.8 ± 1

nature of the dominant contribution into the peak broadening from

Fig. 3. Cross-sectional SEM images of Ta films grown on Si(1 0 0) substrates (a)
t = 400 nm and (b) t = 500 nm.
the inhomogeneous strain. Comparing the XRD spectra in Fig. 1(a)
and (b), a relatively sharp (1 1 0) peak can be seen in the films grown
on glass substrates.
The electrical resistivity of all the film sets is presented in Fig. 5.
Fig. 5(a) shows the electrical resistivity as a function of film thick-
ness t. It can be seen from Fig. 5(a) that the decreases with the
increase in t for the films grown on glass substrates. On Si(1 0 0) sub-
strates, the was found to be decreased with t for t ≤ 100 nm. The
maximum was observed in 200 nm thick film. Beyond t = 200 nm,
the decreased with t [Fig. 5(a)]. Comparing two data sets in
Fig. 5(a), it can be seen that the films grown on glass substrates
had higher as compared to the films grown on Si(1 0 0) substrates
for t ≤ 100 nm. For t ≥ 100 nm, the was almost similar (except,
t = 200 nm) in all the films grown on Si and glass substrates. How-
ever, the measured in all films of different t was larger than the
bulk resistivity, bulk = 13.5 cm. The dependence of on t was
found to be decreased (approaching to bulk ) with the increase in
t. The increase in grain size with film thickness causes a decrease
in resistivity in the films grown on Si(1 0 0) and glass substrates.
Fig. 5(b) shows the as a function of pAr for the film grown on Si
and glass substrates. It can be seen that the dependence of on pAr
is significantly different on Si(1 0 0) and glass substrates, particu-
larly for low and high value of pAr . On Si substrates, the was found
to be increased with the increase in pAr .
With an increase in pAr , the mean free path l (l ∝ (1/pAr ))
decreased due to increase in collisions between sputter particles
and working gas, which results in different surface morphology.

Fig. 4. AFM 3D topographic images of Ta films grown on Si(1 0 0) substrates (a) t = 20 nm, (b) t = 100 nm, (c) t = 200 nm and (d) t = 400 nm.
1215 A. Javed,
A. Javed,
J.-B.J.-B.
Sun Sun
/ Applied
/ Applied
Surface
Surface
Science
Science
257257
(2010)
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1211–1215
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4. Summary

In summary, we have studied the effect of substrate, film

thickness and sputter pressure on the microstructure and elec-
trical resistivity in Ta films. It was observed that the growth of
Ta films on Si(1 0 0) substrates promoted -phase to grow for
t ≤ 200 nm. Above 200 nm, -phase was found to be co-existed
with metastable tetragonal -phase. On glass substrates, both
and phases were observed at all film thicknesses except for
t = 100 nm. On Si(1 0 0) substrates, a strong (1 1 0) peak correspond-
ing to -phase was observed in all the films grown by varying
pAr except pAr = 7.0 mTorr. A columnar grain growth was observed
for t ≥ 300 nm. The resistivity decreased with an increase in
film thickness on both the substrates, whereas increased with
the increase in pAr . It was found that the grain size and the
surface roughness influence the resistivity in the films. In conclu-
sion, formation and phase depend on the growth conditions
and a single phase ( or phase) films can be grown with
the careful choice of the substrate, film thickness and sputter
pressure.

Acknowledgements

We acknowledge the support from Professor M.R.J. Gibbs dur-

ing this work. We are also thankful to Paul Hawksworth for his
technical assistance during the fabrication of films.

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