Materials Letters 57 (2003) 2965 – 2969

www.elsevier.com/locate/matlet

Effect of in situ H2-plasma cleaning on TiSi2 film properties in

plasma enhanced chemical vapor deposition
Osama A. Fouad a,*, Masaaki Yamazato b, Hiroshi Ahagon b, Masamitsu Nagano b
a
Central Metallurgical Research and Development Institute (CMRDI), P.O. Box 87, Helwan, El-Felezat Street, Cairo, Egypt
b
Department of Applied Chemistry, Faculty of Science and Engineering, Saga University, Honjo 1, Saga 840-8502, Japan
Received 25 April 2002; received in revised form 15 November 2002; accepted 29 November 2002

Abstract

The effect of in situ H2-plasma cleaning on the properties of TiSi2 film was investigated. At high RF plasma power (350 W),
the film surface was rough and had voids due to damage of Si surface. At low RF power (30 W), the film surface was rough due
to residual silicon oxide on the Si substrate surface.
D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Silicides; H2-plasma cleaning; Crystal structure; Electrical properties; Deposition; Surfaces

1. Introduction sity and improved the surface morphology of titanium

Recently, a great interest in preparation of the low
resistivity TiSi2 thin film for the fabrication of ad-
vanced integrated circuits (ICs) via low-pressure
chemical vapor deposition (LPCVD) has arisen [1,2].
However, LPCVD has shortcomings such as nuclea-
tion, which causes high sheet resistance in thin films,
large silicon consumption and large grain size of the
resulting films [2,3]. The main reason for nucleation
problem was the native oxide layer on Si substrate
surface [4,5]. Without Si substrate cleaning, the film
either does not grow or grows only sparse nuclei [3].
Saito et al. [3] reported that in situ silane (SiH4)
cleaning of Si substrate greatly increased nuclei den-
* Corresponding author. Tel.: +20-2-5010643; fax: +20-2-
5010639.
E-mail address: oafouad@yahoo.com (O.A. Fouad).
silicide films in an LPCVD process. Ilderem and Reif
[6] deposited a very thin polysilicon layer immediately
prior to silicide deposition to promote the uniform
nucleation of titanium silicide films.
Alternatively, few works had been done on dep-
osition of titanium silicide films using PECVD [5,7 –
9] to improve the film properties and to overcome
the LPCVD problems. PECVD has improved the
film surface morphology by forming fine silicide
grains [7]. However, the effect of in situ H2-plasma
cleaning conditions on silicide film growth from
TiCl4/H2 gas mixture and Si substrate has not been
clarified yet.
In our previous work, we investigated the prepa-
ration of TiSi2 film by PECVD using TiCl4/H2 gas
mixture without using the hazardous SiH4 gas [9]. By
H2-plasma cleaning prior to silicide deposition, the
deposited film grew uniformly with homogenous sur-
face and smooth interface. In this paper, the effect of

0167-577X/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0167-577X(02)01405-2
2966 O.A. Fouad et al. / Materials Letters 57 (2003) 2965–2969
in situ H2-plasma cleaning on the properties of the
deposited TiSi2 film is explored in detail.
2. Experimental
The PECVD system was described in detail else-
where [9]. In brief, the reactor was a quartz tube to
which H2 (99.99%) and TiCl4 (99.99%) were intro-
duced and controlled by mass flow controllers (MFC)
and needle valves. The plasma source was RF gen-
erator of 1 kW, 13.56 MHz. An electric resistance
furnace was used to heat the substrate and its temper-
ature was monitored by a Pt/Pt-13% Rh thermocou-
ple. The exhausted gases were pumped out using a
combination of rotary pump and oil diffusion pump.
The pressure was monitored by a Penning gauge and a
capacitance manometer.
Titanium disilicide films were deposited on silicon
(100) substrate. All substrates were first cleaned by
dipping in HF solution for 20 s to remove the native
oxide layer on Si substrate surface then rinsed with
Fig. 1. AFM profiles of titanium silicide films deposited on Si (100) substrate after in situ H2-plasma cleaning at different RF powers. (a) 0 W,
(b) 30 W, (c) 100 W and (d) 350 W.
deionized water and dried in a stream of nitrogen gas
prior to loading into the reaction tube. The time from
the substrate cleaning until loading in the reaction
tube was about 5 min. During that period, it was
expected that a thin oxide layer is formed on the
silicon substrate surface. After loading the substrate,
the system was pumped down to a base pressure of
1  10 5 Torr. Prior to deposition, the substrate sur-
face was in situ cleaned by hydrogen plasma. The H2-
plasma cleaning was done at an H2 flow rate of 30
sccm, a substrate temperature of 850 jC, a total
pressure of 5  10 3 Torr, a duration time of 1– 60
min and at different RF powers from 30 to 350 W. The
TiSi2 films were deposited at an H2/TiCl4 flow rate
ratio of 250, a substrate temperature of 850 jC, a
deposition time of 10 min, a total pressure of 0.5 Torr
and an RF power of 130 W.
Films were examined by atomic force microscopy
(AFM), scanning electron microscopy (SEM), X-ray
diffraction (XRD) and X-ray photoelectron spectro-
scopy (XPS). The film resistance was measured using
the DC four-probe method.
 O.A. Fouad et al. / Materials Letters 57 (2003) 2965–2969 2967

3. Results and discussion

AFM profiles of titanium silicide films deposited

on Si substrate after cleaning at different RF powers
(0– 350 W) are shown in Fig. 1. At a low RF power
(0– 30), the deposited film had a rough surface and the
grain density was higher and the grain size was in the
range from about 0.2 to 0.5 Am and formed groups of
cone-shaped grains. As the RF power increased (100
W), the film surface improved and became smoother
and the grains became platelet elongated shaped. At a
high RF power (350 W), the film surface became
rough and had voids and the grain density increased.
This behavior could be attributed to the cleanliness of
the silicon substrate surface. At a low RF power (0–
30 W), the oxide layer on the silicon substrate surface Fig. 3. Dependence of XRD peak intensity of TiSi2 (311) plane on
was not completely removed, and the deposition was RF power. The peak intensity was normalized by Si (400) peak
not uniform. As the RF power increased (100 W), the intensity.
oxide layer on the silicon substrate surface was
effectively removed and the deposited film became was z 40 min. Also at lower substrate temperatures
uniform and smoother. At a high RF power (350 W), < 800 jC, the removal of the oxide layer was not
the silicon substrate surface was damaged by the effective and the deposited film grew in the form of
dense plasma as was observed from SEM images, separated particles.
and thus, the deposited film was not uniform and had XRD patterns of titanium silicide films deposited
voids. It is worth mentioning that voids were observed after substrate cleaning at different RF powers are
on Si substrate surface when the duration of cleaning shown in Fig. 2. We clearly see for all films the

Fig. 2. XRD patterns of the as-deposited TiSi2 films deposited on Si (100) substrate after in situ H2-plasma cleaning at different RF powers. (a) 0 W,
(b) 30 W, (c) 100 W and (d) 350 W.
2968 O.A. Fouad et al. / Materials Letters 57 (2003) 2965–2969
Fig. 4. Dependence of electrical resistivity of TiSi2 film on RF
power.
diffraction peaks corresponding to (111), (220), (311),
(040), (022) and (331) diffraction planes of C54 –
TiSi2 phase, respectively. It is obvious that the depos-
ited films are polycrystalline with the preferred (311)
orientation.
The XRD intensity of the (311) plane was normal-
ized by the intensity of Si (400) and shown as a
function of RF power in Fig. 3. It is obvious that as
the RF power of H2-plasma cleaning increased, the
intensity of the (311) plane increased to reach a
maximum at an RF power of 100 W and then
decreased as the RF power increased up to 350 W.
This behavior could be attributed to the nature of the
silicon substrate surface as observed from the AFM
profiles. At a low RF power, the deposited film was not
uniform and discontinuous due to the lack of reaction
between TiCl4 and the residual SiO2. This discontinu-
ity led to low-intensity XRD peaks. As the RF power
increased (100 W), the oxide layer was effectively
removed and the film deposited uniformly resulted in
increasing the intensity of the XRD peak. At a high RF
power (350 W), the film surface had voids that might
have affected the XRD peak intensities.
XPS analysis showed that the films were composed
mainly of Si and Ti. Oxygen and carbon contamina-
tion was found on the film surfaces, which were easily
etched by Ar+ ion, ruling out the formation of any
oxide phase. This observation also suggested that
oxygen and carbon were only adsorbed on the film
surface due to exposure to air for a period of time
before XPS measurements were performed.
TiSi2 has two crystallographic structures, the ortho-
rhombic base-centered C49 of high resistivity
( f 80 –100 AV cm) and the orthorhombic face-cen-
tered C54 of low resistivity ( f 15 –25 AV cm). Fig. 4
shows the variation of the TiSi2 film resistivity as a
function of the RF power. As the RF power increased
from 0 to 100 W, the electrical resistivity of the TiSi2
film decreased from about 100 AV cm to reach a
minimum value of f 25 AV cm, respectively. This
resistivity is in agreement to the reported one of the
C54 phase [10]. The film resistivity is intimately
related to its morphology and thickness. The high
resistivity at low and high RF powers might be due to
rough surface, discontinuity of the film and uneven
thickness. At an RF power of 100 W, the film surface
was smooth and homogenous resulting in lowering
the electrical resistivity.
4. Conclusion
The effect of in situ H2-plasma cleaning prior to
deposition on the structural and electrical properties of
TiSi2 films was investigated. It was found that H2-
plasma cleaning was an effective route to remove the
oxide layer from the silicon substrate surface. How-
ever, careful change of H2-plasma condition was
recommended to achieve the desired cleaning, avoid-
ing surface damage and indeed rough film surface
with high resistivity. The electrical resistivity could be
lowered to an acceptable value by depositing film
with smooth and homogenous surface.
Acknowledgements
This work was partly supported by the Sasakawa
Scientific Research Grant (No. 13-346) from the
Japan Science Society.
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