©Freund Publishing House Ltd International Journal o f Nonlinear Sciences and Numerical Simulation 3, 379-382, 2 0 0 2

Fabrication and Characterization of Nickel Titanium Shape

memory Thin Films by RF Magnetron Sputtering for MEMS
Applications

F. F. Gong, Q. P. Sun
Department of Mechanical Engineering, The Hong Kong University of Science and Technology,
Clear Water Bay, Kowloon, Hong Kong. Email: meffgong@ust.hk; meqpsun@ust.hk

Abstract

Nickel titanium shape memory thin films for M E M S applications were sputter-deposited, patterned, etched and
released, which were compatible with those of microelectronics fabrication techniques. The detailed sputter-
deposition conditions, patterning process, annealing conditions and oxidation prevention were investigated.
Crystallization temperature of the as-deposited thin films was determined to be approximately 500°C by differential
thermal analyzer. Structures of the nickel-titanium thin films annealed under different temperatures and annealing
time were characterized by x-ray diffraction patterns. The as-deposited nickel titanium thin films can be crystallized
under 525°C for 30 min to 60 min to obtain B2 (CsCl-type) austenite structure, rhombohedral structure, and
martensite (monoclinic) structure. The crystallized nickel titanium thin films obtained have very good quality.

Keywords: fabrication, characterization, nickel titanium shape memory thin films, M E M S applications.

1. Introduction output energy density. In recent decades, nickel

titanium thin film alloys have been studied with
great efforts to the applications in M E M S
Of several types of functional materials
devices including micro- valves and micropumps
proposed for microsystems, nickel-titanium alloy
[1-4]. Although the microfabrication processing
is one of the promising candidates because of its
for nickel titanium shape memory thin films,
excellent mechanical properties, such as shape
which should be compatible with that of
memory effect, superelasticity, large deformation,
microelectronics fabrication, have been studied
high damping, and biocompatibi- lity. Moreover
for more than fifteen years, improvements are
it is thought to be smart for it can act as both
still required especially in composition and
sensors and actuators. However, the bulk nickel-
structure control and oxidation prevention [1-4],
titanium alloy has some disadvan- tages, such as
In this paper, we will focus on the control of
expensive, slow response, and heat dissipation.
compositions, structures and oxidation preven-
In order to enhance its advan- tages and
tion during processing so as to manufacture the
overcome its disadvantages, nickel- titanium
quality shape memory thin film for M E M S
shape memory alloy is expected to reduce its
applications.
dimensions. Thus nickel-titanium shape memory
thin film becomes one of the promising materials
for microeiectromechanical system (MEMS) 2. Processing and Experiment
applications [1-4], which demonstrates the
advantages of low cost, fast response, and large

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 p-type, {100}-oriented silicon wafers (grade
one) with diameter 4 inch were employed after
cleaned by de-ionized water. Then by ARC 601
sputtering system (Sputtering Module: ARC-
12M, USA), chromium thin films with thickness
of 500 nm as a buffer and sacrificial layer were
sputter-deposited on silicon wafer that was
oxidized to form an oxidation layer of thickness
of 100 nm. The sputter-deposition conditions of
chromium thin films are shown in Table 1. These
procedures are carried out in the clean room.
Table 1. Sputter-deposition conditions of
chromium thin films
rf power Process sputtering uniformity
gas rate
120watts Argon 8 nm/min ± 10%
Near-equiatomic nickel titanium thin films of
thickness approximately 1 μηι to 6 pm were
deposited onto chromium by magnetron
sputtering (DVISJ /24 LL, Denton Vacuum, USA)
with a sputtering power of 160 watts, and other
parameters were similar to reference [4], The
nickel-titanium alloy target was a disk of 2 inch
in diameter and 0.125 inch in thickness with an
atomic symbol composition of Ni49Ti51 (at%)
with the purity of 99.9% (Kurt J. Lesker
Company, USA). The as-deposited nickel
titanium thin film adheres well with the substrate.
No crack and oxidation can be detected in the
as-deposited thin film.
Composition of the as-deposited nickel
titanium thin film was determined by energy
dispersive x-ray analysis (RIGAKU, Japan)
while its thickness was determined by RIGAKU
6300 electron microscope (RIGAKU, Japan).
Then patterning procedures were carried out in
the clean room, which were compatible with
those of standard microfabrication techniques.
The patterning procedures can be described in
details as follows: First, a positive photoresist
HPR 204 of thickness 1300 nm is spin-coated at
speed of 4 krpm on the as-deposited thin film.
Second, a mask, which is made by Software Ledit,
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is placed on the surface of the dried photoresist
HPR 204 by using Canon PLA-501F Contact
Aligner; then exposed to UV light by exposure
time of (5 ± 0.5) sec; finally solvent developer is
employed to solve the exposure parts of
photoresist HPR 204. Third, the nickel-titanium
alloy thin film can be wet-etched by an etchant,
which is a mixture of hydrofluoric acid (HF),
nitric acid (HNO3) and deionized water (DI-H 2 0)
with the ratio of 1HF : IHNO3 : 20 DI-H 2 0. The
etching rate of the nickel-titanium alloy thin film
is approximately 500 nm/min, which depends on
its exposed surface area and the crystallinity.
Fourth, the unexposure parts of photoresist are
solved by solvent MS2001, which is no harmful
to metal. Fifth, the free-standing nickel-titanium
alloy thin films can then be obtained by wet
etching of chromium layer using chromium
etchant CEP-200 of Microchrome Technology
(USA). Chromium etching rate is approximately
240 nm/min, which depends on the width of
specimens with the preferred upside-down
wafers in the chromium etchant.
1 1 1 1 • 1 1
0
\ I increase of temperature
. 1 . 1 . 1 . 1 . 1 .
0 100 200 300 400 500 600
Temperature (°C)
Figure 1. The crystallization temperature of the free-
standing amorphous nickel titanium thin films
measured by differential thermal analyzer.
By energy dispersive x-ray analysis, the
average composition of the films was about
49.0at%NiTi. The as-deposited nickel titanium
thin films were amorphous. The crystallization
temperature of the free-standing amorphous
nickel titanium thin films was measured to be
approximately 500°C by differential thermal
analyzer (TGA/DTA TGA 92 model,
SETARAM, France), as shown in Figure 1. This
result is in agreement with previous work [4],
The free-standing films were annealed in a
vacuum chamber with pressure below 3 χ 10"6
torr, and then cooled in situ to 100°C at the rate of
20°C/min.
A Rigaku D/max rA rotating target x-ray
diffractometer (RIGAKU, Japan) was employed
annealed at 550°C or even higher for different
time, B2 austenite structure and/or precipitates
arose in the thin films [4], These results indicate
that crystal structure of the thin films can be
controlled by the above annealing conditions.
(a) as-deposited

to study structure of the nickel-titanium thin (b) 500°C for 30min

films annealed under different conditions.

3. Results a n d D i s c u s s i o n

C o m p o s i t i o n C o n t r o l : The composition of
10 20 30 40 50 60 70 80 90
nickel titanium thin films during sputtering was 2theta (degree)

controlled due to the obvious influence of their

transformation temperatures. According to the Figure 2. The x-ray diffraction patterns o f (a) as-
previous work [4], the deposition conditions of deposited nickel titanium thin films and (b) nickel
the nickel titanium thin films were determined as titanium thin films annealed at 5 0 0 ° C for 30min.
shown in Table 2. Moreover pre-sputter for at
least 30 min was preferred before sputtering on
the substrate in addition to the above sputter-
deposition parameters.

Table 2. Sputter-deposition condition o f nickel

titanium thin films
rf power 160watts
process gas argon
sputtering rate 40nm/min
substrate-target distance 80mm
substrate temperature ambient temperature
Figure 3. The x-ray diffraction pattern o f nickel

Effect of Annealing Conditions: Annealing titanium thin films annealed at 5 2 5 ° C for 30min.
conditions are critical in order to obtain the
desired crystal structure. Figure 2(a) shows that 6000

the as-deposited nickel titanium thin films were 5000

amorphous by x-ray diffraction patterns. While

<000
Figure 2(b) demonstrated that Ti 2 Ni phase 3
0
precipitated after the films were annealed at —
« 3000
8
500°C for 30min. After they were annealed at
I 2000
525°C for 30min, B2 austenite structure
1000
appeared as shown in Figure 3. However, after
030 35 40 45 50 55 60 65
they were annealed at 525°C for 60min, 2thela (degree)

martensite structure together with rhombohedral

structure formed as shown in Figure 4. In Figure 4. The x-ray diffraction pattern o f nickel
addition, when the as-deposited thin films were titanium thin films annealed at 5 2 5 ° C for 60min.

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 Oxidation Prevention: Oxidation prevention
plays a critical role in the fabrication of quality
nickel titanium thin films. The temperature
dependence of chamber pressure due to the
outgassing is shown in Figure 5. When no
specimen was placed in the vacuum chamber
during heating, three jumps of chamber pressure
can be demonstrated at approximately 150°C,
300°C and 540°C. Consequently the sharp
increase of the chamber pressure during heating
can be ascribed to the outgassing of the chamber.
Nevertheless, when NiTi thin films were put into
the vacuum chamber during heating, the three
jumps become much gentle at the corresponding
temperatures. This implies that the oxidation of
the thin films during annealing is mainly due to
the outgassing of the chamber. Therefore the
following methods were adopted to prevent the
oxidation of the thin films during annealing.
I ' • ί
100 200 300 400
temperature (°C)
Figure 5. Temperature dependence
pressure at constant pump rate.
First, the vacuum system with stainless steel
walls and quartz glass walls were baked so as to
remove most of the dissolved gases to obtain high
vacuum pressure before the annealing of thin
films. Second, a titanium sponge getter was used
to prevent volatilization from the films and acted
as an oxygen getter during annealing. Third, the
as-deposited nickel titanium thin films were
coated by gold of thickness 10 nm as a protective
layer using CVC magnetron sputtering because
gold is very stable and its processing is
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compatible with the microelectronics fabrication
techniques. The gold film can be removed by
etchant after the specimens are annealed.
The crystallized nickel titanium thin films
demonstrate the same metal luster as that of
amorphous ones. The process is repeatable and
reliable in obtaining the desired nickel titanium
thin films.
4. Conclusion
Well-crystallized nickel titanium thin films for
promising MEMS applications can be obtained
successfully by control of composi- tions and
structures and prevention of oxidation. The
further characterization and mechanical testing
of the fabricated thin films are in progress.
Acknowledgments
This work was supported by the Research
Grant Council of Hong Kong SAR Government
(RGC project No. HKUST6038/99E).
References
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2656-
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