©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 is placed on the surface of the dried photoresist
one) with diameter 4 inch were employed after HPR 204 by using Canon PLA-501F Contact
cleaned by de-ionized water. Then by ARC 601 Aligner; then exposed to UV light by exposure
sputtering system (Sputtering Module: ARC- time of (5 ± 0.5) sec; finally solvent developer is
12M, USA), chromium thin films with thickness employed to solve the exposure parts of
of 500 nm as a buffer and sacrificial layer were photoresist HPR 204. Third, the nickel-titanium
sputter-deposited on silicon wafer that was alloy thin film can be wet-etched by an etchant,
oxidized to form an oxidation layer of thickness which is a mixture of hydrofluoric acid (HF),
of 100 nm. The sputter-deposition conditions of nitric acid (HNO3) and deionized water (DI-H 2 0)
chromium thin films are shown in Table 1. These with the ratio of 1HF : IHNO3 : 20 DI-H 2 0. The
procedures are carried out in the clean room. etching rate of the nickel-titanium alloy thin film
is approximately 500 nm/min, which depends on
Table 1. Sputter-deposition conditions of its exposed surface area and the crystallinity.
chromium thin films Fourth, the unexposure parts of photoresist are
rf power Process sputtering uniformity solved by solvent MS2001, which is no harmful
gas rate to metal. Fifth, the free-standing nickel-titanium
120watts Argon 8 nm/min ± 10% alloy thin films can then be obtained by wet
etching of chromium layer using chromium
Near-equiatomic nickel titanium thin films of etchant CEP-200 of Microchrome Technology
thickness approximately 1 μηι to 6 pm were (USA). Chromium etching rate is approximately
deposited onto chromium by magnetron 240 nm/min, which depends on the width of
sputtering (DVISJ /24 LL, Denton Vacuum, USA) specimens with the preferred upside-down
with a sputtering power of 160 watts, and other wafers in the chromium etchant.
parameters were similar to reference [4], The
nickel-titanium alloy target was a disk of 2 inch 1 1 1 1 • 1 1
in diameter and 0.125 inch in thickness with an
0
\ I increase of temperature
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 . 1 . 1 . 1 . 1 . 1 .

0 100 200 300 400 500 600
titanium thin film was determined by energy Temperature (°C)
dispersive x-ray analysis (RIGAKU, Japan)
while its thickness was determined by RIGAKU Figure 1. The crystallization temperature of the free-
6300 electron microscope (RIGAKU, Japan). standing amorphous nickel titanium thin films
measured by differential thermal analyzer.
Then patterning procedures were carried out in
the clean room, which were compatible with By energy dispersive x-ray analysis, the
those of standard microfabrication techniques. average composition of the films was about
The patterning procedures can be described in 49.0at%NiTi. The as-deposited nickel titanium
details as follows: First, a positive photoresist thin films were amorphous. The crystallization
HPR 204 of thickness 1300 nm is spin-coated at temperature of the free-standing amorphous
speed of 4 krpm on the as-deposited thin film. nickel titanium thin films was measured to be
Second, a mask, which is made by Software Ledit, approximately 500°C by differential thermal
analyzer (TGA/DTA TGA 92 model,

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SETARAM, France), as shown in Figure 1. This annealed at 550°C or even higher for different
result is in agreement with previous work [4], time, B2 austenite structure and/or precipitates
The free-standing films were annealed in a arose in the thin films [4], These results indicate
vacuum chamber with pressure below 3 χ 10"6 that crystal structure of the thin films can be
torr, and then cooled in situ to 100°C at the rate of controlled by the above annealing conditions.
20°C/min.
A Rigaku D/max rA rotating target x-ray
diffractometer (RIGAKU, Japan) was employed (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 compatible with the microelectronics fabrication
plays a critical role in the fabrication of quality techniques. The gold film can be removed by
nickel titanium thin films. The temperature etchant after the specimens are annealed.
dependence of chamber pressure due to the
outgassing is shown in Figure 5. When no The crystallized nickel titanium thin films
specimen was placed in the vacuum chamber demonstrate the same metal luster as that of
during heating, three jumps of chamber pressure amorphous ones. The process is repeatable and
can be demonstrated at approximately 150°C, reliable in obtaining the desired nickel titanium
300°C and 540°C. Consequently the sharp thin films.
increase of the chamber pressure during heating
can be ascribed to the outgassing of the chamber. 4. Conclusion
Nevertheless, when NiTi thin films were put into
the vacuum chamber during heating, the three
jumps become much gentle at the corresponding Well-crystallized nickel titanium thin films for
temperatures. This implies that the oxidation of promising MEMS applications can be obtained
the thin films during annealing is mainly due to successfully by control of composi- tions and
the outgassing of the chamber. Therefore the structures and prevention of oxidation. The
following methods were adopted to prevent the further characterization and mechanical testing
oxidation of the thin films during annealing. 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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layer using CVC magnetron sputtering because
gold is very stable and its processing is

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