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The TiNi shape-memory alloy and its applications for MEMS

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 1998 J. Micromech. Microeng. 8 213 (http://iopscience.iop.org/0960-1317/8/3/007) View the table of contents for this issue, or go to the journal homepage for more

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J. Micromech. Microeng. 8 (1998) 213221. Printed in the UK

PII: S0960-1317(98)87262-8

The TiNi shape-memory alloy and its applications for MEMS

H Kahn, M A Huff and A H Heuer
Department of Materials Science and Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106, USA Department of Electrical Engineering and Applied Physics, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106, USA Received 1 September 1997, accepted for publication 26 February 1998 Abstract. The shape-memory effect is a solid state phenomenon which exploits a reversible phase transformation to repeatedly achieve an initial shape, even after some deformation of the material. Numerous metal alloys exhibit this effect. One of the most widely used shape-memory alloys is TiNi, due to its large range of recoverable deformations and its relative ease of processing. In bulk and wire form, TiNi has been applied to a number of applications, and as a thin lm, TiNi is an excellent material for use as a microactuator in microelectromechanical systems (MEMS), due to its large recovery forces and high recoverable strains. Several TiNi-actuated MEMS devices have already been reported.

1. Titaniumnickel as MEMS actuators In the past several years, considerable commercial and military interest in MEMS has developed. In the most general form, MEMS is the integration of mechanical elements, sensors, actuators and electronics on a common silicon substrate through the utilization of silicon microfabrication technology. MEMS promises to revolutionize the performance of a wide range of products by merging silicon-based microelectronics with micromachining technologies, enabling complete systems-on-a-chip to be realized. While the electronics are fabricated using integrated circuit (IC) processes (e.g., standard CMOS fabrication), the micromechanical components are fabricated using compatible micromachining processes that selectively etch away parts of the silicon wafer or add new structural layers to form mechanical and electromechanical devices. MEMS enables the development of smart products by augmenting the computational ability of microelectronics with the perception and control capabilities of microsensors and microactuators. The microsensors gather information from the environment through measuring mechanical, thermal, biological, chemical, optical and magnetic phenomena; the microelectronics process the information derived from the sensors and, through some decision-making capability, direct the microactuators to respond by moving, positioning, regulating, pumping or ltering, thereby controlling the environment for some desired outcome or purpose. A crucial topic for the continued maturation of MEMS technology is the development of suitable microactuators for practical applications. Various types of microactuator device have been reported in the literature, including microvalves [13], micropumps [46], optical switches [7], imaging displays [8, 9] and microrelays [10]. Each
0960-1317/98/030213+09$19.50 c 1998 IOP Publishing Ltd

of these devices used one of a variety of integrated actuator mechanisms based on electrostatic, magnetic, piezoelectric, bimetallic or thermopnuematic phenomena. Although it may at rst glance appear that there are a considerable number of microactuation technologies to choose from, each of the ones listed above has signicant disadvantages which render them unsuitable for many applications. In particular, many applications require an integrated microactuation mechanism that is compatible with microfabrication, and able to provide a large displacement and a large actuation energy density. None of these microactuator technologies is capable of simultaneously satisfying these requirements. Thin-lm shape-memory alloys (SMAs) have been recognized as a promising material from which to make MEMS microactuators for nearly a decade. However, due to a lack of understanding of the basic material properties and lack of control of the deposition parameters, they have not received as much attention from the MEMS community as other microactuator technologies. Walker et al [11] rst described SMA actuators in 1990; they used a simple doubly supported beam of sputter-deposited TiNi, which had been surface micromachined and was made to undergo the martensite to austenite phase transformation by Joule heating. (The terms martensite and austenite are dened in the next section.) The residual stress in the released beam caused the beam to be deformed in the martensite state, but upon heating and transformation to the austenite state, the beam remembered its parent shape and became straight and taut. By turning off the Joule heating current, the beam was allowed to cool back to room temperature and transform to the martensite phase, at which point the beam deformed. This cycle could be repeated many times.
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Also in 1990, Busch and Johnson reported on a normally closed gas microvalve using thin-lm TiNi microactuation [12]. Their device used a pneumatic pressure bias to deform a TiNi diaphragm positioned over an outlet orice and thereby close the valve. The martensite to austenite phase transformation was induced by passing a current through the thin lm to cause heating, whereupon the diaphragm became at and the valve opened to allow the uid to ow. This device employed one important advancement, a mechanical bias to close the device in the martensite state, which enabled the valve to have repeatable characteristics under cyclical use. In 1992, Ray et al [13] reported on an improved microvalve design which employed a mechanical spring to bias the valve closed in the off state. A mechanical spring is preferable to a pneumatic bias because of its smaller temperature sensitivity and easier fabrication. Kim et al [14] reported on a thermo-mechanical switch employing a TiNi thin-lm microactuator. This device was primarily used to study the interaction of the substrate, in this case silicon, and a sputter-deposited TiNi thin lm. The substrate stiffness had a profound inuence on the output energy of the TiNi layer. Further, the switching characteristics were greatly improved by depositing a second thin lm of amorphous TiNi on the other side of the device. This additional TiNi thin lm, which was not re-crystallized and therefore did not undergo any thermally induced phase transformation, compensated for the thermal stress in the transforming TiNi layer and allowed well behaved switching behavior to be realized. Kuribayashi and Taniguchi reported on a microactuator suitable for robotic manipulators using a reversible TiNi thin lm [15]. This microactuator employed a two-layer lm of TiNi, in which the top layer was composed of nearly stoichiometric TiNi and was able to undergo the shape-memory effect. The bottom TiNi layer contained disc-shaped Ti3 Ni4 precipitates oriented parallel to the lm surface, and acted as a biasing spring for the composite thin lm. Consequently, this device overcomes the need for an additional spring as in previously reported designs, greatly simplifying fabrication. Using such a microactuator design, this group successfully realized a micro-exible robotic arm able to undergo large movements out of the plane of the substrate. More recently, our group reported on a normally closed microvalve suitable for modulating the ow of liquids using TiNi thin-lm microactuators [16]. All previously reported microvalves were designed for control of gases. The control of liquids using a microvalve is one application where a large displacement is imperative; the maximum displacement of the actuator sets the stroke of the valve, and a low stroke causes the open ow resistance to be too high to allow liquids to ow through the structure at normal pressures. High strokes are possible with TiNi SMAs due to the high recoverable strains. For example, previously reported microvalves (using other integrated actuation schemes) were capable of producing strokes of only a few tens of microns, a deection such that the maximum strain in silicon is below the maximum fracture strain of 0.2%. In comparison, the maximum recoverable
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Figure 1. Schematic cross-sectional drawings of a TiNi-actuated microvalve in the (a) closed and (b) open positions. See text for more details.

strain of TiNi is at least 3%, resulting in over an order of magnitude increase in the stroke of the microvalve. As the ow resistance of the open microvalve is inversely proportional to the stroke cubed, a TiNi microvalve displays an open ow resistance three orders of magnitude lower than microvalves using other actuation methods. Further, TiNi microactuators are capable of providing sufcient force to modulate uids at pressures seen in practical applications. Our rst microvalve design employed an external biasing spring [16], while subsequent designs employed integrated polyimide diaphragm springs [17] to bias the structure closed in the off state, and was actuated to the open state using Joule heating. Testing with ltered DI water demonstrated that this liquid-handling microvalve had an open ow rate of over 5 ml min1 at a differential pressure of 0.2 psid, the highest open ow rate reported to date in a microvalve, thereby demonstrating the feasibility of MEMS devices for controlling liquid ows. The latest version of the microvalve employs a microfabricated singlecrystal silicon spring [17]. In the off/unpowered position (gure 1(a)) the microspring deects the martensitic TiNi lm downward, pressing the boss against the orice opening. When heated (gure 1(b)), the austenitic TiNi becomes nearly at, deecting the microspring upward, lifting the boss away from the orice and allowing uid to ow. This microvalve exhibits an on:off ow rate ratio of 1000:1 for water ows of 0.9 ml min1 . Our group also recently reported on the rst MEMS micropump device using a thin-lm TiNi microactuator [18]. MEMS-based micropumps are generating considerable attention for many microuidic applications, such as micro on-chip chemical analysers and implantable drug delivery systems, due to their small reagent usage and small dead volumes. Similar to the microvalve application, TiNi is an attractive material for use

The TiNi shape-memory alloy and its applications for MEMS

Figure 2. Schematic cross-sectional drawings of a TiNi-actuated micropump. See text for more details.

as an actuator for micropumps because its high recoverable strain levels and actuation forces enable large pumping rates and pressure heads to be realized. The novel feature of our pump design was the recognition that in order to maximize the stroke of the device, the biasing spring should have a nonlinear loaddeection characteristic. That is, the stiffness of the spring should decrease as the spring compression is increased. To realize a nonlinear spring, a second TiNi thin-lm layer is used and operated in tandem with the rst TiNi layer. These two TiNi layers are separated from each other by a silicon spacer layer. The micropump is operated by alternating the Joule heating to the two layers to achieve cyclic motion of the actuator. Upon heating of the top TiNi layer and the lack of Joule heating of the bottom TiNi layer, the actuator is positioned in its most downward position (gure 2(a)). On the next half-cycle, the Joule heating to the top layer is turned off and the bottom layer is heated. This causes the actuator to move to its most upward position (gure 2(b)). This cycle is repeated to achieve a cyclical pumping motion. Check valves made from polyimide are positioned on either side of the micropump actuator to achieve unidirectional uid ow in the desired direction. Testing with ltered DI water demonstrated that the micropump had a maximum pumping rate of over 49 ml min1 at an excitation frequency of 0.9 Hz. The excitation current and voltage were 0.9 A and 0.6 V, respectively, resulting in a required pumping power of 0.5 W. 2. The shape-memory effect (SME) Having discussed SMA-based MEMS devices, we now discuss the material science of SMAs. The shape-memory

effect is displayed in materials which exhibit two distinct solid phases, where the lower-temperature phase (known as martensite) is relatively compliant due to its particularly glissile boundaries, and the higher-temperature phase (known as austenite) is less compliant. The material assumes its parent shape while in the austenite phase. When cooled through the phase transformation, it becomes compliant and can be deformed. Then, when re-heated to the austenite phase eld, the material recovers its remembered parent shape. This shape recovery generates a displacement with a signicant accompanying force. The transformation temperature can be engineered to be either above or below the ambient temperature, depending on the specic material and the desired application. Since the transformation temperature varies with the applied stress (higher stress yields a lower transformation temperature), if the austenitic material is subjected to a high enough stress, it will isothermally transform into martensite, which can then be deformed. When the applied stress is relieved, the material returns to the austenite phase and assumes its parent shape. This phenomenon is called pseudoelasticity (PE). As just noted, the basis of the SME is a reversible solid state phase transformation, of the type known to materials scientists as martensitic transformations. These are diffusionless transitions, meaning that the atomic displacements involved in the transformation are small with respect to interatomic distances, allowing the reaction front to advance at near the speed of sound. Furthermore, no chemical differences exist between the parent and product phases. The transformation to martensite involves a small shape change of the sample (much smaller than the shape change of the unit cell), which is accommodated in material exhibiting the SME by the establishment of alternating twin or martensite variants, as is shown schematically in gure 3. When a force is applied to the martensite, the twin boundaries migrate in order to increase the fraction of those twin variants oriented parallel or nearly parallel to the applied stress. This results in strain created solely by twin boundary motion, which can occur at relatively low stresses. Of course, there is a limit to the strains that can be achieved in this manneri.e., when only a single twin variant remains. At this point, a dramatic increase in force is required to achieve higher strains, which will be produced by standard plastic deformation, accompanied by dislocation formation, migration and multiplication. If the martensitic material is deformed exclusively by twin boundary migration, the parent shape can be regained by re-heating into the austenite phase eld, as seen in gure 3. The two solid phases differ not only in microstructure, but also in a variety of properties, such as Youngs modulus, thermal and electrical conductivity, coefcient of thermal expansion and damping capacity. Consequently, the shapememory effect offers many opportunities for dynamic sensing and actuation. The martensitic phase transformation is hysteretic, in that it takes place over a range of temperatures, as seen in the generic graph in gure 4. On cooling, the
Glissile in materials science jargon implies the ability to migrate under an applied shear stress.

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Figure 3. Schematic drawing of the shape-memory effect: (a) high-temperature austenite phase, (b) low-temperature martensite phase, (c) twin boundary migration to accomodate stress, d) re-heating to austenite.

Figure 5. Apparent stress (as determined by substrate curvature) as a function of temperature for a 1.5 m TiNi lm on a silicon wafer, showing the hysteretic behavior for both full and partial transformation.

Figure 4. Generic graph for a shape-memory material, showing transformation temperatures on heating and cooling.

transformation begins at the martensite start temperature (Ms) (i.e., the onset of the forward transformation) and concludes at the martensite nish temperature (Mf). On re-heating, the martensite persists to a higher temperature, and begins transforming back to austenite at the austenite start temperature (As) and ending at the austenite nish temperature (Af) (i.e., the start and nish of the reverse transformation). The hysteretic behavior is one hallmark of martensitic transformations. An analogous hysteresis is found in the stress versus strain curves associated with the PE effect. The shape-memory behavior described above, and shown schematically in gure 3, is known as the one-way SME, because spontaneous shape change occurs only on heating. It is possible to achieve two-way shape memory, whereby the material will alternate between two distinct
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shapes as it is thermally cycled through the martensitic transformation. The material must be trained to establish two-way behavior. This is accomplished by appropriate stress and thermal cycling, which limits the number of variants of martensite formed [19]. Stressing the material while cooling favors the initial formation of particular variants; repeating the cycle eventually trains the structure to achieve both shapes in the absence of an external stress. The microstructural basis for this training is not well understood, but it is believed that individual dislocations and dislocation arrays play a role [2022], and possibly also precipitates [15]. Inasmuch as the martensite is inherently compliant in SME materials, relatively small applied forces will deform the material, even if it has been trained. Therefore, the two-way SME is limited to those applications where the material is not subjected to any substantial forces when in the martensite phase. The hysteresis at the heart of the SME suggests analogies to ferromagnetic and ferroelastic behavior, and indeed, alloys capable of the SME can be said to be ferroelastic. These three classes of ferroic materials all depend on domain wall migration to switch the material from one state to the other. (A material is ferroic when it has two or more orientation states in the absence of a mechanical stress, an electric eld and a magnetic eld and can shift from one to another of these states by means of a mechanical stress, an electric eld, a magnetic eld or a combination of these [23].) A striking example of ferroic behavior involving thinlm SMAs is shown in gure 5. Here, the transformation behavior of a 1.5 m TiNi thin lm sputter deposited onto a 4 inch silicon wafer is monitored by the curvature of the wafer; not only is the hysteretic behavior evident, but a minor loop due to partial transformation can be seen. Thin-lm TiNi SMAs are discussed further in a later section of this paper.

The TiNi shape-memory alloy and its applications for MEMS

3. The discovery of shape-memory alloys (SMAs) Shape-memory-related materials properties were rst reported in 1932 for a goldcadmium alloy [24] and in 1938 for brass [25]. (The martensitic transformation in steels has been known since the 19th century [26].) However, it was not until 1951 that the phenomenon was explained crystallographically [27]. Later that decade, shape-memory behavior was described for CuZn [28] and CuAlNi [29] alloys, two viable engineering materials. In 1961, researchers at the US Naval Ordnance Laboratory discovered the SME in TiNi; they were rst alerted to the unique properties of the alloy when they noticed that a rod would give a dull thud when dropped cold, but produced a sharp ring when dropped warm [30]. The martensitic transformation of TiNi was described fully in 1965, when the term memory was rst used to describe the shape recovery behavior [31]. Since that time, the SME has been discovered in numerous metallic alloys, including AgCd, NiAl, InAl, NbTi, NbU, UMo, Nb3 Sn and V3 Si [32]. Currently, the three most commonly used SMAs in engineering applications are TiNi and the copper-based alloys, CuZnAl and CuAlNi. Of these, TiNi is better suited for use as a microactuator, because it is less brittle and is capable of maximum recoverable strains about twice that of the Cubased alloys [33]. This large strain allows for increased travel of moving parts for such applications as liquidow microvalves. Several iron-based SMAs, such as FePt, FePd and FeMnSi, are also being developed for industrial applications [34]. Ternary additions to TiNi are also being explored. Substituting the ternary element Cu for Ni in TiNi (in amounts between 10 and 20 percent) can reduce the hysteresis; however, the Af temperatures are slightly lower than for the equiatomic TiNi [35]. In addition, for TiNiCu alloys with Cu contents greater than 15 percent, the lowtemperature martensitic phase has orthorhombic, rather than monoclinic symmetry, resulting in a slightly decreased recoverable strain [36]. Other ternary additions to TiNi (in particular Zr, Hf, Pd, Pt and Au) have been studied as a means of increasing the transformation temperatures for high-temperature applications [37]. 4. The titaniumnickel shape-memory alloy The TiNi SMA displays a martensitic transformation between a cubic high-temperature austenite phase and a low-temperature monoclinic martensite phase. The transformation temperature is highest (centered at 150 C) for the equiatomic TiNi alloy, dropping sharply as the Ni content is increased (to 50 C at 53% Ni) and dropping gradually as the Ti content is increased (to 75 C for 53% Ti) [31]. The crystal structure of the austenite is the cubic B2 or CsCl structure, with a lattice parameter of 0.3015 nm [38]. The martensite phase has a monoclinic crystal structure, known as B19 , with lattice parameters of a = 0.2889, b = 0.4120 and c = 0.4622 nm, with a angle of 96.8 [38] or a = 0.2898, b = 0.4108 and c = 0.4646 nm, with a angle of 97.78 [39].

As discussed above, the crystallographic shape change brought about by the transformation from austenite to martensite is accommodated by the formation of a set of differently oriented martensite twin variants. The change from cubic to monoclinic symmetry provides many possible shape changes by combining various monoclinic variants, and allows cooperative deformation between grains [33]. This leads to signicant recoverable strains. For TiNi single crystals, the recoverable strains range from approximately 3% near the [001] direction to approximately 10% for directions close to [011] and [111] [40, 41]. For polycrystalline specimens, observed recoverable strains are typically 68% for both the thermally driven SME [41, 42] and the PE effect [43]. In some instances, the austenitic TiNi will undergo an intermediate transformation to a rhombohedral (R-) phase before achieving the monoclinic martensite phase. The Rphase crystal structure can be thought of as a rhombohedral distortion along the [111] direction of the B2 parent lattice; the R-phase is often described by a hexagonal unit cell with lattice parameters of a = 0.738 and c = 0.532 nm [44]. It is not completely understood why the R-phase appears in certain TiNi specimens; however, various processing conditions such as cold working, thermal annealing, thermal cycling, variation of Ni content and introduction of ternary elements can bring about its occurrence [4447]. Since the SME associated with the R- phase transformation is limited to less than 1% recoverable strain [48], the austenite to rhombohedral phase transformation is not as effective for actuator applications as the austenite to monoclinic phase transformation. Along with the enhanced compliance as TiNi transforms from austenite to martensite, there is also an increase in the damping capacity of the material, so that TiNi alloys have attracted attention for use in vibration suppression applications [49, 50]. The origin of the damping is related to the internal friction associated with the movement and interaction of internal interfaces such as twin or intervariant boundaries [51]. In fact, the damping capacity of TiNi peaks during the martensitic and R-phase transformations, presumably due to the motion of interphase interfaces. Another important property of TiNi that changes with the solidsolid phase transformation is the electrical resistivity [49, 52]. The variation is seen for both thermally induced and strain-induced transformations, with austenite having a lower resistivity than martensite. The resistivity versus temperature or resistivity versus strain curves display the hysteresis characteristic of martensitic transformations, as do the unit cell or macroscopic sample dimensions. For any engineering applications, it is essential that the SME be repeatable and predictable, even after many cycles through the phase transformation. Unfortunately, cycled TiNi actuators sometimes show a decreased recovery force and decreased recoverable strain, an increased permanent strain and undergo shifts in the transformation temperatures. This fatigue should properly be called transformation fatigue; i.e., for SMAs, the term fatigue has a different meaning than for traditional structural alloys, where it pertains to mechanical cycle-induced fracture.
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On the other hand, a small number of cycles has actually been demonstrated to have a benecial effect on SMA behavior. Cycling through the transformation 50 times while under 100 MPa stress improved the recoverable strain of wires of TiNi containing 6% Cu from 4.8 to 5.3%; at 50 MPa, 250 cycles were required to increase the recoverable strain from 2 to 3% [53]. This enhancement in the SME is the result of training of the material. As noted above, however, larger numbers of cycles can have a detrimental effect. Under zero load, the Af and Mf temperatures of TiNi wires decreased by 15 and 20 C, respectively, after 600 cycles; under 35 MPa stress, Mf was unchanged, but Af was lowered by 15 C after 800 cycles [54]. TiNi wires experienced a 0.5% permanent strain after 1800 cycles at 100 MPa stress; similar strain was found after 50 000 cycles when the maximum temperature in the wires (created by current-induced Joule heating) was closely controlled to be just above the Af temperature [55]. This result emphasizes the importance of preventing overheating the material. TiNi springs have also demonstrated fatigue, showing decreases in recovery force and recoverable strain by 30% after 1000 cycles, and by 60% after 10 000 cycles [56]. Deection of TiNi springs against a bias force also degraded by at least 20% after aging at 95 C for 2000 hours [57]. The stress-induced transformations of the PE effect display similar fatigue phenomena as the thermal transformations. Permanent strain in TiNi wires reached 1% after only 10 cycles and 2.5% after 800 cycles, for a maximum stress of 600 MPa [54]. This unrecoverable strain increases upon cycling at higher strain rates [58]. Also, a TiNi alloy with 50.9% Ni performed better than a 50.0% Ni alloy, because of the higher critical stress for slip [59]. The origins of fatigue in TiNi are not completely understood, but likely issues include dislocation formation due to overstraining, and precipitate formation due to overheating. It is not surprising that processing conditions affect the observed resistance to fatigue [57, 60]. TiNi in bulk or wire form has been applied to a number of engineering applications. One of the earliest uses was as mechanical couplings for pipes [19]. The coupling is expanded in the martensite phase, tted over the ends of two pipes, and then heated to induce austenite formation, thereby forming a tight seal. TiNi springs are utilized in the automotive industry in a number of ways, including compensating for changing temperatures in automatic transmissions by adjusting pressure [42], improving the performance of shock absorbers [42] and opening fog-lamp louvers [19]. TiNi springs are also used to control air conditioner systems [61] and the positioning of the space shuttle antennae [62]. TiNi wires and springs provide motion in many robotics operations. Because of its biocompatibility, TiNi is found in many medical applications. The continuous low-magnitude applied forces are ideal for orthodontic tasks [63]. Bronchial prostheses [64] and bone clamps [65] have also been developed, as have eyeglass frames [66]. The potential for controlled snakelike motion is being explored for small, active catheters [67], and expandable TiNi lters can be fed through the catheters to break up blood clots and prevent embolisms [66].
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5. Titaniumnickel thin lms As discussed above, the shape-memory properties of TiNi are also being exploited in thin-lm form for use as microactuators in microeletromechanical systems (MEMS). The TiNi lms are typically sputtered onto silicon wafers using a TiNi alloy target [6870]. Films deposited onto unheated substrates are amorphous as deposited and are usually crystallized by annealing while still under vacuum. While sputtering is a well understood deposition process, the fabrication of TiNi lms suitable for MEMS applications is still complex. Titanium is a very reactive species. Thus, a very low base pressure is necessary in the sputtering chamber before the admittance of the argon sputtering gas, in order to reduce contaminants (principally Ti oxide precipitates) in the lm which could adversely affect the SME. For a target-to-substrate distance of 6 cm, a base pressure of at least 107 Torr is required [71]. It was discovered quite early that the composition of the sputtered lm does not match the composition of the target; specically, the lms are Ti poor with respect to the target (by 24 percent) [72]. This results from a combination of effects: differential sputtering rates of the two elements from an alloy target; differential re-sputtering rates from the substrate and differential capture by reactive contaminants; in addition, as the target begins to wear, the typical magnetron sputtering target develops a circular groove in use, and the sputtering prole and ejection angle will change, which can also lead to composition changes [72]. The simplest and most common solution to this problem is to place small pieces of pure Ti onto the target, to achieve the correct lm stoichiometry [68, 73, 74]. Increasing or decreasing the amount of Ti (or Ni, or any ternary element) can result in a lm of any desired composition. It has also been demonstrated that adjusting the target-to-substrate distance and the sputtering gas pressure can change the TiNi stoichiometry from 47 to 52% Ti, while using a stoichiometric (50% Ti) target [75]. Another strategy to control stoichiometry is the use of multiple sputtering guns. This approach was tried and reported for TiNiCu lms; however, the sputtering system was incapable of substrate rotation during deposition, and so the relative stoichiometry across the substrate varied signicantly [76]. For multiple sputtering guns, inasmuch as the atomic species no longer originate at the same location, it is critical to rotate the substrate in order to achieve uniform deposition. In addition, with the sputtering rate of each element under separate control, an in situ monitor of the atomic ratio in the plasma (which is possible using optical emission spectroscopy [75] or atomic absorption spectroscopy [77]) and the appropriate electronic feedback would allow the adjustment of the deposition rates during lm deposition to obtain precise lm stoichiometry. As mentioned above, the as-deposited amorphous lms must be annealed to achieve crystallinity. This also promotes adhesion to the substrate, almost certainly through the formation of thin (40 nm) reaction layers [68, 78]. An alternative would be to heat the substrates during deposition, resulting in an as-deposited crystalline state, but this leads to very ne grain sizes (100200 nm) [72],

The TiNi shape-memory alloy and its applications for MEMS

Figure 6. The titaniumnickel binary equilibrium phase diagram [90]. Equiatomic TiNi could exist in equilibrium below 630 C in a very narrow composition region [90].

which inhibits the SME, and thick (200 nm) reaction layers [68], which could alter the lm stoichiometry. The crystallization temperature of TiNi lms has been variously determined by differential scanning calorimetry to be 464 C [79], by in situ transmission electron microscopy (TEM) to be 477 C [73] and by ex situ TEM to be 400 C [80]. It was determined by cross-sectional TEM of TiNi lms on oxidized silicon substrates that a 100 nm thick region of TiNi adjacent to the substrate will not transform to martensite, presumably due to the mechanical constraints imposed by the substrate [81]. TEM experiments also determined that freestanding Ti50.2% Ni lms thinner than 100 nm will not transform to martensite [82], though TEM sample preparation and experimental vagaries could also be important. TiNi lms exhibit a strong (110) texture in the austenite phase when deposited on oxidized [81] or bare [83] silicon substrates. Besides crystallization, the annealing procedure will strongly affect the lm microstructure and the SME. Slightly Ni-rich lms underwent the transformation to the R-phase, as well as the normal martensitic transformation, when annealed at 500 C, but only the martensitic transformation when annealed at 700 C [84]. TiNi lms which had rst been crystallized by a 700 C anneal exhibited a single transformation; subsequent aging at 500 C induced the intermediate R-phase transformation [73]. As would be expected from the TiNi binary phase diagram (gure 6), nonequiatomic TiNi lms can experience precipitate formation when annealed, due to conventional diffusive processes. After annealing at 500 C, Ti50.0% Ni lms exhibited no precipitates, Ti48.4% Ni and Ti46.8% Ni lms contained Ti2 Ni precipitates and Ti51.4% Ni lms contained Ti3 Ni4 precipitates [74]. Experiments on Ti48.5% Ni lms showed very ne plate-shaped Ti-rich precipitates forming at 500 C and spherical Ti2 Ni precipitates forming above 600 C [80]; the plate-shaped precipitates increased the stress necessary for permanent deformation, leading to an improved SME [79]. Ti3 Ni4 precipitates found in Nirich lms have been associated with training of the TiNi, presumably due to the establishment of internal stress elds caused by the preferential orientation of the precipitates

along the (111) planes [15, 72]; however, this issue is still under investigation. In general, TiNi thin lms demonstrate the same transformation temperatures as bulk specimens, although transformation in thin lms can also be affected by heat treatments. For equiatomic TiNi, no change in transformation temperatures was found for annealing between 500 and 700 C; however, Ti-rich lms displayed increased transformation temperatures as the annealing temperature increased, whereas Ni-rich lms displayed decreased transformation temperatures [85]. It is likely that the higher annealing temperatures led to greater precipitate formation, which affected the overall stoichiometry of the lm, and thus changed the transformation temperatures. TiNi thin lms also display the PE effect, similar to bulk specimens [85]. The maximum recoverable strains reported for TiNi lms range from 2.6 to 6% for recovery forces of 117 to 600 MPa [86, 74, 79]. TiNi square diaphragm experiments have demonstrated recoverable deections of 400 m at 0.02 MPa for 8.4 mm wide diaphragms [16] and 125 m at 0.2 MPa for 2 mm wide diaphragms [78], corresponding to recoverable strains of 1.3% and 1.7%, respectively. The work density performed by TiNi lms varies between 5 and 25 MJ m3 [68, 12, 87], signicantly higher than for any other MEMS actuation material. TiNi thin lms are expected to experience the same fatigue problems as bulk specimens, though there has been little published work in this area. For TiNi(7% Cu) lms attached to silicon substrates, the recovered stress for the martensitic transformation was reduced from 500 MPa for the rst cycle to 350 MPa after 2000 cycles (the lm strain is 0.2%) [87]. From this result, one prediction would be that stressing the lms at 350 MPa would result in no fatigue effects for up to 2000 cycles. Freestanding 7 m thick TiNi lms were cycled through the martensitic transformation up to 100 times, with no observed change in the recoverable strain, which ranged from 0.7 to 1.8 to 2.2% for 100, 250 and 400 MPa of applied force, respectively; however, permanent strain developed in the lms subjected to 250 MPa (0.3%) and 400 MPa (3.2%) [88]. It was also reported that a TiNi thin-lm actuated microvalve, operating at 1% strain, survived more than two million cycles (possible degradation of the valve performance was not mentioned) [89]. 6. Conclusions The shape-memory effect is a solid state phenomenon whereby materials which have been deformed can recover their initial shape merely by heating through a phase transformation. In the process, high forces can be generated. One particular shape-memory alloy, TiNi, can recover at least 3% strain in either bulk, wire or thin-lm form. As a thin lm, TiNi is an excellent material for use as a microactuator in microelectromechanical systems, due to its high recoverable strains and its large recovery forces, and several TiNi-actuated MEMS devices have already been reported. One potential drawback to this technology is the stability of the shape-memory effect in thin-lm
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TiNi over the millions of cycles required of these devices; however, development efforts under way by our group and others are expected to ameliorate this phenomenon, resulting in the desired device stability. Acknowledgments Research at CWRU on TiNi SMA-actuated microdevices is supported by DARPA under contract No DABT63-95C0070. References
[1] Jerman H 1990 Proc. IEEE Solid-State Sensor and Actuator Workshop (Hilton Head, SC) p 65 [2] Zdeblick M J, Anderson R, Jankowski J, Kline-Schoder B, Christel L, Miles R and Weber W 1994 Proc. IEEE Solid-State Sensor and Actuator Workshop (Hilton Head, SC) p 251 [3] Huff M, Gilbert J and Schmidt M Proc. IEEE Int. Conf. on Solid-State Sensors and Actuators, Transducers 93 (Yokohama, 1993) [4] Van Lintel H T G, Van De Pol F C M and Bouwstra S 1988 Sensors Actuators 15 153 [5] Folta J A, Raley N F and Lee E W 1992 Proc. IEEE Solid-State Sensor and Actuator Workshop (Hilton Head, SC) p 22 [6] Ahn C H and Allen M G 1995 Proc. IEEE Int. Micro Electro Mech. Syst. Workshop (Amsterdam, 1995) [7] Walker J 1995 Proc. IEEE Int. Conf. on Solid-State Sensors and Actuators, Transducers 95 (Stockholm, 1995) [8] Van Alstyne L J 1984 Texas Instruments US Patent 4 441 791 [9] Bloom D M 1997 Proc. Conf. on Projection Displays III SPIE vol 3013 (Bellingham, WA: SPIE) [10] Roy S and Mehregany M 1995 Proc. IEEE Int. Micro Electro Mech. Syst. Workshop (Amsterdam) p 353 [11] Walker J A, Gabriel K J and Mehregany M 1990 Sensors Actuators A 2123 243 [12] Busch J D and Johnson A D 1990 Proc. IEEE Int. Micro Electro Mech. Syst. Workshop (Napa Valley, CA) p 40 [13] Ray C A, Sloan C L, Johnson A D, Busch J D and Petty B R 1992 Mater. Res. Soc. Symp. Proc. vol 276 (Pittsburgh, PA: Materials Research Society) p 161 [14] Kim T, Su Q and Wuttig M 1995 Mater. Res. Soc. Symp. Proc. vol 360 (Pittsburgh, PA: Materials Research Society) p 375 [15] Kuribashi K and Taniguchi T 1992 Mater. Res. Soc. Symp. Proc. vol 276 (Pittsburgh, PA: Materials Research Society) p 167 [16] Kahn H, Benard W L, Huff M A and Heuer A H 1997 Mater. Res. Soc. Symp. Proc. vol 444 (Pittsburgh, PA: Materials Research Society) p 227 [17] Benard W L, Kahn H, Prabhu V R, Heuer A H and Huff M A unpublished results [18] Benard W L, Kahn H, Heuer A H and Huff M A 1997 Proc. IEEE Int. Conf. on Solid-State Sensors and Actuators, Transducers 97 (Chicago, IL) p 361 [19] Kubel E J Jr 1984 Mech. Eng. 106 27 [20] Airoldi G, Ranucci T, Riva G and Sciacca A 1996 Scr. Mater. 34 287 [21] Favier D, Liu Y and Manach P Y 1995 J. Physique Coll. IV 5 C2 391 [22] Liu Y and McCormick P G 1990 Acta Metall. Mater. 38 1321 [23] Aizu K 1970 Phys. Rev. B 2 754 [24] Olander A 1932 J. Am. Chem. Soc. 54 3819 [25] Isaitschev I, Kaminsky E and Kurdyumov G V 1938 Trans. AIME 128 365 220

[26] Smith L S 1992 Martensite ed G B Olson and W S Owen (ASM International) pp 219 [27] Chang L C and Read T A 1951 J. Met. Trans. AIME 191 47 [28] Genevray R M 1953 Thesis MIT Suoninen E J 1954 Thesis MIT [29] Chen C W 1957 J. Met. Trans. AIME 209 1202 [30] Wayman C M and Harrison J D 1989 JOM 41 26 [31] Wang F E, Buehler W J and Pickart S J 1965 J. Appl. Phys. 36 3232 [32] Golestaneh A A 1984 Phys. Today 37 62 [33] Bhattacharya K and Kohn R V 1996 Acta Mater. 44 529 [34] Schetky L M 1996 MRS Bull. 21 50 [35] Furuya Y, Matsumoto M and Masumoto T 1992 Mater. Res. Soc. Symp. Proc. vol 246 (Pittsburgh, PA: Materials Research Society) p 355 [36] Moberly W J, Duerig T W, Proft J L and Sinclair R 1992 Mater. Res. Soc. Symp. Proc. vol 246 (Pittsburgh, PA: Materials Research Society) p 55 [37] Beyer J and Mulder J H 1995 Mater. Res. Soc. Symp. Proc. vol 360 (Pittsburgh, PA: Materials Research Society) p 443 [38] Knowles K M and Smith D A 1981 Acta Metall. 29 101 [39] Kudoh Y, Tokonami M, Miyazaki S and Otsuka K 1985 Acta Metall. 33 2049 [40] Miyazaki S, Kimura S, Otsuka K and Suzuki Y 1984 Scr. Metall. 18 883 [41] Saburi T, Yoshida M and Nenno S 1984 Scr. Metall. 18 363 [42] Stoeckel D 1990 Adv. Mater. Processes 138 33 [43] Miyazaki S, Otsuka K and Suzuki Y 1981 Scr. Metall. 15 287 [44] Beyer J 1995 J. Physique Coll. IV 5 C2 433 [45] Mulder J H, Thoma P E and Beyer J 1993 Z. Metallk. 84 501 [46] Jinfang G, Yuying C, Ming Z, Long S and Guansen Y 1992 Mater. Res. Soc. Symp. Proc. vol 246 (Pittsburgh, PA: Materials Research Society) p 283 [47] Nishida M and Honma T 1984 Scr. Metall. 18 1293 [48] Ling H C and Kaplow R 1981 Metall. Trans. A 12 2101 [49] Carballo M, Pu Z J and Wu K H 1995 J. Intell. Mater. Syst. Struct. 6 557 [50] Wu K, Dalip S K, Liu Y and Pu Z 1995 Proc. Conf. on Smart Structures and Materials SPIE vol 2441 (Bellingham, WA: SPIE) p 139 [51] Van Humbeeck J, Stoiber J, Delaey L and Gotthardt R 1995 Z. Metallk. 86 176 [52] Riva G and Airoldi G 1995 J. Physique Coll. IV 5 C8 623 [53] Bigeon M J and Morin M 1995 J. Physique Coll. IV 5 C2 385 [54] McCormick P G and Liu Y 1994 Acta Metall. Mater. 42 2407 [55] Neukomm P A, Bornhauser H P, Hochuli T, Paravicini R and Schwarz G 1990 Sensors Actuators A 2123 247 [56] Tamura H, Mitose K and Suzuki Y 1995 J. Physique Coll. IV 5 C8 617 [57] Michael A D 1995 J. Physique Coll. IV 5 C2 349 [58] Strnadel B, Ohashi S, Ohtsuka H, Miyazaki S and Ishihara T 1995 Mater. Sci. Eng. A 203 187 [59] Strnadel B, Ohashi S, Ohtsuka H, Ishihara T and Miyazaki S 1995 Mater. Sci. Eng. A 202 148 [60] Thoma P E, Blok A M and Kao M-Y 1992 Mater. Res. Soc. Symp. Proc. vol 246 (Pittsburgh, PA: Materials Research Society) p 321 [61] Thoma P E, Ivshin Y and Schachner K D 1995 Mater. Res. Soc. Symp. Proc. vol 360 (Pittsburgh, PA: Materials Research Society) p 507 [62] Stevens T 1991 Mater. Eng. 108 18 [63] Gil J, Planell J A and Libenson C 1993 J. Mater. Sci.: Mater. Med. 4 281 [64] Leclercq S, Lexcellent C and Gelin J C 1996 J. Physique Coll. IV 6 C1 225 [65] Filip P, Musialek J, Lorethova H, Nieslanik J and Mazanec K 1996 J. Mater. Sci.: Mater. Med. 7 657

The TiNi shape-memory alloy and its applications for MEMS [66] Duerig T W 1995 Mater. Res. Soc. Symp. Proc. vol 360 (Pittsburgh, PA: Materials Research Society) p 497 [67] Lim G, Park K, Sugihara M, Minami K and Esashi M 1996 Sensors Actuators A 56 113 [68] Wolf R H and Heuer A H 1995 J. Microelectromech. Syst. 4 206 [69] Jardine A P, Madsen J S and Mercado P G 1994 Mater. Characterization 32 169 [70] Busch J D, Johnson A D, Lee C H and Stevenson D A 1990 J. Appl. Phys. 68 6224 [71] Jardine A P 1995 J. Vac. Sci. Technol. A 13 1058 [72] Grummon D S, Hou L, Zhao Z and Pence T J 1995 J. Physique Coll. IV 5 C8 665 [73] Miyazaki S and Ishida A 1994 Mater. Trans. JIM 35 14 [74] Kawamura Y, Gyobu A, Horikawa H and Saburi T 1995 J. Physique Coll. IV 5 C8 683 [75] Bendahan M, Seguin J-L, Canet P and Carchano H 1996 Thin Solid Films 283 61 [76] Krulevitch P, Ramsey P B, Makowiecki D M, Lee A P, Northrup M A and Johnson G C 1996 Thin Solid Films 274 101 [77] Wang W, Fejer M M, Hammond R H, Beasley M R, Ahn C H, Bortz M L and Day T 1996 Appl. Phys. Lett. 68 729 [78] Stemmer S, Duscher G, Scheu C, Ruhle M and Heuer A H 1997 J. Mater. Res. 12 1734 [79] Kajiwara S, Kikuchi T and Ogawa K 1996 Phil. Mag. Lett. 74 137 [80] Nakata Y, Tadaki T, Sakamoto H, Tanaka A and Shimizu K 1995 J. Physique Coll. IV 5 C8 671 [81] Su Q, Hua S Z and Wuttig M 1994 J. Alloys Compounds 211/212 460 [82] Kuninori T, Sukedai E and Hashimoto H 1996 Mater. Trans. JIM 37 1404 [83] Kahn H and Heuer A H unpublished results [84] Ishida A, Sato M, Takei A, Kase Y and Miyazaki S 1995 J. Physique Coll. IV 5 C8 701 [85] Ishida A, Takei A, Sato M and Miyazaki S 1996 Thin Solid Films 281/282 337 [86] Miyazaki S, Nomura K and Ishida A 1995 J. Physique Coll. IV 5 C8 677 [87] Krulevitch P, Lee A P, Ramsey P B, Trevino J C, Hamilton J and Northrup M A 1996 J. Microelectromech. Syst. 5 270 [88] Nomura K and Miyazaki S 1995 Proc. Conf. on Smart Structures and Materials SPIE vol 2441 (Bellingham, WA: SPIE) p 149 [89] Johnson A D 1991 J. Micromech. Microeng. 1 34 [90] Murray J L (ed) 1987 Phase Diagrams of Binary Titanium Alloys (Metals Park, OH: ASM International)

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