1039MRS BULLETIN ? VOLUME 37 ? NOVEMBER 2012 ? www.mrs.org/bulletin? 2012 Materials Research Society Introduction The vast and continuing reduction in the size and power con- sumption of sensors and complementary metal oxide semi- conductor (CMOS) circuitry has led to a focused research effort on onboard power sources that can replace batteries. The concern with batteries has been that they must be charged before use. Similarly, sensors and data acquisition components in distributed networks require centralized energy sources for their operation. In applications such as sensors for structural health monitoring in remote locations, geographically inacces- sible temperature or humidity sensors and battery charging or replacement operations can be tedious and expensive. The need to replace batteries in a large-scale sensor network can be prob- lematic and costly and is nearly impossible in hazardous, harsh, and large terrain deployment. An example would be embedded sensor networks in urban battlefi elds. Logically, the emphasis in such cases has been on developing on-site generators that can transform any available form of energy at that location into electrical energy. 1 Recent advances in low-power very large-scale integration design have enabled ultrasmall power integrated circuits, which can run with only tens of nW to hundreds of ? W of power. 2 This scaling trend has opened the door for on-chip energy harvesting solutions, eliminating the need for chemical batteries or complex wiring for microsensors, thus forming the foundation for battery-less autonomous sensors and network systems. An alternative to conventional batteries as the power supply is to make use of the parasitic energy available locally in the environment. Unused energy is produced by industrial machines, human activity, vehicles, structures, and environ- ment sources, which could be excellent sources for capturing small amounts of power without affecting the source itself. In recent years, several energy harvesting approaches have been proposed using solar, thermoelectric, electromagnetic, piezo- electric, and capacitive schemes at the meso-, micro-, and nano- scales. 1,3,4 These can be simply classifi ed into two categories: (1) energy harvesting for sensor and communication networks using a microelectromechanical systems (MEMS)/thin-fi lm Piezoelectric MEMS for energy harvesting Sang-Gook Kim , Shashank Priya , and Isaku Kanno Piezoelectric microelectromechanical systems (MEMS) have been proven to be an attractive technology for harvesting small magnitudes of energy from ambient vibrations. This technology promises to eliminate the need for replacing chemical batteries or complex wiring in microsensors/microsystems, moving us closer toward battery-less autonomous sensors systems and networks. To achieve this goal, a fully assembled energy harvester the size of a US quarter dollar coin (diameter = 24.26 mm, thickness = 1.75 mm) should be able to robustly generate about 100 ? W of continuous power from ambient vibrations. In addition, the cost of the device should be suffi ciently low for mass scale deployment. At the present time, most of the devices reported in the literature do not meet these requirements. This article reviews the current state of the art with respect to the key challenges such as high power density and wide bandwidth of operation. This article also describes improvements in piezoelectric materials and resonator structure design, which are believed to be the solutions to these challenges. Epitaxial growth and grain texturing of piezoelectric materials is being developed to achieve much higher energy conversion effi ciency. For embedded medical systems, lead-free piezoelectric thin fi lms are being developed, and MEMS processes for these new classes of materials are being investigated. Nonlinear resonating beams for wide bandwidth resonance are also being developed to enable more robust operation of energy harvesters. Sang-Gook Kim, Department of Mechanical Engineering , MIT , Cambridge , MA ; sangkim@mit.edu Shashank Priya, Center for Energy Harvesting Materials and Systems , Virginia Tech , Blacksburg , VA ; spriya@vt.edu Isaku Kanno, Department of Mechanical Engineering , Kobe University , Japan ; kanno@mech.kobe-u.ac.jp DOI: 10.1557/mrs.2012.275 PIEZOELECTRIC MEMS FOR ENERGY HARVESTING 1040 MRS BULLETIN ? VOLUME 37 ? NOVEMBER 2012 ? www.mrs.org/bulletin approach, and (2) energy harvesting for other electronic devices using bulk devices. This article mainly focuses on small-scale power energy harvesting techniques ( ? 1?100 ? W) using the MEMS/thin-fi lm approach for the self-supported operation of portable or embedded microdevices and systems. Further, we focus on mechanical vibration energy as the prime source for generating electric power since it is abundant and has an infi nite life time. The question one might ask at this stage is: ?What is the best mechanism for converting mechanical energy into electrical energy at ? mm 3 dimensions?? There are several mechanisms that can be utilized to convert vibration mechanical energy into electrical energy, including electromagnetic, piezoelectric, magnetoelectric, dielectric elastomers, and electrets. Marin et al. have studied the scaling of output power as a function of effective material volume ( v ) for different mechanisms. 5 B y taking into account constitutive equations for the respective con- version mechanisms, the output power of the electromagnetic mechanism is proportional to v 2 , while that of the piezoelectric mechanism is proportional to v ? . Thus, at smaller scales, the piezoelectric mechanism becomes more attractive as compared to electromagnetics. To obtain an approximation of the critical size where piezoelectricity becomes more useful, Figure 1 plots harvester volume versus normalized output power (normalized by acceleration and multiplied by frequency) for various piezoelectric and electromagnetic prototypes reported in the literature. 5 From Figure 1 , it can be determined that the critical size is in the vicinity of ? 0.5 cm 3 . At a smaller device volume than this critical size, the electromagnetic transformation factor (similar to electromechanical coupling in piezoelectrics) Tcccoilcb (,)( )cos(?(,) ()BL'! % ' ? yyyzz (1) reduces sharply with a decrease in magnitude of induction and length of the coil. Here B represents the magnetic fi eld, L is the length of the coil, ? is the angle between ? & & z B and the differential conductor length ))& ld , y c and z c are coordinates in the plane of the coil, and y b is the coordinate on the beam. The transforma- tion factor directly couples the input mechanical energy to the output electrical energy. A reasonable assumption for four-bar electromagnetic energy harvesters is that coil velocity (dz/dt) is orthogonal to the magnetic fi eld vector B given the close proximity of magnets and coil. In order to estimate the voltage, the expression in Equation 1 is integrated over the length of the coil. Thus, dl is the integral variable. Another major problem with inductive harvesters at small scales is their low output voltage, which makes it difficult to use rectification and ac/dc conversion circuits. 6 In addition to the normalized power and output voltage, assembly at this scale critically affects the cost of the system. Below the critical volume, assembly of the conductive coil and magnetic layer becomes challenging since monolithic MEMS fabrication is not readily avail- able at the present time. The mechanisms at this scale can be cost-effective if they can be fabricated by monolithic MEMS processes without substantial post-assembly efforts. Thus, for MEMS-scale energy harvesters smaller than ? 0.5 cm 3 , pie- zoelectric transduction is the most appropriate scenario since standard MEMS processes are available for many piezoelectric materials. Electrostatic harvesters need separate voltage sources and are relatively bulkier than piezoelectric harvesters at the same power output. 7 Most importantly, piezoelectric harvesters can directly convert mechanical energy into electrical energy and can be directly integrated into monolithic MEMS-scale systems. 3 , 8 ? 13 Another question often posed is, ?How can one achieve self- powering when the power required is much larger than what can be achieved by MEMS-scale piezoelectric harvesters?? Most reported piezoelectric devices show orders of magnitude smaller normalized power density than required by the sensors and systems at the present time. In scenarios where multiple environmental resources are available besides mechanical energy, self-powering may be achieved by developing a smart architecture, which utilizes all the environmental resources, such as wind, magnetic fi elds, light, sound, temperature gradi- ents, and radio frequency waves. However, the best scenario for cost and size is to develop MEMS-scale piezoelectric harvester technology to generate suffi cient power. The general principle for conversion of low frequency mechanical stress into electrical energy using a piezoelectric transducer is shown schematically in Figure 2 . 14 This trans- formation from mechanical to electrical energy is obtained through the direct piezoelectric effect. The resulting energy can be stored after using a rectifi er and dc-dc converter circuit. Figure 1. Output power as a function of effective material volume for piezoelectric and electromagnetic vibration energy harvesting mechanisms. Variation of output power normalized by acceleration and multiplied by frequency as a function of device volume for various energy harvesters found in literature and commercially. 5 The red and green lines are the linear fi t to the data. This fi gure shows that below ? 0.5 cm 3 , the piezoelectric mechanism has an advantage over electromagnetic mechanism. PIEZOELECTRIC MEMS FOR ENERGY HARVESTING 1041MRS BULLETIN ? VOLUME 37 ? NOVEMBER 2012 ? www.mrs.org/bulletin There are three primary steps in power generation as outlined in this schematic: (1) trapping the mechanical ac stress from the available source, (2) converting the mechanical energy into electrical energy with the piezoelectric transducer, and (3) processing and storing the generated electrical energy. Depending on the frequency and amplitude of the mechanical stress, one can design the required transducer, its dimensions, vibration mode, and the desired piezoelectric material. The power density of a harvesting system is dependent upon the strategies that maximize the trapping of energy and that reduce the losses occurring at each step, namely, mechanical loss due to mismatch in mechanical impedance and electromechanical loss depending upon the magnitude of the electromechanical coupling factor of the piezoelectric material. 15 ? 18 The electrome- chanical coupling factor represents the ratio of input mechanical energy to the output electrical energy or vice-versa. Most reported piezoelectric harvesters utilize the resonance of a cantilever beam structure, which amplifi es the small ambient vibration into an in-plane strain governed by the Euler?Bernoulli beam equation. 1 , 3 , 8 This standard governing equation of motion can be used to fi nd the relative displacement that is a function of position and time. The natural frequency of transversal vibration of a continuous cantilever beam can be obtained analytically from the decoupled form of the equation. In order to harvest power robustly, the resonance bandwidth of a linear cantilever beam harvester should be wide enough to accommodate the uncer- tain variance of ambient vibrations. 9 Therefore, the resonance bandwidth is an important characteristic for trapping a suffi cient amount of energy onto the beam and should be accounted for in determining the performance of energy harvesters. Piezoelectric MEMS technology is a cost- effective energy harvesting technology if it can meet the requirements for power density and bandwidth. Three major attributes to make the piezoelectric MEMS energy harvesting technology deployable for real applications are the cost of the system, the normalized power density, and the operational frequency range (bandwidth and the center frequency). The current state of the art of piezoelectric MEMS technology is reviewed in this article with respect to these attributes. The physics behind piezoelectric- based power sources is reviewed in this article along with approaches to enhance the power density by addressing the performance of pie- zoelectric materials and nonlinear structural designs. Review of piezoelectric energy harvesting The basic principle of piezoelectric cantile- ver based energy harvesting can be explained by accounting for the fl ow of energy between different domains in Phase I and Phase II in Figure 2 . Ambient vibrations inject energy into the system through the base excitation at each cycle. This input energy is converted to kinetic energy of the proof mass, M, in Figure 3 and then to potential energy stored as the beam?s mechanical strain. 19 Part of the elastic energy stored in the beam is transformed into electrical energy in the form of induced charge across the piezoelectric layer, which is deposited on the beam. Piezoelectric energy har- vesters generally have bimorph or unimorph cantilever beam structures 11 , 20 ( Figure 3 ). However, at the MEMS scale, bimorph piezoelectric cantilevers are less manufacturable with existing microfabrication processes. For example, lead zirconate titanate (PZT) MEMS devices are mostly spin coated, which makes it very diffi cult to deposit PZT on the top and bottom of a beam. As a result, MEMS cantilevers mostly have a unimorph confi guration. A proof mass is usually attached at the tip of the cantilever to adjust the resonant frequency to the available environmental frequency, normally below 100 Hz. 21 , 22 Recently, MEMS technologies have been applied toward the development of integrated energy harvesters, and many piezo- electric MEMS energy harvesters have been developed. 3 , 9 , 12 , 21 ? 45 Useful metrics in comparing these devices are their active area, active volume, resonant frequency, harvested power, and power densities in volume or area. Devices with relatively higher power densities (in volume or area) or non-PZT materials such as AlN and lead-free potassium sodium niobate (KNN) are selectively shown in Table I . In order to understand the performance attributes defi ned earlier and to better compare the devices reported, basic models of vibration kinematics and piezoelectrics are summarized. Figure 2. Energy fl ow of a piezoelectric generator. 14 First, the source excitation is converted into cyclic oscillations through mechanical assembly. This step results in a loss of some energy through unmatched mechanical impedance, damping, and backward refl ection. In the second phase, the cyclic mechanical oscillations are converted into cyclic electrical energy through the piezoelectric effect. This step results in loss of some energy through electromechanical losses of piezoelectric material. Electromechanical coupling factor ( k ) represents the effi ciency of the mechanical to electrical conversion process. The product of a piezoelectric stress coeffi cient ( d ) and a piezoelectric voltage coeffi cient ( g ) represents the material fi gure of merit. In the third phase, the generated electrical energy is conditioned through rectifi cation and dc/dc conversion. This step results in some losses due to power consumption by the circuit. PIEZOELECTRIC MEMS FOR ENERGY HARVESTING 1042 MRS BULLETIN ? VOLUME 37 ? NOVEMBER 2012 ? www.mrs.org/bulletin Vibration kinematics Vibration as a common ambient energy source can be found in household appliances (refrigerators, microwave ovens, washing machines), large civil structures (buildings, bridges), industrial plants (refi neries), automobiles, and many other common locations. Table II shows some of the common sources of mechanical energy that can be harnessed through piezoelec- trics. Table III quantifi es the vibration energy available in some of these environments. 46 , 47 The general model of a vibration energy harvester is a typical mass-spring-damper system. Maximum power is achieved when the excitation frequency ? is equal to the natural frequency ? n of the system. All practical systems dissipate energy when they vibrate. To account for this, we must consider damping. Maximum extractable electrical power in terms of mass, m , mechanical damping ratio ? m , electrical damping ratio ? e , and acceleration A becomes, () 2e 2 ne m ? . 4? ? ? PA= + m (2) Several conclusions can be drawn from Equation 2 . 48 The extractable power from the beam is inversely proportional to the resonance frequency at a fi xed acceleration, A; therefore the energy harvester should be designed for the lowest pos- sible frequency to achieve the highest power. The extractable power is also proportional to the (acceleration), 2 which limits the energy available for conversion with low acceleration vibrations whatever the specifi c design is chosen. It can also be seen that power is proportional to the proof mass, so a large proof mass is always desirable for energy harvesting. Finally, the term composed of the mechanical and electrical damping ratio implies that the maximum power is achieved when the electrical damping matches the mechanical damp- ing. 49 When the electrical damping is equal to mechanical Figure 3. Basic structures of piezoelectric energy harvesters: (a) bimorph structure that has two independently polarized piezoelectric layers, and (b) unimorph structure that has one piezoelectric layer and an elastic substrate layer. Note: M, proof mass. Table I. Comparison of recent small-scale piezoelectric energy harvesters. Reference Active Material Active Area, mm 2 Active Volume, mm 3 Acceleration, g Frequency, Hz Power, ? W Power Density, ? W/mm 3 Muralt 2009 25 PZT, d 33 0.96 0.48 2.0 870 1.4 7.78 Morimoto 2010 13 PZT, d 31 92.5 0.26 0.5 126 5.3 20.5 Hajati 2010 19 PZT, d 33 120 0.02 4.0 1300 22 1100.0 Durou 2010 28 PZT 9.45 1.89 0.2 76 13.9 7.35 Defosseux 2011 30 AIN, d 31 3.573 (est.) 2.8 0.275 214 0.63 0.23 Marzencki2008 31 AIN, d 31 (vac.) 1.573 (est.) ? 0.126 214 0.55 ? Hirasawa 2010 32 AIN ? 1.63 1.0 857 0.18 0.110 Elfrink 2010 38 AIN ? 15 0.2 599 69 4.60 Xu 2011 39 PZT ? 20.9 1.0 329 7.35 0.35 Lei 2011 40 PZT ? 18.6 1.0 235 14 0.75 Park 2010 41 PZT, d 33 1.8 1.05 0.39 528 1.1 1.05 Fang 2006 42 PZT, d 31 2.65 0.78 1.0 608 2.16 2.77 Aktakka 2011 45 PZT, d 31 49 27 1.5 154 205 7.59 Kanno 2012 76 KNN, d 31 56.1 0.168 1.0 1036 1.1 6.54 Initial data were taken from Park et al. 41 and Aktakka. 45 Devices with typical non-PZT material are selected. PZT, lead zirconate titanate; KNN, potassium sodium niobate. PIEZOELECTRIC MEMS FOR ENERGY HARVESTING 1043MRS BULLETIN ? VOLUME 37 ? NOVEMBER 2012 ? www.mrs.org/bulletin damping ( ? e = ? m ) , the maximum electrical power that can be generated is given as () 223 n e,max n nm m ? ?, 16? ? 16? AY P mm == (3) where the acceleration amplitude A and proof mass defl ection Y are related by the relationship 2 n ?.AY= (4) Equation 3 represents the theoretical maximum of extractable power, which can be dissipated in the electrical load. This is actually a limiting factor for all linear resonator based energy harvesters if the transformation capacity of the piezoelec- tric layer is not a limiting factor. It has been reported that a nonlinear resonator based energy harvester can circumvent this limit and is able to generate much higher power than the mechanical damping, which will be discussed in the next section. Another parameter of interest in the design of thin- fi lm harvesters is the generalized electromechanical coupling (GEMC) factor, K . 20 The GEMC factor is obtained from the equation: 22 short open2 2 short ?? , ? K ? = (5) where ? short and ? open are the angular resonance frequencies of the associated short and open circuits, respectively. The GEMC represents the power generation performance of the vibration harvesters, and this value can be theoretically derived from the mechanical properties, thickness ratio, and electromechanical coupling factors of piezoelectric thin fi lms. 50 Piezoelectrics, energy conversion, and figures of merit Piezoelectricity is one common outcome of the lack of center of inversion symmetry in the crystal lattice. Piezoelectric generators produce high voltages and low currents and require no voltage source to operate. Some believe they are more diffi - cult to integrate into microsystems due to the high temperature required for crystallization, 21 but there have been several suc- cessful implementations of MEMS scale piezoelectric energy harvesters (see Table I ). Piezoelectric energy harvesters can be categorized by their power sources, such as ambient vibrations, impacts, fl uid, and human power. Regardless of the vibration energy sources, the basic working principle is the same?the environment applies a stress on the piezoelectric material, and by the direct piezoelectric effect, the input mechanical energy is converted to electrical energy. Two piezoelectric modes, d 31 or d 33 , are commonly used in piezoelectric microdevices ( Figure 4 ). The relative directions of the electric fi eld and the strain distinguish them: d 31 when the electric fi eld is perpendicular to the input strain, and d 33 when they are parallel. 51 Conventional MEMS piezoelectric devices/ actuators have a d 31 confi guration in which a piezoelectric layer is sandwiched between top and bottom electrodes. For a d 31 mode energy harvester, the generated voltage is proportional to the thickness of the piezoelectric layer ( t xx ), the effective piezoelectric constant, g 31,f (Vm/N), and the applied stress, ? xx . 31 31,f .V xx xx gt=? (6) For typical values of g 31,f and acceleration, the generated voltage becomes too small for the rectifying circuits, as the thickness of the piezoelectric layer drops below 1 ? m (mostly less than 0.5 ? m) in MEMS- scale harvesters. Therefore, the d 31 mode of the piezoelectric device is often not favorable for energy harvesting applications even though the generated power could be higher. For high permittivity ferroelectric piezoelectrics, the d 33 mode can generate higher open-circuit voltages by increasing the spacing between the inter- digitated electrodes where polarization wraps from one electrode to the next in alternating directions, as shown in Figure 4 . Jeon et al. showed that operating piezoelectric elements Table II. Sources of energy available in the surroundings that can be tapped for generating electricity. Human Body Vehicles Structures Industrial Environment Walking, arm motion, fi nger motion, jogging, swimming, eating, talking Aircraft, unmanned air vehicle, helicopter, automobiles, trains Bridges, roads, tunnels, farm house structures Motors, compressors, chillers, pumps, fans Wind, solar, temperature gradient, daily temperature Breathing, blood pressure, exhalation, body heat Tires, tracks, peddles, brakes, shock absorbers, turbines Control switch, heating ventilation and air conditioning systems, ducts, cleaners, etc. Conveyors, cutting and dicing, vibrating machine Ocean currents, acoustic waves, electromagnetic waves, radio frequency signal The two rows in this table represent the difference in the scale of the mechanical energy. Table III. Peak acceleration and frequency of common structures. 46 , 47 Vibration Source Peak Acceleration (m/s 2 ) Frequency (Hz) Base of a 5 HP 3-axis machine tool 10 70 Notebook computer while CD is being read 0.6 75 Clothes dryer 3.5 120 Second story fl oor of a wood frame offi ce building 0.2 100 Railway 1.078?1.568 12?16 Truck 1.96?3.43 8?15 Ship 0.98?2.45 12?13 PIEZOELECTRIC MEMS FOR ENERGY HARVESTING 1044 MRS BULLETIN ? VOLUME 37 ? NOVEMBER 2012 ? www.mrs.org/bulletin in the d 33 mode is more advantageous than in the d 31 mode for MEMS-scale PZT harvesters. 12 But, recently developed high e 31,f coeffi cient piezoelectric materials such as epitaxial PZT, Pb[Mg 1/3 Nb 2/3 ]O 3 ?PbTiO 3 (PMN-PT) or AlN can circumvent this problem, enabling d 31 mode harvesters. The power trapped in each cycle from Equation 2 is dis- sipated to structural and aerodynamic damping as well as to electrical energy via the piezoelectric effect. To maximize the harvested power, the electrical damping needs to be increased, while the structural and aerodynamic damping need to be min- imized. With the strain and electromechanical coupling, the electrical power generated via the d 33 mode piezoelectric effect of a unimorph cantilever can be expressed as 22 piezo piezo piezo exc 33 PES= vfk (7) and 2 2 33 piezo2 33 33 piezo piezo piezo stored _ energy , input _ mechanical _energy ? ? === dE e k E (8) where v piezo , E piezo , S , f exc , k 33 , and ? piezo are the volume of the piezo material, Young?s modulus, strain, excitation frequency (Hz), electromechanical coupling coeffi cient, and dielectric permittivity, respectively. As long as the beam?s stored energy minus the mechanical loss (dissipated via structural and aerody- namic damping), which can be defi ned as ?extractable energy,? is bigger than the ?conversion energy? from Equation 7 , the maximum harvested energy is determined by the piezoelectric layer volume and coupling coeffi cient. A similar statement can be made for the d 31 mode piezoelectric harvesters. The coupling coeffi cient described in Equation 7 may only be applied to conditions where the passive elastic layer stiffness can be neglected. For most MEMS energy harvesters where the piezoelectric layer is much thinner compared to the passive elastic layer, Equation 8 may not be accurate. For an energy harvester, which consists of a thin layer of piezoelectric material and a much thicker passive elastic layer, the coupling factor can be written as: 52 ()( ) ) 2 storedelectricalenergy total input mechanicalenergy stored electricalenergy mechanicalenergy input to elasticlayer mechanicalenergy input to piezoelectriclayer . = = + k (9) It can be readily seen that only a portion of the input mechanical energy is injected into the piezoelectric layer to be converted into electrical energy, while much of the energy stays in the elastic layer as strain energy and will not be converted. Therefore, the coupling coeffi cient will be lower than the real conversion rate of the piezoelectric material. A more precise fi gure of merit (FOM) for the piezoelec- tric energy harvesters can be derived by considering the power response of the piezoelectric transducer. Recently, Oliver and Priya conducted detailed modeling of the piezoelectric cantilever 53 and proposed a dimensionless fi gure of merit (DFOM) for the piezoelectric transducer material in an energy harvesting application as 54 2 31 m 31 31 11 DFOM , tan? g s   ?? ?? ?? ?? ? ? ? ?? ?? ?? ?? ?? kQ d E off resonance on resonance (10) where k 31 is the transversal electromechanical coupling factor, Q m is the mechanical quality factor (inverse of the Q m repre- sents the mechanical loss), E 11 s is the elastic compliance at the constant fi eld condition, d 31 is the transversal piezoelectric strain constant, g 31 is the transversal piezoelectric voltage constant, tan ? is the loss factor, and ? is the phase lag between the real and imaginary components of the dielectric constant. Please note the reduced tensor notation here. For example, elastic compliance is a fourth-order tensor but has been written in the reduced form as s 11 . The variable 11 indicates that the stress and strain are occurring along the 1-axis of the chosen coordinate system. The DFOM is a product of two FOMs representing off-resonance and on-resonance conditions. By comparing DFOMs for commercial piezo- electric compositions, the better piezoelectric composition could be identifi ed for energy harvest- ing applications. Defosseux et al. compared the off-resonance FOM for PZT and AlN and noticed a higher magnitude for AlN (7.8 ? 10 ?11 m 2 /C as compared to 4 ? 10 ?11 m 2 /C for PZT). 55 For PZT, the values were taken to be ? 33 / ? o = 935, d 31 = ?110 ? 10 ?12 m/V, and tan ? = 3.6% (measured on PZT 53/47 {100}-textured 2 ? m thin fi lm 56 ) . For AlN, the values were taken to be ? 33 / ? o = 10, d 31 = ?2.6 ? 10 ?12 m/V, and tan ? = 0.1% (dielectric properties measured at 10 kHz for a fi lm with a thickness of 2 ? m by Martin et al., 57 and piezo- electric properties were reported by Tsubouchi and Mikoshiba for a 1- ? m-thick fi lm 58 ). Considering Figure 4. Two modes of piezoelectric conversion of input mechanical energy depending on the relative direction of the stress, ? (or strain, ? ) and the electric fi eld, )& E . 12 The bottom drawings show the cross-section of the cantilevers shown above. They are distinguished by whether the electric fi eld is perpendicular to the input stress (or strain) direction ( d 31 mode) or parallel to it ( d 33 mode). PIEZOELECTRIC MEMS FOR ENERGY HARVESTING 1045MRS BULLETIN ? VOLUME 37 ? NOVEMBER 2012 ? www.mrs.org/bulletin that AlN processing can be made compatible with CMOS, these results indicate the promise of AlN fi lms for developing MEMS energy harvesters. Challenges of piezoelectric MEMS energy harvesters Many piezoelectric MEMS energy harvesters have been devel- oped, as listed in Table I . Their form factors are all different and can only be compared with the power density that can be defi ned as the ratio of generated power over the active material volume (volume power density, ? W/mm 3 ) or over the active material area (area power density, ? W/mm 2 ). But harvesters with high resonant frequency or those that require high accel- eration ambient vibration are less favorable considering the low frequency, low g characteristics of most ambient vibrations. In order to generate a comparative fi gure, normalization was done with respect to both area and volume of harvesters, natural frequency, and input acceleration. Based upon Equation 3 , the maximum extractable output power is proportional to (1/frequency) and (acceleration) 2 . From Equation 7 , the converted electrical power is proportional to the excitation frequency. Thus, some researchers have taken into account both frequency and acceleration variations by normal- izing the power with frequency or (acceleration) 2 . Most reported devices show orders of magnitude smaller normalized power density than required (see Table I ). One of the direct solutions to address this challenge is to improve the electromechanical coupling coeffi cient of the piezoelectric thin fi lms. Another approach is to seek new resonating beam structure designs from which more energy can be extracted at lower frequency and acceleration. 9 Another metric commonly used in literature is the normal- ized FOM, which takes into account bandwidth. 59 Bandwidth is also an important characteristic and should be accounted for in order to determine the performance of piezoelectric harvesters under unpredictable or uncontrollable spectra of ambient vibra- tions. Most piezoelectric energy harvesters have been designed based on a linear resonator (e.g., a cantilever with a proof mass). The extractable power of an energy harvester based on a linear resonator is proportional to the gain (quality factor) of the resonator, which is inversely proportional to the bandwidth. If the center frequency of a beam is off by about 2% from the input frequency, the amplitude of the beam bending drops to about 50% of the resonance peak. If it is off by 5%, then there is no resonance to amplify the strain on the piezoelectric mate- rial. Accordingly, there is a trade-off between the output power and the bandwidth. Since we cannot control the frequency of ambient vibrations, an energy harvester with a narrow bandwidth (most linear resonators) is impractical in most real applications. Several approaches have been adopted to circumvent this gain- bandwidth dilemma. For example, the natural frequency of resonating beams can be tuned by changing the axial tension of a beam through non-contact mechanisms, such as mag- netic attractive and repulsive forces. Beam dimensions and proof mass have also been tuned mechanically to widen the bandwidth. 60 , 61 However, frequency tuning inevitably con- sumes power, the tuning effi ciency is low, and the tuning range is limited. Multiple beams of different lengths have also been utilized to address this challenge, which may not be practical in terms of size and cost. Simpler and less costly methods have been sought that can provide both the wide bandwidth and high power density required for practical MEMS-scale devices are described later. Recent advances in piezoelectric MEMS energy harvesting In order to address the challenges described previously, advances have been achieved recently in piezoelectric mate- rials and resonating beam structures to achieve higher power densities and wider bandwidth. Grain textured and epitaxial piezoelectric fi lms The most simple and direct solution to enhance the output power at the fi xed size of a device is to increase the piezoelec- tric coeffi cient value. Grain texturing has been shown to be an effective method for improving the magnitude of physical con- stants in piezoelectrics by achieving a domain-engineered state. In the vicinity of the morphotropic phase boundary (MPB), a rhombohedral composition oriented along the <100> direction is known to exhibit optimum magnitudes of electromechanical coeffi cients. 62 Several studies have been conducted on tuning the piezoelectric properties through interfacial stress. Recent results by Han et al. have shown ? 90% enhancement of fer- roelectric and piezoelectric properties in MPB composition PZT thick fi lms by tailoring the magnitude of residual stress by choosing substrates with different coeffi cients of thermal expansion. 63 ? 66 The results of this study are summarized in Table IV . The electrical properties showed that the fi lms on yttria-stabilized zirconia (YSZ) substrates with highest in-plane compressive stress had the best piezoelectric properties, while that on a Si wafer with tensile in-plane compressive stress Table IV. Relationship between in-plane stress and electric/piezoelectric properties in PZT thick fi lms deposited on various substrates. Substrate In-Plane Stress [MPa] d 33 eff [pm V ?1 ] ? r [1 kHz] tan ? [1 kHz] ? P r /2 [ ? C cm ?2 ] ? E c /2 [kV cm ?1 ] Silicon 119.5 ? 4.1 (Tensile) 26.4 1026 0.025 17.0 52.6 Sapphire ?131.5 ? 1.1 (Compressive) 59.8 1260 0.023 23.4 37.4 YSZ ?270.6 ? 4.9 (Compressive) 66.1 1265 0.039 25.5 30.0 The effective piezoelectric constants ( d 33 eff ) were measured by the laser beam interferometry method. 63 ? , dielectric constant; tan ? , dielectric loss factor; P r , remanent polarization; E c , coercive fi eld; YSZ, yttria-stabilized zirconia. PIEZOELECTRIC MEMS FOR ENERGY HARVESTING 1046 MRS BULLETIN ? VOLUME 37 ? NOVEMBER 2012 ? www.mrs.org/bulletin showed lower properties. The enhanced piezoelectric properties were attributed to the fact that the c-domains parallel to the thickness direction were easy to form under in-plane compres- sive stress. This technique of inducing a compressive stress in the fi lms is quite appealing, as it can be easily implemented in the fabrication of MEMS components. Epitaxial PZT thin fi lms with c -axis orientation are also ideal materials for MEMS energy harvesters because the c -axis orientation of the tetragonal PZT results in large piezo- electric properties and a low dielectric constant. 29 , 67 However, epitaxial substrates, such as MgO and SrTiO 3 , are usually not suitable for unimorph cantilevers because of their brittleness and diffi culty of microfabrication. One solution is to transfer the epitaxial PZT fi lms onto fl exible cantilevers. Qi et al. transferred epitaxial PZT thin fi lms deposited on MgO sub- strates to fl exible polydimethylsiloxane substrates and evalu- ated fundamental piezoelectric characteristics. 68 Morimoto et al. developed high effi ciency piezoelectric energy harvesters using c -axis oriented PZT thin fi lms, which were transferred onto stainless steel. 13 The fabrication process from this study is shown in Figure 5 . The c -axis oriented PZT thin fi lms were grown on (100) MgO single crystals with epitaxial (001) Pt bottom elec- trodes. Reciprocal lattice space maps of the (204) PZT before and after the transfer process clearly show spotty diffractions of the (204) PZT, indicating that the transfer process did not degrade the crystal structure of the epitaxial PZT fi lm. After the PZT fi lm was bonded to 50- ? m-thick stainless steel sheets with epoxy resin, the MgO substrate was etched out using phosphoric acid. A photograph of a stainless steel cantilever beam covered with the epi- taxial PZT is shown in Figure 5 . The relative dielectric constant ? r of the transferred fi lms on stainless steel was as low as 166, while the piezoelectric coeffi cient e 31,f of the transferred PZT fi lms was around ?6 C/m 2 . The thickness and length of the stainless steel cantilever were 50 ? m and 18.5 mm, respectively. Because of the thin dimensions of the metal cantile- ver, the fi rst resonance was found to occur at 126 Hz. 13 Experimental peak-to-peak voltage, and experimental and calculated averaged output power are plotted in Figure 6 (accel- eration: 5 m/s 2 ). A maximum output electric power of 5.3 ? W across a load resistance of 50 k ? was measured. In this measurement, the GEMC, K 2 , was calculated to be 1.3 ? 10 ?2 , which is much larger than the value for poly- crystalline PZT thin fi lms on Si substrates. 20 This result was attributed to the large elec- tromechanical coupling coefficient k 31 of c -axis oriented epitaxial PZT thin fi lms. The output power increased monotonically with acceleration, reaching 244 ? W at 50 m/s 2 . The fl exible metal cantilever enables considerable reduction of the resonant fre- quency and offers enhanced toughness compared with brittle Si-based cantilevers. It is well-known that oriented relaxor ferroelectric single crystals, such as Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 (PMN-PT) and Pb(Zn 1/3 Nb 2/3 )O 3 -PbTiO 3 (PZN-PT), show about a 10 times larger piezoelectric coeffi cient than conventional PZT ceram- ics due to the domain engineered state. 69 , 70 Recently, Baek et al. successfully grew epitaxial PMN-PT thin fi lms on SrTiO 3 ?buffered miscut Si substrate by off-axis sputtering (see the Baek et al. article in this issue). The piezoelectric coeffi cient e 31,f in their work was reported to be ?27 C/m 2 , which is the highest value ever reported. 71 Using these fi lms, they fabricated a unimorph micro-cantilever and confi rmed the excellent inverse piezoelectric performance. Because of the large electromechanical coupling coeffi cient k 31 (or fi gure of merit: e 2 31,f / ? r ) of PMN-PT epitaxial thin fi lms, this system is quite promising for improving the performance of current MEMS energy harvesters. Figure 5. Fabrication fl ow and photograph of transferring epitaxial lead zirconate titanate (PZT) thin fi lms to a stainless steel cantilever: 13 (step 1) deposition of c -axis oriented PZT thin fi lms on Pt/MgO; (step 2) deposition of Cr top electrode; (step 3) bonding the PZT thin fi lms to a stainless steel cantilever; and (step 4) etching out the MgO substrate. PIEZOELECTRIC MEMS FOR ENERGY HARVESTING 1047MRS BULLETIN ? VOLUME 37 ? NOVEMBER 2012 ? www.mrs.org/bulletin Lead-free piezoelectric fi lms For powering medical implants and human use of energy harvesters, a lead-free piezoelectric material is desirable due to the toxicity of Pb. Potassium sodium niobate (K x Na 1? x NbO 3 ), or KNN, is considered to be a very promising lead-free piezo- electric material owing to its high Curie temperature and high ferroelectric orthorhombic?ferroelectric tetragonal transition temperature. 72 The piezoelectric properties of KNN-based com- positions are directly correlated to the fraction of orthorhombic (O) and tetragonal (T) phases, as shown in Figure 7 a. One of the strategies for achieving a higher piezoelectric response has been to modulate the composition such that the O/T transition lies close to room temperature. 73 Another strategy adopted for designing lead-free compositions is based upon the trend between the atomic weight ratio of A to B sites ( R w = W a / W b ) and the longitudinal piezoelectric constant d 33 , as shown in Figure 7b . 74 It can be observed that 1/ R w for KNN ceramics (for Na/K ratio of 0.5) is similar to R w for PZT ceramics at the MPB composition, and both of these materials exhibit high piezoelectric response. Piezoelectric com- positions show a large response when R w for A-site heavy perovskites and 1/ R w for B-site heavy perovskites are higher than 2.0. The fabrication process of these lead-free piezoelectric materials in thin-fi lm form is still under development, and it is expected that these materials will be utilized in the design of MEMS energy harvesters in the near future. Recently, Shibata et al. reported that KNN thin fi lms deposited by radio frequency (RF) magnetron sputtering showed large transverse piezoelectric properties comparable to those of PZT thin fi lms. 75 Kanno et al. have compared the energy harvesting performance of KNN thin fi lms with PZT thin fi lms by using simple unimorph Si-cantilevers. 76 The piezo- electric coeffi cient of both KNN and PZT fi lms showed almost the same value of e 31,f = ?10 C/m 2 . 77 The relative dielec- tric constants of the KNN and PZT fi lms were 744 and 872, respectively. Measurements were performed at the resonance frequency of each cantilever (KNN: 1.0 kHz, PZT: 0.89 kHz; acceleration 10 m/s 2 ). Peak output power for the KNN and PZT fi lms was 1.1 ? W at 1.7 k ? and 1.0 ? W at 1.2 k ? , respec- tively. Because KNN and PZT thin fi lms have almost the same dielectric and piezoelectric properties, the KNN fi lm performs comparably to the PZT fi lm with respect to power generation. GEMC K 2 of KNN and PZT energy harvesters was around 0.6 ? 1.7 ? 10 ?3 , as determined by fi tting the calculated value of Equation 5 to experimental results. 76 Aluminum nitride?A MEMS compatible piezoelectric fi lm Recently, signifi cant progress has been made toward incorpo- rating AlN fi lms in energy harvesting applications. van Schaijk et al. have demonstrated the performance of micomachined AlN cantilevers and have shown that a device with dimensions of 3 ? 1.3 mm 2 was able to provide 10 ? W at the resonance frequency of 1155 Hz under 8g acceleration. 78 Under practical acceleration values of 1g or lower, the power generated was smaller than 1 ? W. Heidrich et al. have investigated the energy generation from [001] textured AlN cantilevers and corrugated membranes for bio-implants. 79 The growth was conducted on Si(001) substrates, which resulted in tensile (< +300 MPa) and compressive strains (> ?100 MPa), depending upon the deposition parameters. In the non-resonant condition of 70 Hz, for a 3 ? 4 corrugated membrane array (radius of individual Figure 6. Output voltage and generated power of transferred epitaxial lead zirconate titanate (PZT) thin fi lms on a stainless steel cantilever as a function of load resistance. 13 The maximum output power reached 5.3 ? W at the low acceleration of 5 m/s 2 due to the large electromechanical coupling factor k 31 of c -axis oriented PZT thin fi lms. Figure 7. A piezoelectric coeffi cient can be tuned by adjusting the intermediate phase transition temperature in a polymorphic phase boundary system and A-site to B-site weight ratio in perovskites. (a) Variation of longitudinal piezoelectric coeffi cient ( d 33 ) with orthogonal phase (O)?tetragonal phase (T) transition temperature ( T O-T ) in the potassium sodium niobate (KNN) system; 73 (b) variation of longitudinal piezoelectric coeffi cients as a function of weight ratio in bulk perovskites. 74 PT, PbTiO 3 ; PZT, Pb(Zr,Ti)O 3 ; PZN, Pb(Zn 1/3 Nb 2/3 )O 3 ; PNN, Pb(Ni 1/3 Nb 2/3 )O 3 ; PMN, Pb(Mg 1/3 Nb 2/3 )O 3 ; BNT, (Na 1/2 Bi 1/2 )TiO 3 ; BKT, (K 1/2 Bi 1/2 )TiO 3 ; BT, BaTiO 3 ; LN, LiNbO 3 ; LS, LiSbO 3 ; LNTS, (Li,Na)(Ta,Sb)O 3 ; ST, SrTiO 3 ; CT, CaTiO 3 ; BCuN, Ba(Cu 1/3 Nb 2/3 )O 3 . Clearly, a large piezoelectric coeffi cient is obtained by shifting T O-T toward room temperature and by keeping the weight ratio within a narrow range. PIEZOELECTRIC MEMS FOR ENERGY HARVESTING 1048 MRS BULLETIN ? VOLUME 37 ? NOVEMBER 2012 ? www.mrs.org/bulletin membrane = 400 ? m), a peak power of 10 ? W was measured across 10 k? with a bias of 1 V and an acceleration of 0.01g. 79 Yen et al. conducted detailed experimentation and modeling of the corrugated AlN cantilever structures. At a resonance frequency of 853 Hz, a cantilever with a width of 2400 ? m, a length of 500 ? m, and a 2- ? m-thick piezoelectric layer was able to provide 0.17 ? W under an acceleration of 1g using a tip mass of dimensions 2400 ? 500 ? 680 ? m 3 . 80 Stoppel et al. conducted a simulation study in this area that computed the effect of thickness on power generation. 81 It was pointed out that since the Young?s modulus of AlN (345 GPa) is about 4x that of PZT, the thickness of AlN for maximum power output is about 3x smaller than that of PZT. For a cantilever with 2- ? m-thick AlN operating at a resonance frequency of 105.6 Hz under an acceleration of 1 m/s 2 , an output power of 0.8 ? W was measured across a 21 M? load. Based upon the experimental data available in the literature, the normalized output power (power/frequency ? acceleration) for AlN microdevices ranges between 2.034 ? 10 ?5 and 757 ? 10 ?5 ? W/(Hz ? m/s 2 ). Ignoring the data from Stoppel et al., the spread is more reasonable from 2.034 ? 10 ?5 to 11 ? 10 ?5 ? W/(Hz ? m/s 2 ). These values are quite good, and considering the compatibility of AlN with CMOS processing and the long history in optimizing the deposition process, we expect that this area will continue to grow. Nonlinear resonance-based energy harvesting structures Most of the reported vibration energy harvesters use a linear cantilever resonator structure to amplify small ambient vibrations. While such structures are easy to model, design, and build, they typically have a narrow bandwidth. In contrast, nonlinear resonators have a differ- ent dynamic response and greatly increase the bandwidth by hardening or softening the res- onance characteristics of the beam structure. In addition, it has been found that nonlinear resonating beams can extract more electrical energy than linear resonating beams. 9 , 82 Nonlinearity may come from a magnetic force or constrained mechanical structures. The magnetic force between the iron mass at the tip of a cantilever and an external magnet (or vice versa) creates a nonlinear spring, whose nonlinearity is determined by the strength of the magnets and the size of the air gap between the magnets and the iron stator. Due to the mutual attraction, the ferromagnetic beam has three equilibrium positions (stati- cally bi-stable confi guration), and the vibra- tion mode has the form of the bi-stable Duffi ng resonance. Electromagnetic energy harvesters have been reported showing hardening or soft- ening resonance characteristics. 83 ? 86 However, magnet-based beams require assembly of hard magnets, which is expected to be costly as the size of the device shrinks. Nonlinear resonance could be better achieved by monolith- ically fabricated MEMS structures. Efforts have been made to achieve wide bandwidth piezoelectric energy harvesters by exerting axial compression and forming a buckled confi gu- ration to make a bi-stable oscillator. 87 Recently, Hajati et al. demonstrated a monolithic MEMS-based nonlinear resonant piezoelectric micro energy harvester, which achieved an ultra- wide bandwidth of >20% of the center frequency and generated power more than 22 ? W (see Figure 8 ). 9 More than one order of magnitude improvements were demonstrated compared to devices previously reported for the power bandwidth (see Table I ). The basic design is based on a doubly clamped beam resonator with dimensions of 6 mm ? 6 mm ? 5.5 ? m (length ? width ? height) and a PZT thickness of 0.25 ? m. Four of these resonators are arranged perpendicular to each other and form one energy harvester, which is about the size of a US quarter coin ( Figure 8a ). At large defl ection (exceeding 2?3 times the thickness of the beam), a net stretching in addition to bending results, changing the dynamic response to a nonlinear one ( Figure 8b ). Based on the measured open-circuit voltage in Figure 8c , the internal capacitance (8.5 nF), and resistance (3.5 M ? ) of the measurement circuit, the generated power is Figure 8. The fabricated nonlinear beam microelectromechanical systems energy harvester shows ultra-wide bandwidth and high power density energy harvesting: (a) fabricated device on a US quarter dollar coin; (b) simulated dynamic response of a nonlinear resonator, which shows a tilted resonance peak; (c) measured open-circuit voltage versus excitation frequency; (d) Curve 1: extractable strain energy stored in the beam, and Curve 2: generated power 45 ? W. By increasing the thickness of the piezoelectric layer to 0.75 ? m, up to 80 ? W can be harvested at the same harvesting condition. 9 PIEZOELECTRIC MEMS FOR ENERGY HARVESTING 1049MRS BULLETIN ? VOLUME 37 ? NOVEMBER 2012 ? www.mrs.org/bulletin estimated as shown in Figure 8d . The result shows orders of magnitude improvement in bandwidth, as compared in Table I . Unlike a linear resonance system, where the electrical damping cannot exceed the mechanical damping, 49 Hajati et al. showed that electrical damping in a nonlinear resonance sys- tem could surpass the mechanical damping, extracting a much higher output power than that of the linear systems. The nonlin- ear impedance serves as a negative feedback and stabilizes the defl ection when the electrical damping changes. 88 This is why the power bandwidth of nonlinear systems can be much wider than that of linear systems at equivalent beam dimensions. A smart electronic interface such as adaptive synchronized switch harvesting on an inductor will be ideal to extract high power from nonlinear beam harvesters. 89 Summary Microelectromechanical system (MEMS) piezoelectric energy harvesters with ? mm 3 dimensions will lead to battery-less autonomous sensor systems and networks with 10s to 100s of ? W of power that can be extracted from the ambient vibration continuously, robustly, and at low cost. The key attributes to make a good piezoelectric MEMS energy harvester include its compactness, output voltage, bandwidth, operating frequency, input vibration amplitude, lifetime, and cost. Among them, higher power density and wider bandwidth of resonance are the two biggest challenges currently facing the technology. But the state of the art is still about one order smaller than what is needed for practical applications. Recent advances in piezoelectric materials and harvester structural design, individ- ually or in combination, are bringing us closer to battery-less autonomous sensor systems and networks. Giant piezoelectric coeffi cient materials, epitaxially grown fi lms, grain textured piezoelectric materials and thin fi lms, and high performance lead-free piezoelectric materials are recent advancements made toward increasing the electromechanical energy con- version of piezoelectric harvesters. Nonlinear resonators are extremely promising to extract more electrical energy from the beam with much wider bandwidth. We expect that in the near future, a coin-sized harvester will be able to harvest about 100 ? W of continuous power below 100 Hz at less than 0.5 g vibration and at reasonable cost. 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NOVEMBER 2012 ? www.mrs.org/bulletin i???i?]???U??/i?\???n??n???xx?? ?>?i?J??????>V?V????U?????????>V?V?? Need Nano particles or coatings? Call 800-99ULVAC or email sales@us.ulvac.com. The ULVAC Arc Plasma Deposition System (APD) produces extremely smooth thin fi lms and uniformly sized nano particles. The APD System deposits magnetic, DLC and metal fi lms in R&D, material science, fuel cell and automotive applications. /?i?* ?-???i??`i???i??\ U Extremely smooth ultra-thin fi lms ? 0.01 to 0.3 nm/sec U Size-controlled nano particles ? 1 nm to 30 nm dia. U Dense fi lm formation without process gas U Small target size: 10 mm dia. x 17 mm U Uniformity +/- 10% over 50 mm diameter coated area Nano Particles and Coatings Iron and carbon multi-layer fi lm. MRS BOOTH 713 44. B.S. Lee , S.C. Lin , W.J. Wu , X.Y. Wang , P.Z. Chang , C.K. Lee , J. Micromech. Microeng. 19 ( 6 ), 065014 ( 2009 ). 45. E.E. Aktakka , PhD thesis, University of Michigan ( 2012 ). 46. S. Priya , J. 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