Proceedings of the XIth International Congress and Exposition June 2-5, 2008 Orlando, Florida USA 2008 Society

for Experimental Mechanics Inc.

Mechanical Properties of PZT Films and their Composites for RF-MEMS

S. Yagnamurthy1, I. Chasiotis1, J. Lambros1, R. Polcawich2, J. Pulskamp2, M. Dubey2

1

Aerospace Engineering, University of Illinois at Urbana-Champaign, IL 61801, U.S.A. 2 US Army Research Laboratory, Adelphi, MD 20783, U.S.A.

ABSTRACT The mechanical response of Lead Zirconate Titanate (PZT) in thin film form has been investigated by microscale uniaxial tension experiments of PZT stacks. Due to the difficulty in fabricating individual freestanding PZT films, thin film stacks were fabricated in combinations of Silicon Oxide (SiO2), Titanium (Ti), Platinum (Pt) and PZT. The specimens tested were stacks of SiO2-TiPt-PZT-Pt, SiO2-TiPt-PZT, and individual SiO2 and Pt thin films, with gauge lengths of 1000 microns and widths of 50-100 microns. Full-field strain measurements were conducted with the aid of a fine speckle pattern (1 m particle size) generated on the samples and analyzed by digital image correlation. The composite mechanical properties of the PZT stacks were computed from the stress vs. strain plots, while the mechanical properties of individual PZT films were computed from those of the PZT stack and the properties of SiO2 and Pt films.

1.

INTRODUCTION

The increasing demand for miniaturization led to design of Microelectromechanical Systems (MEMS) containing composite thin films as their structural components. A better understanding of the mechanical behavior of these materials is required to design devices with greater longevity and durability, currently subject to mechanical failures. Of these, Lead Zirconate Titanate (PZT) films are used in MEMS devices to produce large actuation forces upon the application of a voltage potential. These materials have also been proposed for energy harvesting applications, such as back-pack straps, shoes, etc, to convert mechanical into electrical energy [1]. Hence, understanding the mechanical behavior of PZT films is important for the reliability of the aforementioned systems. The literature on mechanical properties of PZT films is very limited. Almost all available data have been obtained by nanoindentation [2,3] and membrane bending techniques [4] that were applied to measure the elastic modulus of PZT films. These films are almost exclusively fabricated in conjunction with Silicon Oxide (SiO2) and Platinum (Pt), and therefore the properties of SiO2 and Pt are also needed. The former is commonly used in a thin film PZT stacks as a thermal and electrical insulating layer, while the latter serves as electrode to bias the PZT layer. Over the last decade, silicon dioxide thin films were investigated for their properties by different techniques, such as nanoindentation [5], bulge tests [6], resonance tests [7] and uniaxial tensile tests [8,9]. However, the modulus values reported for SiO2 materials are widely scattered, due to material differences, e.g. porosity, and experimental uncertainties. In this paper we present the first systematic experimental investigation of the properties of PZT as they are derived from composite properties of freestanding thin film stacks consisting of combinations of SiO2, Titanium (Ti), Pt, and PZT. The latter was considered as nominally brittle material and its properties were obtained from the composite stress-strain curves. Two different combinations of stacks were used and the properties derived for PZT from each material system were very consistent.

2.

MATERIALS AND EXPERIMENTAL METHODS

Uniaxial tension was employed to test specimens made of various combinations of SiO2, Ti, Pt, and PZT. Experiments were conducted on specimens made of SiO2-TiPt-PZT-Pt, SiO2-TiPt-PZT, and individual SiO2 thin films, with gauge lengths of 1000 m and widths of 50-100 m. The mechanical response of the PZT films was extracted, using basic lamination theory assuming isostrain condition since no delaminations were detected in post-failure SEM imaging. Individual Pt films were not tested, but prior results from work by this group by the work by Jonnalagadda et al [10] were used in the analysis. The patterned samples were fabricated by chemical vapor deposition on a silicon substrate followed by chemical etching to obtain freestanding dog bone thin films as shown in Figure 1. The specimens one end remained fixed to the substrate and the other was freestanding with the support of tethers. The SiO2 specimens were thin films with a gauge length of 1000 m, 100 m width, and 0.284 m thickness. SiO2-TiPt-PZT-Pt and SiO2-TiPt-PZT stacks were of similar shape and gauge length but differed in their width and thickness, Figure 2(a). The sample dimensions are listed in Table 1.

Figure 1. Freestanding SiO2-TiPt-PZT-Pt film with its one end fixed and other tethered to silicon wafer.

In this study it was important that strain measurements were obtained directly from the specimen surface. Our group has already developed high resolution methods, such as the Atomic Force Microscopy/Digital Image Correlation (AFM/DIC) [11,12] to resolve strain fields directly from MEMS-scale specimens with widths as small as 6 m. More recently, we have reported on optical-based high resolution measurements of strains with the aid of DIC [10,13]. The latter approach was further refined in this work by developing a very fine and dense speckle pattern on the specimen surface. We applied silicon or alumina nanoparticles on the specimen surface, measuring less than a micron in diameter. Developing such a pattern in not a simple task, due to the particles natural tendency to agglomerate because of moisture or static charges, and the fact that the thin films are extremely fragile and cannot be exposed to wet conditions. Table 1. Geometry of PZT composite stacks tested in this work Layer thickness Layer SiO2 SiO2/TiPt/PZT SiO2/TiPt/PZT/Pt (nm) 284 410/104/1007 320/112/1072/120 Total thickness (nm) 284 1521 1624 Specimen width (m) 100 50 100

Figure (2b) shows a sample pattern generated on the surface of a 100-m wide. Using this surface speckles we have shown in previous works that an accuracy in displacement resolution of at least 23 nm is be achieved [14]. This refined pattern allowed us to measure both axial and transverse strain and therefore calculate both the elastic modulus and Poissons ratio for the materials at hand.

SiO2 Pt PZT Pt

(a)

(b)

Figure 2. (a) Cross sectional image of SiO2-TiPt-PZT-Pt, and (b) specimen with fine speckle pattern for direct and full-field strain measurements. The uniaxial tensile testing setup consisted of a sturdy platform with a mounted PZT actuator to generate loading, and a loadcell to measure the load in the sample, similar to that reported before [11,12]. Adjustable stages were used to mount the PZT actuator and loadcell on the platform. The die containing specimens was fixed onto a metal holder connected to the loadcell. A thin glass grip, as wide as the specimens peddle, connected to the PZT actuator was attached to the freestanding end of the specimen by a using UV curable adhesive. The tethers supporting the specimen standing freely on silicon wafer were broken by a tungsten filament mounted to a probing stage. The platform was placed under an optical microscope with a CCD camera, to capture magnified (200) pictures of the specimens gauge section while loading. The specimens were loaded at a strain rate of 610-4 s-1, while the load developed in the film was measured and recorded by a loadcell. With the help of DIC and the very fine speckle pattern, the strain in the specimen was computed and the stress-strain curves were plotted.

3.

RESULTS AND DISCUSSION

Analysis was conducted on the specimens tested to compute stress-strain curves, and from them compute basic mechanical properties, i.e. elastic modulus, tensile strength, and ultimate strain for SiO2, SiO2-TiPt-PZT-Pt, SiO2TiPt-PZT films. The elastic modulus of PZT was then extracted from the results of the composite materials and available data in our group for Pt [10]. Figures 3(a,b) show typical axial and transverse displacement fields measured from a SiO2 specimen. It should be noted that both contours are very well aligned with the specimen edges which denotes the excellent alignment of the specimen in the tensile apparatus. A total of 11 SiO2 specimens were tested. An example stress strain curve is shown in Figure 3(c). The asfabricated specimens were slightly curved out-of-plane in the axial direction due to pre-stress and hence measuring strain from absolute zero loading could not be achieved. However, SiO2 showed excellent elastic behavior as evident from the stress-strain plot and significant strain-to-failure compared to bulk glass. The modulus of SiO2 was measured as 72 GPa which agrees very well with the modulus of bulk silicon oxide 73 GPa. The maximum stress measured was 1.17 GPa at a maximum strain of 1.6%, larger compared to typical failure strain of brittle materials, due to only few defects in the present films and the very good definition of the specimen edges. The failure strain was not the same for all dies. For instance, specimens tested different dies, fabricated in different lots, broke at strains as low as 1.2%. While one may attribute this to a Weibull effect, the failure strains (or strengths) from specimens in the same lot were very consistent. Strain in the lateral directions was also computed by DIC to plot the Poissons ratio of the material, as shown in the Figure 3(b,d). From figures similar to that in Figure 3(d) the Poissons ratio of SiO2 was measured for the first time from MEMS thin films as was equal to 0.20, which compares well with bulk values (0.18).

(a)
1400 1200 1000 800 600 400 200

(b)
0.5

E = 72.3 GPa
0.4

Stress (MPa)

Poisson's Ratio

0.3 0.2 0.1 0 0 -0.1 0.005

= 0.20

0.01

0.015

0 0 0.005 0.01 0.015

-0.2

Strain

Axial Strain

(c)

(d)

Figure 3. (a,b) Contour plots of axial and transverse displacement distributions, (c) stress-strain plot of freestanding SiO2 film and, (d) Poissons ratio plotted against axial (elastic) strain. The deviation at smaller strains is due to a slight curvature in the transverse direction that is removed as the specimen is axially loaded.

The stress-strain plots of PZT thin film stacks consisting of SiO2-TiPt-PZT-Pt and SiO2-TiPt-PZT are shown in Figure 4. Each plot includes an elastic loading-unloading segment and final reloading to fracture. The composite moduli for SiO2-TiPt-PZT-Pt and SiO2-TiPt-PZT films were 94.7 GPa and 87.8 GPa, respectively, with failure strains being 0.65% and 0.5%, respectively. The difference in the failure strain is attributed to the additional layer of strong and ductile Pt (see Figure 5) in SiO2-TiPt-PZT-Pt. The stress strain curves of SiO2-TiPt-PZT-Pt and SiO2-TiPt-PZT specimens showed inelastic behavior (i.e. there is elastic limit) after approximately 0.35% strain. The properties of the PZT thin film were extracted from the mechanical response of SiO2-TiPt-PZT-Pt and SiO2TiPt-PZT composite films using simple lamination theory. PZT stacks fabricated by chemical vapor deposition of the different layers have strong interfacial bonds that subject all laminas to an isostrain condition upon uniaxial loading. This is an assumption in the following calculations, which was supported by SEM images, Figure 2(a), where no interlayer failure was detected. The total tensile load applied to SiO2-TiPt-PZT-Pt specimen was carried cumulatively by all layers in the composite which leads to the following equation for the elastic modulus of PZT:

EPZT =

EStack tStack ESiO2 tSiO2 + 2 EPt t Pt t PZT

(1)

where E and t are elastic modulus and thickness of each layer mentioned in the subscripts.
600 500
600

E = 94.7 GPa R2 = 0.997

Stress (MPa)

500 400 300 200 100 0

E = 87.8 GPa

Stress (MPa)

400 300 200 100 0 0 0.002 0.004 0.006 0.008

0.001

0.002

0.003

0.004

0.005

0.006

Strain

Strain

(a)

(b)

Figure 4. (a) Stress vs. strain plot of freestanding SiO2-TiPt-PZT-Pt film and, (b) SiO2-TiPt-PZT film. Both plots include the loading-unloading and final reloading segments of the stress-strain curves. A titanium layer measuring few nanometers was used as adhesive material between SiO2 and Pt, but because of its small thickness it was not taken into account in the calculations of the PZT properties. The thickness of the individual layers of the composite was measured by cross-sectional SEM imaging, Figure 2(a). It was found to vary in different dies and fabrication lots, and it was often different from the nominal values estimated by deposition rates and times. Similarly, for the composite film SiO2-TiPt-PZT, the PZT modulus was calculated by

EPZT =

EStack tStack ESiO2 tSiO2 + EPt t Pt t PZT

(2)

Substituting the values for the moduli of freestanding SiO2, SiO2-TiPt-PZT-Pt, and SiO2-TiPt-PZT measured in this study, and for Pt (E=173.2 GPa) from reference [10] in Equations (1) and (2), the elastic modulus of PZT for each stack was 82.4 GPa and 85.3 GPa, respectively. The mechanical properties of all materials tested are listed Table 2. Figure 5 shows a comparison of the different stress-strain plots for each material. Equations similar to (1) and (2) were used to calculate the failure strength of PZT assuming that fracture was initiated in the PZT layer. This is supported by the fact that the failure strain of SiO2 was systematically higher than that of the composite stacks. By virtue of a maximum principal strain criterion it is deduced that PZT was the weakest link in all composite films. The average tensile strength of the PZT layer varied in the range 426-495 GPa (average 460 GPa). In Figure 5, it is noticed that due to the plastic deformation of the Pt layers, the stress-strain curves of the PZT stacks demonstrated inelastic behavior after 0.35%. Therefore, considering this as the elastic limit of the PZT composites, this limiting strain is of vital information in the design of PZT stacks in MEMS structural components. Furthermore, Figure 5 shows clearly the elastic limit for the softening behavior of SiO2-TiPt-PZT-Pt, and SiO2TiPt-PZT corresponds to the elastic limit of Pt loaded at the same strain rate (~10-3 s-1) as the composite samples. It must be noted that this value of the elastic limit is strain rate dependent and can be used only in this particular strain rate. A thorough study of the effect of strain rate on the mechanical response of Pt films can be found in [10].

Figure 5. Stress-strain curves of the different layers tested in this work. All curves include the loading-unloading and final reloading segments. Table 2. Mechanical properties of the PZT composites and their components Material SiO2 SiO2-TiPt-PZT-Pt SiO2-TiPt-PZT PZT (Extracted) Elastic modulus (GPa) 72 93.5 87.9 83.8 Tensile strength (MPa) 1046 511 412 460 Range of failure strains (%) 1.2 - 1.6 0.5 - 0.6 0.4 - 0.5 0.4 - 0.6

4.

CONCLUSIONS

In this paper, the mechanical properties of PZT film stacks with different combinations of SiO2, Ti, Pt and PZT were reported for the first time. The elastic modulus of freestanding SiO2 thin films was found to agree very well with bulk measurements, E= 72 GPa, with maximum tensile strength and strain of 1,170 MPa and 1.6%, respectively. The Poissons ratio of SiO2 was measured for the first time from thin films and it was found to be 0.20, which also agrees well with reported values for bulk silicon oxide. The failure strength of SiO2-TiPt-PZT-Pt and SiO2-TiPt-PZT composites was in the range of 410-510 MPa. From the stress-strain curves of freestanding SiO2-TiPt-PZT-Pt and SiO2-TiPt-PZT thin films, the average elastic modulus for PZT was 83.8 GPa and the average tensile strength varied in the range 426-495 GPa (average 460 GPa). Both PZT stacks exhibited inelastic behavior at 0.35% strain which sets an upper limit for the mechanical and thermal stresses to be exhibited by a MEMS device.

5.

ACKNOWLEDGMENTS

The UIUC authors acknowledge the support by the Army Research Office Grant# W911NF-05-1-0063 with Dr. Bruce LaMattina as the Program Manager, and by the National Science Foundation under grant CMS-0555787.

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