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Fabrication and mechanical property of nano piezoelectric fibres

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2006 Nanotechnology 17 4497 (http://iopscience.iop.org/0957-4484/17/17/036) View the table of contents for this issue, or go to the journal homepage for more

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INSTITUTE OF PHYSICS PUBLISHING Nanotechnology 17 (2006) 44974501

NANOTECHNOLOGY doi:10.1088/0957-4484/17/17/036

Fabrication and mechanical property of nano piezoelectric bres

Shiyou Xu1 , Yong Shi1,3 and Sang-Gook Kim2
Mechanical Engineering, Stevens Institute of Technology, Hoboken, NJ 07029, USA Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA
2 1

E-mail: [email protected]

Received 28 June 2006, in nal form 24 July 2006 Published 21 August 2006 Online at stacks.iop.org/Nano/17/4497 Abstract Aligned piezoelectric (PZT) nanobres were fabricated by electrospinning using PZT solgel as precursor. A pure perovskite phase with an average grain size of 10 nm was obtained at 650 C. The average diameter of these bres could be controlled to range from 52 to 150 nm by varying the concentration of poly(vinyl pyrrolidone) (PVP) in the precursor. Special samples of PZT nanobres were deposited across the microfabricated trenches on a silicon wafer. Atomic force microscopy (AFM) was used to measure the mechanical properties of a single nanobre. The elastic modulus of an individual PZT nanobre that was obtained was 42.99 GPa, which was smaller than that of a thin-lm PZT. The possible reasons for the reduction in elastic modulus of the nanobres were discussed. (Some gures in this article are in colour only in the electronic version)

1. Introduction
Lead zirconate titanate (PbZr1x Ti x O3 , PZT) is a typical piezoelectric material with a high electromechanical coupling coefcient, high dielectric constant and large remnant polarization [1]. The advantages of PZT-based devices include high bandwidth, fast response, and high sensitivity. Although the commonly used forms of PZT are bulk and thin lm, PZT bres have attracted more attention because they provide more exibility in their applications. PZT bres are suitable for inclusion in composite structures and novel actuators and sensor devices, such as energyharvesting devices, high-frequency transducers, self-powered in vivo medical devices [2], composite force sensors [3], hydrophones [4], ultrasonic imaging [5] and therapeutics [6], condition monitoring [7], etc, because of their increased anisotropy, excellent exibility and improved strength over monolithic PZT ceramics [8]. Nano-scale PZTs are expected to nd wide applications in nano-electronics, photonics, sensors and actuators [9, 10]. There are many methods for fabricating PZT bres with micro-size diameters, while there are only about three methods for the synthesis of PZT nanobres, which
3 Author to whom any correspondence should be addressed.

include hydrothermal synthesis [11], sol electrophoretic deposition [12], and the metallo-organic decomposition (MOD) electrospinning method [13]. However, the bres (or nanowires) produced by bottom-up methods such as hydrothermal and electrophoretic deposition are discontinuous, which limits their applications in creating working devices [14]. In contrast, the electrospinning method can produce continuous bres with diameters from tens to hundreds of nanometers, and it is easy to get aligned bres using simple auxiliary methods [15]. Solgel processing is a wet chemical route for the synthesis and processing of inorganic and organicinorganic hybrid materials. Solgel processing offers many advantages, including low processing temperature and molecular-level homogeneity [12]. Measuring the mechanical properties of an individual nanobre is a key challenge for its application. On the one hand, the diameters of nanobres are rather small, prohibiting the applications of well-established testing techniques; on the other hand, the small sizes of the nanobres make their manipulation rather difcult, and specialized techniques are needed for picking up and installing individual nanobre. A combination of an atomic force microscope (AFM) with microfabrication techniques makes the testing of nanobre properties possible. It was reported that the elastic properties 4497

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2006 IOP Publishing Ltd Printed in the UK

S Xu et al

There are several methods for obtaining aligned electrospun bres [20, 21]. We have developed a similar process for obtaining well-aligned nanobres. 2.2. Characterization of nanobre elastic property
Power source Pump & syringe Si substrate

Tip

Figure 1. Schematic diagram of the electrospinning setup.

of carbon nanotube [16], ZnO nanowire [17] and poly (Llactic acid) (PLLA) nanobre [18] has been tested by AFM. A similar approach can be adopted to measure the mechanical properties of piezo nanobres. In this paper, we present a new approach for developing aligned PZT nanobres which utilizes electrospinning and solgel processing. The morphology, crystal structure and nanostructure of PZT nanobres were investigated, and the relationship between the materials concentration and the bre diameter was obtained. Furthermore, the elastic modulus of the PZT nanbre was obtained by performing a nanoscale threepoint bend test on a single bre over a microfabricated trench in a silicon wafer using AFM.

Both mechanical and piezoelectric properties of the nanobres are important for the design of nano-actuators or nano-active composites. Mechanical characterization of the nanobres was conducted with the assistance of microfabrication. Microtrenches were patterned on the silicon wafer and etched using deep reactive ion etching (DRIE) for nanobre sample preparation. A single bre was deposited across the trench, with the orientation of the nanobre perpendicular to the edges of the trench. The lateral force mode of the AFM was used to investigate the boundary conditions of the nanobre on the trench edge, while the contact force imaging mode was used to obtain the force and the deection of the nanobre at the centre point. SEM images were taken using a eld-emission scanning electron microscope (LEO 982) operated at an accelerating voltage of 5 and 3 kV. The diameters of the nanobres were quantitatively determined by SEM. TEM images were taken using a Philips CM20 microscope operated at 80 kV. The x-ray diffraction (XRD) pattern was recorded using a Simens 6000 (Cu K radiation) at a scanning rate of 0.05 with 2 ranging from 20 to 60 . The forcedeection curve was obtained by a multi-mode scanning probe microscopy (SPM) AFM operated in the lateral force and force imaging modes, respectively.

3. Results and discussion

A typical SEM image of PZT nanobres collected on the substrate is shown in gure 2(a). These bres form uniform, continuous, aligned arrays over a large area. The high-magnication image (gure 2(b)) shows that the diameter of a bre is about 150 nm. The average diameter of about 100 nanobres was computed to be 150 12 nm using the high-magnication SEM images. The average diameter of the PZT/PVP green bre is about 200 20 nm. This dimensional reduction could be explained by the loss of PVP and other organics from the green nanobres as well as the crystallization of PZT during the annealing process. Many parameters can inuence the transformation of polymer bres from electrospinning [11] into ceramic nanobres. The concentration of PVP in the PZT precursor affects the diameter of nanobres (shown in gure 3). The average diameter of the nanobres increases as the PVP concentration is decreased. When the PZT solgel was xed at 0.07 g ml1 and an electric eld of 10 kV was applied, the average diameter of PZT nanobres can be tuned in the range 52 8 nm to 150 12 nm. Higher PVP concentration could decrease the averaged diameter gradually until no bres were able to be collected because of the loss of PVP after the annealing process. Figure 4 shows XRD patterns for PZT nanobres annealed at 550 and 650 C, respectively. The patterns show that, after being annealed at 550 C, the bres are mainly composed of two phases, perovskite and pyrochlore, but the fraction of pyrochlore phase is very small. In contrast, the pure PZT perovskite phase is observed at 650 C. Due to the advantage of solgel processing,

2. Experimental details
2.1. Fabrication of PZT nanobres The starting material, PZT(52/48) solgel (MMC Electronics America Inc.), and poly(vinyl pyrrolidone) PVP (Aldrich), were obtained commercially, and alcohol was used as a solvent for PVP. The purpose of adding PVP is to modify the viscosity of PZT solgel, and to make it electro-spinnable. In addition to PVP and alcohol, acetic acid was added to stabilize the solution and to control the hydrolysis reactions of the solgel precursor [19]. PVP was dissolved in alcohol, and acetic acid was added to PZT solgel. This mixture was stirred vigorously at room temperature for two hours. In the experiment, different PVP concentrations were tried to determine their inuence on the diameters of PZT nanobres. A (100) silicon wafer was used as the substrate. A schematic diagram of a home-made electrospinning setup is shown in gure 1. There are basically three components for fullling the process: a high-voltage supply, a stainless-steel needle with a small diameter (200 m), and a collecting plate. The needle size was controlled appropriately so that a small drop was maintained at the needle tip due to the surface tension of the solution. The high voltage is used to create an electrically charged jet of the precursor solution. The potential difference between the tip and collecting plate was 10 kV. The negative electrode was connected to the collecting plate. After electrospinning, the green bres were annealed in a furnace to obtain the proper crystal structure. 4498

Mechanical property of nano piezoelectric bres

(a)

PZT(110)

Intensity (a.u.)

PZT(100) Pyro PZT(211) PZT(111) PZT(200) PZT(201) 550C

20um
20 30 40 50

650C

60

70

(b)

2 (degree)

Figure 4. XRD pattern of PZT nanobres annealed at 550 and 650 C.

200nm
50 nm

50 nm

10 nm

10 nm

Figure 2. SEM images of PZT nanobres: (a) aligned bres; (b) single bre.

Figure 5. TEM images of PZT nanobre.

160

140

120

100

80

60

40 0.005

0.010

0.015

0.020

0.025

0.030

PVP concentration (g/ml)

Figure 3. The relationship between the concentrate of PVP and the average diameter of PZT nanobres.

the annealing temperature for PZT nanobres obtained by solgel electrospinning is lower than that using MOD electrospinning [22]. Figure 5 shows TEM images of the cross-section and surface of PZT nanobres. These images conrmed that the diameter of the bres is about 150 nm, and the gain size of the nanobres is about 10 nm in diameter. There are some voids between grain boundaries. Reference [19] has also reported this phenomenon; the reason for this porous

structure results from the precursor solution of the solgel process. By modifying the precursor and carefully controlling the electrospinng parameters, a denser nanostructure can be obtained. Systematic investigation is underway. Boundary conditions of the nanobre over the trench are very important for the determination of the Youngs modulus of the nanobre. Figure 6 shows the experimental process for conrming the boundary conditions, which were assumed to be xedxed. First, we used an AFM operated at a high scanning rate to break the nanobre at point A (gure 6(a)). The nanobre on the substrate remained at the same place before and after it was broken. Second, we used the lateral force mode of the AFM to push the suspended part of the bre until it was broken at the other end. After the suspended bre was broken, the position of the remaining bre on the substrate did not change (gure 6(b)). The results of these two steps conrmed that the adhesion between the nanobre and the substrate was secure and the nanobre can be assumed as xedxed at both ends. The nanobre was treated as an elastic beam under pure bending as the force was applied by the AFM [23]. A silicon nitride AFM tip with a nominal spring constant of 0.58 N m1 was chosen for contact force imaging. A scanning rate of 1 Hz was used to nd the middle point of the suspended nanobre. The elastic modulus was obtained from the three-point bending of a beam with two ends xed [18]:

Average diameter of fibres (nm)

E=

F L3 192 I
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S Xu et al

(a)

20.0

(b)

10.0

Trench A Trench
10.0

7.5

5.0

Fibre

Fibre

2.5

10.0

20

0 0 2.5 5.0 7.5 10.0

Figure 6. AFM images for conrmation of boundary conditions: (a) bre broken at one edge; (b) bre broken at both edges.

20.0

10.0

(a)

10.0

0 20.0 m

(b)

Figure 7. (a) Schematic diagram of a nanobre with mid-span deected by the AFM tip; (b) AFM image of a single bre with a diameter of 300 nm over a silicon trench.

where F is the maximum force applied, L is the length of the suspended nanobre, is the deection of the beam at midspan, and I is the second moment of area of the beam (where I = D 4 /64 for the bre, and D is the bre diameter). The method for obtaining and F can be found from the AFM manual. A schematic diagram of the suspended nanobre is shown in gure 7(a), and the AFM image of a PZT nanobre with a suspended length L 5 m over a trench is shown in gure 7(b). From the force plot of a single PZT nanobre (gure 8), we can obtain = 1.1 nm, and the deection angle of nanobre is 0.01 . The extending and retracting plots overlap completely, which means that the nanobre performed pure elastic deformation. The elastic modulus of PZT nanobre was found to be 42.99 GPa. The elastic modulus of this PZT nanobre is lower than that of the bulk, which ranges from 63 to 94 GPa [24]. Three factors probably contribute to the reduction of Youngs modulus ( E ) of the PZT nanobre. First, the porosity of the nanobre causes the Youngs modulus to be lower than that of the bulk PZT [25]. Second, the grain size will also affect the elastic modulus of PZT nanobres. The mechanical properties of materials are determined by the nanostructure of the materials. Research on alloys has shown that the Youngs modulus of the Ti alloys decreased drastically with a decrease in their grain size [26]. The grain size of the nanobres, which is 10 nm, is much smaller than that of bulk or thin-lm PZT, 4500

Figure 8. Force plot of a suspended nanobre over a trench.

which is about 100 nm. Finally, when the diameter of the bre is very small, shear deformation becomes signicant, which will cause the elastic modulus to decrease [18]. A systematic investigation of these issues is underway.

4. Conclusions
We have demonstrated diameter-controllable PZT nanobres fabricated by electrospinng and solgel processing. By appropriate control of the electric eld, well-aligned nanobres can be obtained on a silicon substrate. An experimental study by AFM shows that the adhesion force between a nanobre

Mechanical property of nano piezoelectric bres

and a silicon substrate is sufciently large for the assumption that both ends of the nanobre were xed. The combination of AFM and microfabrication techniques can be used to measure the mechanical properties of a nanobre, nanowire, nanotube, etc. Further tests are to be performed for the measurement of the piezoelectric constants. The size effect of nano-structures is also under investigation.

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