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Integrated Ferroelectrics: An International Journal


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Nanomechanical and Dielectric Properties of Sol-Gel Derived PZT Thin Films Annealed with Microwave Energy
A. Rambabu , K. Sudheendran & K. C. James Raju
a a a a

School of Physics, University of Hyderabad, Hyderabad, 46, India Version of record first published: 01 Dec 2010.

To cite this article: A. Rambabu , K. Sudheendran & K. C. James Raju (2010): Nanomechanical and Dielectric Properties of Sol-Gel Derived PZT Thin Films Annealed with Microwave Energy, Integrated Ferroelectrics: An International Journal, 119:1, 13-21 To link to this article: http://dx.doi.org/10.1080/10584587.2010.489495

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Integrated Ferroelectrics, 119:1321, 2010 Copyright Taylor & Francis Group, LLC ISSN: 1058-4587 print / 1607-8489 online DOI: 10.1080/10584587.2010.489495

Nanomechanical and Dielectric Properties of Sol-Gel Derived PZT Thin Films Annealed with Microwave Energy
A. RAMBABU, K. SUDHEENDRAN, AND K. C. JAMES RAJU
School of Physics, University of Hyderabad, Hyderabad-46, India

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Lead zirconium titanate Pb (Zr0.58 Ti0.42 ) O3 (PZT) thin lms were deposited on silicon substrates by sol-gel process. The structural, morphological, dielectric and nano mechanical properties of these lms have been studied systematically. The thicknesses of the lms were around 160 nm. During the deposition of each layer, the lms were baked in a microwave oven which in turn resulted in a low temperature crystallization of these thin lms compared to the conventional method. The crystallite sizes of the lms were ranged between 2535 nm depending up on the annealing temperature. The dielectric constant of the lms decreased with increase in frequency whereas the loss has increased and ranged between (480100) and (0.030.30), respectively. The DFM (Dynamic force microscopy) images of the lms shows the spherical grains with uniform microstructure and an average grain size of 80110 nm. The hardness of the lms ranged between 25 GPA. The lm annealed at 600 C was having a dielectric constant of 400 with hardness of 4.8 GPa which is suitable combination of properties for micromechanical systems. Keywords PZT thin lms; sol-gel; nanomechanical properties; dielectric properties; microwave annealing

Introduction
PZT thin lms have attracted attention for many applications such as infrared sensors, optical shutters, electro-optic devices, modulators, actuators, multi-layer capacitors, ferroelectric RAM, and display systems [13]. PZT based MEMS devices have many advantages such as ne resolution, large force generation, fast response time, low power consumption as well as vacuum and clean room compatibility. However, thin lm PZT based MEMS technology has lot of draw backs mainly due to the poor mechanical properties of the lms grown. For the wider and effective use of the thin lm PZT based MEMS technology one should be able to grow the lms with very good mechanical and electrical properties. Investigation of the mechanical properties of the PZT thin lms and its correlation with the electrical properties is an important area of research because of the increase in demand for the piezoelectric devices suitable for various applications [4]. The properties of the PZT thin lms are mostly dependent on the composition ratio, bottom electrode, thickness and annealing temperature conditions. A variety of chemical and physical deposition techniques have been adapted to fabricate PZT thin lms such as sol-gel, sputtering, and metal organic chemical vapor deposition [58]. Among the
Received December 13, 2009; in nal form March 2, 2010. Corresponding author. E-mail: kcjrsp@uohyd.ernet.in

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chemical methods sol-gel technique is a simple and promising technique due to its large area deposition, easy composition control and low cost [9]. It is already known that the PZT thin lms possess some of the highest piezoelectric coefcients and its electromechanical properties have been investigated for several years. It has been reported that the materials mechanical properties are inuencing the dielectric and piezoelectric properties of these materials in thin lm form. Therefore in order to have a comprehensive understanding of the factors inuencing the dielectric and piezoelectric properties, a detailed study of the mechanical properties of these thin lms is a necessity. PZT thin lms have not been characterized extensively in terms of their nanomechanical properties. It is interesting to understand whether the mechanical behavior of thin lms inuences the measured values of dielectric constant. It is well known that the piezoelectric coefcients depend on the strain in the lms, which are related to the mechanical behavior of the lms grown on different substrates. The study of nanomechanical properties of thin lms has become an active area of research recently because it could correlate the piezoelectric properties. For measuring the properties of the thin lms, such as a Youngs modulus and hardness on the scale, nanoindentation is the most frequently used technique [1012]. In this paper we report the effect of annealing temperature on the nanomechanical properties of the sol gel grown PZT thin lms. The observed mechanical properties of these lms were explained in terms of its structural and micro structural characteristics. The effect of mechanical properties on the observed dielectric properties and a possible correlation between them are also discussed. In the microwave process, the heat is generated internally within the material on account of absorption of microwave energy instead of originating from external sources, and hence there is an inverse heating prole. The heating is very rapid as the material is heated by energy conservation rather than by energy transfer, which occurs in conventional techniques. Microwave annealing has many advantages over conventional methods [13] which include shorter process time, energy saving and higher temperature leading to ne microstructure as well as improved dielectric and mechanical properties. Microwave sintering is especially important for Pb-based ferroelectric materials because this route can yield processing at lower temperatures resulting in reduced Pb volatization leading to a stoichometric composition.

Experimental Details
PZT thin lms were prepared by sol-gel method. For the preparation of PZT a stock solution of lead acetate (C4 H6 O4 Pb.3H2 O) zirconium propoxide (Zr C3 H7 O) and Titanium isopropoxide Ti [(CH3 )2 CHO]4 were used as a precursors. Acetic acid, water and propanol were used as solvents. The lead acetate (C4 H6 O4 Pb.3H2 O) was dissolved in heated acetic acid glacial (CH3 COOH). The solution was heated to 110 C to remove the water and the then solutions are cooled to 70 C before the required quantities of zirconium n-propoxide and titanium isopropoxide were added sequentially. Zirconium n-propoxide must add rst because it reacts with acetic acid to form a solution which will not hydrolyze the titanium isopropoxide. The stock solution is reuxed for 23 h and then cooled to room temperature. The solution was agitated by mixing in a heater cum magnetic stirrer until all the condensed solid had dissolved. Ethylene glycol was added in the proportion of 1 ml to 10 g of lead acetate in solution. The initial solution, which is the mixture of lead acetate, zirconium propoxide and titanium isopropoxide solution had to be complete before ethylene glycol was added since residual titanium isopropoixde and zirconium propoxide alcolyze with

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ethylene glycol to form a condensed solid. The solution was diluted with water or propanol to adjust the viscosity. Finally the solution was ltered using a membrane lter and clear light yellow PZT stock solution was formed. This solution was stable and there was no precipitation formed for several months. The precursor solution was deposited on Si substrates by spin-coating at 3000 rpm for 40 sec. The as deposited lms were pre-annealed at 300 C in a microwave oven for 3 min. A SiC susceptor of 25 mm diameter and 5 mm thickness was used to absorb the microwave energy and transfer the heat to the lm, since the volume of the lm and substrate are insufcient to couple with microwave eld. The temperature of the susceptor was measured using an infrared pyrometer. The spin coating and drying process were repeated to obtain desired thickness of lms. The thin lms were structurally characterized by X-ray diffraction (XRD) using Cu K radiation in the mode of a -2 scan. Atomic force microscope (AFM) was used to obtain an accurate image of the sample surface and the evaluation of some parameters, such as roughness and mean grain size. The dielectric properties were measured on the thin lms in a metal-ferroelectric-semiconductor (MFS) conguration, using an Agilent HP4294A impedance analyzer. [14]. The nanomechanical properties of the PZT thin lms were characterized by a Hysitrons Triboindenter using a three sided pyramidal sharp Berkovich tip with a diameter of 100 nm. The hardness H is dened as H = P A(hc ) (1)

where P is the load and A is the projected area of the contact. Reduced Modulus Er is given as Er = S /2 A(hc ) (2) Where S is the stiffness of contact and A is the area of the indentation at the contact depth hc (the depth of the residual indentation), and is a geometrical constant of the order of unity. A (hc ) is often approximated by a tting polynomial as shown below for a Berkovich tip:
1/4 A(hc ) = 24.5h2 + C1 h1 + C2 h1/2 + C3 jc + C8 h1/128 c c c c

(3)

The reduced modulus Er is related to the modulus of elasticity Es of the test specimen through the following relationship from contact mechanics:
2 1/Er = (1 vi2 )/Ei + (1 vs )/Es .

(4)

Here, the subscript i indicates a property of the indenter material and is Poissons ratio. For a diamond indenter tip, Ei is 1140 GPa and i is 0.07. Poissons ratio of the specimen, s , generally varies between 0 and 0.5 for most materials (though it can be negative) and is typically around 0.3.

Results and Discussion


Morphological and Structural Characterization We examined the surface morphologies of PZT thin lms using an atomic force microscope in the dynamic force mode. Figure 1(a), (b), (c) shows the surface morphologies of crystalline, PZT thin lms which were annealed at sample (a) 500, sample (b) 600 and sample

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Figure 1. Dynamic Force Mode (DFM) images of PZT thin lms annealed at (a) 500 C for 2 hours; (b) 600 C for 2 hours; (c) 700 C for 2 hours.

(c) 700 C respectively. The PZT thin lms annealed at 500 and 600 C shows denser and ner grains and the distribution was uniform. The PZT thin lms crystallized at 600 C showed better morphology than lms crystallized at 500 and 700 C. The lms annealed at 700 C shows non-uniform grain morphology with a porous microstructure. This may be due to the kinetic effects on the grains at high temperatures. These results suggest that the surface morphology is closely related to the annealing temperature of the PZT thin lms. Figure 2(a) shows the XRD patterns of PZT thin lms annealed at various temperatures from 500 C to 700 C about 2 h respectively. All of the characteristic peaks of PZT, especially the peak at (110), became much stronger and sharper for the lms annealed at 600 C. These results indicate that the PZT thin lms annealed at 600 C showed better crystallinity than the lms annealed at other temperatures. The higher annealing temperature leads to Pb volatization, and hence it reduces the quality of the lms [15]. The crystallite sizes of the lms were calculated from the x-ray diffractograms using Scherrers equation. Correlation between the annealing temperature, grain size and RMS surface roughness of the samples (a), (b) and (c) is obtained and shown in Fig. 2 (b). It can

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Intensity(Arbitary units)

Sample C

700 C

Sample {110} B 111 020

211

221 600 C

500 C Sample A

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20

30

40

50

60

70

80

2
Figure 2a. XRD pattern of the PZT thin lms annealed at (a) 500 C for 2 hours. (b) 600 C for 2 hours. (c) 700 C for 2 hours.

be seen that the mean grain size of the samples vary from 80 to 110 nm with increasing temperature from 500 to 700 C. The increase of annealing temperature leads to a prominent variation in the RMS surface roughness from 5.1 to 8.6 nm as well. Analogous trend was obtained by Wen et.al who observed an increase in an average grain size and average roughness of the samples with increasing annealing temperature [16]. Mechanical Properties Prior to perform indentation tests on the thin lms nanoindenter was carefully calibrated using standard quartz supplied by Hysitron, USA and a Berkovich type tip was used for indentation at a constant rate of 0.05 mN/s both for loading and unloading process. The hardness and Youngs modulus of the PZT thin lms were calculated using Oliver and Pharr [17, 18] method. The load-displacement (L-D) curves obtained from the PZT lms
110 6.5 6.0 100 5.5 95 5.0 90 4.5 85 4.0 80 500 550 600 650 700
Annealing tempurature ( C)
0

Figure 2b. Crystalline size and RMS roughness as a function of annealing temperature.

RMS Roughfness(nm)

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Crystalline size (nm)

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Applied load (N)

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2500 2000 1500 1000

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500 0 0 50 100 150

Contact depth (nm)


Figure 3. Typical indentation curves of the PZT thin lms. The upper and lower curves corresponding to the maximum and minimum values measured on the experimental data.

are shown in Fig. 3. The loading portions of L-D curves overlap with each other indicating that the lm microstructure and thickness are uniformly distributed over the entire substrate resulting in repeatability in the results. Each point of the hardness and modulus values are the average of four indentations at different places to avoid microstructural effects on mechanical properties. In general, the maximum penetration depth should be 10% of the lm thickness to avoid substrate induced effects on the mechanical properties. But in the present case, we have taken the limit up to 30% of the lm thickness and no substrate effects were found in the data. It shows that most of the plastic deformation caused is within the thin lms. Figure 4 shows the variation of hardness and Youngs modulus with contact depth of PZT lms when varying the annealing temperature. It is seen that both hardness and modulus increases from 2.4 to 5 GPa and 70 to 90 GPa, respectively. The highest hardness and modulus are achieved for the lms annealed at 600 C and their values were low at remaining other two temperatures. It could be because of better packing density at 600 C with a very uniform microstructure. Figure 2 shows the differences in the preferred orientation of the PZT lms annealed at different substrate temperatures on the silicon substrates. The lms annealed at 600 C have (110) preferred orientation, whereas the lms annealed at 700 C exhibit (221) preferred orientation with a weak PZT (110) peak. These experimental results show that the preferred orientation of the PZT lm changes from the (110) to the (221) plane as the annealing temperature increases. It is clear that there exists a competition between surface energy and strain energy in determining the orientation of the lms between 600 C and 700 C. There could be other reasons also for exhibiting higher hardness and modulus values at 600 C. From this observation it can be noted that lms that are grown in (110) orientation will exhibit better mechanical properties than (221) orientation for PZT. The results conrm that the mechanical properties of PZT thin lms are better when their grains are grown and oriented along (110), porosity is lower and

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Hardness (GPa)

(a)

500 C

Youngs modulus (GPa)

6 5 4 3 2 1
30 40 50 60

600 C 0 700 C

88 (b) 84
500 C
0

80 76 72 68

600 C 0 700 C

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70

80

90 100

Contact depth (nm)

30 40 50 60 70 80 90 100 Contact depth (nm)

Figure 4. (a) Hardness versus contact depth of the PZT thin lms annealed at different temperatures; (b) Youngs modulus versus contact depth of PZT thin lms annealed at different temperatures. (See Color Plate X)

packing density is higher. Similar phenomenon was also observed by Fang et al. [19]. An increased mean grain size leads to a hardening of the material. It is also important to consider effect of surface roughness on the mechanical properties of the lms. Delobelle et al. [20] have examined the effect of the surface roughness on mechanical properties of the thin lms and found that more the disorientation of the lms were, the greater was the standard deviation of modulus for the same penetration depth. As a result, the evolution of Youngs modulus and hardness was quite dispersed in terms of the lower crystalline quality of the lms in terms its higher surface roughness. But in our case we have not found any difference in the standard deviation indicates surface roughness has not played a major role in determining the hardness and modulus values.

1000 900 800 700 600 500 400 300 200 100 0

(a)

0.5

Dielectric constant

sample (C) sample (B) sample (A)

(b)
0.4 0.3

sample C sample A sample B

tanD

600 C 500 C 700 C


2.0x10 4.0x10 6.0x10 8.0x10 1.0x10
5 5 5 5

0.2 0.1 0.0

Frecquency (Hz)

2.0x10 4.0x10 6.0x10 8.0x10 1.0x10

frequency (Hz)

Figure 5. (a) Frequency dependent dielectric constant of PZT thin lms annealed at different temperatures; (b) Frequency dependent loss tangent of PZT thin lms annealed at different temperatures. (See Color Plate XI)

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(a)
Dielectric constant

400 350 300 250 200 150 100 50

(b)

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500

550

600

650
0

700

Annealing tempurature ( C)

500 550 600 650 0 700 Annealing tempurature ( C)

Figure 6. (a) Hardness versus annealing temperatures of PZT thin lms; (b) Dielectric constant versus annealing temperatures of PZT thin lms.

Dielectric Properties The frequency dependent dielectric constant and loss tangent of the PZT thin lms annealed at different temperatures is shown in Fig. 5. The lms annealed at 500 C (sample a) and 600 C (sample b) exhibit nearly dispersion free dielectric behavior at higher frequencies. The lms annealed at 700 C (sample c) shows a high frequency dispersion of dielectric constant. The dielectric loss tangents of these lms are found to be increasing with the increase of frequencies. To understand the relations between the mechanical properties and the dielectric properties, we have plotted the variation of dielectric constant, and hardness of the lms as a function of annealing temperature. Figure 6(a) and 6(b) shows the variation of hardness and dielectric constant of the PZT thin lms as a function of different annealed temperatures. We could see from these gures that both the mechanical and dielectric properties are following quite similar trends. The lms having higher dielectric constant are exhibiting higher hardness. This shows that the same electric dipoles behave identically when they are perturbed either mechanically or electrically. The hardness of the material is primarily related to the microstructure. It has seen from the DFM pictures that the lms annealed at 600 C are having very dense microstructure which in turn resulting in high dielectric constant and low loss tangents. It is clear from these results that the PZT lms with very high dielectric constant and low loss tangent will exhibit very good mechanical properties also. From these studies it is revealed that the lms annealed at 600 C is having a high dielectric constant, low loss and very good mechanical properties which are suitable combination of properties useful for MEMS applications.

Conclusions
We have investigated the structural, microstructural nanomechanical and dielectric properties of PZT thin lms deposited on silicon substrates. The microwave annealing of these lms during the process results in low temperature crystallization compared to the conventional method. The lms are having a dielectric constant in between 100480 and dielectric loss tangent between 0.030.3 depending up on the annealing temperature. The hardness of the lms ranged between 25 GPa. The lms annealed at 600 C were having a dielectric

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constant of 400 with a hardness of 4.8 GPa, which is suitable combination of characteristics for micromechanical systems.

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