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Effect of the electrode structure on the electrical properties of alkoxide derived ferroelectric thin film
Materials Letters 64 (2010) 1742–1744
Contents lists available at ScienceDirect
Materials Letters j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t
Effect of the electrode structure on the electrical properties of alkoxide derived ferroelectric thin film Tomoya Ohno a,⁎, Takeshi Matsuda a, Takero Nukina b, Naonori Sakamoto b, Naoki Wakiya b, Shou Tokuda c, Hisao Suzuki b a b c
Department of Materials Science and Engineering, Kitami Institute of Technology, 165 Kouen-chi, Kitami, Hokkaidoh 090-8507, Japan Department of Materials Science, Shizuoka University, 3-5-1, Johoku, Hamamatsu, Shizuoka 432-8561, Japan Technical Division, Kitami Institute of Technology, 165 Kouen-cho, Kitami, Hokkaido 090-8507, Japan
a r t i c l e
i n f o
Article history: Received 18 March 2010 Accepted 14 April 2010 Available online 21 April 2010 Keywords: Thin films Ferroelectrics Stress engineering Chemical solution deposition
a b s t r a c t Effect of the thermal expansion coefficient of electrode on the electrical properties in lead zirconate titanate (PZT) with morphotropic phase boundary (Pb(Zr0.53,Ti0.47)O3: MPB) composition film was demonstrated in this paper. The lanthanum nickel oxide (LaNiO3: LNO) and lanthanum strontium cobalt oxide ((La0.5,Sr0.5)CoO3: LSCO) was deposited by chemical solution deposition (CSD) as bottom electrode on Si wafer. Highly (100)oriented LSCO layers were successfully prepared by CSD on Si wafer using (100)-oriented LNO layers as seeding layer for the crystal orientation control. As a result, (100) and (001) oriented PZT film was also successfully prepared on LSCO/LNO/Si stacking structure. The obtained dielectric and ferroelectric properties changed according to the thermal stress which was influenced by the bottom electrode thickness. © 2010 Elsevier B.V. All rights reserved.
1. Introduction Ferroelectric thin film is very promising for electronic devices such as capacitors, and actuators [1], because of their high dielectric, ferroelectric and piezoelectric properties. It is well known that the electrical properties in ferroelectric thin film depend on numerous factors, such as microstructure, crystal orientation, residual stress [2], and electrode [3]. Lately, the residual stress in a thin film has much attention to improve the electrical properties as "stress engineering" [2,4]. In our previous studies, we demonstrated that the stacking structure was very a important factor to control the residual stress in the alkoxide derived thin film. For example, if we use the LNO as bottom electrode, the PZT with compressive residual stress was attained on the commercial Si substrate, because LNO acted as the buffer layer for stress control [5]. These results indicate the relaxation mechanism of the constrain force from Si wafer and the thermal expansion coefficient of the bottom electrode was a very important factor for "stress engineering" for alkoxide derived film. In this study, we attempted stress engineering using the metal oxide electrode with a larger thermal expansion coefficient. Here, LSCO is a conductive material which has large thermal expansion coefficient (20.0 × 10−6/°C [6]). Therefore, LSCO was selected as the bottom electrode in this study. In addition, (100) oriented LSCO layer
⁎ Corresponding author. E-mail address: [email protected] (T. Ohno). 0167-577X/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2010.04.028
is also required to obtain the (100) and (001) oriented PZT film which leads to higher electrical properties. However, highly (100) oriented alkoxide derived LSCO on Si wafer has not been deposited. Therefore (100) oriented LNO layer was used as a seeding layer to obtain (100) oriented LSCO on Si wafer in this study. Namely, stress engineering for alkoxide derived PZT film was attempted using LSCO/LNO/Si stacking structure with different electrode thickness. 2. Experimental procedure LNO, LSCO and PZT layers were deposited on Si wafer by CSD. LNO layer was deposited on a commercial Si(100) wafer with 500 μm thick by spin coating. The experimental details of LNO precursor solution with 0.3 M have been described in our previous report [7]. The thickness of the deposited LNO layer was controlled by changing the number of the deposition process. Secondly, the LSCO layer was deposited on the obtained LNO/Si stacking structure. The starting reagents for the LSCO precursor solution with 0.1 M were La(NO3)3·6H2O, metal Sr, Co(CH3COO)2·4H2O, and 2-methoxyethanol was used as a solvent. All starting reagents were separately dissolved to 2-methoxyethanol for 2 h at room temperature. After that, La precursor solution and Sr precursor solution were mixed for 2 h. Lastly, the obtained La and Sr precursor solution and Co precursor solution were mixed at room temperature for 2 h to obtain the LSCO precursor solution. The as-deposited LSCO layer was dried at 150 °C for 10 min, and annealed at 700 °C for 5 min under the oxygen flow. The thickness of the deposited LSCO was also controlled by changing the number of the deposition process. Finally, PZT with MPB composition layer
T. Ohno et al. / Materials Letters 64 (2010) 1742–1744
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was deposited on the obtained LSCO/LNO/Si stacking structure. The experimental details of the PZT precursor solution with 0.6 M have been described in our previous report [8]. The thickness of PZT layer was adjusted to be 700 nm. The film thickness of each layer was confirmed by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM). The electrical resistivity of the bottom electrode was examined by the four-probe method. The crystal orientation degree was estimated by XRD analysis. The dielectric property and the ferroelectric property were determined by impedance analyzer and the ferroelectric test system, respectively. 3. Results and discussion Fig. 1(a) exhibits a high resolution TEM (HR-TEM) image of the interface between LNO and LSCO layers. In addition, the fast Fourier transform (FFT) image (Fig. 1(b)) was obtained from Fig. 1(a). The FFT analysis provides that the (100) plane of LSCO grows from (100) plane Fig. 2. XRD diffraction pattern of PZT/LSCO/LNO (200 nm)/Pt/Si stacking structure with different LSCO thickness (a) 30 nm, (b) 45 nm (c) 60 nm and (d) 75 nm.
of LNO. Namely, the (100) oriented LNO layer effectively acts as the seeding layer to obtain (100) oriented LSCO layer. Fig. 2 shows the respective XRD patterns for the obtained PZT film on LSCO/LNO/Si structure with different LSCO layer thickness. In this study, (100) oriented LSCO layers were successfully deposited on (100) oriented LNO layer, and highly (100) oriented PZT layer was also successfully deposited on LSCO/LNO/Si stacking structure. The crystal orientation degree was nearly the same in all cases. Therefore, in this study, effect of the crystal orientation on the electrical properties is possible to ignore in the discussion. In addition, the crystallite size was calculated using Scherrer's equation, and the obtained crystallite sizes were nearly the same in all the samples. Thus, the effect of the crystallite size on the electrical properties is also possible to ignore. Fig. 3 shows a change in the electrical resistivity as a function of the LSCO layer thick. The electrical resistivity of LNO layer with 100 and 200 nm thickness was approximately 8.0 × 10−3 and 5.0 × 10−3 Ω cm, respectively. However, the electrical resistivity of LSCO/LNO/Si increased with increasing LSCO layer thickness in both cases. This result indicates that the electrical resistivity of LSCO layer was higher than that of LNO, although well crystallized LSCO was obtained by CSD. In general, the electrical properties in thin films are influenced by the electrical resistivity of the bottom electrode. In fact, the remanent polarization of the obtained PZT/LSCO/LNO decreased with the increase of the electrical resistivity of the bottom electrode. Therefore,
Fig. 1. Cross sectional images of the obtained PZT/LSCO (8 layers)/LNO (4 layers)/Si stacking structure. (a) High resolution TEM image of the interface between LSCO and LNO layers, and (b) the Fast Fourier transform (FFT) image obtained from the interface between LSCO and LNO layers.
Fig. 3. Change in the electrical resistivity of LSCO/LNO/Si stacking structure as a function of the LSCO layer thickness.
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Fig. 4. P–E hysteresis loops for Au/PZT/LSCO/LNO/Si stacking structure. o: sample 1, and ●: sample 2. Fig. 5. change in the P–E hysteresis loops for sample 1 with different applied voltages.
we selected the LSCO (60 nm)/LNO (200 nm) (sample 1), and LSCO (30 nm)/LNO(100 nm) (sample 2) stacking structure, because of nearly the same electrical resistivity of approximately 11 × 10−3 Ω cm. Fig. 4 shows the P–E hysteresis loops for samples 1 and 2. Ferroelectric property in sample 1 was better than that of sample 2. 2Pr of samples 1 and 2 was determined at 53.6 and 37.8 μC/cm2, respectively. In addition, the dielectric constant at 1 kHz in sample 1 (εsample1 = 1327) was higher than that of sample 2 (εsample2 = 658). Namely, if the effect of the electrical resistivity on the electrical properties was ignored, both dielectric and ferroelectric properties improved with increasing bottom electrode thick. Choi et al. reported that the compressive residual stress leads to the improvement of the ferroelectric property [4]. They demonstrated this phenomena using (001) oriented barium titanate (BTO) thin film on the single crystal substrate. The residual stress is defined as the sum of the epitaxial stress, thermal stress, and the phase transition stress [9]. Here, it has been reported that the epitaxial stress relax by 10 nm film thick [10], and the phase transition stress change according to the crystal orientation [11]. In contrast, the obtained samples have over 10 nm film thick, and the nearly the same crystal orientation degree in all cases. Therefore, the epitaxial stress and the phase transition stress should be omitted to discuss the stress effect on the electrical properties in this study. On the other hand, the thermal stress is calculated using σthermal =
Ef T ∫ a ðα −αs Þdt ð1−νf Þ T0 f
where, αf and αs indicate the thermal expansion coefficients of the film and the substrate, respectively. T and T0 indicate the annealing temperature and room temperature, respectively. The thermal expansion coefficient of LNO, LSCO is larger than that of PZT. Thus, the thermal stress should be compressive direction. In our previous study, we demonstrated that the residual compressive stress increased with increasing buffer layer thickness [5]. In the case of the alkoxide derived film, the obtained film includes some pores and boundary, although the well crystallized film. Thus, these pores help to cancel out the huge constrain force from Si wafer, resulting in the compressive residual stress in PZT film. From this consideration, the residual compressive stress in sample 1 should be larger than that in sample 2, because of the electrode thickness. Therefore, the ferroelectric property in sample 1 was better than that in sample 2. In contrast, in the case of (100) oriented ferroelectric films, the dielectric constant increases with increasing residual compressive stress. However, the obtained PZT film could not distinguish between
(100) and (001) planes, because of nearly the same lattice constant in MPB composition. Here, in the case of (100) oriented films, the ferroelectric property should be decreased with increasing compressive residual stress, although the dielectric constant increases. However, both the dielectric and the ferroelectric properties are enhanced with increasing compressive residual stress in this study. We considered this reason came from the domain switching by applying the electric field for the ferroelectric measurement. Namely, the measurement of the dielectric behavior, (100) domain was still (100) domain. In contrast, in the case of the measurement of the ferroelectric behavior, (100) domain switched to (001) domain by the applied voltage for the measurement. Fig. 5 exhibits the P–E hysteresis loops for sample 1 with different applied voltages. The P–E hysteresis loops improved with increasing applied voltage. Namely, (100) domain switched to (001) domain by applied voltage. Therefore, both the dielectric and the ferroelectric properties improved with increasing residual compressive stress in this study. 4. Conclusions (100) oriented LSCO layers were successfully deposited on Si wafer using (100) oriented LNO layers as seeding layer. As a result, highly (100) and (001) oriented PZT with MPB composition was deposited on LSCO/LNO/Si stacking structures. The dielectric and the ferroelectric properties enhanced with increasing the bottom electrode thickness which could be due to the increase of the compressive residual stress. The design of the bottom electrode structure was key factor for "stress engineering" for the alkoxide derived thin films. References [1] Kim C, Kim S, Lee S. Mater Lett 2003;57:2233–7. [2] Ito S, Funakubo H, Koutsaroff I, Zelner M, Cervin-Lawry A. Appl Phys Lett 2007;90(142910):1–3. [3] Li J, Yao X. Mater Lett 2004;58:3447–50. [4] Choi K, Biegalski M, Li Y, Sharan A, Schubert J, Uecker R, et al. Science 2004;306: 1005–9. [5] Ohno T, Malič B, Fukazawa H, Wakiya N, Suzuki H, Matsuda T, et al. J Ceram Soc Jpn 2009;117:1089–94. [6] Wang S, Zheng R, Suzuki A, Hashimoto T. Solid State Ionics 2004;174:157–62. [7] Miyazaki H, Goto T, Miwa Y, Ohno T, Suzuki H, Ota T, et al. J Euro Ceram Soc 2004;24:1005–8. [8] Ohno T, Kunieda M, Suzuki H, Hayashi T. Jpn J Appl Phys 2000;39:5429–33. [9] Zhou Y, Yang Z, Zheng X. Surf Coat Technol 2003;162:202–11. [10] Tybell T, Ahn C, Triscome J. Appl Phys Lett 1999;75:856–8. [11] Ohno T, Malič B, Fukazawa H, Wakiya N, Suzuki H, Matsuda T, et al. Jpn J Appl Phys 2008;47:7514–8.
Contents lists available at ScienceDirect
Materials Letters j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t
Effect of the electrode structure on the electrical properties of alkoxide derived ferroelectric thin film Tomoya Ohno a,⁎, Takeshi Matsuda a, Takero Nukina b, Naonori Sakamoto b, Naoki Wakiya b, Shou Tokuda c, Hisao Suzuki b a b c
Department of Materials Science and Engineering, Kitami Institute of Technology, 165 Kouen-chi, Kitami, Hokkaidoh 090-8507, Japan Department of Materials Science, Shizuoka University, 3-5-1, Johoku, Hamamatsu, Shizuoka 432-8561, Japan Technical Division, Kitami Institute of Technology, 165 Kouen-cho, Kitami, Hokkaido 090-8507, Japan
a r t i c l e
i n f o
Article history: Received 18 March 2010 Accepted 14 April 2010 Available online 21 April 2010 Keywords: Thin films Ferroelectrics Stress engineering Chemical solution deposition
a b s t r a c t Effect of the thermal expansion coefficient of electrode on the electrical properties in lead zirconate titanate (PZT) with morphotropic phase boundary (Pb(Zr0.53,Ti0.47)O3: MPB) composition film was demonstrated in this paper. The lanthanum nickel oxide (LaNiO3: LNO) and lanthanum strontium cobalt oxide ((La0.5,Sr0.5)CoO3: LSCO) was deposited by chemical solution deposition (CSD) as bottom electrode on Si wafer. Highly (100)oriented LSCO layers were successfully prepared by CSD on Si wafer using (100)-oriented LNO layers as seeding layer for the crystal orientation control. As a result, (100) and (001) oriented PZT film was also successfully prepared on LSCO/LNO/Si stacking structure. The obtained dielectric and ferroelectric properties changed according to the thermal stress which was influenced by the bottom electrode thickness. © 2010 Elsevier B.V. All rights reserved.
1. Introduction Ferroelectric thin film is very promising for electronic devices such as capacitors, and actuators [1], because of their high dielectric, ferroelectric and piezoelectric properties. It is well known that the electrical properties in ferroelectric thin film depend on numerous factors, such as microstructure, crystal orientation, residual stress [2], and electrode [3]. Lately, the residual stress in a thin film has much attention to improve the electrical properties as "stress engineering" [2,4]. In our previous studies, we demonstrated that the stacking structure was very a important factor to control the residual stress in the alkoxide derived thin film. For example, if we use the LNO as bottom electrode, the PZT with compressive residual stress was attained on the commercial Si substrate, because LNO acted as the buffer layer for stress control [5]. These results indicate the relaxation mechanism of the constrain force from Si wafer and the thermal expansion coefficient of the bottom electrode was a very important factor for "stress engineering" for alkoxide derived film. In this study, we attempted stress engineering using the metal oxide electrode with a larger thermal expansion coefficient. Here, LSCO is a conductive material which has large thermal expansion coefficient (20.0 × 10−6/°C [6]). Therefore, LSCO was selected as the bottom electrode in this study. In addition, (100) oriented LSCO layer
⁎ Corresponding author. E-mail address: [email protected] (T. Ohno). 0167-577X/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2010.04.028
is also required to obtain the (100) and (001) oriented PZT film which leads to higher electrical properties. However, highly (100) oriented alkoxide derived LSCO on Si wafer has not been deposited. Therefore (100) oriented LNO layer was used as a seeding layer to obtain (100) oriented LSCO on Si wafer in this study. Namely, stress engineering for alkoxide derived PZT film was attempted using LSCO/LNO/Si stacking structure with different electrode thickness. 2. Experimental procedure LNO, LSCO and PZT layers were deposited on Si wafer by CSD. LNO layer was deposited on a commercial Si(100) wafer with 500 μm thick by spin coating. The experimental details of LNO precursor solution with 0.3 M have been described in our previous report [7]. The thickness of the deposited LNO layer was controlled by changing the number of the deposition process. Secondly, the LSCO layer was deposited on the obtained LNO/Si stacking structure. The starting reagents for the LSCO precursor solution with 0.1 M were La(NO3)3·6H2O, metal Sr, Co(CH3COO)2·4H2O, and 2-methoxyethanol was used as a solvent. All starting reagents were separately dissolved to 2-methoxyethanol for 2 h at room temperature. After that, La precursor solution and Sr precursor solution were mixed for 2 h. Lastly, the obtained La and Sr precursor solution and Co precursor solution were mixed at room temperature for 2 h to obtain the LSCO precursor solution. The as-deposited LSCO layer was dried at 150 °C for 10 min, and annealed at 700 °C for 5 min under the oxygen flow. The thickness of the deposited LSCO was also controlled by changing the number of the deposition process. Finally, PZT with MPB composition layer
T. Ohno et al. / Materials Letters 64 (2010) 1742–1744
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was deposited on the obtained LSCO/LNO/Si stacking structure. The experimental details of the PZT precursor solution with 0.6 M have been described in our previous report [8]. The thickness of PZT layer was adjusted to be 700 nm. The film thickness of each layer was confirmed by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM). The electrical resistivity of the bottom electrode was examined by the four-probe method. The crystal orientation degree was estimated by XRD analysis. The dielectric property and the ferroelectric property were determined by impedance analyzer and the ferroelectric test system, respectively. 3. Results and discussion Fig. 1(a) exhibits a high resolution TEM (HR-TEM) image of the interface between LNO and LSCO layers. In addition, the fast Fourier transform (FFT) image (Fig. 1(b)) was obtained from Fig. 1(a). The FFT analysis provides that the (100) plane of LSCO grows from (100) plane Fig. 2. XRD diffraction pattern of PZT/LSCO/LNO (200 nm)/Pt/Si stacking structure with different LSCO thickness (a) 30 nm, (b) 45 nm (c) 60 nm and (d) 75 nm.
of LNO. Namely, the (100) oriented LNO layer effectively acts as the seeding layer to obtain (100) oriented LSCO layer. Fig. 2 shows the respective XRD patterns for the obtained PZT film on LSCO/LNO/Si structure with different LSCO layer thickness. In this study, (100) oriented LSCO layers were successfully deposited on (100) oriented LNO layer, and highly (100) oriented PZT layer was also successfully deposited on LSCO/LNO/Si stacking structure. The crystal orientation degree was nearly the same in all cases. Therefore, in this study, effect of the crystal orientation on the electrical properties is possible to ignore in the discussion. In addition, the crystallite size was calculated using Scherrer's equation, and the obtained crystallite sizes were nearly the same in all the samples. Thus, the effect of the crystallite size on the electrical properties is also possible to ignore. Fig. 3 shows a change in the electrical resistivity as a function of the LSCO layer thick. The electrical resistivity of LNO layer with 100 and 200 nm thickness was approximately 8.0 × 10−3 and 5.0 × 10−3 Ω cm, respectively. However, the electrical resistivity of LSCO/LNO/Si increased with increasing LSCO layer thickness in both cases. This result indicates that the electrical resistivity of LSCO layer was higher than that of LNO, although well crystallized LSCO was obtained by CSD. In general, the electrical properties in thin films are influenced by the electrical resistivity of the bottom electrode. In fact, the remanent polarization of the obtained PZT/LSCO/LNO decreased with the increase of the electrical resistivity of the bottom electrode. Therefore,
Fig. 1. Cross sectional images of the obtained PZT/LSCO (8 layers)/LNO (4 layers)/Si stacking structure. (a) High resolution TEM image of the interface between LSCO and LNO layers, and (b) the Fast Fourier transform (FFT) image obtained from the interface between LSCO and LNO layers.
Fig. 3. Change in the electrical resistivity of LSCO/LNO/Si stacking structure as a function of the LSCO layer thickness.
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Fig. 4. P–E hysteresis loops for Au/PZT/LSCO/LNO/Si stacking structure. o: sample 1, and ●: sample 2. Fig. 5. change in the P–E hysteresis loops for sample 1 with different applied voltages.
we selected the LSCO (60 nm)/LNO (200 nm) (sample 1), and LSCO (30 nm)/LNO(100 nm) (sample 2) stacking structure, because of nearly the same electrical resistivity of approximately 11 × 10−3 Ω cm. Fig. 4 shows the P–E hysteresis loops for samples 1 and 2. Ferroelectric property in sample 1 was better than that of sample 2. 2Pr of samples 1 and 2 was determined at 53.6 and 37.8 μC/cm2, respectively. In addition, the dielectric constant at 1 kHz in sample 1 (εsample1 = 1327) was higher than that of sample 2 (εsample2 = 658). Namely, if the effect of the electrical resistivity on the electrical properties was ignored, both dielectric and ferroelectric properties improved with increasing bottom electrode thick. Choi et al. reported that the compressive residual stress leads to the improvement of the ferroelectric property [4]. They demonstrated this phenomena using (001) oriented barium titanate (BTO) thin film on the single crystal substrate. The residual stress is defined as the sum of the epitaxial stress, thermal stress, and the phase transition stress [9]. Here, it has been reported that the epitaxial stress relax by 10 nm film thick [10], and the phase transition stress change according to the crystal orientation [11]. In contrast, the obtained samples have over 10 nm film thick, and the nearly the same crystal orientation degree in all cases. Therefore, the epitaxial stress and the phase transition stress should be omitted to discuss the stress effect on the electrical properties in this study. On the other hand, the thermal stress is calculated using σthermal =
Ef T ∫ a ðα −αs Þdt ð1−νf Þ T0 f
where, αf and αs indicate the thermal expansion coefficients of the film and the substrate, respectively. T and T0 indicate the annealing temperature and room temperature, respectively. The thermal expansion coefficient of LNO, LSCO is larger than that of PZT. Thus, the thermal stress should be compressive direction. In our previous study, we demonstrated that the residual compressive stress increased with increasing buffer layer thickness [5]. In the case of the alkoxide derived film, the obtained film includes some pores and boundary, although the well crystallized film. Thus, these pores help to cancel out the huge constrain force from Si wafer, resulting in the compressive residual stress in PZT film. From this consideration, the residual compressive stress in sample 1 should be larger than that in sample 2, because of the electrode thickness. Therefore, the ferroelectric property in sample 1 was better than that in sample 2. In contrast, in the case of (100) oriented ferroelectric films, the dielectric constant increases with increasing residual compressive stress. However, the obtained PZT film could not distinguish between
(100) and (001) planes, because of nearly the same lattice constant in MPB composition. Here, in the case of (100) oriented films, the ferroelectric property should be decreased with increasing compressive residual stress, although the dielectric constant increases. However, both the dielectric and the ferroelectric properties are enhanced with increasing compressive residual stress in this study. We considered this reason came from the domain switching by applying the electric field for the ferroelectric measurement. Namely, the measurement of the dielectric behavior, (100) domain was still (100) domain. In contrast, in the case of the measurement of the ferroelectric behavior, (100) domain switched to (001) domain by the applied voltage for the measurement. Fig. 5 exhibits the P–E hysteresis loops for sample 1 with different applied voltages. The P–E hysteresis loops improved with increasing applied voltage. Namely, (100) domain switched to (001) domain by applied voltage. Therefore, both the dielectric and the ferroelectric properties improved with increasing residual compressive stress in this study. 4. Conclusions (100) oriented LSCO layers were successfully deposited on Si wafer using (100) oriented LNO layers as seeding layer. As a result, highly (100) and (001) oriented PZT with MPB composition was deposited on LSCO/LNO/Si stacking structures. The dielectric and the ferroelectric properties enhanced with increasing the bottom electrode thickness which could be due to the increase of the compressive residual stress. The design of the bottom electrode structure was key factor for "stress engineering" for the alkoxide derived thin films. References [1] Kim C, Kim S, Lee S. Mater Lett 2003;57:2233–7. [2] Ito S, Funakubo H, Koutsaroff I, Zelner M, Cervin-Lawry A. Appl Phys Lett 2007;90(142910):1–3. [3] Li J, Yao X. Mater Lett 2004;58:3447–50. [4] Choi K, Biegalski M, Li Y, Sharan A, Schubert J, Uecker R, et al. Science 2004;306: 1005–9. [5] Ohno T, Malič B, Fukazawa H, Wakiya N, Suzuki H, Matsuda T, et al. J Ceram Soc Jpn 2009;117:1089–94. [6] Wang S, Zheng R, Suzuki A, Hashimoto T. Solid State Ionics 2004;174:157–62. [7] Miyazaki H, Goto T, Miwa Y, Ohno T, Suzuki H, Ota T, et al. J Euro Ceram Soc 2004;24:1005–8. [8] Ohno T, Kunieda M, Suzuki H, Hayashi T. Jpn J Appl Phys 2000;39:5429–33. [9] Zhou Y, Yang Z, Zheng X. Surf Coat Technol 2003;162:202–11. [10] Tybell T, Ahn C, Triscome J. Appl Phys Lett 1999;75:856–8. [11] Ohno T, Malič B, Fukazawa H, Wakiya N, Suzuki H, Matsuda T, et al. Jpn J Appl Phys 2008;47:7514–8.