Distribution in orientation axis of thin film grown by pulsed laser deposition

Orientations of LaNiO₃ (LNO) and Pb(Zr_0.52Ti_0.48)TiO₃ (PZT) films deposited by laser ablation were evaluated using X-ray diffraction. (001)-oriented PZT and LNO films were achieved under optimized deposition conditions. Pole-figure measurements of both LNO and PZT films showed that (001) out-of-plan orientation was affected by plume direction. It was found that the (001) axes of both LNO and PZT films at locations away from the plume center were significantly tilted. The incline angle of tilt increases with the distance away from the center of the plume. The films grown in columnar structures and the column axis coincided with the crystalline orientation. Polarization of the PZT film was slightly affected by the difference in orientation tilt angles of the film investigated.     

Microstructure and electrical properties of Pb(Zr0.52Ti0.48)O3 ferroelectric films on different bottom electrodes

The crystalline quality, dielectric and ferroelectricity of the Pb(Zr_0.52Ti_0.48)O₃ (PZT) films deposited on the LaNiO₃ (LNO), LNO/Pt and Pt bottom electrodes were comparatively analyzed to investigate the possibility for their application. LNO thin films were successfully prepared on Si (100) and Pt(111)/Ti/SiO₂/Si substrates by modified metallorganic decomposition (MOD). The PZT thin films were spin-coated onto the LNO, LNO/Pt and Pt bottom electrodes by sol–gel method. The crystallographic orientation and the microstructure of the resulting LNO films and PZT thin films on the different bottom electrodes were characterized by X-ray diffraction analysis. The dielectric and ferroelectric properties of PZT films on the different bottom electrodes are discussed. The PZT films deposited onto Pt/Ti/SiO₂/Si and LNO/Si substrates show strong (110) and (100) preferred orientation, respectively, while the films deposited onto LNO/Pt/Ti/SiO₂/Si substrates show the peaks of mixed orientations. PZT films on LNO and LNO/Pt bottom electrodes have larger dielectric constant and remnant polarizations compared with those grown on the Pt electrode.     

Investigation of PbZr0.4Ti0.6O3 capacitors with room temperature as-grown LaNiO3 electrodes

LaNiO₃ (LNO) film grown at room temperature (RT) by RF magnetron sputtering is used as the electrode for integrating LaNiO₃/PbZr_0.4Ti_0.6O₃/LaNiO₃ (LNO/PZT/LNO) capacitor on SrTiO₃ (STO) substrate. For comparison, LNO film grown at 250 °C is also used as the electrode of PZT capacitor. Reflection high energy electron diffraction (RHEED) technique is used to characterize the LNO film, it is found that LNO film prepared at 250 °C is epitaxial although no diffraction pattern is found for RT as-grown LNO. Ferroelectric properties of PZT films strongly depend on the LNO bottom electrodes. The remanent polarization (P _r) and coercive voltage (V _c), measured at 5 V, for the capacitors with LNO bottom electrodes prepared at RT and 250 °C, are 20 and 37 μC/cm², 1.67 and 1.95 V, respectively. No obvious degradation of polarization for PZT capacitors with RT as-grown LNO electrodes can be found. Room temperature as-grown LNO as both bottom and top electrodes to fabricate ferroelectric capacitors can save 2/3 thermal budgets, which may pay a way to decrease the potential challenges of devices resulting from the oxidation, interdiffusion or reactions during integrating ferroelectric capacitors with Si technologies.     

Deflection of wafers and cantilevers with Pt/LNO/PZT/LNO/Pt/Ti/SiO2 multilayered structure

The present paper describes a Pt/LNO/PZT/LNO/Pt/Ti/SiO₂ multilayers deposited on 4-inch Si wafers. We have evaluated the variation of the deflection of the Si wafers with deposition of each of the thin films. The deposition of the multilayers has resulted in downward deflection (center is higher than edge) of the Si wafers. The multilayers have been also deposited onto SOI wafers and fabricated into piezoelectric micro cantilevers through MEMS bulk micromachining. The micro cantilevers have shown the upward deflection. We have characterized the ferroelectric and piezoelectric properties of the PZT thin films through electrical tests of the micro cantilevers. The dielectric constant, saturation polarization, remanent polarization and coercive field were measured to be 1050, 31.3 μC/cm², 9.1 μC/cm² and 21 kV/cm, respectively. The transverse piezoelectric constant, d₃₁, was measured to be − 110 pm/V from the DC response of the micro cantilevers.     

The effect of LaNiO3 buffer layer thickness on the electric properties of Pb(Zr0.53Ti0.47)O3 thin films deposited on titanium foils

Sol-gel derived Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films were prepared on LaNiO₃ (LNO) buffered titanium foils. The effect of LNO buffer layer thickness on the electric properties of PZT thin films was investigated. The room temperature dielectric constant of PZT thin films increased with increasing LNO thickness. The remnant polarization of PZT thin films on 150 and 250 nm LNO was about 20 uC/cm². Curie temperatures of PZT thin films were 310, 330 and 340 °C for LNO of 250, 150 and 50 nm respectively. The current-voltage characteristics of PZT thin films were examined for different LNO buffer layer thicknesses, and the space charge limited conduction model was followed in PZT thin films on 50 nm LNO.     

Characterization of lead zirconate titanate thin film deposition onto Pt/Ti/SiO2/Si substrates

Lead zirconate titanate, (Pb(Zr_0.52Ti_0.48)O₃PZT) thin films were deposited onto a Pt/Ti/SiO_2/Si substrate using radio frequency (r.f.) planar magnetron sputtering in this study. The deposited PZT thin films were almost amorphous before the annealing processes and developed a perovskite structure after the annealing process. If the annealing temperature was too low or annealing time too short, pyrochlore would form. However, if the annealing temperature was too high or annealing time too long, the thin film structure would degrade due to the volatilization of PbO. The significant finding in this experiment is that high quality perovskite PZT thin films on Pt/Ti/SiO_2/Si substrates can be obtained by adjusting the annealing temperature to a range of 650 °C to 850 °C and annealing time to a range from 5 to 80 min. In this experiment, the optimal annealing condition was an annealing temperature of 650 °C and time of 20 min. The properties of PZT thin film annealed at 650 °C for 20 min were dielectric constant _r = 869 free dielectric constant ^T ₃₃ = 893 piezoelectric constant d₃₃ = 2.03p m V^-1 piezoelectric constant g₃₃ = 2.57 x 10^-4 V m N^-1, remanent polarization P₁ = 112.5 nC cm^-2 and coercive field E_c= 0.061 kV cm^-1.     

Effect of LaNiO3 electrodes and lead oxide excess on chemical solution deposition derived Pb(Zrx,Ti1 − x)O3 films

The effects of LaNiO₃ (LNO) and Pt electrodes on the properties of Pb(Zr_x,Ti_1 − x)O₃ (PZT) films were compared. Both LNO and PZT were prepared by chemical solution deposition (CSD) methods. Specifically, the microstructure of LNO and its influence on the PZT properties were studied as a function of PbO excess. Conditions to minimize the Pyrochlore phase and porosity were found. Remnant polarization, coercive field and fatigue limit were improved in the PZT/LNO films relative to the PZT/Pt films. Additionally, the PZT crystallization temperature over LNO was 500 °C, about ~ 50 °C lower than over Pt. The crystallization temperature reported here is amongst the lowest values for CSD-based PZT films.     

Effect of the electrode structure on the electrical properties of alkoxide derived ferroelectric thin film

Effect of the thermal expansion coefficient of electrode on the electrical properties in lead zirconate titanate (PZT) with morphotropic phase boundary (Pb(Zr_0.53,Ti_0.47)O₃: MPB) composition film was demonstrated in this paper. The lanthanum nickel oxide (LaNiO₃: LNO) and lanthanum strontium cobalt oxide ((La_0.5,Sr_0.5)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.     

Effect of heat-treatment on LaNiO3 film electrode of PZT thin films derived by a sol–gel method

Lanthanum nickel oxide (LaNiO₃ or LNO) conducting thin films that could be used as electrodes for improving fatigue and aging properties of ferroelectric thin films were investigated. In this paper, LNO films were directly spin-coated onto SiO₂/Si(1 0 0) substrates followed by thermal treatment in air and in oxygen. It was found that crack-free dense and uniform films with good crystallinity and medium grains were obtained, preferentially (1 0 0)-oriented LNO thin films could be formed at a lower annealing temperature of 550 °C and that with the increase in thermal annealing temperature the LNO thin film possessed better electrical properties especially at 750 °C. However, the LNO film displayed a structure transformation above 850 °C. A phenomenon was found that the first heat-treatment temperature and time played a key role to determine the crystallite size of LNO films. A subsequent deposition of a sol–gel derived Pb(Zr_0.53Ti_0.47)O₃ (PZT53/47) thin film on the LNO-coated SiO₂/Si(1 0 0) substrates was also found to have a (1 0 0)-oriented texture. Moreover, the Au/PZT/LNO capacitor was found to significantly improve the fatigue and the effects of the LNO electrodes to the fatigue were discussed.     

Effect of heat-treatment on LaNiO3 film electrode of PZT thin films derived by a sol–gel method

Lanthanum nickel oxide (LaNiO₃ or LNO) conducting thin films that could be used as electrodes for improving fatigue and aging properties of ferroelectric thin films were investigated. In this paper, LNO films were directly spin-coated onto SiO₂/Si(1 0 0) substrates followed by thermal treatment in air and in oxygen. It was found that crack-free dense and uniform films with good crystallinity and medium grains were obtained, preferentially (1 0 0)-oriented LNO thin films could be formed at a lower annealing temperature of 550 °C and that with the increase in thermal annealing temperature the LNO thin film possessed better electrical properties especially at 750 °C. However, the LNO film displayed a structure transformation above 850 °C. A phenomenon was found that the first heat-treatment temperature and time played a key role to determine the crystallite size of LNO films. A subsequent deposition of a sol–gel derived Pb(Zr_0.53Ti_0.47)O₃ (PZT53/47) thin film on the LNO-coated SiO₂/Si(1 0 0) substrates was also found to have a (1 0 0)-oriented texture. Moreover, the Au/PZT/LNO capacitor was found to significantly improve the fatigue and the effects of the LNO electrodes to the fatigue were discussed.     

Enhanced ferro- and piezoelectric properties in (100)-textured Nb-doped Pb(ZrxTi1 − x)O3 films with compositions at morphotropic phase boundary

To develop high-performance piezoelectric films on conventional Pt(111)/Ti/SiO₂/Si(100) substrates, sol-gel-derived highly [100]-textured Nb-doped Pb(Zr_xTi_1 − x)O₃ (PNZT) thin films with different Zr/Ti ratios ranging from 20/80 to 80/20 were prepared and characterized. The phase structure, ferroelectric and piezoelectric properties of the PZNT films were investigated as a function of Zr/Ti ratios, and it was confirmed that there was distinct phase transition of the PNZT system from tetragonal to rhombohedral when the Zr/Ti ratio varied across the morphotropic phase boundary (MPB). The Nb-doped PZT films showed enhanced remanent polarization but reduced coercive field, whose best values reached 75 μC/cm² and 82 kV/cm, respectively at the composition close to MPB. In addition, the [100]-textured PNZT film at MPB also shows a high piezoelectric coefficient up to 161 pm/V. All these properties are superior to those for undoped PZT films.     

Epitaxial growth and electrical measurement of single crystalline Pb(Zr0.52Ti0.48)O3 thin film on Si(001) for micro-electromechanical systems

We report in this work the epitaxial growth and the electrical characteristics of single crystalline Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin film on SrTiO₃(STO)-buffered Si(001) substrate. The STO buffer layer deposited by molecular beam epitaxy allows a coherent oxide/Si interface leading enhanced PZT crystalline quality. 70 nm-thick PZT (52:48) layer was then grown on STO/Si(001) by sol-gel method. X-ray diffraction demonstrates the single crystalline PZT film on Si substrate in the following epitaxial relationship: [110] PZT (001)//[110] STO (001)//[100] Si (001). The macroscopic electrical measurements show a hysteresis loop with memory window of 2.5 V at ± 7 V sweeping range and current density less than 1 μA/cm² at 750 kV/cm. The artificial domains created by piezoresponse force microscopy with high contrast and non-volatile properties provide further evidence for the excellent piezoelectric properties of the single crystalline PZT thin film.     

The effects of the PbO content and seeding layers upon the microstructure and orientation of sol-gel derived PZT films

This paper systematically studied the factors including Pb content of precursor, PT seeding layer and TiO₂ and ZrO₂ seeding layers, which influence greatly the crystal orientation of lead zirconate titanate (PZT, Zr/Ti = 52/48) thin films fabricated by a sol-gel process. We find that the PZT films deposited by precursor with 20% mole excess Pb displayed strong (111) preferred orientation, with 5% mole excess Pb showed a little (100) orientation and pyrochlore phase. PT seeding layer was found prompting the PZT films phase transformation with (110) preferred orientation. In addition, the results show that the TiO₂ and ZrO₂ seeding layers had totally different effects on the preferred orientation of PZT films. The films with TiO₂ seeding layer were highly (111) oriented and exhibited better ferroeletric properties (remnant polarization Pr = 14.2 μC⋅ cm⁻², coercive field Ec = 59.1 Kvcm⁻¹) than those of the films with ZrO₂ seeding layer shown (100) orientation (Pr = 7.4 μC⋅cm⁻², Ec = 42.9 Kvcm⁻¹).     

Preparation and ferroelectric properties of (124)-oriented SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> ferroelectric thin film on (110)-oriented LaNiO<Subscript>3</Subscript> electrode

A (124)-oriented SrBi₄Ti₄O₁₅ (SBTi) ferroelectric thin film with high volume fraction of was obtained using a metal organic decomposition process on SiO₂/Si substrate coated by (110)-oriented LaNiO₃ (LNO) thin film. The remanent polarization (P _r) and coercive field (E _c) for (124)-oriented SBTi film are 12.1 μC/cm² and 74 kV/cm, respectively. No evident fatigue of (124)-oriented SBTi thin film can be observed after 1 × 10⁹ switching cycles. Besides, the (124)-oriented SBTi film can be uniformly polarized over large areas using a piezoelectric-mode atomic force microscope. Considering that the annealing temperature was 650 °C and the thickness of each deposited layer was merely 30 nm, a long-range epitaxial relationship between SBTi(124) and LNO(110) facets was proposed. The epitaxial relationship was demonstrated based on the crystal structures of SBTi and LNO.     

锆钛酸铅(PZT)薄膜的自发极化与压电响应

用溶胶－凝胶法在Ｐｔ／Ｔｉ／ＳｉＯ２／Ｓｉ（１００）基片上制备了近等原子比的压电ＰＺＴ薄膜,在准同型相界附近的ＰＺＴ薄膜的应变机制是受极化控制的压电效应,内电场导致薄膜的自发极化定向,使薄膜未经极化就具有明显的压电响应。     

Effects of bottom electrodes on dielectric properties of epitaxial 2% Mn doped Ba(Zr<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>)O<Subscript>3</Subscript> thin films

2 mol% Mn doped Ba(Zr_0.2Ti_0.8)O₃ (Mn-BZT) thin films were prepared by pulsed laser deposition (PLD) on single crystal oxide substrates LaAlO₃(001) and MgO(001), with conductive oxide bottom electrodes LaNiO₃ and SrRuO₃, respectively. Both the Mn-BZT films and the bottom electrode films could be c-axial oriented with a cube-on-cube arrangement on the corresponding substrates. The dielectric properties measured with parallel plate capacitor configurations of Au/Mn-BZT/LNO and Au/Mn-BZT/SRO revealed that the Mn-BZT film on LNO bottom electrode exhibited comparatively higher dielectric constant, larger dielectric tunability and lower dielectric loss than that on SRO. It could be mainly attributed to the better epitaxial growth characteristics and mismatch stress of Mn-BZT thin film on LNO, as well as less misfit dislocation and the better morphology of LNO bottom electrode.     

Comparative analysis for the crystalline and ferroelectric properties of Pb(Zr,Ti)O3 thin films deposited on metallic LaNiO3 and Pt electrodes

The crystalline quality and ferroelectricity of the Pb(Zr,Ti)O₃ (PZT) films deposited on the metallic LaNiO₃ (LNO) and Pt electrodes were comparatively analyzed to investigate the possibility for their application to non-volatile memory devices. LNO thin films were successfully deposited on various substrates by using r.f. magnetron sputtering even at a low temperature ranging from 250 to 500 °C, and the ferroelectric PZT thin films were spin-coated onto the LNO and Pt bottom electrodes. Metallic LNO thin films exhibited [100] orientation irrespective of the substrate species and PZT films coated onto LNO films had highly a- and c-axis orientations, while those with Pt bottom electrode were polycrystalline. PZT films with LNO bottom electrode had smaller grain size and larger dielectric constant compared to those grown on the Pt electrode. The ferroelectric thin films fabricated on LNO bottom electrode displayed an asymmetric D–E hysteresis loop, which was explained by the defect effects formed at the interface. Especially, the LNO/PZT/LNO capacitor was found to significantly improve the polarization fatigue and the effects of the LNO electrodes to the fatigue were discussed.     

Development of phases and texture in sol-gel derived lead zirconate titanate thin films prepared by three-step heat-treatment process

Lead zirconate titanate (PZT) films were fabricated by the addition of 10 mol% excess Pb to the starting solution which was spin-coated onto Pt/Ti/SiO₂/Si substrates. The effect of film thickness on texture was investigated, and it is clear that the (100) texture gradually increases and the (111) texture decreases with increasing film thickness. A Pt _x Pb intermetallic metastable phase was observed by X-ray diffraction, and it is found that the position of this peak shifted from 38.30° 2 (d : 0.2348 nm) to 37.10° 2 (d : 0.4213 nm) with increasing firing temperature from 350°C to 550°C. The (111) preferred orientation in the PZT film was promoted by the metastable Pt _x Pb phase. The formation of the (100) texture of perovskite phase in the multilayer films was mainly attributed to the effects of both substrates and crystal growth rates which depend on the crystal orientation.     

Properties of epitaxial, (001)- and (110)-oriented (PbMg1/3Nb2/3O3)2/3-(PbTiO3)1/3 films on silicon described by polarization rotation

Epitaxial (PbMg_1/3Nb_2/3O₃)_2/3-(PbTiO₃)_1/3 (PMN-PT) films with different out-of-plane orientations were prepared using a CeO₂/yttria stabilized ZrO₂ bilayer buffer and symmetric SrRuO₃ electrodes on silicon substrates by pulsed laser deposition. The orientation of the SrRuO₃ bottom electrode, either (110) or (001), was controlled by the deposition conditions and the subsequent PMN-PT layer followed the orientation of the bottom electrode. The ferroelectric, dielectric and piezoelectric properties of the (SrRuO₃/PMN-PT/SrRuO₃) ferroelectric capacitors exhibit orientation dependence. The properties of the films are explained in terms of a model based on polarization rotation. At low applied fields domain switching dominates the polarization change. The model indicates that polarization rotation is easier in the (110) film, which is ascribed to a smaller effect of the clamping on the shearing of the pseudo-cubic unit cell compared to the (001) case.     

Ferroelectric and piezoelectric behavior of (111)-oriented Pb(ZrxTi1−x)O3 thin films on cobalt ferrite nano-seed layered Pt(111)/Si substrate

Perfect (111)-oriented Pb(Zr_xTi_1?x)O₃ (PZT) thin films were grown on cobalt ferrite buffered Pt(111)/Ti/SiO₂/Si substrate by pulsed laser deposition method using various targets with different Zr/Ti ratios ranging from 30/70 to 70/30. The results of X-ray diffraction analyses indicated that the composition of morphotropic phase boundary in the present PZT films is same as the bulk PZT (Zr/Ti = 52/48). The effect of Zr/Ti ratio of the PZT films was investigated by the ferroelectric domain structure and the piezoelectric characteristics of the films by piezoresponse force microscopy, as well as polarization measurement. The results revealed that the present tetragonal PZT film has a higher ferroelectric domain switching than rhombohedral one and the film with composition of Zr/Ti = 52/48 showed relatively high value of squareness of P–E loop and E_c as well as high piezoresponse.