Self-Organized (100)-/(001)-Preferred Orientation in Pb(Zr,Ti)O3 Films Grown on Polycrystalline Substrates by Metalorganic Chemical Vapor Deposition

Lead zirconate titanate [Pb(Zr _x Ti_{1 ? x} )O₃, PZT] films were grown on (100), (110) and (111)SrRuO₃//SrTiO₃ substrates at 600°C by metalorganic chemical vapor deposition (MOCVD). The crystal orientation dependence of the growth rate was investigated for these films. The growth rate of (100)-/(001)-oriented epitaxial films was approximately 1.7 and 2.0 times higher than that of (110)-/(101)- and (111)-/(11&1macr;)-oriented epitaxial films, respectively. On the other hand, the growth rate of (100)-/(001)-preferred oriented PZT films grown on (111)Pt/TiO₂/SiO₂/(100)Si substrates was almost the same with that of (100)-/(001)-oriented epitaxial films. The deposition rate of these films was approximately 1.5 μm/h. High growth rate of (100)-/(001)-oriented PZT grains makes (100)-/(001)-preferred orientation on (111)Pt/TiO₂/SiO₂/(100)Si substrate. From transmission electron microscopy observation, (100)-/(001)-oriented grains were found to be directly grown on (111)-oriented Pt grains without obvious another oriented grains. As a result, orientation-controlled PZT films were successfully grown on (100)Si substrates having (111)-oriented Pt bottom electrodes.     

Low-Leakage Epitaxial PZT Thin Films Grown on Ir/MgO Substrates by Metalorganic Chemical Vapor Deposition

250 nm-thick PZT films were grown on (001)lr/(001)MgO substrates by metalorganic chemical vapor deposition (MOCVD). It was ascertained that PZT films on lr substrates are epitaxially grown without the formation of large amount of lrO 2 phase. Crystal structure and the electrical properties of Pt/PZT/(001)lr/(001)MgO structure was compared with Pt/PZT/ (001)c SrRuO 3 /(001)SrTiO 3 structure with the same Zr/(Zr+Ti) ratio of 0.50. X-ray diffraction pattern was almost the same to be identified as (001)- and (100)-oriented tetragonal PZT phase. P-E hysteresis loops and saturation properties of the remanent polarization ( P r ) and the coercive field ( E c ) were also the same, because of the same volume fraction of (001)-oriented grains that contributed to polarization. On the other hand, the leakage current density of Pt/PZT/lr/MgO structure was superior to that of Pt/PZT/SrRuO 3 /SrTiO 3 structure. As a result, lr/MgO substrate is suitable for epitaxial PZT film with low-leakage and good ferroelectricity.     

Epitaxial growth of multilayered (Bi,La)4Ti3O12/Pb(Zr,Ti)O3 ferroelectric thin films with different orientations

Epitaxial (Bi,La)₄Ti₃O₁₂ (BLT) thin films, epitaxial Pb(Zr,Ti)O₃ (PZT) thin films, and epitaxial multilayered BLT/PZT ferroelectric thin films with different orientations were prepared on SrTiO₃ (STO) single crystal substrates by pulsed laser deposition. From X-ray pole-figures and electron diffraction patterns, the epitaxial orientation relationships between BLT layers, PZT layers, and STO substrates were identified to be (1) BLT(001)//PZT(001)//STO(001), and BLT[110]//PZT[100]//STO[100] for the multilayered thin films on (001)-oriented STO substrates, and (2) BLT(118)//PZT(011)//STO(011), and $ {\text{BLT}}{\left[ {\overline{1} \overline{1} 0} \right]}//{\text{PZT}}{\left[ {100} \right]}//{\text{SrTiO}}_{3} {\left[ {100} \right]} $ for the multilayered films on (011)-oriented STO substrates. Tri-layered films of the same compositions showed well-defined hysteresis loops as well as a high fatigue resistance up to 1?×?10¹⁰ switching cycles.     

Polarization Switching in (100)/(001) Oriented Epitaxial Pb(Zr, Ti)O3 Thin Films

Thin films made of (100)/(001)-oriented Pb(Zr, Ti)O₃ (PZT) were deposited by liquid-delivery metal-organic chemical vapor deposition on Ir/MgAl₂O₄/SiO₂/Si(100) substrates. For comparison, PZT thin films were also deposited on Ir/MgO(100) substrates. The X-ray scan spectra for the (202) reflections revealed that the PZT films have four-fold symmetry. It indicates that the PZT films were epitaxially grown as a cube-on-cube structure on both substrates. The switchable polarization (Q_sw) of the PZT capacitors on the silicon substrate was only 23 C/cm² at 1.8 V; however, Q_sw of PZT capacitors on MgO was 99 C/cm². In the case of PZT films deposited on silicon, the volume fraction of (001)-oriented domains (which contribute to polarization switching) was 15.1% (calculated from an XRD pattern). This result is due to the lower Q_sw of PZT capacitors on silicon. By piezoresponse-force microscopy, switchable and unswitchable domains could be identified by imaging color contrast, namely, (001) and (100) domains, respectively. Consequently, domain distribution of the PZT film on a silicon substrate indicates that the (001) domain exists in the (100) domain matrix.     

Optical properties of epitaxial plzt thin films

In the epitaxial (Pb_1?x , La _x )(Zr_1?y , Ti _y )_1?x/4O₃ [PLZT] films, the composition dependence of the refractive index and electric-optic (EO) coefficient near the morphotropic phase boundary (MPB) composition was investigated. A (100/001)-oriented PLZT 10/65/35 epitaxial film is found to have isotropic optical properties. Highly (100/001)-oriented epitaxial PLZT films with compositions near the MPB on Nb–SrTiO₃ substrates were fabricated using a sol–gel process. The value of birefringence from 4?×?10^?3 to 5?×?10^?4 in PLZT epitaxial film was smaller than that of lithium niobate single crystal. The refractive index decreases with increasing lanthanum content. The difference in the refractive index obtained depended upon the lanthanum content up to 2%. This value is adequate for fabrication of waveguide structures. The EO coefficient of PLZT 9/65/35 thin films was 45 pm/V, which is larger than that of lithium niobate single crystal. A very small polarization dependence of the EO coefficient was also observed.     

Dielectric properties and morphotropic phase boundaries in the xPb(Zn1/3Nb2/3)O3−(1−x)Pb(Zr0.5Ti0.5O3 pseudo-binary system

Ceramics in the xPb(Zn_1/3Nb_2/3)O₃−(1−x)Pb(Zr_0.5Ti_0.5)O₃ [xPZN–(1−x)PZT] solid solution system are expected to display excellent dielectric, piezoelectric, and ferroelectric properties in compositions close to the morphotropic phase boundary (MPB). The dielectric behavior of ceramics with x = 0.1−0.6 has been characterized in order to identify the MPB compositions in this system. Combined with X-ray diffraction results, ferroelectric hysteresis measurements, and Raman reflectivity analysis, it was consistently shown that an MPB exists between x = 0.2 and x = 0.3 in this binary system. When x ≤ 0.2, the tetragonal phase dominates at ambient temperatures. In the range of x ≥ 0.3, the rhombohedral phase dominates. For this rhombohedral phase, electrical measurements reveal a profound frequency dispersion in the dielectric response when x ≥ 0.6, suggesting a transition from normal ferroelectric to relaxor ferroelectric between 0.5 ≤ x ≤ 0.6. Excellent piezoelectric properties were found in 0.3PZN–0.7PZT, the composition closest to the MPB with a rhombohedral structure. The results are summarized in a PZN–PZT binary phase diagram.     

Piezoelectric and Pyroelectric Properties of Pb(Zr,Ti)O3 Films for Micro-Sensors and Actuators

The piezoelectric and the pyroelectric properties of PZT films are systematically investigated for tetragonal (Zr/Ti = 30/70), morphotropic (52/48), and rhombohedral (70/30) compositions. The magnitude of the effective longitudinal piezoelectric coefficient (d₃₃) and pyroelectric coefficient (p) of these films is measured by atomic force microscopy and Byer-Roundy method, respectively. All films are consistently highly textured (111) orientation and have dense microstructures. Slightly less degree of texture in higher Zr-rich composition is observed due to the lattice mismatch between PZT and Pt bottom electrode and higher activation energy for nucleation. Squareness of polarization hysteresis loops is optimized in tetragonal composition, which indicates the tetragonal PZT is closer to the ideal hysteresis behavior than other compositions. It is shown that the piezoelectric coefficient and the pyroelectric figure of merit are dependent on the dielectric properties of the films. The morphotropic PZT films with high dielectric constant and low pyroelectric figure of merit show the largest piezoelectric coefficient values, while the tetragonal PZT films with low dielectric constant and high remanent polarization values show the largest pyroelectric figure of merit compared to other compositions, which indicate the suitability for PIR sensor devices.     

Structural and Electrical Properties of Ba(ZrxTi1-x)O3 Films Prepared by RF-magnetron Sputtering Using Metal Targets

Ba(Zr_xTi_1-x)O₃ (BZT) thin films with different Zr contents were deposited on (100)MgO and (100)Pt/(100)MgO substrates by RF-magnetron sputtering using metal targets. The BZT thin films had a single perovskite phase with only (001)/(100) orientation. In all cases, the ratio of Ba/Ti was stoichiometry and BZT films possess a dense microstructure. The grain size was decreased and BZT thin films showed ferroelectric-to-paraelectric properties with increasing Zr content. At room temperature, the tunability of nearly 30% was achieved at 1 MHz; meanwhile, a relatively low dielectric loss was obtained. These results indicated that we succeeded in depositing high-quality and potential tunable ferroelectrics.     

Device effects of various Zr/Ti ratios of PZT thin-films prepared by sol-gel method

Abstract

PZT, PbZr_xTI_1?xO₃, thin-films with various Zr/Ti ratios, 100/0 (lead zirconate) to 0/100 (lead titanate), were prepared by the sol-gel method. Basic electric properties, dielectric constant, tan σ, P-E hysteresis curve, switching properties were measured respectively as a function of composition. Dielectric constant indicated a specific peak value (～1100) around the morphotropic phase boundary between tetragonal and rhombohedral phase. Satisfactory low-voltage saturated hysteresis curves were observed for the compositions of PZT(90/10) through PZT(20/80). The remanent polarization and the coercive field increased as the titanium content decreased. The result of X-ray measurement showed that the lattice constants of thin-Film PZT are different from bulk ceramics for compatible compositionsS. The boundary, on which the c/a ratio must be 1 (rhombohedral phase), was slightly shifted to PbTiO₃ side. This distortion in crystal structure is considered to be due to the thin-film effect, which the lattice mismatch between the platinum substrate and the PZT layer, restricted the ions to position into proper cites.     

Characterization of Pb(Zr,Ti)O3 thin films on SOI prepared by excimer laser deposition

Abstract

Ferroelectric Pb(Zr,Ti)O₃ (PZT) thin films were prepared by pulsed excimer laser deposition on Silicon-on-Insulator (SOI) substrates with and without an electrode. Their properties can be improved by rapid thermal annealing, based on the structural and interfacial characteristics analysis by X-ray diffraction, Rutherford backscattering spectroscopy and automatic spreading resistance measurements. The thin films were revealed of to be polycrystalline perovskite structure with mainly ?100? and ?110? orientations; the crystallite size and the structure are dependent on the annealing time. The PZT thin films did not interact with the top silicon layers of SOI, and the composition was on the tetragonal side of the morphotropic phase boundary in the PbTiO₃-PbZrO₃ phase diagram.     

Effect of Zr/Ti Ratio on Microstructure and Electrical Properties of Lead Zirconate Titanate Thin Films Derived by Pulsed Laser Deposition

PZT films were fabricated using various targets of Pb(Zr_xTi_{1 – x})O₃ with Zr/Ti ratios of 70/30, 58/42, 52/48, 45/55 and 30/70, and with excess PbO of 20 wt% on Pt/Ti/SiO₂/Si(100) substrates. The rosette structure was observed in the films derived from the target with a Zr/Ti ratio of 70/30 and disappeared with increasing titanium composition. The observations on surface and cross-sectional microstructure were consistent with a higher perovskite nucleation for the higher Ti content films. The PZT films derived from the target with a Zr/Ti ratio of 45/55 had a polycrystalline columnar microstructure extending throughout the thickness of the film and no pyrochlore phase on the surface was observed. The PZT films derived from the target with a Zr/Ti ratio of 45/55 exhibited better electric properties than those derived from the target with a Zr/Ti ratio of 52/48.     

Optimized PZT Thin Films for Pyroelectric IR Detector Arrays

A planar multi target sputtering technology was used to deposit highly (111) oriented Pb(Zr _x Ti_1–x )O₃ (PZT) thin films with x ranging from 0–0.6. The preparation of a stable Pt/ZrO₂ electrode is described and analyzed in terms of stress and stress-temperature behavior. The PZT films with low Zr content are under compressive stress after deposition. The dielectric constant and loss peaks occur at a composition close to the morphotropic phase boundary. Films on the tetragonal side of the phase diagram with a Zr content up to about 25% exhibited a strong self polarization and strong voltage shifts in the C(V) curves. High pyroelectric coefficients of >2×10^–4 C/(m²K) have been measured on these films without additional poling. The self polarization fades out with increasing Zr content. The low values of the pyroelectric coefficient for the PZT film with 60% Zr is discussed in terms of the possible crystallographic variants after distortion and the tensile stress state during the phase transition. Based on the systematic study of stress and electrical properties of PZT films with a wide range of composition presented in this paper, films with a Zr content up to about 25% turned out to give the best properties for the use in pyroelectric detector arrays.     

Preparation and characterization of PZT ferroelectric thin films by plasma enhanced metalorganic chemical vapor deposition

Abstract

PZT thin films with a uniform distribution of components were prepared by plasma enhanced chemical vapor deposition (PECVD) using Pb(C₂H₅)₄, Z (O-i-C₄H₉)₄, Ti(O-i-C₃H₇)₄, and oxygen. The crystallization of films was occure after annealing in the temperature range between 450 and 550°C under O₂ ambient for 1 hr. The significant change of Pb concentration in PECVD PZT thin films was not observed in the relation to annealing temperature and time. The dielectric constant PECVD PZT thin films increased with the Ti content, showed the maximum value in the vicinity of morphotropic phase boundary (MPB) composition of PZT material, and decreased with the Ti content. The leakage current density of PZT (65/35) thin film of 180 nm in thickness was 3·37 × 10^?7 A/cm² at the applied voltage of 3 V. Remanent polarization increased with increasing of Zr content in the film and coercive field was nearly independent of the composition. The typical values of electrical properties were ε_r = 570, E_c = 90 kV/cm, and P_r = 19 μC/cm² in the PECVD PZT (54/46) thin film of 220 nm in thickness.     

Processing optimization of solution derived PbZr1−xTixO3 thin films for piezoelectric applications

Abstract

Processing optimization allowed the sol-gel fabrication of 1 μm thick, phase pure perovskite thin films with identical grain size and controlled texture. This made it possible to fabricate stress compensated beams to measure the transverse piezoelectric coefficient over the whole composition range of PbZr_1?xTi_xO₃. The highest value of -12.1 C/m² was measured for (100)/(001) textured PZT53/47. For (111) textured films the maximum value of -8.7 C/m² was found to be in the tetragonal phase field at 55% Ti.     

Preparation of BaPbO3 Electrode Thin Films by RF Magnetron Sputtering

For electrode materials of Pb(Zr,Ti)O₃ (PZT) thin films in ferroelectric random access memory (FeRAM), various materials have been studied. As new electrode material with which the polarization and fatigue properties are improved, we take notice of barium metaplumbate BaPbO₃ (BPO). Because the BPO contained lead (Pb) and oxygen is conductor that adopted same perovskite structure as PZT. BPO thin films were prepared by rf magnetron sputtering on various substrates. (SiO₂/Si, MgO, Al₂O₃ and Pt-coated substrates), and influence of growth conditions (sputtering gas, rf power, the substrate-heating temperature and post anneals) on crystallization and conductivity were investigated. In case of post anneal after sputtering at room temperature, perovskite single phase was obtained above 400°C. In case of substrate heating while sputtering, without post anneal, perovskite single phase was obtained at 350–500°C on SiO₂/Si substrates (110) preferred orientation BPO films obtained at low temperature, and resistivity of the films decreased at decreasing sputtering temperature. Resistivity of the film at substrate temperature 350°C was 3 × 10^?3 Ω cm. In the case of single crystal substrate, the BPO films were epitaxially grown. Orientation of the films was varied with the sputtering condition. The epitaxial PZT thin films were also grown on the BPO, revealing that PZT(111)[011] //BPO(111)[011] //Pt(100)[011] //MgO(100)[011] and PZT(111)[011] //BPO(111)[011] //Pt(111)[011] //Al₂O₃(001)[100] structures were obtained, and their ferroelectric properties were also evaluated.     

Pb(Zr,Ti)O3 thin film growth on yttrium-treated Si(100)

Abstract

Pulsed laser ablation has been used to deposit ferroelectric Pb(Zr, Ti)O₃ (PZT) thin films on Si(100) and on yttrium-treated Si(100) substrates. The yttrium (Y) treatment of a Si surface followed by oxidation resulted in formation of a very thin, Y-enhanced SiO₂ antidiffusion barrier layer, thereby suppressing the undesirable PZT/Si interdiffusion. The best PZT film grown on Y-treated Si(100) had a breakdown voltage of 0.6 MV/cm, a coercive field of 71 KV/cm, and a remanent polarization of 18 μC/cm².     

Microwave Dielectric Properties of Ferroelectric Pb(Zr1 − x Ti x )O3 Thin Films Using Interdigital Capacitors

Ferroelectric Pb(Zr_{1 ? x} Ti _x )O₃ (PZT) films were deposited on (001) MgO single crystals using sol-gel method. Structural properties and surface morphologies of PZT films were investigated using an X-ray diffractometer and a scanning electron microscopy, respectively. The dielectric properties of PZT films were investigated with the dc bias field of 0–135 kV/cm using interdigitated capacitors (IDC) which were fabricated on PZT films using a thick metal layer by photolithography and etching process. The small signal dielectric properties of PZT films were calculated by a modified conformal mapping method with low and high frequency data, such as capacitance measured by an impedance gain/phase analyzer at 100 kHz and reflection coefficient (S-parameter) measured by a HP 8510C vector network analyzer at 1–20 GHz. The IDC on PZT films exhibited about 67% of capacitance change with an electric field of 135 kV/cm at 10 GHz. These PZT thin films can be applied to tunable microwave devices such as phase shifters, tunable resonators and tunable filters.     

Preparation and evaluation of sub-100 nm Pb(Zr,Ti)O3 films derived from modified sol-gel solutions for low-voltage operation of feram

Abstract

Sub-100 nm PbZr_0.3Ti_0.7O₃ (PZT) films were prepared on Pt/SiO₂/Si substrates from modified sol-gel solutions without using any seeding layers. Firstly, we studied Pb content [Pb/(Zr+Ti)] dependence of 90-nm-thick films. In the wide Pb content region of 108 – 125%, the films had perovskite-single-phase fine columnar grains with (111)-orientation and no voids. Electric properties were dependent on Pb content. The film with good microstructure, rectangular hysteresis, high remanent polarization (P_r), and low leakage current was gained for Pb content of 116%. Secondly, we studied film thickness dependence of PZT(116/30/70) films. Films from 90 down to 61 nm in thickness were prepared. We found that the sub-100 nm films with good microstructures could be prepared from the modified solutions. The sub-100 nm films had saturation voltage of 1.25 V and high P_r even at 1 V or less. In particular, a 61-nm-thick film had high.P_r of 17 μC/cm2 at 0.75 V.     

Slow Dielectric Relaxation in Pb(Zr,Ti)O3 and (Ba,Sr)TiO3 Ferroelectric Thin Films

An impedance analysis of Ni/Pb(Zr,Ti)O₃/Pt thin-film structures based on measurements at the frequencies from 100 Hz to 100 MHz, along with the data of Grazing Angles XRD, TEM and photo-electric study, is used to obtain electronic structure of the PZT thin films deposited by sol-gel method on silicone substrates. Both slow capacitance relaxation and charging/discharging currents versus time under step-voltage excitation have been studied in (Ba,Sr)TiO₃ thin films between SrRuO₃ electrodes.     

Growth and characterization of non-c-axis-oriented SrBi2Ta2O9 epitaxial thin films on Si(100) substrates with SrRuO3 bottom electrodes

Abstract

We have successfully grown non-c-axis-oriented epitaxial ferroelectric SrBi₂Ta₂O₉ (SBT) films with (116) and (103) orientations on Si(100) substrates using epitaxial (110)- and (111)-oriented SrRuO₃ (SRO) bottom electrodes, respectively. The SRO orientations have been induced by coating the Si(100) substrates with epitaxial YSZ(100) and MgO(111)/ YSZ(100) buffer layers, respectively. All films were sequentially grown by pulsed laser deposition. Specific in-plane orientations of the epitaxial SBT films were found, which are in turn determined by specific in-plane orientations of the epitaxial SRO bottom electrodes. These include a diagonal rectangle-on-cube epitaxy of SRO(110) on YSZ(100) and a triangle-on-triangle epitaxy of SRO(111) on MgO(111).