Ferroelectric SrBi 2 Nb 2 O 9 Thin Films by Aqueous Chemical Solution Deposition

SrBi 2 Nb 2 O 9 (SBN) thin films on a Pt/Ti/SiO 2 /Si substrate were prepared by aqueous chemical solution deposition. The precursor solution was synthesized by means of an 'aqueous solution-gel method', starting with stable, inexpensive and easily available inorganic salts which are dissolved in an aqueous solution of chelating or coordinating ligands (acetates and citrates). Afterwards the synthesized precursor was spin-coated. However, problems arose as a consequence of insufficient 'wetting' of the substrate surface by the aqueous solution (poor film-substrate adhesion). Instead of improving surface adhesion by the addition of a surface-wetting reagent, a new strategy was developed: prior to spin-coating the platinum surface characteristics were modified using a UV/ozone technique. In this way the precursor solution was not chemically changed. Wetting/wettability was verified by means of contact angle measurements. A uniform, three-layer thin film with a total thickness of about 200 nm was obtained after thermal treatment, as could be verified using SEM and XRD.     

Enhancement of Ferroelectric Properties of Pb(Zr,Ti)O3 Films Grown by Metal-Organic Chemical Vapor Deposition on Noble-Alloy Bottom Electrodes

Pb(Zr,Ti)O₃ (PZT) films grown on Ir electrodes by a metal-organic chemical vapor deposition (MOCVD) have suffered from high leakage and rough surface. We sputtered Pt and Ir simultaneously onto Ti/SiO₂/Si substrates and formed Ir-Pt alloy bottom electrodes with various compositions. With an optimal composition of Ir and Pt, PZT films grown by MOCVD on this substrate showed smoother surface and suppressed leakage via the bottom interface. At the specific composition of Ir and Pt, two different phases seemed to be acquired. They constituted the electrodes and affected the PZT grain nucleation independently so that the grains with different origins grew and restrained the vicinal grains, and finally soothed the faceted-grain-formation. No fatigue was observed even in PZT on Ir-Pt alloy with much Pt content.     

PHOTO INDUCED CURRENT IN (Pb0.97La0.03) (Zr0.52Ti0.48)O3 THIN FILMS OF DIFFERENT THICKNESSES

ABSTRACT

Photovoltaic effect in ferroelectric materials exhibits potential for applications of sensors and remote controls in micro-electro-mechanical systems, and a systematic evaluation on the photovoltaic behavior in ferroelectric materials becomes important. However, as a critical parameter that determines the photovoltaic output in ferroelectric thin films, the film thickness effect on photocurrent output has not been investigated for thin film samples. In this work, a theoretical model has been developed to describe the thickness-dependent photocurrent in (Pb_0.97La_0.03)(Zr_0.52Ti_0.48)O₃(PLZT) thin films with a sandwich electrode structure. This model indicates that photocurrent increases exponentially with the decrease in film thickness. Therefore, a significantly enhanced photocurrent can be expected in thinner PLZT films. The predicted thickness dependence of the short circuit photocurrent was also supported by our experimental results.     

Pulsed Laser Deposited Ba(Mg1/3Ta2/3)O3 Microwave Dielectric Thin Films

Ba(Mg_1/3Ta_2/3)O₃ (BMT) microwave dielectric thin films were successfully synthesized by a modified pulsed laser deposition (PLD) process, which includes low temperature (200°C) deposition and high temperature (>500°C) annealing. Crystalline structured BMT thin films were obtained when the PLD-deposited films were post-annealed at a temperature higher than 500°C in oxygen atmosphere. The characteristics of BMT thin film, including crystallinity, grain size, film roughness, and dielectric properties were improved with annealing temperature, achieving dielectric constant K = 23.5 and dissipation factor tan δ = 0.015 (at 1 MHz) for the 800°C-annealed films.     

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.     

Preparation and electrical properties of 0.4Pb(Zn1/3Nb2/3)O3-0.6Pb(Zr0.4Ti0.6)O3 thin films by 2-step annealing method

Films of (1−x)Pb(Zn_1/3Nb_2/3)O₃-xPb(Zr_0.4Ti_0.6) O₃ (x = 0.6, 40PZN-60PZT) were deposited on Pt/TiO₂/ SiO₂/Si substrate through spin coating. Using a combination of homogeneous precursor solution preparation and two-step pyrolysis process, we were able to obtain the 40PZN-60PZT thin films of perovskite phase virtually without pyrochlore phase precipitation after annealing above 650^∘C. But since annealing done at the high temperatures for extended time can cause diffusion of Pt, TiO₂ and Si, and precipitation of nonstoichiometric PbO, we adopted 2-step annealing method to circumvent these problems. The 2-step annealed films show dense microstructure than the 1-step films annealed at higher temperature. Furthermore, the root-mean-square surface roughness of 220 nm thick films which are annealed at 720^∘C for 1 min and then annealed at 650^∘C for 5 min was found to be 3.9 nm by atomic force microscopy as compared to the 12 nm surface roughness of the film annealed only at 720^∘C for 5 min. The electrical properties of 2-step annealed films are virtually same and those of the 1-step annealed films annealed at high temperature. The film 2-step annealed at 720^∘C for brief 1 min and with subsequent annealing at 650^∘C for 5 min showed a saturated hysteresis loop at an applied voltage of 5 V with remanent polarization (P _r) and coercive voltage (V _c) of 25.3 μC/cm² and 0.66 V respectively. The leakage current density was lower than 10⁻⁵A/cm² at an applied voltage of 5 V.     

Dielectric and Ferroelectric Properties of Ba(Zr0.35Ti0.65)O3 Thin Films Grown by a Sol-Gel Process

The Ba(Zr_0.35Ti_0.65)O₃ (BZT) thin films were deposited via sol-gel process on LaNiO₃-coated silicon substrates. XRD showed that the crystallinity of BZT film grown on LaNiO₃ coated silicon substrates is better than that of BZT film grown on Pt. Both films showed perovskite phase and polycrystalline structure. The temperature dependent dielectric measurements revealed that the thin films had the relaxor behavior and diffuse phase transition characteristics. The capacitor tuning was about 44% for each BZT film grown on LaNiO₃/Pt and Pt electrodes at 1 MHz. Especially, the values of dielectric loss at 1 MHz ranged from 0.02 to 0.009 in the bias range of 0 to 514 kV/cm, respectively. The leakage currents density of thin films grown on LaNiO₃/Pt and Pt electrodes at 300 kV/cm was about 8.5 × 10^–7 and 1.1 × 10^–5 A/cm², respectively. This work demonstrates a potential use of BZT films for application in tunable microwave devices.     

Pulse-Extended Excimer Laser Crystallisation of Pb(Zr,Ti)O 3 Thin Films for Integration on Low Thermal Budget Substrates

Excimer laser annealing has been used to convert low temperature (non-ferroelectric) deposited lead zirconate titanate (PZT) to the perovskite phase without significantly heating underlying layers. A pulse-extension technique has been used to lengthen the laser pulse duration from 25 ns to 374 ns, lowering the surface temperature and improving the heat distribution in the PZT, as compared to the non-extended case, but still not significantly heating the substrate. Initial experiments are reported which have shown the technique to be capable of crystallising over half a 500 nm thick PZT film to perovskite although a melting effect limited the converted thickness. The thickness crystallised is however of the order of that used in FeRAM devices and modelled temperature profiles suggest that the technique provides a tractable solution for high temperature processing of ferroelectric thin films of thickness 200-300 nm on low thermal budget substrates.     

Synthesis of Pb(Ni1/3Nb2/3)0.72Ti0.28O3 perovskite ceramics by a reaction-sintering process

Pb(Ni_1/3Nb_2/3)_0.72Ti_0.28O₃ (PNNT) perovskite ceramics produced by a reaction-sintering process were investigated. Without any calcination, the mixture of PbO, Ni(NO₃)₂, Nb₂O₅ and TiO₂ was pressed and sintered directly into PNNT ceramics. PNNT ceramics of 100% perovskite phase were obtained. For PNNT sintered for 2 h in PbO compensated atmosphere, maximum density reaches a value 8.49 g/cm³ (99.8% of the theoretical value) at 1250^∘C. A maximum dielectric constant 20600 occurred around 37^∘C at 1 kHz in PNNT sintered at 1250^∘C for 2 h.     

Microwave Performance of Distributed Analog Phase Shifter Using Ferroelectric (Ba,Sr)TiO3 Thin Films

This work presents the design, fabrication and microwave performance of distributed analog phase shifter (DAPS) fabricated on (Ba,Sr)TiO₃ (BST) thin films for X-band applications. Ferroelectric BST thin films were deposited on MgO substrates by pulsed laser deposition. The DAPS consists of high impedance coplanar waveguide (CPW) and periodically loaded tunable BST interdigitated capacitors (IDC). In order to reduce the insertion loss of DAPS and to remove the alteration of unloaded CPW properties according to an applied dc bias voltage, BST layer under transmission lines were removed by photolithography and RF-ion milling. The measured results are in good agreement with the simulated results at the frequencies of interest. The measured differential phase shift based on BST thin films was 24° and the insertion loss decreased from ?1.1 dB to ?0.7 dB with increasing the bias voltage from 0 to 40 V at 10 GHz.     

Effects of PbTiO 3 Seed Layer on the Characteristics of RF-Sputtered Pb(Zr 0.5 ,Ti 0.5 )O 3 Thin Films

The effects of seed layers on the characteristics of rf-sputtered lead zirconium titanate thin films were investigated. Prior to sputtering, PbTiO 3 seed layers (100 nm) were deposited onto the Pt/Ti/Si and Pt/Si substrates by sol-gel (spin coating) processing method. Structure-property relation was studied as functions of substrate temperature and sputtering conditions. Special efforts were given in optimizing the deposition parameters to prepare the films in the perovskite phase without post deposition annealing. Dielectric constant and loss tangent of the films were in the range 800-950 and 0.04 -0.06, respectively. Remanent polarization and coercive field were 23.1 w C/cm 2 and 75kV/cm, respectively, for the films without PbTiO 3 seed layer, where as the corresponding quantities for in situ -deposited perovskite Pb(Zr, Ti)O 3 films on PbTiO 3 seed layer were 28 w C/cm 2 and 65 kV/cm, respectively.     

Sol-gel法制备Bi3.25La0.75Ti2.94Nb0.06O12铁电薄膜及其性能研究

采用溶胶-凝胶法(Sol-gel)在p_Si和Pt/Ti/SiO2/Si衬底上制备Bi3.25La0.75Ti2.94Nb0.06O12(BLTN)铁电薄膜,研究了BLTN薄膜的晶相结构、表面形貌、铁电性能、介电性能和C_V性能。结果表明:所制备的BLTN薄膜具有单一的层状钙钛矿结构,且为随机取向;高于650℃退火处理的BLTN薄膜表面平整致密;铁电性能测试显示较饱和的电滞回线;当退火温度为650℃时,其剩余极化Pr和Ec分别为24.6μC/cm2和96.8 kV/cm,明显优于Bi3Ti4O12(BIT)薄膜的铁电性能;室温下,当测试频率为10 kHz时,薄膜的介电常数为386,介电损耗为0.69%,具有良好的介电性能;C_V曲线为顺时针方向回滞,记忆窗口约为1.5 V,可以实现极化存储。     

Preparation of Pb(Zr,Ti)O3 Thin Films on Silica Substrate by Metallo-Organic Decomposition

In this study, we report the deposition of crack-free transparent PZT films (up to ～859 nm) by metallo-organic decomposition (MOD) process on amorphous silica substrate. Effect of SrTiO₃ (STO) buffer layer on the growth behavior of PZT thin films deposited on SiO₂-coated silicon substrates was systematically studied. Perovskite phase, which cannot be formed directly on SiO₂/Si substrates, has been obtained when a thin STO film (～150 nm) was used as buffer layer. A SIMS examination indicates that the upward diffusion of Si-species into PZT layer is minimal, although downward diffusion of Pb-species into the SiO₂ layer is still observable.     

Influence of Post-Annealing on the Characteristics of Pb(Zr,Ti)O3 Thin Films Deposited by Liquid Delivery MOCVD Using a Cocktail Solution

Ferroelectric PZT thin films were deposited by liquid delivery MOCVD using a cocktail solution. The cocktail solution consisted of Pb(METHD)₂, Zr(METHD)₄ and Ti(MPD)(METHD)₂ diluted with ethylcyclohexane. The films deposited on Pt/Ti/SiO₂/Si at a substrate temperature of 500°C consisted of PZT, PbO and PbPt_x, and showed poor properties. However, after annealing at 450°C in air for thirty minutes, the PbPt_x phase disappeared while the volume of the PbO phase increased. The hysteresis properties were also improved by annealing at 450°C. After annealing at 600°C in air for thirty minutes, the PbPt_x and the PbO phases disappeared perfectly and the PZT thin films showed good hysteresis properties with the remanent polarization of 30 μC/cm² and the coercive field of 88 kV/cm.     

Low Temperature Process for Synthesis of (100) Textured Pb(Zr0.48Ti0.52)O3 Thin Films on Si Substrate by Laser Lift-Off Transferring Technique

(100) textured Pb(Zr_0.48Ti_0.52)O₃ (PZT) films were prepared on silicon substrates by MOD process and laser lift-off technique. Textured PZT films were first grown on (001) Sapphire substrate, using Ba(Mg_1/3Ta_2/3)O₃ (BMT) materials as buffer layer. The (100) textured PZT/BMT/Sapphire films were attached to Si substrate using a transient-liquid-phase Pd-In bonding process, and then were separated from Sapphire substrates by a laser lift-off process, in which, a 38 ns pulse from excimer laser (248 nm) at 600 mJ/cm² fluence melted BMT buffer layer, expelling the Sapphire. The crystallinity of the surface of films was further improved by laser annealing. X-ray diffraction analysis of the PZT films showed that the crystallographic structure of films is maintained during laser lift-off process. Electrical testing of the films after laser lift-off process followed by laser annealing demonstrated that the ferroelectric properties are retained for the transferred films (P_r = 9μ C/cm² and E_c = 74 kV/cm).     

Epitaxial thin film heterostructures of relaxor ferroelectric Pb(Mg1/3Nb2/3)O3-PbTiO3

Abstract

We have grown stoichiometric pure perovskite phase Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) thin films and PMN-PT/SrRuO₃ heterostructures on miscut (100) SrTiO₃ substrates by pulsed laser deposition. X-ray diffraction θ–2θ scans show that the PMN-PT films are purely c-axis oriented. The off-axis Φ scans show that the heterostructures grow “cube-on-cube” with an in-plane epitaxial arrangement of PMN-PT[100], [010] // SrRuO₃[001] // SrTiO₃[100] and PMN-PT[010], [100] // SrRuO₃[110] // SrTiO₃[010]. The crystalline quality of the films found to be comparable to that of bulk single crystals. The AFM images show that the SrRuO₃ and PMN-PT layers have smooth surfaces with root mean square roughness of 9Å. These epitaxial heterostructures can be used for the fabrication of piezoelectric devices.     

Studies of ZnO Thin Films On Sapphire (0001) Substrates Deposited by Pulsed Laser Deposition

ZnO thin films are deposited on sapphire (0001) substrates at different temperatures in the pulsed laser deposition (PLD) system. By measurements of X-ray diffraction (XRD), atomic force microscopy (AFM), and Photoluminescence (PL) at room temperature, fabrication temperatures higher than 400C is found to be the optimum condition for the structural and optical properties of ZnO thin films. With the increase of the fabrication temperature, the grain size becomes bigger and the thin film becomes more homogeneous. In order to get the high-quality ZnO thin film at low temperature, ZnO thin films are deposited at room temperature and annealed in a rapid thermal annealing (RTA) system. It is found that the optical property of the thin film can be greatly improved by annealing in RTA system.     

Pb((Mg0.7Zn0.3)1/3Nb2/3)O3 Relaxor Ferroelectric Ceramics by a Reaction-Sintering Process

Pb((Mg_1/3Nb_2/3)_0.7(Zn_1/3Nb_2/3)_0.3)O₃ (PMZN) relaxor ferroelectric ceramics produced by a reaction-sintering process were investigated. Without any calcination, the mixture of PbO, Mg(NO₃)₂, Zn(NO₃)₂ and Nb₂O₅ was pressed into pellets and sintered directly. PMZN ceramics of 100% perovskite phase were obtained. Density of 8.11 g/cm³ (> 98% of theoretical value) was obtained after sintered at 1200C for 2 h. 3–9 m grain size was obtained in PMZN ceramics sintered at 1180C–1250C for two hours by reaction-sintering process.Dielectric constant at room temperature under 1 kHz reaches 18200 after sintered at 1200C for 2 h.     

Substituent Effects in 0.65Pb(Mg1/3Nb2/3O30.35PbTiO3 Piezoelectric Ceramics

Pb(Mg_1/3Nb_2/3O₃–-PbTiO₃ (PMN-PT) ceramics with base compositions close to the morphotropic phase boundary are potential materials for many applications such as transducers and actuators due to their high dielectric constants and electromechanical coupling factors. However, their dielectrical and mechanical losses are too high for high-power applications. In this paper, the dielectric and electromechanical properties of piezoelectric PMN-PT ceramics were investigated in specimens containing various A-site and B-site substituents with the goal of developing lower loss materials for wider applications. Emphasis was placed on various transition metal cation substituents of both lower and higher valences. Mn substituent was found to be the most promising substituent investigated for developing high power low loss piezoelectric PMN-PT ceramics.     

Water-Immersible Micromachined Pb(Zr, Ti)O3 Thin Film Actuators

We demonstrate a water-immersible thin film lead zirconate titanate, Pb(Zr, Ti)O₃, [PZT] actuator, without special passivation layer, towards in-vivo or in-vitro scanning probe microscope (SPM) measurements of living cells in water or biological fluids. In order to be water-immersible, the electrodes need to be electrically insulated and the piezoelectric layer needs to be protected against direct water contact. This paper describes our design solution with a simple fabrication process for a water-immersible piezoelectric device, which separates the bottom electrode from the top electrode by having a narrow ditch covered with PZT film. The PZT film is then encapsulated with the top metal electrode without insulation layer. In this structure, the PZT is sandwiched between the top and bottom metal electrodes to prevent water permeation. The device is fabricated using lift-off processing for the bottom and top electrodes, sol-gel spinning for the PZT thin film and wet etching for the PZT patterning. The piezoelectric constant, d₃₁, is about –100 pC/N. The dielectric polarization and fatigue properties of the devices were measured in air and water. The spontaneous polarization, remnant polarization, coercive field and dielectric constant are 54 C/cm², 15 C/cm², 60 kV/cm and 1200, respectively. The polarization property of the device was unchanged in either air or water up to 1 × 10⁹ continuous cycles.