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.     

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.     

Investigation on the Dielectric and Polarization Behavior of Sol-Gel Derived Erbium Doped Pb(Zr 0.53 Ti 0.47 )O 3 Thin Films

We have studied the effect of Er 3+ doping on the dielectric and polarization hysteresis behavior of sol-gel derived Pb 1.05 (Zr 0.53 Ti 0.47 )O 3 thin films. Up to 1 at% Er doping, the dielectric constant of undoped PZT increases from 1245 to 1477 (measured at 50 kHz, 500 mV oscillation voltage), whereas the remnant polarization increases from 30 to 41 w C/cm 2 . Under the subswitching external field, the dielectric permittivities follow the Rayleigh law. The Rayleigh coefficient ( f ) was considered as a measure of the ease of domain wall motion. Up to 1 at% Er doping, the increase of f indicates minimal defect-domain wall interaction due to lower defect concentration. Under the switching field, the irreversible part of the switchable polarization was estimated from the C-V and hysteresis measurements. At the saturation field it was observed that up to 1 at% Er doping the irreversible component at switchable polarization increases and reversible component remains low. The improvements of dielectric and ferroelectric properties for up to 1 at% Er doping have been correlated to the relative site occupancy of Er 3+ as a function of Er content in PZT host lattice.     

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.     

Preparation of Textured Growth Pb(Zr,Ti)O3 Thin Films on Si Substrate Using SrTiO3 as Buffer Layers

PZT thin films are deposited on SiO₂/Si substrate by metallo-organic decomposition (MOD) process, using SrTiO₃ (STO) as buffer layer for textured growth. The STO layers deposited on SiO₂/Si substrate by pulsed laser deposition process show (100)/(200) preferred orientation, whereas the STO buffer layer deposited on silica substrate using spin-coating technique show random orientation behavior. The use of STO as buffer layers enhanced the crystallization and the preferred orientations of the PZT films. The PZT on STO buffered SiO₂/Si substrates thus obtained possess high refractive index, (n)_PZT/STO = 2.1159, and are of good enough quality for optical waveguide applications.     

Thermal hysteresis in the permittivity and polarization of leadzirconate titanate/vinylidenefluoride-trifluoroethylene 0-3 composites

The permittivities of 70/30 vinylidene fluoride-trifluoroethylene copolymer and lead zirconate titanate/vinylidene fluoride-trifluoroethylene 0-3 composites have been measured at 1 kHz over the temperature range of 20 to 120°C. Thermal hysteresis was observed for the 0-3 composites and abrupt changes in the permittivities occurred at different temperatures upon heating and cooling. Good agreement was found between the measured permittivities and the predictions of the Bruggeman model. Implications of the thermal hysteresis behavior on the poling of 0-3 composites are also discussed     

Leaf-Like-Dendritic Cesium Nitrate:Poly (Ethylene Oxide) Composite Films and Their Thermal and Ferroelectric Properties

Leaf-like-dendritic structures of cesium nitrate: poly (ethylene oxide) (CsNO₃:PEO) composite films have been fabricated by a simple solvent-cast method. The field emission scanning electron microscopy image analysis revealed that the dendritic structures were composed of multilevel generations with a long main trunk and many well-aligned side branches. The diameters of the trunks, branches, and sub-branches were controlled with variation of wt.% of CsNO₃ in the composition. The curly PEO chains conceivably play a key role in growth of leaf-like-dendritic structures. The crystallite size in the composite films was found to be large as compared to pure CsNO₃ film, and maximum for 40–60 wt.% CsNO₃ in composite films. The ferroelectric phase transition peak was observed in the differential scanning calorimetry scan. The optimization of the ferroelectric properties of the composite films as a function of composition gave 50 wt.% to be the optimum value.     

(La1-xTbx)2/3Sr1/3MnO3薄膜的巨磁电阻效应

利用脉冲激光沉积法制备了（La1-xTbx)2/3Sr1/3MnO3系列薄膜样品。在77－300K的温度范围内,对样品的微观结构、磁化强度、电阻率和巨磁电阻效应等物理性质进行了系统研究。随着Tb含量x的增大,铁磁－顺磁转变温度随之下降,在x=0. 33样品中,最大磁化场μ0H=1.2T时,观察到34％的巨磁电阻。本文对其机理进行了研究和讨论。     

Atomic Layer Deposition (ALD) of Bismuth Titanium Oxide Thin Films Using Direct Liquid Injection (DLI) Method

We report on atomic layer deposition of bismuth titanium oxide thin films for use in ferroelectric random access memory (FRAM). Bismuth titanium oxide thin films were grown on ruthenium and platinium coated silicon substrates respectively. We used tris(1-methoxy-2-methyl-2-propoxy)bismuth, Bi(mmp)₃ and tetrakis(1-methoxy-2-methyl-2-propoxy)titanium, Ti(mmp)₄ as metal organic precursors, which were mixed together in organic solvent, ethyl cyclo hexane (ECH), and then put through the vaporizer. The variations of the composition and growth rate with wafer temperature over 350～450 and 250～500C was investigated. The process window for ALD is below 350C and bismuth content in films starts to decrease above 425C. The as-grown films at 300C were amorphous. After post deposition annealing at 700C for 5 minitues we had well-cystallised Bi₄Ti₃O₁₂ thin films. However, we didn't have well-saturated hysterisis curve, which the remenant polization is 8.9 uC/cm² at 7 V. The dielectric constant is about 320 and the leakage current is below 10^?8 A/cm² at 0.8 MV/cm.     

Ferroelectric and Pyroelectric Properties of Sol-Gel Derived PbCaTiO3 Thin Films Using Low-Temperature Annealing

PCT7030 (Pb_0.7Ca_0.3TiO₃, PCT7030) films have been prepared by a sol-gel method on platinum-coated Si substrate. PCT7030 films were treated at different radiation densities using CO₂ laser annealing to obtain good ferroelectric properties without causing thermal deterioration of the underlying layer. In addition, metallic oxide LaSrMnO₃ buffer layer was employed to improve the electrical properties of PCT7030 films. From XRD measurements, we found that fully perovskite phase of PCT7030 films could be obtained at a radiation density below 572 W/cm². On the other hand, perovskite phase of PCT7030 films with co-existing TiO_x were observed for specimens treated at a higher radiation density. The correspondent P-E curves of PCT7030 films with entirely perovskite phase exhibited saturated hysteresis loops and the specimens possessing perovskite PCT7030 and co-existing TiO_x phase showed serious leakage. Microstructural investigations imply that grain size increases with increasing radiation density, and voids may evolve on the grain boundaries when high radiation density was employed, indicating that atomic species evaporation of PCT7030 films or coarsening-induced voids may be produced at an over-annealing condition and therefore electrical properties were deteriorated. In the pyroelectric measurement, pyroelectric coefficient of CO₂ laser-annealed PCT7030 films varied as a function of calcium content and a pyroelectric coefficient maximum were obtained at a composition near PCT7030, indicating that low temperature laser-annealing process can be employed in ferroelectric and pyroelectric thin film preparation.     

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.     

Structure and Properties of Preferential (110) Orientation BiFeO3 Thin Films by Sol-Gel Method

Abstract

Multiferroic materials, coexisting of ferroelectric, ferromagnetic and ferroelastic properties, possess potential applications in functional devices. BiFeO₃ (BFO) is a unique room temperature multiferroic material with high ferroelectric Curie temperature and Neel temperature. The BFO thin films were prepared on Si (111) substrate by sol-gel method in this paper. XRD analyses show that the thin films exhibit pure phase and preferred (100) orientation when annealing temperature is 500?°C. Field emission scanning electron microscopy shows that the crystallization degree of the films is getting better with the increase of annealing temperature. The thickness of the sample is about 400?nm. The hysteresis loop of BFO films annealing at 500?°C show 1.93?µC/cm² remnant polarizations. However, the hysteresis loop is not perfect, which may be caused by a large leakage current. The magnetic hysteresis loop of BFO films is tested as well, indicating that the BFO film is antiferromagnetic and the residual magnetization (Mr) and coercive field (Hc) of the BFO films were 0.054?emu/g and 1026.4?Oe, respectively.     

Growth of (Ba,Sr)TiO 3 Thin Films by MOCVD: Stoichiometry Effects

(Ba x Sr 1 m x )TiO 3 thin films were deposited in a planetary multi-wafer MOCVD reactor combined with a liquid delivery system using 0.35 molar solutions of Ba(thd) 2 and Sr(thd) 2 and a 0.4 molar solution of Ti(O-i-Pr) 2 (thd) 2 . The film growth on Pt-(111) was investigated within a wide parameter field, e.g., the deposition temperature was varied between 560C and 650C, which yields films with microstructures ranging from randomly oriented polycrystalline to perfectly (100)-textured columnar structures. Special emphasis is given to film stoichiometry: starting with (Ba 0.7 Sr 0.3 )TiO 3 the Group-II/Ti content was varied from 0.9 to 1.1 and the Ba content was reduced to the limit of pure SrTiO 3 films. The electrical properties of MIM structures were investigated after deposition of Pt top electrodes. The nominal thickness of the films was varied between 5 and 100 nm and permittivity and leakage current both are shown to depend strongly on the film thickness. These dependencies on the film thickness are analyzed within the phenomenological dead layer model. The dependence of the electrical properties on stoichiometry are discussed in detail.     

Interface Structures and Epitaxial Behavior of Ferroelectric (Ba,Sr)TiO 3 Thin Films

Perovskite Ba 0.6 Sr 0.4 TiO 3 thin films were epitaxially grown on (001) LaAlO 3 and (001) MgO by using pulsed laser ablation. The films are single crystal cubic structure with interface relationship of (001) BST // (001) MgO and <100> BST // <100> MgO for the films on (001) MgO and (001) BST // (001) LAO and <100> BST // <100> LAO . High-resolution transmission electron microscopy studies indicated that the initially grown layer of the film on both (001) MgO and (001) LAO is TiO 2 monolayer. Equally spaced misfit dislocations were found to form at the interface to release the lattice mismatch energy. Physical property measurements show that the films exhibit excellent room temperature dielectric behavior with very low dielectric loss of 0.007 and very large tenability of 45% at 1 MHz. The figure of merit of 60°/dB has been achieved for the microwave phase shifter operated at 24 GHz and room temperature.     

Structure of Ferroelectric (Ba,Sr)TiO3 Thin Films for Tunable Microwave Devices

Ferroelectric (Ba,Sr)TiO₃ films have been deposited on (001) MgO single crystals by a pulsed laser deposition with oxygen background while heating the substrates. Deposited BST films exhibit epitaxial growth along (001), which are confirmed by x-ray diffraction measurement. Structure of (Ba,Sr)TiO₃ along in-plane and surface normal direction have been investigated and found to have a tetragonal distortion depend on the deposition conditions, such as oxygen pressure. Lattice parameter decreases with increasing oxygen pressure, and tetragonallity (c/a) changes from 1.005 to 0.997 as oxygen pressure increase. Interestingly, energy gap measured by FTIR decreases with decreasing oxygen pressure until it reach a certain oxygen pressure, then increases again with increasing oxygen pressure. Furthermore, microwave properties of devices measured by a HP 8510C vector network analyzer from 0.045–20 GHz suggest that the least distorted films exhibit a larger dielectric constant changes with dc bias field.     

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.     

Ni65Co35薄膜各向异性磁电阻性能的研究

选用Ｎｉ６５Ｃｏ３５合金靶材，利用射频磁控溅射的方法成膜，采用四控针法测量磁电阻率，分别研究了溅射工艺参数（工艺气压、偏压、功率、基片温度等）对薄膜电阻性能的影响，并对影响的机理作了理论上的分析；另外还对Ｎｉ６５Ｃｏ３５薄膜的热处理动力学进行了研究，求取了激活能。研究结果表明，溅射工艺参数对Ｎｉ６５Ｃｏ３５薄膜的电阻力有较大的影响，适当的溅射参数能有效地提高磁电阻率；Ｎｉ６５Ｃｏ３５薄膜退火处理后     

Initial Stage Nucleation and Growth of Epitaxial SrRuO3 Thin Films on (0 0 1) SrTiO3 Substrates

We have investigated the initial stage nucleation and growth of epitaxial SrRuO₃ thin films grown on both polished (as received) and buffered HF (BHF) etched single crystal (0 0 1) SrTiO₃ substrates by 90° off-axis sputtering. Atomic force microscopy indicates a dramatic difference in the initial stage growth of SrRuO₃ films on the two substrates. The films on polished substrates nucleate as rectangular islands, which merge together to form a continuous film as the thickness increases. Complete coverage is obtained at film thickness of 20 nm. In contrast, the film on BHF etched substrate nucleates as finger-shaped islands at the step sites and continues to grow by adatom diffusion to the step sites. Complete coverage is obtained at a film thickness of 10 nm. This difference in the initial stage nucleation is attributed to the difference in surface morphology and termination layer of the two substrates. However, the thicker films on both as received and BHF etched substrates have identical surface morphologies. Such studies on the initial stage nucleation will also help us understanding the growth kinetics and development of surface morphology and interfaces in multilayered perovskite thin film heterostructures and devices.     

Optimum Reflection-Type Phase Shifter Using (Ba,Sr)TiO3 Thin Film

In this paper, in order to obtain a large differential phase shift with a little change in applied voltage, a ferroelectric reflective load circuit has been designed on top of barium strontium titanate (Ba,Sr)TiO₃ [BST] thin film. The design of the ferroelectric reflection-type phase shifter is based on a reflection theory of terminating circuit, which has a reflection-type analogue phase shifter with two ports terminated in symmetric phase-controllable reflective networks. To achieve large amounts of phase shift in low bias-voltage range, the effects of change of capacitance and transmission line connected with two coupled ports of a 3-dB 90° branch-line hybrid coupler have been investigated. A large phase shift with a small capacitance change in the parallel terminating circuit has been demonstrated in the paper.     

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.